All issues
Volume 30, Issue 8
Displaying 1-50 of 62 articles from this issue
-
JUNICHI ODO, MASAAKI NISHIO, YUTAKA SAITO, YOSHIMASA TANAKA1982 Volume 30 Issue 8 Pages 2661-2666
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe infrared spectra of [Cu (glutamate)·(H2O)]n·(H2O)n, [Zn (glutamate)·(H2O)]n·(H2O)n and their isotopic complexes containing metal and hydrogen isotopes have been measured in the region between 4000 and 200 cm-1. The isotope shifts on 63Cu and 65Cu substitution have been observed for bands at 404, 352 and 279 cm-1 of the Cu complex. Bands at 300, 245 and 227 cm-1 of the Zn complex are apparently sensitive to 64Zn and 68Zn substitution. The frequency shifts on N, O-deuteration indicated that a Cu-OOC stretching vibration is localized for the Cu complex whereas Zn-OOC stretching vibrations couple with Zn-NH2 and/or Zn-OH2 stretching vibrations.View full abstractDownload PDF (647K) -
YOSHIHIRO KURODA, AKIO KUWAE, YASUHIRO FUJIWARA1982 Volume 30 Issue 8 Pages 2667-2672
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCorrelations between 13C nuclear magnetic resonance protonation shifts and protonation-induced charge densities on the carbon atoms as calculated by the INDO-MO method have been examined for mono- and dicationic species of 4-aminoazobenzene. The paramagnetic shielding constants have been calculated with the average excitation energy approximation. It is concluded that the deviation from the correlation between 13C protonation shifts and protonation-induced charge densities on some carbon atoms (Cl, C3, 5 etc.) is mainly due to variations in the average excitation energy term which are attributable to delocalization of lone-pair electrons assisted by resonance structure which makes the molecule planar.View full abstractDownload PDF (677K) -
HIROSHI NAKAHARA, SATOSHI OKADA, KENSHU MOCHIDA1982 Volume 30 Issue 8 Pages 2673-2681
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPancreatic lipase activity toward vinyl laurate (VL) solubilized in sodium deoxycholate (NaDC) micelles was investigated kinetically. The inhibition by substrate-free NaDC micelles, M, was observed, and a Lineweaver-Burk plot and a plot of the reciprocal of initial rate vs. [M] indicated that the inhibition may be fully competitive or fully mixed inhibition, depending on the value adopted for the aggregation number of NaDC micelles. However, further consideration of the interaction of various species in the system led us to favor a fully competitive inhibition mechanism. The Michaelis constant, Km, and the inhibition constant, K4, which is the dissociation constant of lipase-NaDC micelle complex, were estimated. It was shown that Km indicates the lower limit of the dissociation constant of lipase-NaDC micelle solubilizing VL, K1. The results are discussed in relation to the results of other studies on the inhibition of the enzyme by bile salts in emulsion systems.View full abstractDownload PDF (830K) -
MASANORI TAKAMATSU, YOSHIYASU TERAO, MINORU SEKIYA1982 Volume 30 Issue 8 Pages 2682-2687
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS2, 2, 2-Trichloro- and 2, 2-dichloroethylamines were found to suffer monoalkylation with Grignard reagents and alkyllithiums giving, in the main, chain-lengthened β, γ- or α, β-unsaturated amines. Which product is formed depends upon the individual structures of the substrates and organometallic compounds.View full abstractDownload PDF (572K) -
TOKUMI MARUYAMA, SUMIKO SATO, MIKIO HONJO1982 Volume 30 Issue 8 Pages 2688-2697
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCyclization of 5-iodo-1-(β-D-xylofuranosyl) uracil and -cytosine with sodium methoxide afforded 6, 3'-O-cyclouridine (IIa) and -cytidine (IIc), respectively. The rate of cyclization of 5-iodopyrimidine nucleosides is greatly dependent on the ring size formed on cyclization. Introduction of a trityl group at the 5'-position of the nucleoside brought about a decrease in the rate of cyclization. The ease with which ring-opening of 6-O-cyclouracil nucleoside isomers was effected with diluted sulfuric acid was in the opposite order to that of cyclization. The ultraviolet, circular dichroism and mass spectra of 6-O-cyclopyrimidine nucleosides and their isomers were compared.View full abstractDownload PDF (997K) -
SHIGERU OZASA, YASUHIRO FUJIOKA, EIICHI IBUKI1982 Volume 30 Issue 8 Pages 2698-2704
