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KEIICHI ITO, MINORU SEKIYA
1969 Volume 17 Issue 5 Pages
861-865
Published: May 25, 1969
Released on J-STAGE: March 31, 2008
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Catalytic hydrogenations of hydroamides under high hydrogen pressure in the presence of ammonia and of butylamine were examined to see effects of these bases on the composition of products. The product analyses show the predominant formation of primary amine in the former case and in the latter case the formation of primary and secondary amines possessing butyl residue at 2 : 1 molar ratio. From these results comments on the course of the hydrogenation are given.
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HIDESUKE IWASAKI, TAKAAKI KAMIYA, OSAMU OKA, JISABURO UEYANAGI
1969 Volume 17 Issue 5 Pages
866-872
Published: May 25, 1969
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DL-erythro-α-Amino-3-oxo-5-isoxazolidineacetic acid (I) was synthesized from dialkyl β-hydroxyglutamate. Optical resolution afforded L- and D-isomers, of which the former was proved to be identical with tricholomic acid, a flycidal and tasty constituent of Tricholoma muscarium KAWAMURA. The D-isomer lacked the biological activities.
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HIDESUKE IWASAKI, TAKAAKI KAMIYA, CHITOSHI HATANAKA, YUTAKA SUNADA, JI ...
1969 Volume 17 Issue 5 Pages
873-878
Published: May 25, 1969
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DL-threo-α-Amino-3-oxo-5-isoxazolidineacetic acid, an isomer of tricholomic acid, was synthesized in a 3-step sequence starting from dialkyl N-acyl-β-chloroglutamate. Several isolations have been attempted to separate the threo- and erythro-isomers from their mixture. The threo-isomer was devoid of good taste and flycidal activity which are characteristic of the erythro-isomer.
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TAKAAKI KAMIYA
1969 Volume 17 Issue 5 Pages
879-885
Published: May 25, 1969
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Racemic tricholomic acid and its threo-isomer (I) were prepared by a new route starting from the diastereoisomers of β-hydroxyglutamic acid (II) through α-mono esters (XI) and γ-benzyloxyamides (XIII).
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TAKAAKI KAMIYA
1969 Volume 17 Issue 5 Pages
886-889
Published: May 25, 1969
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Racemic tricholomic acid and its threo-isomer (I) were successfully synthesized by extending the previous method to diastereoisomers of N-carbobenzoxy-β-hydroxyglutamic acid α-benzyl ester (III), which were prepared by the selective partial esterification of the corresponding N-carbobenzoxyamino acids (III).
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TAKAAKI KAMIYA
1969 Volume 17 Issue 5 Pages
890-894
Published: May 25, 1969
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Four optically active isomers (I) of tricholomic acid were synthesized by the method reported previously for the synthesis of its racemates starting with the corresponding optically active isomers of β-hydroxyglutamic acid (VII). A new resolution technique was used for the synthesis of the starting materials.
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TAKAAKI KAMIYA
1969 Volume 17 Issue 5 Pages
895-900
Published: May 25, 1969
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Two diastereoisomers of isotricholomic acid (II), structural isomers of tricholomic acid (erythro-L-I) were synthesized from the corresponding diastereoisomers of β-hydroxyglutamic acid γ-ester (V) by the method for the synthesis of I. During the synthesis of II, the diastereoisomers of I were obtained by a novel intramolecular rearrangement.
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KIICHIRO KAKEMI, HITOSHI SEZAKI, MASAHIRO NAKANO, KIICHIRO OHSUGA, TAK ...
1969 Volume 17 Issue 5 Pages
901-905
Published: May 25, 1969
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Rate constants for alkaline hydrolysis (in 0.1N NaOH) of aromatic amides such as nicotinamide, benzamide, phenylacetamide, cinnamamide, and their corresponding N-alkyl substituted analogs were determined at 25°and 90°in order to investigate the effect of molecular structure on the stability of these amides against hydroxyl ion attack. Stability constants of these aromatic amide complexes with theophylline and 8-methoxycaffeine at 25°were also computed from phase-solubility data. The results have shown that cinnamamides are most stable against hydroxyl ion attack and formed the most stable complexes with the alkylxanthines while phenylacetamides are least stable in alkaline hydrolysis and least associative with alkylxanthines among benzene derivatives. Both hydrolytic behavior and associative tendency of these amides are discussed in relation to the extent of conjugation of the amide group with the rest of the molecule.
