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堀江 正信, 馬場 茂雄
1978 年 26 巻 4 号 p.
1009-1014
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
For the investigation of metabolism of 3-phenylpropyl carbamate in man, drugs labeled with deuterium and carbon-13 were synthesized. Physicochemical properties of labeled compounds, especially mass spectrometric behavior, were examined. The deuterium-hydrogen exchange reaction was observed in 3-phenylpropyl [arom.-d
5] carbamate but in the case of carbon-13 labeled compounds, there was no isotope effect occurring in mass chamber. Calibration curve for dilution analysis was examined by use of methyl benzoate single-labeled with carbon-13 and linear correlation was obtained between 1 and 300 fold dilutions.
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糸川 秀治, 亀山 省司, 稲葉 利和, 田崎 敏夫, 春田 龍二, 川添 豊, 前田 満和
1978 年 26 巻 4 号 p.
1015-1020
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
N-substituted quinoline derivatives such as 〓N
+-Me, 〓N
+O
-, 〓N
+-NH
- were derived to methyl substituted compound at C-2 and/or C-4 by radical methylation and by radical hydroxymethylation. In the case of radical methylation and radical hydroxymethylation of quinoline 1-oxides, carbon at C-2 was preferentially nucleophilic than at C-4. Useful way to synthesize the alkyl substituted derivatives at C-2 selectively was to proceed the alkylation after forming N-oxide.
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北川 進, 田中 久
1978 年 26 巻 4 号 p.
1021-1025
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
A new dithio ligand containing sulfhydryl and thioamido group, N-phenyl-β-mercapto-thiocinnamamide, was prepared and its properties were studied. Although the nuclear magnetic resonance (NMR) spectrum did not show the SH signal, the v(SH) was observed in the infrared (IR) spectrum. The mass spectrum and the molecular weight estimation revealed that the ligand has a monomer structure. The λ
max (ε) in EtOH are as follows ; 347 nm (15600), 265 and 229 sh. The pK
a value in 10% EtOH aqueous solution was determined spectrophotometrically to be 3.16±0.03. The low pK
a value was supposed to be an existence of a strong hydrogen bond.
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北川 進, 田中 久
1978 年 26 巻 4 号 p.
1026-1030
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Bis (N-phenyl-β-mercaptothiocinnamamido) Pd (II) was prepared and its chemical properties were investigated. It was revealed that the complex is coordinated with two sulfur atoms of the ligand and capable of containing two pyridine molecules when it is recrystallized from its pyridine solution. These pyridine molecules do not coordinate with the central palladium ion, but were supposed to be included as clathrate and probably interact with the protons of the thioamido groups of the ligands.
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岡田 昌二, 望月 信夫, 為政 脩
1978 年 26 巻 4 号 p.
1031-1038
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The three aminoquinone compounds, 2-amino-1, 4-naphthoquinone imine (ANQI), 2, 5-diamino-1, 4-naphthoquinone imine (DANQI) and 2-hydroxyamino-1, 4-naphthoquinone (HANQ), which had been reported to interact with deoxyribonucleic acid (DNA) in vitro and to inhibit DNA synthesis in Ehrlich ascites carcinoma cells, caused strand breaks in DNA of the carcinoma cells. ANQI and DANQI, when incubated with the carcinoma cells, induced the single strand breaks producing the fragments of homogeneous size. These two aminoquinones, however, did not cause the strand breaks in the carcinoma DNA when i.p. injected into the carcinoma-bearing mice. HANQ, on the other hand, induced both the single and double strand breaks in the DNA when applied on either the cells or the carcinoma-bearing mice. Since both types of the breaks occurred at the same concentration or dose of HANQ, the double strand scission might be its dominant action. From these results, the relationship between the strand scission and the inhibition of the DNA synthesis or the antitumor activity was discussed.
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堀江 正信, 馬場 茂雄
1978 年 26 巻 4 号 p.
1039-1043
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The human urinary metabolites of 3-phenylpropyl carbamate (I) were analysed by using an ion cluster technique. After oral administration of an equimolar mixture of non-labeled I and deuterium labeled I, neutral metabolites were extracted with ethyl acetate at pH 7.0, trimethylsilylated and subjected to gas chromatograph-mass spectro-meter. In the case of the analysis of acidic metabolites, the urine of human receiving deuterium labeled I alone was used. The obtained acidic metabolites were methylated with diazomethane and subjected to gas chromatograph-mass spectrometer. As neutral metabolites, 3-hydroxy-3-phenylpropyl carbamate, 2, 3-dihydroxy-3-phenylpropyl carbamate and 3, 4'-dihydroxy-3-phenylpropyl carbamate were identified. Unchanged I, however, was not detected. Benzoic and hippuric acids originated from I could be clearly distinguished from the corresponding compounds endogenously produced.
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横山 照由, 梅田 常雄, 黒田 耕司, 渡辺 厚
1978 年 26 巻 4 号 p.
1044-1048
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Refractive indices and related optical properties of 3 polymorphs and 2 solvates of sulfamethoxydiazine were determined by a polarizing microscope. A morphological measurement was also made for form I and III by a goniometer. All these data were useful for the simple and rapid identification of each form of sulfamethoxydiazine in a hospital pharmacy using a polarizing microscope. Especially the differences in key refractive indices between form II, the most active one, and form I or III are advantageous for discriminating form II from other less active forms in pharmaceutical preparations. Transition behaviors were also examined using a heating stage, from which the stability of 3 polymorphic forms were determined.