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSix sexiphenyls, including four new isomers, 2, 3'-di (4-biphenylyl) biphenyl (2), 4-(2-biphenylyl)-o-(4), 4-(2-biphenylyl)-m-quaterphenyl (5), and 2-phenyl-p-quinquephenyl (6), were synthesized by the Ullmann cross-coupling of iodobiphenyl and diiodobiphenyl or of two kinds of iodoterphenyls. The characteristic bands of the infrared spectra (680-920 cm-1) and signals of the proton magnetic resonance spectra of the sexiphenyls were assigned tentatively and are discussed briefly. The remarkable high field shifts of the p-phenylene proton signals in 4 (1.23 and 0.89 ppm) as compared with that of p-terphenyl (δ 7.68) presumably reflect the ring current effects caused by the presence of adjacent o-phenylene rings. Ultraviolet spectral studies indicated that the absorption curves of the sexiphenyls were related closely to those of the polyphenyls corresponding to their partial structures.View full abstractDownload PDF (742K) -
MASAYUKI OYA, SUSUMU ITO, KENICHI HARADA, MAKOTO SUZUKI, AKIRA TATEMAT ...1982 Volume 30 Issue 8 Pages 2705-2713
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe electron impact mass spectra of (2R, 4R)-2-(2-hydroxyphenyl)-3-(3-mercaptopropionyl)-4-thiazolidinecarboxylic acid (1), SA 446, and the related compounds 2-7 are discussed. The fragmentation patterns were classified into three types of characteristic ring fragmentation (1, 3-, 2, 5- and 3, 5-cleavages) with or without substituent cleavage. The fragment ions were established by the shifting method with the labelled derivatives 4'and 4"and the elemental compositions were confirmed by high-resolution mass spectrometry.View full abstractDownload PDF (630K) -
KENJIRO TANAKA, MICHIKO SHIMAZAKI, YASUOKI MURAKAMI1982 Volume 30 Issue 8 Pages 2714-2722
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFor the structure determination of thiazolo [3, 2-a] benzimidazol-3 (2H)-one derivatives (2 or 3) they were converted to the corresponding 1-acetylbenzimidazoles (4) by desulfurization. The latter compounds (4) were alternatively prepared by the cyclization of 2-aminoacetanilide derivatives (5) with CS2 in dimethylformamide (DMF), followed by desulfurization with Raney Ni. However, the reactions of 5 with ethyl orthoformate/H2SO4 in DMF gave a mixture of 4 and its acetyl-rearranged product (7).View full abstractDownload PDF (830K) -
TAKUSHI KURIHARA, KEIKO NASU1982 Volume 30 Issue 8 Pages 2723-2731
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSNucleophilic additions of phenol and aniline analogs to 6, 7-bis (ethoxycarbonyl) pyrazolo [1, 5-a] pyrimidine-3-carbonitrile (1) in the presence of triethyloxonium fluoroborate are described. For example, though phenol or o-cresol (having no substituent at the para-position) reacted with 1 to give the cyclohexadienylidene derivatives (3, 4), p- or m-cresols, p-methoxyphenol, and α-or β-naphthol gave the corresponding spiro lactones (6, 7, 8, 10 and 12). When 1 was treated with several kinds of aniline analogs, three types of products were obtained. Namely, while aniline or o-toluidine gave the 7-(4-aminophenyl) adducts (13, 15), p-anisidine, p-chloroaniline or p-nitroaniline afforded the 7-anilino derivatives (17, 20 or 21). Treatment of p-toluidine with 1 under the same reaction conditions gave a mixture of the spiro-indole-3 (2H), 7'(4'H)-pyrazolo [1, 5-a] pyrimidin-2-one (22) and the pyrazolo [1', 5' : 1, 2] pyrimido [5, 6-c] quinoline (23).View full abstractDownload PDF (914K) -
TOSHIO MIYASE, AKIRA KOIZUMI, AKIRA UENO, TADATAKA NORO, MASANORI KURO ...1982 Volume 30 Issue 8 Pages 2732-2737
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo new acyl glycosides, leucosceptosides A (IV) and B (V), have been isolated from Leucosceptrum japonicum (MIQ.) KITAMURA et MURATA, together with martynoside (III), acteoside (I) and an acteoside isomer (II). The structures of IV and V were determined to be 2-(3, 4-dihydroxyphenylethyl) 1-O-α-L-rhamnopyranosyl-(1→3)-β-D-(4-O-caffeyl)-glucopyranoside and 2-(3-hydroxy-4-methoxyphenylethyl) 1-O-α-L-rhamnopyranosyl-(1→3)-O-[β-D-apiofuranosyl (1→6)]-β-D-glucopyranoside, respectively, on the basis of chemical and spectral data.View full abstractDownload PDF (681K) -
CHUZO IWATA, YASUO IDA, KAZUYUKI MIYASHITA, TSUTOMU NAKANISHI, MINORU ...1982 Volume 30 Issue 8 Pages 2738-2741
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS(±)-Agarospirol (8) and (±)-hinesol (9) were simultancously synthesized via a useful synthon in the synthesis of spirovetivane-type sesquiterpenes, i. e., (2S*, 5S*, 10R*)-2-hydroxy-6, 10-dimethylspiro [4.5] dec-6-en-8-one (1), which had previously been prepared from the corresponding phenolic α-diazoketone via the spiro-annelation reaction and subsequent stereo-controlled Birch reduction, both reported in our previous communications.View full abstractDownload PDF (551K) -