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NOBUO IKEKAWA, OSAMU HOSHINO, YASUSHI HONMA
1969 Volume 17 Issue 5 Pages
906-909
Published: May 25, 1969
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Mercurations of quinoline N-oxide with various reagents under different conditions were investigated using gas chromatographic analysis of the bromoquinolines derived from the reaction products. Mercuration in acetic acid or perchloric acid gave 8-mercurichloride as a main product and small amounts of 3-, 5-, 6- and 7-isomers. The reaction with mercuric sulfate without solvent gave all of the isomers, although the total yield was poor.
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AKIRA TAKAMIZAWA, KENTARO HIRAI, SAICHI MATSUMOTO, SHOJI SAKAI, YUZO N ...
1969 Volume 17 Issue 5 Pages
910-919
Published: May 25, 1969
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Thiamine and related thiazolium ylids react with alkyl isothiocyanates to give spiro-(perhydrofuro [2, 3-d] thiazole-2, 4'-imidazolidine) derivatives (IIa-i) involving two step cycloaddition. Confirmation of the structures is provided by chemical degradations and by infrared, ultraviolet, nuclear magnetic resonance spectroscopic evidences as well as by characteristic mass spectral fragmentations. On heating in acetic acid, some of these (1 : 2) adducts are readily converted to dihydroimidazo [4, 5-d] thiazole derivatives (XIa-d) involving a novel intramolecular cyclization.
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TOHRU UEDA, HIROKO NISHINO
1969 Volume 17 Issue 5 Pages
920-926
Published: May 25, 1969
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The ORD, CD and UV of various 2-thiopyrimidine nucleosides have been measured and a tentative rule pertaining to the sign of ORD is presented. A nucleoside possessing a non-conjugated 2-thiocarbonyl group exhibits a negative Cotton effect at 300 to 360 mμ in the n-π
* region, while the nucleoside with a conjugated 2-thiocarbonyl function exhibits a positive Cotton effect. Protonation or deprotonation which alters the structure of the base moiety effects the sign of ORD. The possible usefulness of ORD measurements for the detection and identification of the thiopyrimidine nucleosides in transfer ribonucleic acids is discussed.
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KAZUKO EIDA, MOTOSUKE KIKUTANI
1969 Volume 17 Issue 5 Pages
927-931
Published: May 25, 1969
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Enzymic formation of porphyrins in the extract of Harderian gland of a rat was examined. Porphyrins formed from δ-aminolevulinic acid by the extract of Harderian gland were uroporphyrin, coproporphyrin-III, a small quantity of protoporphyrin-IX, and unidentified porphyrins. According to the quantitative study of porphyrins at specified incubation time, the main part of porphyrins formed were uroporphyrin and coproporphyrin-III, and protoporhyrin-IX was formed only in a small amount.
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MASAO NISHIKAWA, KAZUHIDE KAMIYA, YUTAKA ASAHI, HIDEO MATSUMARU
1969 Volume 17 Issue 5 Pages
932-938
Published: May 25, 1969
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The crystal structure of thiamine propyl disulfide (TPD) was determined by the three dimensional Patterson superposition method and by application of least squares treatment and Fourier syntheses. The unit cell is monoclinic, space group P2
1/a, with a=21.04, b=11.35, c=8.53 A and β=101°36'. The propyl disulfido group has been found to lie cis to the N-formyl group, the result being consistent with the hitherto proposed structure for TPD. The structure of the pyrimidine portion was discussed in comparison with the results of earlier workers. The stereochemical structure of TPD and a unique hydrogen bonding in the crystal were also discussed.
