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951f66c7af2b0c0cd787c63189b2562b63eb1947
helen murray free was an american chemist and
helen murray free was an american chemist and educator. she is most known for revolutionizing many in vitro self-testing systems for diabetes and other diseases while working at miles laboratories. the tests are still marketed today with blood tests as ascensia diabetes care, and urine tests under siemens healthineers....
wikipedia
4b4dd4f23414a727c839d070ee0137fa4259a88b
the work of helen and al free in
the work of helen and al free in developing diagnostic test strips was designated a national historic chemical landmark by the american chemical society on may 1, 2010, at the ethos science center in elkhart, indiana. she was inducted into the national women's hall of fame one year later.
wikipedia
1c72d09098290c9b4d7e4bb24d19cf665c47672d
free was elected president of the american chemical
free was elected president of the american chemical society in 1993. as president, she considered her top priority to be to raise public awareness of the positive role chemistry has played in our lives. the acs named an award in her honor, the helen m. free award for public outreach.
wikipedia
e23b2f0e7747d30dd733df32cce406501946b9a4
in 1947 she married alfred free, a fellow
in 1947 she married alfred free, a fellow researcher in urinalysis. together, they had six children: eric, kurt, jake, bonnie, nina, and penny. also, she helped raise three stepchildren: charles, jane and barb.
wikipedia
a988e25a281cb3f6e58f5a104fbfc4d7110438a1
by 1975, free had earned seven patents for
by 1975, free had earned seven patents for her improvements in medical and clinical urinalysis testing. in that year, she and her husband co-authored their second book, urinalysis in laboratory practice, which is still a standard work in the field. she retired in 1982, but continued to work as a consultant for bayer di...
wikipedia
f6eaf65d9c1f6714b05cd5efdeed0f3f447c9d28
it was from developing the ictotest that got
it was from developing the ictotest that got the frees thinking. free worked with her husband to make the tests even more convenient than tablets by creating strips. the duo introduced clinistix (the famous “dip-and-read” test) in 1956. it was the first dip-and-read diagnostic test strip for monitoring glucose in urine...
wikipedia
c81815724db7c9bed600f3bf5a6025255b1e1392
originally they researched different antibiotics before they moved
originally they researched different antibiotics before they moved on to dry reagent systems. the first thing alfred and his team were tasked with was further refining clinitest to make it more sensitive. clinitest was a tablet that measured glucose levels in the urine of diabetic patients when a diluted solution of ur...
wikipedia
7231977c0cd90b8ecda6594407ee57d2cc5efa56
free's career search began even before completing her
free's career search began even before completing her college education. during her final year at wooster, she took interest in the koppers chemical company in orrville, ohio. however, she was put down after hearing that her job would be testing the creosote that fence posts were dipped in before they were sold to loca...
wikipedia
87db5e4aeba3d25434d137bf22864211dd3f913a
free received her early education from the public
free received her early education from the public schools in youngstown, ohio, and graduated in 1941 as the valedictorian of poland seminary high school. while attending a summer camp at the college of wooster, she set her heart on attending wooster. greatly influenced by her high school english teacher, she originally...
wikipedia
46ed8aacc83ce58370a10096fb06c7c56ce18dec
free was born in pittsburgh, pennsylvania, on february
free was born in pittsburgh, pennsylvania, on february 20, 1923. her father, james s. murray, worked as a coal company salesman; her mother, daisy piper murray, died during an influenza epidemic when free was six.
wikipedia
1f321e5221150ac78ffdf1cc2c5c7b09bdc8cba0
helen murray free (february 20, 1923 – may
helen murray free (february 20, 1923 – may 1, 2021) was an american chemist and educator. she is most known for revolutionizing many in vitro self-testing systems for diabetes and other diseases while working at miles laboratories. the tests are still marketed today with blood tests as ascensia diabetes care, and urine...
wikipedia
688cd94b41e84ad0e70e7d1abd9119be8d232925
in october 2020, doké was handed his maiden
in october 2020, doké was handed his maiden call up into the togo national team by claude le roy at the age of 16 years. he made his debut on 12 october 2020, after coming on in the 79th minute for gilles sunu in a friendly match against sudan. the match ended in a 1–1 draw.
wikipedia
02f1d10f1cd9625e0dc1ddc9704a00fe1ceb25bc
her work focuses on the history of women
her work focuses on the history of women and gender in england from the eighth to the early twelfth century, and on the same topics in the history of the franks from the eighth to the ninth century, as well as on the anglo saxon chronicles after alfred.
wikipedia
7915e00f58a8b0534b7df37453890c21c984be25
butenafine, sold under the brand names lotrimin ultra,
butenafine, sold under the brand names lotrimin ultra, mentax, and butop, is a synthetic benzylamine derived antifungal drug. it is structurally related to the allylamine antifungals terbinafine & naftifine.