TAKUSHI KURIHARA, KEIKO NASU, YUMIKO MIZUHARA, KAZUE HAYASHI1982 Volume 30 Issue 8 Pages 2742-2746
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of 3-[3-(2-nitrophenyl)-2-propenylidene]-2, 4-pentanedione (3) with hydroxylamine hydrochloride in methanol gave a 1 : 1 mixture of (E)-4-[3-methoxy-3-(2-nitrophenyl)-1-propenyl]-3, 5-dimethylisoxazole (4) and (E)-4-[1-methoxy-3-(2-nitrophenyl)-2-propenyl]-3, 5-dimethylisoxazole (5) in 49.3% yield. Similarly, when acetonitrile was used as the solvent in this reaction, 2-(3, 5-dimethyl-4-isoxazolyl)-chloromethyleneindolin-3-one (6) (36.3%), (E)-4-acetyl-3-methyl-5-(2-nitrostyryl) isoxazole (7) (6.3%) and 4-[1-(hydroxyimino) ethyl]-3-methyl-7-(2-nitrophenyl)-1, 2-oxazepine (8) (1.8%) were obtained.View full abstractDownload PDF (619K) -
TAKAO KONOSHIMA, TOKUNOSUKE SAWADA1982 Volume 30 Issue 8 Pages 2747-2760
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo triterpenoid saponins, gleditsia saponins B (GS-B, XIX) and C (GS-C, XX) which were isolated from Gleditsia japonica cv. 'Saponifera', were characterized as 3, 28-O-bisglycosides of echinocystic acid acylated with monoterpene carboxylic acids. On the basis of 13C-nuclear magnetic resonance spectra and the results of chemical and enzymatic hydrolysis, it was established that the positions of acylation with the mono-terpenes (IV) and (V) were C-2 and C-3, respectively, of the terminal rhamnose of the 28-O-glycoside moiety in the molecules of GS-C and GS-B.View full abstractDownload PDF (1189K) -
HISASHI ISHII, ERI KAWANABE, NOBORU FUKASAKU, TETSUYOSHI YOKOSHIMA, MI ...1982 Volume 30 Issue 8 Pages 2761-2765
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS[methylenedioxy-14C] Cepharanthine was synthesized via the selective demethylenation of cepharanthine and reconstruction of cepharanthine by methylenation of the demethylenated product with [14C] methylene iodide. A derivative of cepharanthine which has an ethylenedioxy group in the place of the methylenedioxy group was prepared for examination of biological activity.View full abstractDownload PDF (614K) -
MITSUHIRO WAKIMASU, CHIEKO KITADA, MASAHIKO FUJINO1982 Volume 30 Issue 8 Pages 2766-2779
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe 4-methoxy-2, 3, 6-trimethylbenzenesulfonyl (Mtr) group was introduced as a protecting group for the amino function, especially the ε-amino function of lysine, and the imidazole ring of histidine. The Nε-Mtr group was removable by dilute methanesulfonic acid-containing trifluoroacetic acid-thioanisole, but was stable to trifluoroacetic acid or catalytic hydrogenation. The Nlm-Mtr group was removable by trifluoroacetic acid-dimethylsulfide or 1-hydroxybenzotriazole, but was more stable than the Nlm-Tos or the Nlm-Mbs group with triethylamine. To examine the usefulness of the Mtr group as a protecting group for use in peptide synthesis, mastoparan X and chicken gastrin releasing peptide (c-GRP) were synthesized, and this group was found to be very convenient for general solution synthesis. In particular, the introduction of Lys (Mtr) made possible a new strategy in peptide synthesis.View full abstractDownload PDF (1474K) -
TAICHI OHMOTO, KEIJI IKEDA, TAKEO CHIBA1982 Volume 30 Issue 8 Pages 2780-2786
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe new sterols 4α, 14-dimethyl-9, 19-cyclocholestan-3β, 24ξ-diol (IIIa) and 4α, 14-dimethyl-9, 19-cyclocholestan-3β, 24ξ, 25-triol (IVa) were isolated, together with lophenonc, lophenol and cholest-7-en-3β-ol, from the pollen grains of Ambrosia elatior LINNE. The structures were elucidated on the basis of spectroscopic studies and chemical evidence.View full abstractDownload PDF (735K) -
YINGCHE KUO, TOYOHIKO AOYAMA, TAKAYUKI SHIOIRI1982 Volume 30 Issue 8 Pages 2787-2792
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSα-Acyl-α-benzylsulfonyldiazomethanes (2a-d) have been converted to α-benzylsulfonyl-α-substituted-acetic acids (7a-d) by means of the Wolff rearrangement. Reductive removal of the benzylsulfonyl group of 7b-d can be achieved by the use of sodiumethanol in tetrahydrofuran. α-Benzylsulfonyl-α-substituted-propionic acids (9a-d), prepared from benzyl α-benzylsulfonyl-α-substituted-acetates (3a-d), were also debenzyl-sulfonylated under similar reductive conditions. The overall process, in combination with the Arndt-Eistert synthesis of α-sulfonylacetates from acyl chlorides and benzylsulfonyl-diazomethane (1), provides a new, safe method for the homologation of carboxylic acids.View full abstractDownload PDF (679K) -