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岸田 健一
1978 年 26 巻 4 号 p.
1049-1053
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Huckel molecular orbital method and Hansch and Fujita's extrathermodynamic method were employed to characterize the chemical structure of 1, 3, 4-thiadiazole-5-sulfonamide derivatives which are potent carbonic anhydrase inhibitors. Regression analysis showed that a good correlation exists between the positive charge on nitrogen-10 and the inhibitory activity. It is also shown that the hydrophobicity of the side chain is another factor of development of enzyme inhibition. These results are consistent with the findings of X-ray crystallographic works.
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西海枝 東雄, 北川 徳治郎
1978 年 26 巻 4 号 p.
1054-1060
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Kinetic studies of the thermolytic Curtius rearrangement of set A of 5-substituted 2-furoyl azides (1-6), 5-substituted 2-thenoyl azides (7, 8 and 9) and 2-pyrroyl azide (10), and set B of p-substituted benzoyl azides (11, 12 and 13) and 2-, 3- and 4-pyridinemonocarbonyl azides (14, 15 and 16) in toluene were executed by means of IR (infrared) spectrophotometric method. It was found through the relationship between log k and 1/T that the isokinetic temperature (Q) of the set A and B are Q=371°and 353°K, respectivery. Based on ΔE
=⃥ and ΔS
=⃥, it seems to be reasonable that the reactivity of the each of unsubstituted acyl azides (2, 7, 9 and 12) is very nearly parallel to that the each resonance energy of the parent rings of the above four acyl azides. Additionally, it was found that the substituent dependence on ΔS
=⃥ in the rearrangement of the 5-substituted 2-furoyl azides (2-6) and also the 5-substituted 2-thenoyl azides (9 and 10) is indifferent to whether the substituents are electron releasing or attracting groups, and on the other hand, the rearrangement of p-substituted benzoyl azides (12 and 13) has ΔS
=⃥ decreased, respectively.
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平田 雅春, 二口 眞也, 田村 孝子, 小田口 州宏, 田中 明
1978 年 26 巻 4 号 p.
1061-1065
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Plasma corticosteroids level was determined after rectal administration of Gly
1-α
1-18 ACTH amide to hypophysectomized rat. When the aqueous solution of the peptide was administered, the corticosteroidogenic response was detected in 5 min and reached its maximum in 15 to 30 min after the administration. The half maximum effective dose from dose response curve was estimated to be 40 μg/kg. The extent of absorption of the peptide was markedly influenced by suppository bases as well as the nonionic surfactants added to the bases. Polyoxyethylene (20) cetyl ether (BC-20TX) enhanced the absorption from both hydrophobic and hydrophilic bases while BC-7 stimulated that from only hydrophobic bases.
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佐々木 喜男, 藤原 英明, 川木 秀子, 岡崎 雄交
1978 年 26 巻 4 号 p.
1066-1070
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
1 : 1 Complex formation between Eu (DPM)
3 and aliphatic alcohol was confirmed under the condition of [Eu (DPM)
3] ≳ [ROH] in a dilute solution, where the concentrations of donor [ROH] and acceptor [Eu (DPM)
3] are below 0.02M, respectively. Of the two parameters K
c and Δ
c estimated by the computer simulation of the equilibrium equation, the formers are solvent dependent, whereas the latters are not. Δ
AD and ΔG estimated from the solute-solvent interaction model are comparable with the 1 : 1 complex shift Δ
c and free energy obtained from the temperature dependence of K
c, and the infinite concentration shifts Δ
ic are also comparable with Δ
c.
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菅田 節朗, 松島 美一
1978 年 26 巻 4 号 p.
1071-1074
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The kinetics of incorporation of zinc (II) into meso-tetraphenylporphine in N, N-dimethylformamide (DMF), at 30°, were affected by the trace water in the solvent and by the presence of acetate ion (OAc-). The reaction was one half order in Zn (ClO
4)
2·6H
2O, whereas first order in Zn (ClO
4)
2·6DMF. Addition of HClO
4 to the water containing system retarded the reaction rate and converted the kinetics to the first order with respect to total Zn (II). The main path for the reaction of Zn (ClO
4)
2·6H
2O was concluded to be that involving the monohydroxo species, Zn (OH)
+. Addition of acetate anion increased the rate, until at a ratio [OAc-]/[Zn] of unity the rate reached a maximum ; an increase of the ratio past unity caused a rate decrease. The species, Zn (OAc)
+, is concluded to be more reactive than the fully solvated Zn (II) species and Zn (OAc)
2·
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奈良 潔, 隅野 靖弘, 片本 和義, 秋山 峻一, 浅井 満子
1978 年 26 巻 4 号 p.
1075-1082
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Two aminoglycoside antibiotics active against Gram-positive and -negative bacteria, P-2563 (P) (1) and P-2563 (A) (2) were isolated from a culture broth of Pseudomonas fluorescence P-2563. It was found that 1 (C
15H
31N
3O
9) and 2 (C
14H
29N
3O
9) are acylaminoglycoside having the same new aminopolyol structure in their molecules. 1 and 2 showed low order of acute toxicity in mice.
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奈良 潔, 片本 和義, 鈴木 滋, 秋山 峻一, 水田 栄治
1978 年 26 巻 4 号 p.