wikipedia
02f2d040c7ba159ef5760d29c4bfc5a82786ceb2
reductive amination of 1-naphthaldehyde (1) with methylamine (2)
reductive amination of 1-naphthaldehyde (1) with methylamine (2) gives the intermediate secondary amine (3). alkylation of this with p- tert-butyl benzyl bromide (4) yields the tertiary amine butenafine.
wikipedia
44149c861ad5d1c6d5a005271a6c31d84dd3031d
in addition to being an antifungal, butenafine is
in addition to being an antifungal, butenafine is an anti inflammatory. because fungal skin infections are often accompanied by significant inflammation, this is a desirable property. the fact that butenafine has intrinsic anti inflammatory properties is also desirable since it is not necessary to add topical glucocort...
wikipedia
2dc0c6fbc3f2fa47c1b7843405c99aa0260062f0
like the allylamine antifungals (e.g terbinafine), butenafine works
like the allylamine antifungals (e.g terbinafine), butenafine works by inhibiting the synthesis of ergosterol by binding to and inhibiting squalene epoxidase, an enzyme in the pathway used for creation of the sterols needed in fungal cell membranes. lacking ergosterol, the cell membranes increase in permeability, allow...
wikipedia
eb424ab31ffeb083b7acf6529eee18f658a4353b
butenafine is indicated for the topical treatment of
butenafine is indicated for the topical treatment of tinea (pityriasis) versicolor due to malassezia furfur, as well as athlete's foot (tinea pedis), ringworm (tinea corporis) and jock itch (tinea cruris) due to epidermophyton floccosum, trichophyton mentagrophytes, trichophyton rubrum, and trichophyton tonsurans.
wikipedia
94b97664f828130577ca13b403b64468826eadb1
in 1965, shiji became a manager for toyota
in 1965, shiji became a manager for toyota motors. in 1966, the club joined japanese regional leagues. he promoted the club to new division japan soccer league (jsl) division 2 in 1972 and jsl division 1 in 1973. he resigned in 1974.
wikipedia
c34621445957ad3af1071f38e34a646a6f1e88c2
shiji was born in aichi prefecture on october
shiji was born in aichi prefecture on october 20, 1938. when he was a kwansei gakuin university student, he won 1959 emperor's cup as a member of kwangaku club was consisted of his alma mater kwansei gakuin university players and graduates. after graduating from kwansei gakuin university, he played for his local club t...
wikipedia
a6198818b418cae19fc7a21ad728247b679e929c
the 2015–16 season was the 12th in the
the 2015–16 season was the 12th in the history of adelaide united football club since its establishment in 2003. the club participated in the a-league for the 11th time, the ffa cup for the second time and the afc champions league for the fifth time. ahead of the season, manager josep gombau stood down, citing family r...
wikipedia
695822c9ddf3c1d4676b62395a93db8c3bc443ac
the 2015–16 season was the 12th in the
also be their first time hosting the match. second-placed western sydney wanderers travelled to adelaide oval for the grand final. bruce kamau scored in the 21st minute and won a free kick that was converted by isaías in the 32nd minute. scott neville's goal just shy of the hour mark brought the wanderers back into th...
wikipedia
2fbfa24a1fac72537625bee167901cb2a26a64fb
adelaide played melbourne city in the semi-final. after
adelaide played melbourne city in the semi-final. after a scoreless first half, bruce djite broke the deadlock in the 48th minute, curling the ball into the top right corner from outside the box. djite would double their lead from the penalty spot 12 minutes later. fitzgerald pulled a goal back for melbourne city, but ...
wikipedia
d9439d47cea8c7975c9ab4fcbd5cfe9c9a1bffe4
ahead of the season, manager josep gombau stood
ahead of the season, manager josep gombau stood down, citing family reasons. he was replaced by the club's technical director, guillermo amor, in his first senior managerial role. adelaide united were knocked out of the ffa cup in the quarter-finals by rivals melbourne victory, their first loss in the competition's his...
wikipedia
98b1dfe2eaf14459e1dbf075a5c2d05c6147931c
the 2015–16 season was the 12th in the
the 2015–16 season was the 12th in the history of adelaide united football club since its establishment in 2003. the club participated in the a-league for the 11th time, the ffa cup for the second time and the afc champions league for the fifth time.
wikipedia
48c66d6aaafb2ac80e1adf2b1d1382c16bfb69b7
keijō imperial university was an imperial university in
keijō imperial university was an imperial university in keijō (seoul), korea, empire of japan that existed between 1924 and 1946. the university was seen as the preeminent educational institution in colonial korea. upon the 1945 liberation of korea, it was briefly renamed kyŏngsŏng university, was seized by the united ...