MIYOJI HANAOKA, CHISATO MUKAI, ITSUKO HAMANAKA, KAZUE SEKI, YOSHIO ARA ...1982 Volume 30 Issue 8 Pages 2793-2796
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSimple and biomimetic conversions of tetrahydroberberine (1) and dihydroberberine (6) into noroxyhydrastinine (3), an isoquinolone alkaloid, are described. Photooxygenation of 1 afforded berberal (2), 3, and O-methylpseudopianic acid (4). The same products were obtained more efficiently by photooxygenation of 6.View full abstractDownload PDF (467K) -
KAYOKO OKAMOTO, MASAZUMI WATANABE, MITSURU KAWADA, GIICHI GOTO, YASUKO ...1982 Volume 30 Issue 8 Pages 2797-2819
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to study the structure activity relationship of metabolites of ubiquinone, α-tocopherol and phylloquinone (Ia, b, c, IIa, b, c), 3-carboxy-2-butenyl (IIIa, b, c), 6-hydroxy-3-methyl-2-hexenyl (IVa, b, c), 4-hydroxy-3-methylbutyl (Va, b), 4-hydroxy-3-methyl-2-butenyl (VIb, c), ω-carboxyalkyl (VIIa, b, c), and ω-hydroxyalkyl (VIIIa, b) side chains were introduced into the 6-position of 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone and 2, 3, 5-trimethyl-1, 4-benzoquinone, as well as the 3-position of 2-methyl-1, 4-naphthoquinone. The effects of these quinones on the membrane stability of rat-liver lysosomes and on the activity of bovine heart phosphodiesterase were investigated. A good correlation was observed between these activities of the benzoquinone derivatives (VIIa, b).View full abstractDownload PDF (2094K) -
TOYOKICHI YOSHIDA, SHUNSUKE NARUTO, HITOSHI UNO, HARUKI NISHIMURA1982 Volume 30 Issue 8 Pages 2820-2824
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe title α- and N-halosulfoximides 1-4 undergo base-induced rearrangement reactions to give the same N-sulfinylimines 5, suggesting that these rearrangements all involve the intermediacy of a cyclic sulfoximide, a thiazirine S-oxide 14, which has a novel three-membered ring system with an endocyclic S=N group.View full abstractDownload PDF (567K) -
TSUNEHIKO FUKUDA, MITSUHIRO WAKIMASU, SHIGERU KOBAYASHI, MASAHIKO FUJI ...1982 Volume 30 Issue 8 Pages 2825-2835
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFive substituted benzenesulfonyl groups, p-toluenesulfonyl, p-methoxybenzenesulfonyl, 2, 4-dimethoxybenzenesulfonyl, 2, 4, 6-trimethoxybenzenesulfonyl, and 4-methoxy-2, 3, 6-trimethylbenzenesulfonyl, were introduced at Nin of tryptophan and their protecting group properties were investigated. Among them, 2, 4, 6-trimethoxybenzenesulfonyl and 4-methoxy-2, 3, 6-trimethylbenzenesulfonyl are stable to trifluoroacetic acid, but can be readily removed by hydrogen fluoride or methanesulfonic acid, and suppress decomposition and modification of the tryptophan residue during peptide synthesis. These protecting groups were successfully used in syntheses of bombesin, a potent analog of luteinizing hormone-releasing hormone by the solution method and dynorphin by the solid-phase method.View full abstractDownload PDF (1287K) -
MASAHITO OCHIAI, SHINICHI TADA, MASAO ARIMOTO, EIICHI FUJITA1982 Volume 30 Issue 8 Pages 2836-2839
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of allylsilanes 1a and 1d or allylstannane 1b with thallium (III) salts in nitriles such as acetonitrile, acrylonitrile, propionitrile, and benzonitrile afforded the corresponding N-allylamides. Thus, umpolung of reactivity of allylsilane and allylstannane has been established.View full abstractDownload PDF (515K) -
TOSHIRO IBUKA, HIROYUKI MINAKATA, YOSHINORI MITSUI, KENJI HAYASHI, TOO ...1982 Volume 30 Issue 8 Pages 2840-2859
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA highly stereoselective synthesis of (6S*, 7S*, 8S*)-7-butyl-8-hydroxy-1-azaspiro [5.5]-undecan-2-one (6), a key intermediate for (±)-perhydrohistrionicotoxin synthesis, from the Diels-Alder cycloadduct of 1, 3-bis (trimethylsiloxy)-2-methyl-1, 3-butadiene (15) and ethyl 3-acetoxy-1-cyclohexene-1-carboxylate is described. This key intermediate and its stereoisomer, (6R*, 7S*, 8S*)-7-butyl-8-hydroxy-1-azaspiro [5.5] undecan-2-one (7), were stereoselectively synthesized by means of a conjugate addition reaction using 1-(3-tert-butyldimethylsiloxy-1-cyclohexen-1-yl)-ethanone and BuCu·AlCl3 as the key step.View full abstractDownload PDF (2083K) -
KUNIO HAYASHI, KATSUYA TOKURA, KEI OKABE, KIYOE YAMAMOTO, KATSUYA TAWA ...1982 Volume 30 Issue 8 Pages 2860-2869