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SADAO OIDA, EIJI OHKI
1969 Volume 17 Issue 5 Pages
939-946
Published: May 25, 1969
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Osmium tetroxide oxidation of 2-phenyl-6-tetrahydropyranyloxymethyl-3, 6-dihydro-1, 2-oxazine (5e) afforded 2-phenyl-6β-tetrahydropyranyloxymethyltetrahydro-1, 2-oxazine-4α, 5α-diol (8), whose ditosylate (10) was converted into 2-phenyl-4β, 5β-epiminotetrahydro-1, 2-oxazine-6β-methanol (2) on successive treatment with sodium azide, lithium aluminum hydride, and acids. Conformation of 2 was discussed with reference to the nuclear magnetic resonance spectrum of 2.
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TOSHIO NAMBARA, HIROSHI HOSODA, MASAHIRO USUI
1969 Volume 17 Issue 5 Pages
947-953
Published: May 25, 1969
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Four isomeric 16, 17-ketols of 13α-androstanes were prepared as illustrated in Chart 1. The rearrangements and stabilities of these ketols with acid or base were investigated. The results were compared with those of the corresponding compounds having 13β, 14α-and 13β, 14β-ring systems (see Fig. 1). The stability sequence of these ketols is discussed on the steric and conformational grounds.
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SEIGORO HAYASHI, MITSURU FURUKAWA, YOKO FUJINO, HAYASHI MATSUKURA
1969 Volume 17 Issue 5 Pages
954-958
Published: May 25, 1969
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Reactivities of mono and difunctional thiosulfonates toward several nucleophilic compounds, such as thiols, amines and the related compounds, were examined. In the result, some chemical behaviors unexpected were found in addition to the reactivity anticipated. Namely, in the reaction with piperazine, aralkyl thiosulfonate afforded aralkyltrisulfide in about 20% yield, without any formation of sulfenamide. Moreover, aromatic thiosulfonate gave a comparable good yield of 1-phenyl-2-arylsulfonylhydrazine in the reaction with phenylhydrazine, in addition to the formation of phenylhydrazinium salt of aromatic sulfinic acid.
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HIROSHI HIKINO, KUNIO AGATSUMA, TSUNEMATSU TAKEMOTO
1969 Volume 17 Issue 5 Pages
959-960
Published: May 25, 1969
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A new sesquiterpenic hemiketal has been isolated from zedoary, Curcuma zedoaria (Zingiberaceae), and named isocurcumenol. Chemical and physicochemical studies have established isocurcumenol to be as shown in formula I.
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IKUO MORIGUCHI, NOBUYOSHI KANENIWA
1969 Volume 17 Issue 5 Pages
961-965
Published: May 25, 1969
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The adsorption of cyanocobalamin on talc was remarkably repressed by polyvinylpyrrolidone. An investigation utilizing equilibrium dialysis revealed that the repression by PVP was caused by adsorption of PVP on talc and not by any direct interaction between PVP and cyanocobalamin. Adsorption of PVP on talc was endothermic and the value of the apparent entropy change was positive. PVP and cyanocobalamin adsorbed on talc with obedience to the Langmuir isotherm equation. But the data of adsorption of the binary mixture did not fit the Markham-Benton equations but fitted a modified equations derived with an assumption that adsorption constant for cyanocobalamin on talc varied inversely as adsorbed amount of PVP. This may indicate that approach of cyanocobalamin to surface of talc is interfered by PVP molecules owing to a kind of steric hindrance.