wikipedia
70e3e3e76106a06c10fe03fba4e337d46a0e025a
for korean individuals, admission into keijō imperial university
for korean individuals, admission into keijō imperial university was a very competitive process as the admission of korean students was restricted to between one-fourth and one-third of the total number of enrolled students at keijō imperial university. by 1930, six years after keijō university was established, the num...
wikipedia
dc214fc796f238340336d8719ae2975900a0c131
controversies surrounding keijō imperial university's research of physical
controversies surrounding keijō imperial university's research of physical anthropology and blood typing is related to the use of a racial index. professor ock joo kim of seoul national university states “the japanese researchers put koreans as a race between the mongolian and the japanese. the preoccupation with const...
wikipedia
79a6247efbd8e1bc9424ec30bcaa693669ec09e5
the keijō imperial university research team organised and
the keijō imperial university research team organised and conducted field studies on sampling of blood typing, as well as physical anthropology research from people representative of the korean peninsula. the gathering of men and women by local police and administrative power had been conducted as measuring them was ne...
wikipedia
2de251217fa89683d781f326218bd1cbaa54e557
keijō imperial university published original articles and abstracts
keijō imperial university published original articles and abstracts in journals including shinkeigaku-zassi (neurologia), seishin-shinkei-gaku zassi (psychiatria et neurologia japonica), and the journal of chosun.
wikipedia
21cd44fd2bc6685bceca4212d24f4c8fa346eac3
the remaining properties of keijo university merged with
the remaining properties of keijo university merged with gyeongseong industrial school, gyeongseong mine school, gyeongseong medical school, suwon agriculture school, gyeongseong economics school, gyeongseong dental medicine school, gyeongseong normal school and gyeongseong women's normal school into seoul national uni...
wikipedia
bc61b2c3595491fe38d8065bffa8d62906d46bf4
after the liberation of korea, keijō imperial university
after the liberation of korea, keijō imperial university was renamed to "gyeongseong university" (경성대학; 京城大學). after the war, it was no longer considered a japanese university, and it was closed by the usamgik on august 22, 1946, under us military ordinance no. 102. while speaking to korean officials, the u.s. military...
wikipedia
003c20a0c98980f5ae2bdc627fba4b1129290d00
in 1926, three-year programs for law and literature
in 1926, three-year programs for law and literature were established, as well as a four-year medical program. in 1928, a hospital affiliated with the university finished construction. in april 1929, it graduated its first class of 90 law and literature students, 22 of whom were ethnic koreans. in 1930, it graduated its...
wikipedia
3c0a7d78585b8299f22298f6c32b9b096977abd8
keijō imperial university was founded in 1924. it
keijō imperial university was founded in 1924. it was initially a two-year liberal arts program. they began gradually adding new programs over time, based on what was deemed important for colonial korea. an article in the encyclopedia of korean culture argues that science and engineering programs were deliberately not ...
wikipedia
5181208f00b607cebaa61ff9ad9b6c28e810552f
in 1923, an organization called the korea private
in 1923, an organization called the korea private university foundation committee (조선민립대학기성회; 朝鮮民立大學期成會) was formed. its founding leader was yi sang-jae. in response to their activism, the japanese government-general of chōsen agreed to a proposal (경성제국대학령) to found a university in korea.
wikipedia
42ceda0215877ecd68e9b785693e50f72106fcff
the university was seen as the preeminent educational
the university was seen as the preeminent educational institution in colonial korea. upon the 1945 liberation of korea, it was briefly renamed kyŏngsŏng university, was seized by the united states army military government in korea (usamgik) in 1946, and reorganized into its successor: the present seoul national univers...
wikipedia
ac0dbe085c7a95112f12f807a3d777a83365cd05
in biochemistry, isomerases are a general class of
in biochemistry, isomerases are a general class of enzymes that convert a molecule from one isomer to another. isomerases facilitate intramolecular rearrangements in which bonds are broken and formed. the general form of such a reaction is as follows: there is only one substrate yielding one product. this product has t...
wikipedia
4caa93d4285f9727797497ed00dc55615ed8485d
glucose isomerase is able to catalyze the isomerization
glucose isomerase is able to catalyze the isomerization of a range of other sugars, including d- ribose, d- allose and l- arabinose. the most efficient substrates are those similar to glucose and xylose, having equatorial hydroxyl groups at the third and fourth carbons. the current model for the mechanism of glucose is...