1083-1090
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The plane structure of the aminopolyol moiety of the aminoglycoside antibiotics P-2563 (P) (1) and P-2563 (A) (2) was elucidated to be 1, 4-diamino-1, 4-dideoxyhexitol (3) from physico-chemical and spectroscopic characterizations. The absolute configuration of 3 was determined to be 2S, 3S, 4R and 5S on the basis of transformation of 3 into methyl 3, 6-diacetamido-2, 4-di-O-acetyl-3, 6-dideoxy-α-L-gulopyranoside (12) by the oxidation of the hydroxymethyl group at C-6.
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奈良 潔, 片本 和義, 鈴木 滋, 水田 栄治
1978 年 26 巻 4 号 p.
1091-1099
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The absolute configuration of P-2563 (P) (1) and P-2563 (A) (2) were elucidated to be 3-O-(4-deoxy-4-propionamido-α-D-glucopyranosyl)-(2S, 3S, 4R, 5S)-1, 4-diamino-1, 4-dideoxyhexitol and 3-O-(4-acetamido-4-deoxy-α-D-glucopyranosyl)-(2S, 3S, 4R, 5S)-1, 4-diamino-1, 4-dideoxyhexitol, respectively, from the absolute configuration of the aminopolyol moiety (3), together with the plane structures of 1 and 2 and
13C-NMR studies.
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北川 勲, 白川 清治, 吉川 雅之
1978 年 26 巻 4 号 p.
1100-1110
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The structure of a minor saponin named Mi-saponin C (10), which was previously isolated together with two major saponins Mi-saponin A (4) and Mi-saponin B (5) from the seed kernels of Madhuca longifolia (L.) MACBRIDE (Sapotaceae), has been investigated. On the basis of chemical and physicochemical evidence, the structure of Mi-saponin C has been established as 3-O-β-D-glucopyranosyl-28-O-{[3-O-α-L-rhamnopyranosyl-4-O-β-D-glucopyranosyl]-β-D-xylopyranosyl (1→4)-α-L-rhamnopyranosyl (1→2)-α-L-arabino-pyranosyl}-protobassic acid (10). Mi-saponin A (4), B (5), and C (10) are bisdesmosides of an olean-12-ene-type sapogenol protobassic acid (1).
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八木 晟, 牧野 健司, 西岡 五夫
1978 年 26 巻 4 号 p.
1111-1116
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The phenolic components of the fresh subterranean part and rhizome of Aloe saponaria HAW. were examined to give new four bianthraquinoid pigments A (I), B (II), C (III) and D (IV). On the basis of the spectral and chemical evidences the structures of these compounds were established to be (+)-asphodelin (I), 1, 1', 8, 8', 10-pentahydroxy-3, 3'-dimethyl-10, 7'-bianthracene-9, 9', 10'-trione (II), 1, 1', 8, 8'-tetrahydroxy-3, 3'-dimethyl-4, 7'-bianthracene (10'H, 10'H)-9, 9', 10-trione (III) and 1, 1', 8, 8', 10-pentahydroxy-3, 3'-dimethyl-10, 7'-bianthracene (10'H, 10'H)-9, 9'-dione (IV).
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高村 吏, 手島 節三
1978 年 26 巻 4 号 p.
1117-1122
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Selective tosylation of 1, 6-anhydro-4', 6'-O-benzylidene-β-lactose (1), using 2.2 molar equivalents of tosyl chloride in pyridine at 0°, yielded four tosylates which were designated 2 to 5 in the order of decreasing Rf value on thin-layer chromatography. After column chromatography on silica gel, compounds 2-5 were separated as the 2, 3, 3'-tritosylate (2, 1.3%), 2, 3'-ditosylate (3, 21.9%), 3'-tosylate (4, 15%), and 2-tosylate (5, 25.2%), respectively. Selective tosylation of 3, using 8 molar equivalents of tosyl chloride afforded 2 (29%), 15, and 16, together with 3 (15%). Compounds 15 and 16 were identified as 2, 2', 3, 3'-tetratosylate (15, 38.9%) and 2, 2', 3'-tritosylate (16, 17.1%), respectively. Thus, the order of reactivities of the secondary hydroxyl groups in 1 is 2>3'>3>2'. Compounds 2-5 and 16 have potential value in the chemical modification of lactose or the syntheses of lactose-containing oligosaccharides in human milk.
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村瀬 清志, 間瀬 年康, 井田 昶, 高橋 孝三, 村上 増雄
1978 年 26 巻 4 号 p.
1123-1129
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The two pairs of enantiomers (1A and 1B) of 3-formamido-4-hydroxy-α-[[N-(p-methoxy-α-methylphenethyl) amino] methyl] benzyl alcohol (1) were resolved into four isomers ((-)-1A, (+)-1A, (-)-1B and (+)-1B). Two isomers ((-)-1A and (-)-1B) were also obtained from (-)-N-(p-methoxy-α-methylphenethyl) amine (5) and 4'-benzyloxy-3'-nitro-2-bromoacetophenone by several steps. The configurations of the enantiomers of 5 were determined by chemical correlation with those of N-(p-hydroxy-α-methylphenethyl)-amine, whose configuration is known. The configurations of the asymmetric carbon (α) carrying the OH group and the asymmetric carbon (β) located in the amine moiety of (+)-1A were respectively determined by correlation with (+)-4-methoxy-3-nitrobenzoic acid (7) and (+)-5, whose configurations are known, through (+)-3-amino-4-methoxy-α-[[N-(p-methoxy-α-methylphenethyl) amino] methyl] benzyl alcohol (12). On the basis of these experiments the configurations of the four isomers were shown as follows : (-)-1A=αR, βR, (+)-1A=αS, βS, (-)-1B=αS, βR and (+)-1B=αR, βS. Bronchodilator activity of these compounds was found to decrease in the order (-)-1A>(+)-1B>(+)-1A>(-)-1B.