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFomecins A and B, phenolic antibiotics produced by the basidiomycete Fomes juniperinus SCHRENK, and asperugin, a metabolite of Aspergillus rugulosus, were synthesized from gallic acid. Various congeners were also prepared. Their antibacterial and antifungal activities were tested in vitro and some of the products were found to exhibit moderate antifungal activities.View full abstractDownload PDF (969K) -
YUICHI IIIZUMI, TETSUO ADACHI, YOSHIMASA ITO, KAZUYUKI HIRANO, MAMORU ...1982 Volume 30 Issue 8 Pages 2870-2873
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new and specific method for the determination of human urinary γ-esterase activity, which migrates to the γ-globulin region on cellulose acetate electrophoresis, was developed using an antibody-conjugated paper disk. The method was applied experimentally, and the results indicate that an increase of γ-esterase activity in the urine reflects renal damage, that is, urinary γ-esterase activity was increased in patients with nephrotic syndrome (20.3±15.0 units/g of creatinine) and chronic nephritis (8.00±5.23 units/g of creatinine) as compared with that of healthy subjects (3.08±1.90 units/g of creatinine). γ-Esterase was localized at the renal tubules of a patient with renal disease, and it was considered that γ-esterase was excreted in the urine when the renal tubules were damaged. Therefore, the determination of urinary γ-esterase activity by this method should be an effective aid in the diagnosis of renal disease.View full abstractDownload PDF (672K) -
TSUYOSHI TANIMOTO, TAKAO HAYAKAWA, HIDEO FUKUDA, JIRO KAWAMURA1982 Volume 30 Issue 8 Pages 2874-2879
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS20β-Hydroxysteroid dehydrogenase from Streptomyces hydrogenans is inactivated by diethylpyrocarbonate. It was shown by spectrophotometric studies that two histidine residues per molecule of the enzyme are necessary for enzyme activity. The involvement of histidine residues in the enzyme activity is also indicated by the pH dependence of kinetic parameters for NADH, which shows an inflection point at pH 6.4. The carbethoxyhistidine residues in the modified enzyme are slowly hydrolyzed and the enzyme activity is recovered, but this reactivation is suppressed by addition of NADH. The inactivation of the enzyme by diethylpyrocarbonate is largely prevented by reduced coenzymes, though the steroid substrates alone have no protective effects. It is presumed from kinetic data that carbethoxylation of 20β-hydroxysteroid dehydrogenase does not affect the affinity of the enzyme for NADH. These findings suggest that some histidine residues participate in the enzyme activity and that these histidine residues are located near but not at the coenzyme binding site of the enzyme.View full abstractDownload PDF (606K) -
YUKIYASU TOYODA, ICHITOMO MIWA, JUN OKUDA1982 Volume 30 Issue 8 Pages 2880-2884
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHog kidney mutarotase type II was purified to polyacrylamide disc gel electrophoretic homogeneity by a five-step procedure including affinity chromatography with phloretin-linked agarose. The purified enzyme was crystallized, and the crystals were subjected to amino acid analysis. The amino acid composition of the enzyme was similar to that of bovine kidney mutarotase, except for marked differences in the contents of phenylalanine and methionine.View full abstractDownload PDF (721K) -
MITSUGI KOZAWA, KIMIYE BABA, YOUKO MATSUYAMA, TADASHI KIDO, MICHIHIKO ...1982 Volume 30 Issue 8 Pages 2885-2888
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDeoxypodophyllotoxin (anthricin) (I), anthriscinol methyl ether (IV) and (Z)-2-angeloyloxymethyl-2-butenoic acid (VI), isolated from the root of Anthriscus sylvestris HOFFM., exerted insecticidal activity on the adults of Blattella germanica, and on the larvae of Culex pipiens molestus, Plutella xylostella and Epilachna sparsa orientalis. In paticular, the activity of 1, i. e., the main lignan component of A. sylvestris root, was so strong as to cause the death of 80% of the larvae of C. pipiens molestus at a concentration of 5 ppm. The epimer at the 2-position of I, i. e., deoxypicropodophyllin (isoanthricin) (II), however, was not insecticidal.View full abstractDownload PDF (443K) -
MASAHITO FUKUNAGA, YASUO MIZUGUCHI1982 Volume 30 Issue 8 Pages 2889-2893