wikipedia
43945da275cb2ce9d150d6bf8dd91cf296b0a7e3
the isomerization of xylose to xylulose has its
the isomerization of xylose to xylulose has its own commercial applications as interest in biofuels has increased. this reaction is often seen naturally in bacteria that feed on decaying plant matter. its most common industrial use is in the production of ethanol, achieved by the fermentation of xylulose. the use of he...
wikipedia
12f6de46bc1600673704535471556a9ef584d570
the conversion of glucose to fructose is a
the conversion of glucose to fructose is a key component of high-fructose corn syrup production. isomerization is more specific than older chemical methods of fructose production, resulting in a higher yield of fructose and no side products. the fructose produced from this isomerization reaction is purer with no residu...
wikipedia
d008ca461caab11dd417768c43fe0541a14c3088
by far the most common use of isomerases
by far the most common use of isomerases in industrial applications is in sugar manufacturing. glucose isomerase (also known as xylose isomerase) catalyzes the conversion of d- xylose and d- glucose to d- xylulose and d- fructose. like most sugar isomerases, glucose isomerase catalyzes the interconversion of aldoses an...
wikipedia
dd6b10e0d565f0047511714d754bbf3b59c70aa5
supportive measures such as red cell transfusions in
supportive measures such as red cell transfusions in cases of severe anaemia can be taken to treat tpi as well. in some cases, spleenremoval (splenectomy) may improve the anaemia. there is no treatment to prevent progressiveneurological impairment of any other non-haematological clinical manifestation of the diseases.
wikipedia
befb0f468ad9ef12639d665835e1b1e68506f945
treatment for tpi is not specific, but varies
treatment for tpi is not specific, but varies according to different cases. because of the range of symptoms tpi causes, a team of specialist may be needed to provide treatment to a single individual. that team of specialists would consists of pediatricians, cardiologists, neurologists, and other healthcare professiona...
wikipedia
e9fa81e07f389405e7870cc46e2fbae60753fee5
tpi is detected through deficiency of enzymatic activity
tpi is detected through deficiency of enzymatic activity and the build-up of dihyroxyacetone phosphate(dhap), which is a toxic substrate, in erythrocytes. this can be detected through physical examination and a series of lab work. in detection, there is generally myopathic changes seen in muscles and chronic axonal neu...
wikipedia
6ff4ae4e8087dd9f04f4053c86160cfe05ce0f89
individuals with tpi show obvious symptoms after 6–24
individuals with tpi show obvious symptoms after 6–24 months of age. these symptoms include: dystonia, tremor, dyskinesia, pyramidal tract signs, cardiomyopathy and spinal motor neuron involvement. patients also show frequent respiratory system bacterial infections.
wikipedia
be723dfbd1e029326a9ba836ada811b5c0ff5f5f
tpi deficiency is very rare with less than
tpi deficiency is very rare with less than 50 cases reported in literature. being an autosomal recessive inherited disease, tpi deficiency has a 25% recurrence risk in the case of heterozygous parents. it is a congenital disease that most often occurs with hemolytic anemia and manifests with jaundice. most patients wit...
wikipedia
cab314f001436f64254e98730e1f89fc756b9e36
the disease referred to as triosephosphate isomerase deficiency
the disease referred to as triosephosphate isomerase deficiency (tpi), is a severe autosomal recessive inherited multisystem disorder of glycolytic metabolism. it is characterized by hemolytic anemia and neurodegeneration, and is caused by anaerobic metabolic dysfunction. this dysfunction results from a missense mutati...
wikipedia
086980079ac6ea24ab481bbd1ca36720cfcf76f9
the deficiency of phosphohexose isomerase can lead to
the deficiency of phosphohexose isomerase can lead to a condition referred to as hemolytic syndrome. as in humans, the hemolytic syndrome, which is characterized by a diminished erythrocyte number, lower hematocrit, lower hemoglobin, higher number of reticulocytes and plasma bilirubin concentration, as well as increase...
wikipedia
fd2eb8c5249f23198f31a8838a11e2ca17838aba
phosphohexose isomerase deficiency (phi) is also known as
phosphohexose isomerase deficiency (phi) is also known as phosphoglucose isomerase deficiency or glucose-6-phosphate isomerase deficiency, and is a hereditary enzyme deficiency. phi is the second most frequent erthoenzyopathy in glycolysis besides pyruvate kinase deficiency, and is associated with non-spherocytic haemo...
wikipedia
99455498ee4443ace37459e4ffc74e4e40ff38d5
isopentenyl-diphosphate delta isomerase type i (also known as
isopentenyl-diphosphate delta isomerase type i (also known as ipp isomerase) is seen in cholesterol synthesis and in particular it catalyzes the conversion of isopentenyl diphosphate (ipp) to dimethylallyl diphosphate (dmapp). in this isomerization reaction a stable carbon-carbon double bond is rearranged top create a ...