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酒井 立夫, 吉田 由美, 出村 はるみ, 柳田 友道, 明和 正, 大山 馨
1978 年 26 巻 4 号 p.
1130-1134
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The decimal reduction dose of γ-ray on freeze-dried clean Escherichia coli cells and Bacillus subtilis spores was about 7×10
4 rad and it was about three times higher than that on E. coli cells suspened in saline. E. coli cells contained in Takadiastase or trypsin powder showed quite the same susceptibility to γ-irradiation as they were present cleanly. These enzyme activities were not impaired at all even at the dose of 2×10
5 rad. When these enzyme powders containing E. coli cells were stored under varied atmospheric relative humidity, the deleterious effect of γ-ray on bacterial cells was highly enhanced in those samples stored under more than 80.5% relative humidities. The additions of excipients, such as glucose and lactose, and of a protectant, L-cysteine, to the bacteria-containing dry enzyme powder did not show any sign of either enhancement or retardation of γ-ray action on enzyme and bacteria. Based on these observations, the utilizability of radiosterilization on biological medicaments is discussed.
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堀 了平, 荒川 正人, 奥村 勝彦
1978 年 26 巻 4 号 p.
1135-1140
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Tissue distribution and penetration of drugs were measured in the rabbit pancreas cannulated into the pancreatic duct for the collection of pancreatic juice. Drugs with high lipid solubility were found to be easily distributed within the pancreas. The lipid solubility of drugs appears to be the most important factors determining their distribution in the pancreas. Small molecules were rapidly penetrated from blood to pancreatic juice if they are lipid soluble. Permeability of drugs through the pancreas was demonstrated to be dependent upon their molecular size and lipid solubility. Increased penetration of drugs by the retrograde infusion of HgCl
2 solution through the pancreatic duct suggested that both lipid barrier and molecular sieve barrier would be complex multicellular system and exist independently surrounding the pancreatic duct.
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栗原 拓史, 坂本 靖彦, 坂口 寿子, 平野 弘
1978 年 26 巻 4 号 p.
1141-1146
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Reactions of 4-(substituted benzylidene)-3, 5-dimethylisopyrazoles (1a-1c) with acetic anhydride, hydrochloric acid in methanol, bromine in acetic acid, dimethyl sulfate, and acyl chlorides (acetyl chloride, benzoyl chloride, ethyl chloroformate, and p-toluenesulfonyl chloride) in pyridine gave 1, 4-addition products (2-10) in fairly good yield. On the other hand, 4-(o-nitrobenzylidene) isopyrazole (1a) was converted to 5-chloro-3-(1-substituted 3, 5-dimethylpyrazolyl) anthranils (13, 14, and 15) by treatment with acetyl chloride, benzoyl chloride, or ethyl chloroformate without pyridine.
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稲森 善彦, 砂川 成代, 敦賀 真智子, 沢田 洋介, 谷山 兵三, 斎藤 元一, 醍醐 皓二
1978 年 26 巻 4 号 p.
1147-1152
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
In order to investigate the mode of the delayed toxicity of streptothricin antibiotics, racemomycin-A and -D were administered intravenously to mice in a surviving dose. Antimicrobial activity levels in serum declined very rapidly. Localized distribution of antibiotics was conspicuous in the kidneys, and binding rate of the antibiotics with serum proteins in vitro was related to β-lysine units in the molecule. Mice administered with antibiotics showed gradual decrease in their body weight, and they further suffered prominent damages in their liver, spleen, and kidneys. These lesions seemed to kill the mice by the delayed toxicity. The mice that died by the lethal doses of the antibiotics were considered to be due to the respiratory paralysis.
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青野 哲也, 荒木 義昭, 今西 正之, 野口 俊作
1978 年 26 巻 4 号 p.
1153-1161
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
6-Aroyl-1-indancarboxylic acids (V) and isomeric 4-aroyl-1-indancarboxylic acids (XVIII) were prepared in an attempt to obtain information on the receptor sites of anti-inflammatory aroylarylacetic acids. Compounds V were easily obtained by the Friedel-Crafts reaction of ethyl 1-indancarboxylate (III) and aroyl chloride. On the other hand, compounds XVIII were synthesized from 1-oxo-4-indancarboxylic acid (VIII) via the Friedel-Crafts reaction of 1-cyano-4-indancarbonyl chloride (XVI) and benzene or its derivative. Although compounds XVIII showed potent antiinflammatory activity, the activity of V was significantly weaker. The result suggests that locations and conformations of the functional groups in XVIII are considerably close to the actual conformation of a aroylarylacetic acid required for exerting antiinflammatory activity.
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上釜 兼人, 平山 文俊, 小田切 優樹, 小田切 陽子, 池田 憲
1978 年 26 巻 4 号 p.