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSManganese caused mitotic gene conversion and reverse mutation in nuclear genes of yeast Saccharomyces cerevisiae strain D7. Respiration-deficient (petite) mutation and antibiotic-resistant mutations were also induced by treatment with manganese. The presence of propidium had no effect on mitotic gene conversion and reverse mutation induced by manganese. In the case of mitochondrial mutagenesis by manganese, additional petites were produced and induction of antibiotic-resistant mutants were reduced by half when propidium was present during culture. It seems that propidium affects only mitochondrial mutagenesis, not nuclear mutagenesis.View full abstractDownload PDF (572K) -
MASAYOSHI SAMEJIMA, GOICHI HIRATA, YOSHIYUKI KOIDA1982 Volume 30 Issue 8 Pages 2894-2899
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe role and effect of coacervation-inducing agents such as butyl rubber, polyethylene and polyisobutylene in microencapsulation were investigated by using phase separation from cyclohexane solution with change of temperature. Ascorbic acid was used as a core material and ethylcellulose was used as a wall-forming material. Among the three different coacervation-inducing agents, polyisobutylene was suitable for microencapsulation, resulting in low aggregation of microcapsules and a slow dissolution rate. The role of coacervation-inducing agents in microencapsulation was investigated with polyisobutylene. Polyisobutylene changed the gel into a coacervate and resulted in the formation of smooth and thick-walled microcapsules. It also largely prevented the aggregation of microcapsules.View full abstractDownload PDF (1256K) -
SHUNICHI NORO, YOSHIHITO KOMATSU, TAKASHI UESUGI1982 Volume 30 Issue 8 Pages 2900-2905
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn general, it is recognized that emulsion-type bases have outstanding characteristics for suppository products as compared with simple hydrophilic or hydrophobic bases. The purpose of this work was to investigate the effect of some surfactants or polymers on the physicochemical properties of emulsion-type suppository bases. Witepsol S-55, which is a trilauryl acid glycerin ester derivative, was used as the oil phase. The emulsifiers used were commercial grade Amisoft ; CS-11, GS-11, and HS-21, and the polymers used were sodium alginate, sodium carboxymethylcellulose and sodium polyacrylate. In addition, the emulsion stability was evaluated in terms of (1) the rheological properties, (2) the particle size and its distribution, (3) the mean and distribution of electrophoretic mobility. It was found that (1) Amisoft surfactants are excellent emulsifiers when compared with sodium dodecyl sulfate or Tweens based on the particle size and viscosity measurements, and (2) the addition of aqueous polymers is effective in stabilizing emulsion bases. Accordingly, emulsion-type bases should be suitable for pharmaceutical use in suppository products.View full abstractDownload PDF (648K) -
SHUNICHI NORO, YOSHIHITO KOMATSU, TAKASHI UESUGI1982 Volume 30 Issue 8 Pages 2906-2911
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe rheological characteristics of emulsion bases must be chosen so as to produce a suppository having optimum physical, chemical and pharmacological properties. In this study, we measured some rheological characteristics of the emulsion in order to find favorable physicochemical conditions for the preparation of emulsion-type bases. The suppository consisted of Witepsol S-55, aqueous polymer, Amisoft surfactant and water. The preparation procedure was that described in our previous paper. The vicosity and visco-elasticity of suppository bases were measured with a Vismetron and an RM-1 or RV-12 type rheometer. Amisofts had excellent rheological properties as surfactants for emulsion-type suppository bases, as compared with sodium dodecyl sulfate or Tween 80. The activation energy of viscosity increased gradually at first and then sharply with increasing volume concentration of the dispersed phase after passing through the 50% point. The change in the activation energy was substantial when the volume concentration rose over 60%.View full abstractDownload PDF (647K) -
SHUNICHI NORO, YOSHIHITO KOMATSU, TAKASHI UESUGI1982 Volume 30 Issue 8 Pages 2912-2918