wikipedia
729633cab557f2296b444520316cc34ff8836c2c
chorismate mutase is an intramolecular transferase and it
chorismate mutase is an intramolecular transferase and it catalyzes the conversion of chorismate to prephenate, used as a precursor for l-tyrosine and l-phenylalanine in some plants and bacteria. this reaction is a claisen rearrangement that can proceed with or without the isomerase, though the rate increases 10 fold i...
wikipedia
c16fe16fa1d6ab2bec7e88064a4207806c59d4f2
an example of epimerization is found in the
an example of epimerization is found in the calvin cycle when d-ribulose-5-phosphate is converted into d-xylulose-5-phosphate by ribulose-phosphate 3-epimerase. the substrate and product differ only in stereochemistry at the third carbon in the chain. the underlying mechanism involves the deprotonation of that third ca...
wikipedia
6f9d09629deae61b1a140d60610a52d271165872
glucose-6-phosphate first binds to the active site of
glucose-6-phosphate first binds to the active site of the isomerase. the isomerase opens the ring: its his388 residue protonates the oxygen on the glucose ring (and thereby breaking the o5-c1 bond) in conjunction with lys518 deprotonating the c1 hydroxyl oxygen. the ring opens to form a straight-chain aldose with an ac...
wikipedia
1c60a300dff7d09fb83dc4b3a681d23515188578
a classic example of ring opening and contraction
a classic example of ring opening and contraction is the isomerization of glucose (an aldehyde with a six-membered ring) to fructose (a ketone with a five-membered ring). the conversion of d-glucose-6-phosphate to d-fructose-6-phosphate is catalyzed by glucose-6-phosphate isomerase, an intramolecular oxidoreductase. th...
wikipedia
335d6b34ab15a9a1d2be922f96406abfd572c7cb
this category (ec 5.5) includes intramolecular lyases. these
this category (ec 5.5) includes intramolecular lyases. these enzymes catalyze "reactions in which a group can be regarded as eliminated from one part of a molecule, leaving a double bond, while remaining covalently attached to the molecule." some of these catalyzed reactions involve the breaking of a ring structure.
wikipedia
4256d7a1101f2178cd10b0d8032dd1689cf181c0
this category (ec 5.4) includes intramolecular transferases (mutases).
this category (ec 5.4) includes intramolecular transferases (mutases). these isomerases catalyze the transfer of functional groups from one part of a molecule to another. phosphotransferases (ec 5.4.2) were categorized as transferases (ec 2.7.5) with regeneration of donors until 1983. this sub-class can be broken down ...
wikipedia
d3500b1cb1490a8a6bb475cf74c484bbedbfb1d3
this category (ec 5.3) includes intramolecular oxidoreductases. these
this category (ec 5.3) includes intramolecular oxidoreductases. these isomerases catalyze the transfer of electrons from one part of the molecule to another. in other words, they catalyze the oxidation of one part of the molecule and the concurrent reduction of another part. sub-categories of this class are:
wikipedia
069eb49ea3e44755e2fe6a3f5a72cc94e2494bb4
this category (ec 5.2) includes enzymes that catalyze
this category (ec 5.2) includes enzymes that catalyze the isomerization of cis-trans isomers. alkenes and cycloalkanes may have cis-trans stereoisomers. these isomers are not distinguished by absolute configuration but rather by the position of substituent groups relative to a plane of reference, as across a double bon...
wikipedia
f6e0a07a6c190a89f162386aba07c6d4f0eb6237
this category (ec 5.1) includes (racemases) and epimerases).
this category (ec 5.1) includes (racemases) and epimerases). these isomerases invert stereochemistry at the target chiral carbon. racemases act upon molecules with one chiral carbon for inversion of stereochemistry, whereas epimerases target molecules with multiple chiral carbons and act upon one of them. a molecule wi...
wikipedia
25c3c42bf7d6565bcb7416ec028eddeb28791103
generally, "the names of isomerases are formed as
generally, "the names of isomerases are formed as " substrate isomerase" (for example, enoyl coa isomerase), or as " substrate type of isomerase " (for example, phosphoglucomutase)."
wikipedia
99935608c2b705af61e561f7be58f98063157c11
the earliest use of this technique elucidated the
the earliest use of this technique elucidated the kinetics and mechanism underlying the action of phosphoglucomutase, favoring the model of indirect transfer of phosphate with one intermediate and the direct transfer of glucose. this technique was then adopted to study the profile of proline racemase and its two states...