1162-1167
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The interaction of β-cyclodextrin with some sulfonamides in aqueous solution has been investigated by circular dichroism, UV absorption, and solubility techniques. Solubility and spectral changes were quantitatively treated to obtain stoichiometric ratio, which was found to be 1 : 1, formation constants, and thermodynamic parameters for inclusion complexation. All results suggest that steric and hydrophobic factors of the drugs were largely responsible for this interaction.
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杉浦 真喜子, 高尾 楢雄, 岩佐 衣子, 佐々木 喜男
1978 年 26 巻 4 号 p.
1168-1176
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Stereochemistry of benzo [α] quinolizidine derivatives (I-VIb) were examined from C-13 magnetic resonance chemical shifts, and C-6 and C-7 shifts of these compounds were found to be reliable as the indications of favoured conformations-trans, cis "a" or cis "b". This treatment is also available for the conformational analyses of tetrahydroproto-berberine type alkaloids.
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吉田 彰, 吉岡 正則, 酒井 稔夫, 田村 善蔵
1978 年 26 巻 4 号 p.
1177-1181
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
A determination method of urinary vanilpyruvic acid was developed by high-speed liquid chromatography. Sample urine was acidified and extracted with ethyl acetate. After evaporation of the organic solvent, the residue was left over phosphorous pentoxide to complete the conversion of keto form to enol form and dissolved in methanol. The methanol solution was injected into a high-speed liquid chromatograph equipped with a column of Hitachi Gel No. 3010 (spherical porous particles of styrene-divinylbenzene copolymer) and a ultraviolet (UV) monitor (280 nm). Vanilpyruvic acid was eluted with a mixture of 0.05 M tartrate buffer and methanol (85 : 15, v/v) varying the pH of the buffer from 3.15 to 5.25. The quantity of vanilpyruvic acid was determined from the peak height. By the present method, vanilpyruvic acid was found in urine of patients with neuroblastoma, a Parkinsonian patient treated with L-3, 4-dihydroxyphenylalanine. However, this acid was not found in urines of normal subjects.
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相見 則郎, 浅田 善久, 坂井 進一郎, 萩庭 丈寿
1978 年 26 巻 4 号 p.
1182-1187
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Four known (tabersonine (1), tetrahydroalstonine (2), Δ
14-vincamine (6) and 16-epi-Δ
14-vincamine (5)) and four new indole alkaloids (3-oxo-tabersonine (3), 14, 15-epoxy-3-oxo-vincadifformine (4), 16-carbomethoxy-16-hydroxy-14, 15-epoxy-3-oxo-1, 2-dehydroaspidospermidine (7) and tabersonine N
(b)-oxide (8)) were isolated from the seeds of Amsonia elliptica ROEM. et SCHULT. (Apocynaceae). Δ
14-Vincamine (6) and its C
(16)-epimer (5) were partially synthesized from tabersonine (1). Unusual oxidative chlorination was observed when tabersonine hydrochloride was oxidized with m-chloroperbenzoic acid.
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田中 光也, 京坂 重久, 村田 早苗
1978 年 26 巻 4 号 p.
1188-1194
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Three affinity adsorbents, p-aminophenyl β-acetylglucosaminide, p-aminophenyl β-1-thio-acetylglucosaminide and β-acetylglucosaminylamine, each bound to CH-Sepharose 4B (GO, GS and GN, respectively), were examined for the purification of bovine liver β-acetylhexosaminidases. In preliminary experiments with crude enzyme, columns of GO and GS gave three fractions when eluted successively with 0.05M citrate buffer, pH 5.0, 0.1M borate buffer, pH 10, containing 1 M sodium chloride, and 5M urea. Purification procedures involve ammonium sulfate precipitation, treatment at pH 3.8 at 37°, Sephadex G-200 gel filtration, DEAE-cellulose column chromatography and affinity chromatography on GS. A hexosaminidase A was obtained as a electrophoretically pure protein with high specific activity, 137 units per mg. Activity in hexosaminidase B fraction showed multiplicity in its behavior in the affinity chromatography, and the high specific activity (184 units per mg) was obtained only with a GO column. Km values and ratios of acetylglucosaminidase to acetylgalactosaminidase activities were determined for main components. The molecular weights of the hexosaminidase A and B were estimated to be 280000 and 320000, respectively, as determined by gel filtration using the partially purified enzymes.
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上釜 兼人, 平山 文俊
1978 年 26 巻 4 号 p.
1195-1200
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The interaction of prostaglandin F
2α (PGF
2α) with α-and β-cyclodextrins in aqueous solution was investigated by potentiometric titration, solubility, and carbon 13 nuclear magnetic resonance (
13C NMR) techniques. Changes in titration curve and solubility of PGF
2α following the binding to α-and β-cyclodextrins were quantitatively treated to obtain equilibrium constants and thermodynamic parameters. The protolytic dissociation of PGF
2α was significantly suppressed by inclusion complexation.
13C NMR chemical shift changes suggested that binding of PGF
2α to α-cyclodextrin was somewhat different from that to β-cyclodextrin.
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原山 尚, 長 秀連, 犬伏 康夫
1978 年 26 巻 4 号 p.