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSGenerally, drug release from the base is considered to be one of the most important parameters in evaluating the pharmaceutical usefulness of suppositories in vivo and in vitro. In spite of the therapeutic importance and wide applications of suppositories, the absorption mechanisms and the factors determining their absorption characteristics have not been established. The present study was undertaken to investigate the effects of surfactants, polymers, and concentration of the water phase on in vitro drug release emulsion-type suppositories. N1-(2'-furanidyl)-5-fluorouracil (FT-207), theophylline and indomethacin were chosen as model compounds. In order to clarify the behavior of the rectal membrane, the following three different methods for studying drug release (in vitro) were selected : (1) the filter membrane technique, (2) the use of membranes of animal origin, (3) in situ rectal recirculation technique. The following results were obtained. (1) In the case of readily water-soluble compounds such as FT-207, the amount of drug released increased with increase of the water content in the suppository base. (2) On the other hand, no significant effect of concentration of the water phase in the suppository base was found for fatty drugs such as indomethacin. (3) By the addition of aqueous polymer, the amount of drug released could be controlled and the release prolonged in the emulsion-type suppository base.View full abstractDownload PDF (734K) -
YASUYUKI TAKAHASHI, NAOKI NAMBU, TSUNEJI NAGAI1982 Volume 30 Issue 8 Pages 2919-2925
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe interaction of phenothiazines with pectin in the solid state was investigated, and the formation of coprecipitates was confirmed by infrared absorption spectroscopy and powder X-ray diffractometry. There was a positive correlation between the amount of drug in the coprecipitate and the primary binding number n1 of phenothiazines with pectin in aqueous solution. The initial dissolution rate of drug from the coprecipitates in purified water followed zero-order kinetics and was very small compared with that of the intact drug. The dissolution rate of diethazine/pectin coprecipitate was almost independent of the rotating speed in 0.1 N hydrochloric acid. These results suggest that coprecipitates of drugs with pectin might be useful as sustained-release preparations.View full abstractDownload PDF (699K) -
HIROMITSU SEKI, TAIZO HAYASHI1982 Volume 30 Issue 8 Pages 2926-2934
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe nature of the decomposition products of adenosine-5'-triphosphate (ATP) and the kinetics of decomposition in aqueous solution were investigated at 60, 70 and 80°C, ionic strength 0.5, pH 3.2-10.1 by high pressure liquid chromatography. Adenosine-5'-diphosphate (ADP) and adenoside-5'-monophosphate (AMP) were identified as the decomposition products of ATP. The time courses of the ATP and ADP concentrations were measured and the apparent 1st-order rate constants of the decomposition of ATP to ADP (k1), ADP to AMP (k2) and ATP to AMP (k3) were calculated. The order of decomposition rates was k1>k2>k3 in the pH range of 3.2-10.1. The observed decomposition rates of ATP and ADP were influenced significantly by spontaneous or water-catalyzed reaction. The specific rate constants of the ionic species of ATP and ADP were calculated, and it was found that decomposition rate of ATP including its decomposition products could be expressed by the summation of the products of the specific rate constants and mole fractions of the ionic species. The Arrhenius plots of these specific rate constants were linear and the apparent activation energies were all in the range of 28.8-31.8 kcal/mol. The primary salt effects on the decomposition of ATP were almost negligible. Therefore the overall decomposition rate of ATP including its decomposition products could be expressed as a function of the specific rate constants at arbitrary pH, temperature and ionic strength in several buffer species.View full abstractDownload PDF (709K) -
YOICHI SAWAYANAGI, NAOKI NAMBU, TSUNEJI NAGAI1982 Volume 30 Issue 8 Pages 2935-2940
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAs a part of a series of study on pharmaceutical applications of chitin and chitosan, the fluidity and compressibility of combined powders of lactose with chitin and chitosan, and potato starch with chitin and chitosan, as well as the disintegration properties of the tablets made from these powders were investigated in comparison with those of crystalline cellulose with lactose and potato starch. The lubricating properties of combined powders of lactose with chitin and chitosan were also investigated in comparison with those of lactose with crystalline cellulose. The fluidity of combined powders with chitin and chitosan was greater than that of the powder with crystalline cellulose. The hardest tablet was obtained with chitosan, followed by crystalline cellulose and chitin in that order. Tablets containing less than 70% of chitin or chitosan passed the disintegration test of JP X. The ejection force of the tablets of lactose/chitin and lactose/chitosan was significantly smaller than that of lactose/crystalline cellulose tablets. It is suggested that chitin and chitosan may be suitable for use as diluents with friction-lowering properties in direct compression processes.View full abstractDownload PDF (590K) -