wikipedia
9958c42dc01ccfedf35a0d17ca77c7df3382d961
calculating isomerase kinetics from experimental data can be
calculating isomerase kinetics from experimental data can be more difficult than for other enzymes because the use of product inhibition experiments is impractical. that is, isomerization is not an irreversible reaction since a reaction vessel will contain one substrate and one product so the typical simplified model f...
wikipedia
e44aae7acb6687b8a16bda80581529cec7579742
the prevalence of each isomer in nature depends
the prevalence of each isomer in nature depends in part on the isomerization energy, the difference in energy between isomers. isomers close in energy can interconvert easily and are often seen in comparable proportions. the isomerization energy, for example, for converting from a stable cis isomer to the less stable t...
wikipedia
a89da1aede0c568c3a97fc9337200d5a52e9b36d
stereoisomers have the same ordering of individual bonds
stereoisomers have the same ordering of individual bonds and the same connectivity but the three-dimensional arrangement of bonded atoms differ. for example, 2-butene exists in two isomeric forms: cis -2-butene and trans -2-butene. the sub-categories of isomerases containing racemases, epimerases and cis-trans isomers ...
wikipedia
b7ff89bbd7810b181372312a8156a471059de2df
isomerases catalyze changes within one molecule. they convert
isomerases catalyze changes within one molecule. they convert one isomer to another, meaning that the end product has the same molecular formula but a different physical structure. isomers themselves exist in many varieties but can generally be classified as structural isomers or stereoisomers. structural isomers have ...
wikipedia
56fa0199c9875a2518f54b865792888d56593355
there is only one substrate yielding one product.
there is only one substrate yielding one product. this product has the same molecular formula as the substrate but differs in bond connectivity or spatial arrangement. isomerases catalyze reactions across many biological processes, such as in glycolysis and carbohydrate metabolism.
wikipedia
d4534f93c040d2a080f36e44907261f277569cae
in biochemistry, isomerases are a general class of
in biochemistry, isomerases are a general class of enzymes that convert a molecule from one isomer to another. isomerases facilitate intramolecular rearrangements in which bonds are broken and formed. the general form of such a reaction is as follows:
wikipedia
897c8387a4bb2ace3562f656a9d92084d67bcc07
phosphorus-centered porphyrins are conjugated polycyclic ring systems consisting
phosphorus-centered porphyrins are conjugated polycyclic ring systems consisting of either four pyrroles with inward-facing nitrogens and a phosphorus atom at their core or porphyrins with one of the four pyrroles substituted for a phosphole. unmodified porphyrins are composed of pyrroles and linked by unsaturated hydr...
wikipedia
e158a03b17e8283a22bff88bfdd9af388db5a1b2
isophlorins are less stable nonaromatic complexes that engage
isophlorins are less stable nonaromatic complexes that engage in similar chemistry to the porphyrinoids. the 20π systems are synthesized from 18π porphyrins via redox-coupled complexation. although the 4πn conjugated system would suggest that the molecule exhibits antiaromatic character, geometric and magnetic criteria...
wikipedia
5e95d821237e7287f7a6e1558fb324245ef8a96d
calixpyrroles have all four hydrocarbon bridges fully saturated,
calixpyrroles have all four hydrocarbon bridges fully saturated, breaking the conjugation between heterocycles present in other porphyrinoids. a phosphole replacing a pyrrole allows for similar chemistry to other phosphaporphyrinoids with increased flexibility of the tetradentate ligand by virtue of sp hybridization.
wikipedia
fd040c3834f3a7dc311665e26721ca03219541b5
matano et al. in 2006 used the first
matano et al. in 2006 used the first ever p,s-hybridized calixphyrin coordinated to palladium to catalyze the heck reaction to form substituted alkenes. like porphyrins, electronic properties of this complex are also tunable through the influence of various functional groups. in 2009, these molecules were examined in c...
wikipedia
558705057f061e4baa9757ded263b73b397c752c
calixphyrins are analogous to porphyrins with two of
calixphyrins are analogous to porphyrins with two of the hydrocarbon bridges between pyrroles fully saturated. like phosphaporphyrin, a calixphyrin pyrrole can be substituted with a phosphole to form a p-centered calixphyrin. the results of increased saturation are mixed sp and sp hybridization of the ring carbons and ...
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phosphorus (v) is a prevalent ion center in
phosphorus (v) is a prevalent ion center in modified porphyrin complexes but is not the only group 15 element that has been used in place of a transition metal ion. antimony and bismuth have also been identified as suitable porphyrin cores as early as 1991 by barbour et al. stronger electron donating from the less elec...
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phosphaporphyrins after synthesis can be complexed with metals
phosphaporphyrins after synthesis can be complexed with metals like the unmodified porphyrin molecule. nickel, palladium, and platinum can be coordinated as the metal center of a phosphaporphyrin by reacting the conjugated ring with metal salts like ni(cod), pd(dba), and pt(dba) in dcm/dichlorobenzene respectively.