1201-1214
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The total synthesis of dl-chamaecynone (1), which has termiticidal activity, has been accomplished. The key compound (30a), which has the same four chiral centers as chamaecynone (1), was obtained in a single step by taking advantage of the Diels-Alder reaction of 5-ethynyl-2-methylcyclohex-2-en-1-one (3) with 1-methoxy-3-trimethylsiloxy-1, 3-pentadiene (4). The stereostructure of the major adduct of the Diels-Alder reaction was determined to be the formula (30a) by INDOR experiment. The compound (30a) was converted in four steps into dl-chamaecynone. The preliminary examinations of the Diels-Alder reaction of trans-1-methoxy-3-trimethylsiloxy-1, 3-butadiene (2) with l-carvone and the compound (3) were also carried out, respectively.
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吉村 英敏, 小沢 直記, 佐伯 清太郎
1978 年 26 巻 4 号 p.
1215-1221
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The inductive effect of Kanechlor 400 (KC-400), the Japanese polychlorinated biphenyl (PCB) preparation containing 48% chlorine, and several individual PCB isomers on the hepatic microsomal enzymes of rats was investigated. Pretreatment with KC-400 increased significantly the activity of microsomal aminopyrine (AM) demethylase, aniline (AN) hydroxylase and NADPH-cytochrome c reductase, and the content of cytochromes P-450 and b
5 just like phenobarbital (PB)-pretreatment. However, it afforded the CO-difference spectrum revealing the peak at 448 nm same as pretreatment with 3-methylcholanthrene (MC). The inhibitory effect of SKF 525-A and 7, 8-benzoflavone on AM demethylation and AN hydroxylation, respectively, in KC-400-induced microsomes also resembled that in microsomes induced by PB plus MC. Further studies using individual PCBs indicated that these compounds were divided into two groups ; namely, 4, 4'-dichlorobiphenyl (DCB), 2, 5, 2', 5'-and 2, 4, 3', 4'-tetrachlorobiphenyl (TCB) were categorized as PB-type, whereas the other group including 3, 4, 3', 4'-TCB, 3, 4, 5, 3', 4'-pentachlorobiphenyl (PenCB) and 3, 4, 5, 3', 4', 5'-hexachlorobiphenyl (HCB) was categorized as MC-type inducers. Decachlorobiphenyl, the completely chlorinated biphenyl derivative, was found to belong to PB-type. These conclusions were further supported by a spectral study with hexobarbital, which induced type I spectral changes with microsomes from control and 2, 4, 3', 4'-TCB-treated rats, and caused modified type II spectral change with microsomes from 3, 4, 5, 3', 4'-PenCB-treated rats. Considering these results with individual PCBs, it can be assumed that chlorination of both of the para-(4, 4') and two of the meta-positions (3, 3' or 5, 5') of biphenyl is a minimum requirement for the structure to induce cytochrome P-448.
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中嶋 暉躬, 安原 義, 平井 裕子, 北田 千恵子, 藤野 政彦, 武山 正治, 小山 要, 矢島 治明
1978 年 26 巻 4 号 p.
1222-1230
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Amino acid sequence of a new frog skin peptide named granuliberin-R, H-Phe-Gly-Phe-Leu-Pro-Ile-Tyr-Arg-Arg-Pro-Ala-Ser-NH
2, was assessed by two conventional ways of synthesis ; the one by the methanesulphonic acid procedure and the other by the catalytic hydrogenation procedure at the final deprotection steps.
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矢島 治明, 佐々木 敬, 小川 博, 藤井 信孝, 瀬川 富郎, 仲田 義啓
1978 年 26 巻 4 号 p.
1231-1235
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Kassinin, a dodecapeptide amide isolated by Erspamer et al. from the skin of Kassina senegalensis, was synthesized by deprotection of Z (OMe)-Asp (OBzl)-Val-Pro-Lys (Z)-Ser-Asp (OBzl)-Gln-Phe-Val-Gly-Leu-Met (O)-NH
2 with methanesulphonic acid, followed by reduction of the Met (O) residue to Met with 2-mercaptoethanol. The contractile activity of synthetic kassinin in isolated guinea-pig ileum was 0.4 of that of synthetic substance P.
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酒向 孫市, 牧 敬文
1978 年 26 巻 4 号 p.
1236-1239
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
In order to compare with the photochemical reaction resulting to the preferential formation of 3-methylenecepham, the thermal reaction of 4-benzothiazolyldithioazetidinone (1) was examined. Pyrolysis of 1 led to the formation of 2-mercaptobenzothiazole (4), isothiazolone derivatives (5a and 5b), thiazole derivatives (6a and 6b) and bisbenzothiazolyl disulfide (7) in a different manner from the photolysis of 1. Rearrangements of 1 to 5 and 6 are particularly of interest and their possible mechanisms were discussed.
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赤田 良信, 崎谷 陽子, 河野 貞子, 足立 真一
1978 年 26 巻 4 号 p.
1240-1246
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The method was established to quantitate rapidly, simply and accurately by the technique of high-speed liquid chromatography, glycyrrhizin as the active ingredient of glycyrrhiza contained in kanpo (chinese medical) preparations (in the form of tablet, granule, subtle granule, powder or liquid) which are made of glycyrrhiza together with various other crude drugs. Glycyrrhizin contained in such preparations was separated in less than 11 minutes in Du Pont LC 830 with a Permaphase AAX column (50 cm×2.1 mm, i.d.) by gradient elution technique with 1/30M phosphate buffer (pH 5.2) and 0.3M NaClO
4 solution as the eluants. Quantitative determination was made by this method of glycyrrhizin contained in 27 different formulae with 6 forms of preparation. For table form, a relatively satisfactory correlation was found between the glycyrrhiza extract content specified in the prescription and the glycyrrhizin content actually determined. The per cent glycyrrhizin content of preparations containing glycyrrhiza powder (2 granule and 1 powder preparation) was almost identical with the value calculated from the per cent GA content (5.00 per cent) of glycyrrhiza powder referred to in our previous report.