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ATSUSUKE TERADA, YUKICHI KISHIDA
1969 Volume 17 Issue 5 Pages
966-973
Published: May 25, 1969
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Treatment of acetylenic sulfonium salts, dimethyl 3-phenyl-2-propynylsulfonium bromide (VII), dimethyl 2-butynylsulfonium bromide (XII) and methyl bis (3-phenyl-2-propynyl) sulfonium methyl sulfate (XIX), with base gave SNi'reaction products, methyl 2-phenyl-2, 3-butadienyl sulfide (VIII), methyl 2-methyl-2, 3-butadienyl sulfide (XIII) and methyl 1-(2-phenylethynyl)-2-phenyl-2, 3-butadienyl sulfide (XXII), respectively. Similarly, methyl (2-propenyl) (3-phenyl-2-propynyl) sulfonium methyl sulfate (XXIII) was converted to methyl 1-(2-phenylethynyl)-3-butenyl sulfide (XXVII) by SNi'reaction. The reaction of methyl benzyl 3-phenyl-2-propynylsulfonium methyl sulfate (XXXIII) with base, however, afforded the usual Stevens type rearrangement product, methyl 1-benzyl 3-phenyl-2-propynyl sulfide (XXXVI). A mechanistic assumption for the rearrangements of acetylenic sulfonium salts was given.
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ATSUSUKE TERADA, YUKICHI KISHIDA
1969 Volume 17 Issue 5 Pages
974-979
Published: May 25, 1969
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Treatment of allenic sulfides, methyl 2-phenyl-2, 3-butadienyl sulfide (IIa) and methyl 1-(2-phenylethynyl)-2-phenyl-2, 3-butadienyl sulfide (IIb), with methyl iodide gave sulfurfree compounds of 1, 3-diene derivatives, 2-iodo-3-phenyl-1, 3-butadiene (III) and 2-iodo-3, 6-diphenyl-cis-1, 3-hexadien-5-yne (IV-a), respectively. This desulfurization with methyl iodide was extended to some acetylenic sulfides (V, VIII and IX) and the tendency of the cleavage of C-S^
+ bond was determined. Treatment of bis (3-phenyl-2-propynyl) sulfide (IX) with methyl iodide in ether, however, afforded sulfur-involving product, 4-phenyl-1, 3-dihydronaphtho [2, 3-c] thiophene methyl iodide (X).
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SADAO OIDA, EIJI OHKI
1969 Volume 17 Issue 5 Pages
980-986
Published: May 25, 1969
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Some 3, 4-epiminopyrrolidines were synthesized by two alternate methods. Lithium aluminum hydride reduction of N-(p-methoxyphenyl)-1-benzyl-2, 3-aziridinedicarboximide (6) afforded 1-(p-methoxyphenyl)-3, 4-(N-benzylepimino) pyrrolidine (8) in a low yield. Epoxidation of 1-benzoyl-△
3-pyrroline (12) with pertrifloroacetic acid gave 1-benzoyl-3, 4-epoxypyrrolidine (13) which formed 1-benzoyl-trans-3-azido-4-mesyloxypyrrolidine (15) on successive treatment with sodium azide and mesyl chloride. 15 was converted into 1-benzyl-3, 4-epiminopyrrolidine (16) on treatment with lithium aluminum hydride, or into 1-benzoyl-3, 4-epiminopyrrolidine (20) with sodium borohydride and cobalt (II)-tris (α, α'-dipyridyl) bromide, respectively, in a fair yield. The nuclear magnetic resonance spectra of these compounds were evaluated.
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TOSHIHIKO OKAMOTO, MASATAKA MOCHIZUKI
1969 Volume 17 Issue 5 Pages
987-993
Published: May 25, 1969
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Basic kinetic data, rate constants, activation energies, and entropies of activation were elucidated for the reactions of 22 kinds of 4-NQO derivatives with sodium ethoxide in anhydrous ethanol by spectroscopic-method. Correlations existed between the rate constants and carcinogenicities, and half-wave reduction potentials. Hammett paramaters were applied to the rate constants, and a linear correlation existed in 6-and 7-substituted derivatives. Interactions of 4-nitro group and 3- or 5-position substituents retarded the rate, but for 2- or 8-position, only bulky substituents such as methyl group interacted with the N-oxide group.