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phosphorus (v) porphyrins are particularly good electron carriers
phosphorus (v) porphyrins are particularly good electron carriers in redox reactions because of their adjustable reduction potential. poddutoori et al. in 2021 investigated the electron transfer of naphthalene, a commonly excited molecule in photochemistry, to octaethylporphyrin and tep. the relatively low potentials o...
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p-centered porphyrins typically react in redox reactions where
p-centered porphyrins typically react in redox reactions where they serve as tunable intermediate electron carriers in biological reactions for dna degradation as well as other industrial catalytic reactions. tn (ii/iv) oxide is photoreduced by iridium and manganese complexes through p-centered porphyrin electron carri...
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photodynamic therapy (pdt) is used to target and
photodynamic therapy (pdt) is used to target and destroy dna in cases of extreme cell proliferation as is common in cancer. porphyrins are used to generate radical oxygen species in the body to degrade nucleotides, stopping proliferation. tetraphenylporphyrin phosphorus (v) complexes with dna and possesses an oxidation...
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as early as 2002, axial substituents on the
as early as 2002, axial substituents on the phosphorus core have been utilized for photochemistry. reddy and maiya pioneered the use of a p-centered porphyrin with azobenzene substituents capable of reversible (e/z) isomerization upon irradiation at a wavelength of 345 nm. the process of isomerization is made possible ...
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af4c589791ece0425b43507f7743af2cad45608f
phosphaporphyrins have been studied to a lesser degree.
phosphaporphyrins have been studied to a lesser degree. uv-vis and cyclic voltammetry (cv) experiments with phosphaporphyrins reveal that the single pyrrole to phosphole substitution narrows the homo and lumo gap in an 18 π-system, allowing for a more easily accessible excited state and unique electrochemical applicati...
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phosphorus core porphyrins have been researched extensively to
phosphorus core porphyrins have been researched extensively to assess their photo and electrochemical properties. axial groups bonded to the core phosphorus exert influence on the oxidation and reduction potentials of porphyrins. like the electronegativity effects of the axial group on p-n bonding distance and plane ru...
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phosphorus core porphyrins have been researched extensively to
similar application for p-centered porphyrins with tin (iv) oxide and mn(ii)typ. photooxidation of the mn complex allows the reduction of the tin(iv) ion to tin(iii) through the porphyrin as an electron carrier in a similar fashion to the 2015 publication. the photoreduction applications mimic those of the natural por...
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unmodified porphyrins have been identified and used in
unmodified porphyrins have been identified and used in spectroscopic studies because of their highly conjugated π-systems. isolated monolayers of porphyrins with dicationic transition metals yield similar spectroscopic data to those suspended in dilute solution. axial ligand substitution of the metal was proposed as a ...
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phosphaporphyrins possess phospholes usually bound to a phenyl
phosphaporphyrins possess phospholes usually bound to a phenyl group resting above the porphyrin plane in a trigonal pyramidal molecular geometry as is typical of phosphorus centers. in addition to the bound phenyl group, these molecules may also possess a metal ion core that coordinates to the three pyrroles and phosp...
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several varieties of the p-centered porphyrin exist. the
several varieties of the p-centered porphyrin exist. the porphyrin with a core phosphorus (v) ion can be tuned with additional substituents added to either the outside of the polycyclic ring system or axially to the core phosphorus. meso-substituted porphyrins like meso-tetra-p-tolylporphyrin (ttp) and octaethylporphyr...
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metals can be coordinated in the core of
metals can be coordinated in the core of the phosphaporphyrin by introducing metal salts. rhodium metal is very easily inserted into the core of a phosphaporphyrin without the presence of a stabilizing thiophene -substituted pyrrole.
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synthesis of a phosphole-substituted porphyrin or phosphaporphyrin involves
synthesis of a phosphole-substituted porphyrin or phosphaporphyrin involves a more complex chemical route. phosphaporphyrins are not created using an unmodified porphyrin ring as a synthetic reagent. as reported by matano and imahori in 2008, a phosphaporphyrin is constructed with a phosphole linked to two pyrrole func...
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later syntheses have been performed with other phosphorus
later syntheses have been performed with other phosphorus precursors, including phpcl and octaethylporphyrin (oep) in dcm to yield cl. pcl /pocl and kpf yield similar porphyrin products with a pf counterion. other halogens like bromine have been used successfully in place of chlorine for this synthesis method of p-cent...