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小林 義郎, 熊懐 稜丸, 大沢 昭緒, 村上 慎一, 中野 隆治
1978 年 26 巻 4 号 p.
1247-1249
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Photochemical trifluoromethylation of pyridine gave a mixture of three (trifluoromethyl) pyridines. Pyrrole and N-methylpyrrole were trifluoromethylated in α-position. Benzene gave very low yield of benzotrifluoride.
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栗原 弘三, 市川 泉夫
1978 年 26 巻 4 号 p.
1250-1256
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The relation between variation of filling-weight and powder-flowability was studied in connection with filling mechanism. OCF-120 and Hofliger-Karg-GKF-1000 were used as a capsule-filling machine of the pouring type and of the stamping type, respectively. The angle of repose, the minimum orifice diameter and the discharge rate through orifices were measured. The minimum orifice diameter was closely related to the discharge rate through orifices. No good correlations were found between the angle of repose and the minimum orifice diameter. The angle of repose was used as an index of flowability representing the mobility of the particles on the surface of a powder bed and the minimum orifice diameter was used as one representing the mobility of the particles in a powder bed under dynamic conditions. In the case of OCF-120, a good correlation between the variation of filling-weight and the minimum orifice diameter was found. In the case of Hofliger-Karg-GKF-1000, the variation of filling-weight was closely related to the angle of repose but a minimum point appeared in the plots of the angle of repose vs. the coefficient of variation of filling-weight. This finding is explained as follows : as the angle of repose increases, the variation of filling-weight is governed by both the increasing factor and the decreasing factor, namely the variation of the powder-bed-height in the filling box and that of the amounts of jumping-out of the filled powder, respectively.
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仁田 義孝, 相本 太刀夫, 村田 敏郎, 伊藤 圭二
1978 年 26 巻 4 号 p.
1257-1260
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Distribution of ethchlorvynol (EC) to the blood, liver, jejunum, lung, kidney, adipose tissue and brain of rat were studied after oral administration of 150 mg/kg of EC in two dosage forms. The peaks of blood and tissue levels appeared more rapidly after dosing EC suspended in 5% polyethylene glycol 400 aqueous solution (PEG-sol.) than with vegetable oils, while the peak values were almost similar. The most remarkable effect of the oils used was shown in the brain levels of EC. The peak values of brain EC levels were 3.0, 5.9, and 5.9 μg/g wet tissue after dosing with corn oil, peanut oil and soybean oil, respectively, while 19.5 μg/g wet tissue with PEG-sol. The ED
50 and LD
50 of EC in mice were calculated as 138 mg and 357 mg/kg, respectively, when dosed as PEG-sol., while as 185 mg and 424 mg/kg when dosed together with corn oil. Thus, the vegetable oils were shown to inhibit the transport of EC into rat brain.
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三浦 俊明, 小川 教子, 小木曽 健人
1978 年 26 巻 4 号 p.
1261-1266
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Diethyldithiocarbamate (DDC), a copper chelate agent, was used to examine a possible participation of superoxide radicals (O
2-) in the formation of methemoglobin (metHb) under the O
2- generating system of photoactivated riboflavin. Superoxide dismutase in the lysate from DDC-injected rats was inhibited to 93% and catalase remained unchange, however, the formation of metHb was scarcely observed. In the experiments in vitro, superoxide dismutase was completely inhibited by the pretreatment with DDC above 3 mM whereas catalase was partially inhibited. In this case, the formation of metHb was accelerated with increase of DDC concentration. Addition of catalase to the dialyzed lysate resulted in the inhibition of formation of metHb to almost the same level as that in the normal lysate. Superoxide dismutase alone, however, caused a slight increase in the rate of formation of metHb, indicating that catalase but not superoxide dismutase has protective ability to the formation of metHb by O
2-. From these results, O
2-appears to be the source of hydrogen peroxide which accounts for most the observed metHb formation.
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永松 国助, 城戸 靖雅, 浦久保 五郎
1978 年 26 巻 4 号 p.
1267-1273
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Metabolic fate of 2, 5-dimethoxy-4-methylamphetamine (DOM) was investigated in the guinea pig and rabbit. DOM concentration in serum decreased rapidly after a subcutaneous injection and DOM was scarcely obtained at 3 to 4 hours later by radioimmunoassay and thin-layer chromatography. As the metabolites of DOM, 2, 5-dimethoxy-4-hydroxymethylphenyl-2-aminopropane and 2, 5-dimethoxy-4-carboxyphenyl-2-aminopropane were confirmed in the urine of guinea pig and rabbit. 2, 5-Dimethoxy-4-methylphenyl-2-propanol and 2, 5-dimethoxy-4-methylphenyl-2-propanone, which had not been detected in rat urine but in the incubation mixture of DOM with rabbit liver microsome, were identified in guinea pig and rabbit urines. 2, 5-Dimethoxy-4-methylbenzoic acid was firstly detected as a minor metabolic product of DOM in the urine of both species of animals. Principal metabolic pathway of DOM in guinea pig was not regarded as the side-chain oxidation but as the oxidation of methyl group on benzene ring as well as in rabbit.