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ISAO SUGIMOTO
1969 Volume 17 Issue 5 Pages
994-998
Published: May 25, 1969
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Attempts were made to enhance the absorption rate of drug by the complex formation. Following model complexes of rapidly absorbed drugs (A) with slowly absorbed drugs (B) were used : hydroxyethyltheophylline (A)-carbazochrome (B), caffeine (A)-carbazochrome (B), nicotinamide (A)-carbazochrome (B), and salicylic acid (A)-4-methylamino-antipyrine (B). Apparent absorption rate for a slowly absorbed drug with or without a rapidly absorbed one from rat small intestine were determined by the recirculating perfusion method at pH 6.0, and from these results and the equilibrium constant for the complex the absorption rate constants for the complexes were calculated by the equation shown in the previous report. It was found that the intestinal absorption of the drug B increased in the presence of the drug A in those complexes, and the calculated absorption rates for the complexes were higher than those of B and lower than those of A.
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TAI MATSUZAWA, HIROSHI FUJISAWA, KATSUO AOKI, HIROYUKI MIMA
1969 Volume 17 Issue 5 Pages
999-1004
Published: May 25, 1969
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Effect of some non-ionic surfactants on the muscular absorption of Enduracidin was investigated from both the urinary and blood level studies in the rat. Addition of the non-ionic surfactants remarkably promoted the absorption of Enduracidin from the muscles of the rats and Nikkol HCO-50, hydrogenated castor oil polyoxyethylene ether, showed the most pronounced absorption-enhancing ability. It was also found that there was no correlationship between the peak blood level and the concentration of Enduracidin and that the duration of blood level was dependent on the concentration of the antibiotic. A rate-limiting process was proposed to the muscular absorption mechanism of Enduracidin from the result with EDTA.
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MICHIO MATSUI, MASASHI OKADA, MORIZO ISHIDATE
1969 Volume 17 Issue 5 Pages
1005-1009
Published: May 25, 1969
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D-Mannaric acid (II) was isolated and identified from human urine after oral administration of D-mannuronolactone (I). It was also isolated and identified from the incubation mixture containing I, nicotinamide adenine dinucleotide (NAD) and D-glucuronolactone dehydrogenase preparation purified from guinea pig liver, thus demonstrating the conversion of I into II in mammalian systems likewise the conversion of D-glucuronolactone (III) into D-glucaric acid (IV).
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NOBUHARU KAKEYA, MASARU AOKI, AKIRA KAMADA, NOBORU YATA
1969 Volume 17 Issue 5 Pages
1010-1018
Published: May 25, 1969
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A study was made of correlation of carbonic anhydrase inhibitory activity with the chemical structures of 19 derivatives of benzenesulfonamide and 3 heterocyclic sulfonamides in reference to the physicochemical properties of the compounds. A linear correlation was observed for Hammett's σ factor against pK
a, chemical shift of the sulfamoyl protons, and valence-force constant of the S=O bond. Inhibitory activity increased with a decrease of pK
a, and with an increase of Hammett's σ factor, chemical shift of the sulfamoyl protons, and the S=O valence-force constant of the sulfamoyl group. A close correlation was also found between the inhibitory activity and water solubility of the unionized molecules of benzenesulfonamides except for p-CH
3NH and o-NO
2 derivatives.
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MORIO IKEHARA, ICHIRO TAZAWA, TOSHIKAZU FUKUI
1969 Volume 17 Issue 5 Pages
1019-1024
Published: May 25, 1969
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8-Bromo-AMP and 8-bromo-GMP, which are key intermediate for the synthesis of 8-substituted purine nucleotides, were synthesized directly from AMP and GMP by the bromination with bromine-water in buffer solution. 8-Bromo-MP's were converted to 8-oxy compounds by the reaction with sodium acetate in acetic anhydride or in acetic acid. 8-Dimethylamino-GMP was obtained by replacement of 8-bromo-atom with dimethylamine. These 8-substituted purine nucleoside monophosphates were derived to 5'-diphosphates via phosphoromorpholidate. A convenient synthesis of [α-
32P]-8-bromo-ADP was described.