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early experiments with group 15 elements at the
early experiments with group 15 elements at the porphyrin core by barbour et al. in 1992 included syntheses of p-centered porphyrin compounds from meso-tetra-p-tolylporphyrin (ttp). phosphorus oxychloride (pocl) added to h ttp forms the p-centered porphyrin molecule cl. several chemical variants were synthesized by ref...
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phosphorus-centered (or p-centered) porphyrins are conjugated polycyclic ring
phosphorus-centered (or p-centered) porphyrins are conjugated polycyclic ring systems consisting of either four pyrroles with inward-facing nitrogens and a phosphorus atom at their core or porphyrins with one of the four pyrroles substituted for a phosphole. unmodified porphyrins are composed of pyrroles and linked by ...
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in algebra, the milnor–moore theorem, introduced by john
in algebra, the milnor–moore theorem, introduced by john w. milnor and john c. moore (1965) classifies an important class of hopf algebras, of the sort that often show up as cohomology rings in algebraic topology. the theorem states: given a connected, graded, cocommutative hopf algebra a over a field of characteristic...
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13179c5db14d837c8f24f3202061c4233a1c494f
on the left hand side, since x {\displaystyle
on the left hand side, since x {\displaystyle x} is simply connected, π ∗ (Ω x) ⊗ q {\displaystyle \pi _{\ast }(\omega x)\otimes \mathbb {q} } is a q {\displaystyle \mathbb {q} } -vector space; the notation u (v) {\displaystyle u(v)} stands for the universal enveloping algebra.
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where Ω x {\displaystyle \omega x} denotes the
where Ω x {\displaystyle \omega x} denotes the loop space of x, compare with theorem 21.5 from félix, halperin & thomas (2001). this work may also be compared with that of (halpern 1958a, 1958b). here the multiplication on the right hand side induced by the product Ω x × Ω x → Ω x {\displaystyle \omega x\times \omega x...
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fd16e216e6f8be3720ff4467dff97ddce0c2fd80
from the universal enveloping algebra of the graded
from the universal enveloping algebra of the graded lie algebra p (a) {\displaystyle p(a)} of primitive elements of a to a is an isomorphism. here we say a is connected if a 0 {\displaystyle a_{0}} is the field and a n = 0 {\displaystyle a_{n}=0} for negative n. the universal enveloping algebra of a graded lie algebra ...
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e5f3a7918369b1de00c2f34d64acc2534c6bb221
the theorem states: given a connected, graded, cocommutative
the theorem states: given a connected, graded, cocommutative hopf algebra a over a field of characteristic zero with dim a n < ∞ {\displaystyle \dim a_{n}<\infty } for all n, the natural hopf algebra homomorphism
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09c57b8a48ea8b0e925e7ebb92215cd7ff15177e
in algebra, the milnor–moore theorem, introduced by john
in algebra, the milnor–moore theorem, introduced by john w. milnor and john c. moore (1965) classifies an important class of hopf algebras, of the sort that often show up as cohomology rings in algebraic topology.
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c0d3eed961877339147dfb44ea17dd4b5d18054e
the 1975–76 season was the 74th season in
the 1975–76 season was the 74th season in which dundee competed at a scottish national level, playing in the rebranded scottish premier division. in a tight relegation scrap, dundee were relegated for the first time since the 1937–38 season due to inferior goal average. domestically, dundee would also compete in both t...
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c0d3eed961877339147dfb44ea17dd4b5d18054e
the 1975–76 season was the 74th season in
the 1975–76 season was the 74th season in which dundee competed at a scottish national level, playing in the rebranded scottish premier division. in a tight relegation scrap, dundee were relegated for the first time since the 1937–38 season due to inferior goal average. domestically, dundee would also compete in both t...
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39df8958f65b994ba963d3cd6b0afc3b6323cb29
at the conclusion of the 2019 afl season,
at the conclusion of the 2019 afl season, martin again requested a trade to victoria. carlton and the western bulldogs were both interested in signing him. he was expected to nominate carlton as his preferred destination. after the suns and carlton failed to reach a deal during the trade period, martin became a blue in...
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33c3dafc2f844bf152816c4eef899f785fcfa890
at the conclusion of the 2018 afl season,
at the conclusion of the 2018 afl season, martin requested a trade from gold coast to a victorian club. essendon confirmed interest in signing martin, but gold coast were not open to a trade. martin played the 2019 afl season at gold coast.
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6783b73318dd5c6a5b5b54da5a0fabfb7904dfac
martin made his afl debut in round 1
martin made his afl debut in round 1 of the 2014 season against richmond at metricon stadium. while attempting to take a diving mark in the fifth minute of the game, martin injured his left ac joint and was subsequently substituted out of the game. it was initially feared he may be sidelined for the entire 2014 season ...
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