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小松 曼耆, 横江 一朗, 白瀧 義明
1978 年 26 巻 4 号 p.
1274-1278
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Two new benzofuran derivatives [I], mp 235-237°, C
15H
10O
5 and [II], mp 179-181°, C
16H
12O
5, together with l-maackiain, stigmasterol, medicagol, formononetin and 2', 4', 4-trihydroxychalone (isoliquirtigenin) were isolated from the aerial parts of Sophora tomentosa L., and the structures of I and II were established to be 2-(2', 4'-dihydroxyphenyl)-5, 6-methylenedioxybenzofuran and 2-(2'-hydroxy-4'-methoxyphenyl)-5, 6-methylenedioxybenzofuran on the bases of chemical and spectral evidence, respectively.
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関口 慶二, 津田 泰之, 菅家 甫子, 鈴木 悦子, 岩鶴 素治
1978 年 26 巻 4 号 p.
1279-1290
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Ammonia adduct formation was confirmed with 9 barbiturates and ammonia interaction was felt with another 2. Thermal behaviors of the ammonia adducts were investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), and others. Particle size of barbiturates was effectively reduced by formation of ammonia adducts and subsequent desorption of ammonia. Further, the effect of particle size on solubility and heat of fusion was investigated.
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加藤 武彦, 木下 俊夫
1978 年 26 巻 4 号 p.
1291-1294
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Taurine was found to react with carbohydrates by heating at neutral pH giving intense fluorescence. The development of fluorescence was proved to be greatly enhanced by addition of borate in the reaction mixture. This reaction was specific for the reducing sugars having C-2 hydroxyl or C-2 amino groups. The fluorescence intensity of oligosaccharides decreased with the increase in the degree of polymerization of monosaccharide units. Application of these findings provided a rapid, sensitive and reproducible assay method for carbohydrates. Standard curve for glucose was linear in the range of final concentration of 0.1 to 10.0 μg/ml of the sample and the coefficient of variation of 6.0 μg/ml of glucose was 1.4%.
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糸川 秀治, 稲葉 利和, 春田 龍二, 亀山 省司
1978 年 26 巻 4 号 p.
1295-1297
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Radical methylation and radical hydroxymethylation of N-substituted quinoline derivatives were applied to natural products, especially to nicotine and quinine. In both cases, methyl derivatives were obtained in high yield than hydroxymethyl derivatives. Nicotine was substituted preferentially at C-6 position and quinine was substituted preferentially at C-2 position.
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YOUSUFA. AL-FARKH, FAROUKH. AL-HAJJAR, HAYATS. HAMOUD
1978 年 26 巻 4 号 p.
1298-1303
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
The reactions of aroylphenylacetylenes (I) with ethyl and phenyl hydrazinecarboxylates, benzoylhydrazine, phenylacetylhydrazine, α-naphthylacetylhydrazine, methylhydrazine, N, N-dimethylhydrazine, thiourea, guanidine and S-benzylisothiourea were reported. The structure and configuration of the products are based on chemical and spectroscopic evidence.
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高井 均, 曹 金造, 佐々木 喜男
1978 年 26 巻 4 号 p.
1303-1307
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
C-13 nuclear magnetic resonance chemical shifts of 1-substituted-3, 4-dimethoxy-and-3, 4-methylenedioxybenzene derivatives were measured. Reliability of the additivity rule of the shielding parameters of monosubstituted benzenes, and the linear relations between the chemical shifts and shielding parameters or substituent constants were confirmed. Deviations from the additivity rule are mainly attributed to the ortho steric effect.
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小泉 徹, 梁川 由芳, 吉井 英一, 山崎 高應
1978 年 26 巻 4 号 p.
1308-1311
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Preparation and separation of two isomeric 8, 13-diazagona-1, 3, 5 (10)-triene-12-ones are described. The stereochemistry of both isomers is also discussed.
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鹿野 美弘, 木島 正夫
1978 年 26 巻 4 号 p.
1311-1315
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Screening of the inhibitor to the absorption of alkaloid in the Scopolia extract was taken up and following results were obtained. The alkaloid absorption through the intestine in the administration of Scopolia extract is affected by scopoletin, tannin-like substance (s) and others, but is not affected by the acidic component (s).
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三村 務, 大西 昇, 辻坊 裕, 増本 峰子, 青沼 繁
1978 年 26 巻 4 号 p.
1316-1319
発行日: 1978/04/25
公開日: 2008/03/31
ジャーナル
フリー
Several fatty acids, including 2-hexyldecanoic acid, iso-C
15 : 0, iso-C
16 : 0, and iso-C
17 : 0 as branched series and various types of C
16 fatty acids, were examined for protection of erythrocytes from heat-induced or hypotonic hemolysis, of heat-induced denaturation of bovine serum albumin (BSA) in vitro, and for inhibition of carrageenin-induced edema in hind paw of a rat in vivo. All of fatty acids tested were found to have a protective effect on heat-induced hemolysis of rat erythrocytes and heat-induced denaturation of BSA. Inhibitory effect on hypotonic hemolysis was recognized in all fatty acids except 2-hexyldecanoic acid, and iso-series especially showed greater activity. In regard to carrageenin-induced paw edema, only iso-C
15 : 0 and iso-C
16 : 0 exhibited inhibitory an effect, and other fatty acids had no effect.
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