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TARO OGISO, MAMORU SUGIURA
1969 Volume 17 Issue 5 Pages
1025-1033
Published: May 25, 1969
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It had been found that in one of lipase [EC 3. 1. 1. 3] from Mucor javanicus the hydrolysis of fats was accelerated by bile salts. The lipase was purified about 20-fold from the original powder (about 100-fold from the culture broth) by ammonium sulfate precipitation, chromatography on Sephadex G-75, CM-cellulose, and Sephadex G-200. Recovery of the activity was about 18%. The purified enzyme was homogeneous on electrophoresis. Optimum pH for hydrolysis of olive oil was 7.0 by the assay method using a PVA system and 7.5 by that using a shaken system. Optimum temperature was 40°. The enzyme was stable below 30°. It was strongly inhibited by Ag
+, Hg
2+, and N-bromosuccinimide (NBS). The apparent I
50 value of NBS was 1.4×10
-4M, that of both iodine and sodium lauryl sulfate were 2.4×10
-3M. The lipase hydrolyzed tricaprylin most efficiently, and next to it tricaprin and trilaurin. The Michaelis constant (Km) for triglycerides agreed closely with the substrate specificity.
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TARO OGISO, MAMORU SUGIURA
1969 Volume 17 Issue 5 Pages
1034-1044
Published: May 25, 1969
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In order to clear the mechanism of activation by bile salts, their effect on Mucor lipase and substrates was studied. Optimum pH of the lipase was not influenced by the salts. Heat stability of the lipase was slightly deteriorated by their addition. Michaelis constant (Km) and maximum velocity (Vmax) for olive oil in the presence of 5×10
-3M of sodium taurocholate (VII) were 275 (mg) and 1.68 (mg/min), respectively, against 403 and 1.22 in their absence. Activation of the enzyme and the accelerating effect on the substrates by bile salts were not recognized in any concentration tested, though the physical properties, viscosity and surface tension, did change. The number of enzyme molecules adsorbed at oil-water interface increased by the addition of bile salts. A good proportional relation was found between the rate of increased relative activity and quantities of the enzyme adsorbed at the interface, and the quantity increased in proportion to the increasing concentration of bile salts. Analogous results were obtained with pancreatic lipase, but adsorption of Candida lipase slightly inhibited by the salts decreased by the salts. Diffusion of oleic acid from the interface was markedly increased by the addition of bile salts.
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YOSHIRO KOBAYASHI, ITSUMARO KUMADAKI, HARUO SATO
1969 Volume 17 Issue 5 Pages
1045-1050
Published: May 25, 1969
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N-Oxidation of 1, 6-naphthyridine was carried out in various ways and 6-oxide and 1, 6-dioxide were obtained. Reduction of the latter afforded 1-oxide. Reactions of these oxides with acetic anhydride and with phosphoryl chloride were carried out and the structure of each product was determined.
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TETSUJI KAMETANI, HIDEO IIDA, TOYOHIKO KIKUCHI, KAZUMI OHKUBO, KEIICHI ...
1969 Volume 17 Issue 5 Pages
1051-1054
Published: May 25, 1969
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SEIGORO HAYASHI, MITSURU FURUKAWA, YOKO FUJINO, TADASHI OHKAWARA
1969 Volume 17 Issue 5 Pages
1054-1057
Published: May 25, 1969
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SHOJI OKADA
1969 Volume 17 Issue 5 Pages
1057-1060
Published: May 25, 1969
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KANAME TAKAGI, TAKEO UEDA
1969 Volume 17 Issue 5 Pages
1061-1064
Published: May 25, 1969
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MICHIO MATSUI, MASASHI OKADA, MORIZO ISHIDATE
1969 Volume 17 Issue 5 Pages
1064-1071
Published: May 25, 1969
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HIDEO TANINO, SHOJI INOUE
1969 Volume 17 Issue 5 Pages
1071-1072
Published: May 25, 1969
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YOSHIMICHI SHIGERI, TAMOTSU KONDO
1969 Volume 17 Issue 5 Pages
1073-1075
Published: May 25, 1969
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HIROSHI HIKINO, KUNIO ITO, TOMIHISA OHTA, TSUNEMATSU TAKEMOTO
1969 Volume 17 Issue 5 Pages
1078-1079
Published: May 25, 1969
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