HIROYUKI YOSHINO, MASAO KOBAYASHI, MASAYOSHI SAMEJIMA1982 Volume 30 Issue 8 Pages 2941-2950
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe influence of the liquid phase on the A-to-B transition of semisynthetic fatty suppository vehicles during storage was investigated. The addition of a liquid having a high affinity, such as isopropyl myristate, fatty oil, lauryl alcohol, etc., remarkably accelerated the transition, whereas that of a low affinity liquid had little effect. The transition rate evaluated from the time course of transition degree (kT) increased linearly with the weight fraction ratio of liquid phase (fL) to solid phase (1-fL). The case where liquid phase was produced only from molten vehicle containing no liquid additive was also examined. The relation between kT and fL/(1-fL) was investigated 1) for the transition of Witepsol H-15 in the temperature range from 26 to 32°C, and 2) for several commercial vehicles at 30°C. Linear relations also appeared to hold for both cases. Here, the weight fraction of liquid phase at a given temperature was determined by means of differential scanning calorimetry (DSC). The activation energy of transition (E〓) was compared in the presence and absence of liquid additives. E〓 values of Witepsol H-15 containing 10 and 25% fatty oil were about 40 kcal, less than one-half of that of Witepsol H-15 not containing any liquid additives. The transition mechanism was considered to involve dissolution of the solid A-form in the intervening liquid phase followed by crystallization as solid B-form.View full abstractDownload PDF (941K) -
AKIRA KATO, YOSHINOBU TAKAKURA, MITSURU HASHIDA, TOSHIKIRO KIMURA, HIT ...1982 Volume 30 Issue 8 Pages 2951-2957
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHigh molecular weight derivatives of mitomycin C (MMC) were synthesized by using dextrans of various molecular weights (MMC-D), poly-L-glutamic acid (MMC-PGA), and bovine serum albumin (MMC-BSA) as carrier moieties, and their physico-chemical characteristics and antitumor activities were examined. MMC was liberated from MMC-D in vitro with a half-life of about 24 h regardless of the size of dextran, while the liberation half-lives of MMC-PGA and MMC-BSA were 35.5 h and 20.2 h, respectively. The molecular sizes of conjugates determined by gel filtration chromatography were slightly larger than those of the original carrier molecules. MMC-D showed significant antitumor activities in BDF1 mice bearing P388 leukemia or B16 melanoma in an i. p.-i. p. system, depending on their molecular sizes ; i. e., higher maximum activity was obtained at lower dose as the molecular weight increased. MMC-PGA exhibited a superior effect against B16 melanoma in spite of its low molecular weight. These observations suggest the existence of some relationship between the physico-chemical properties of carrier moieties and the antitumor activities of the conjugates.View full abstractDownload PDF (731K) -
ATSUSHI WATANABE, YUMIKO YAMAOKA, KOZO TAKADA1982 Volume 30 Issue 8 Pages 2958-2963
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAspirin crystals having different types of habits were prepared by recrystallization of commercial products from various solvents. The difference in crystal habits was investigated crystallographically and optically by the use of a polarizing microscope to measure habit parameters a, b, and c. The dissolution behavior of these crystals was studied in an artificial gastric juice, and the dissolution constants were calculated by means of the Noyes-Whitney equation using the specific surface areas obtained from the habit parameters. It was found that the dissolution constants of crystals with different habits were not constant, and it seems that the values depend upon the ratio of the area of (001) to the sum of the areas of the remaining faces. It was also found that aspirin dissolved more easily when it was powdered than would be expected from the increased surface area. This phenomenon might be a result of the distortion of crystals which was observed under the polarizing microscope.View full abstractDownload PDF (1041K) -
TSUTAO KURECHI, TETSUTA KATO1982 Volume 30 Issue 8 Pages 2964-2970
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHydrogen-donating processes of combined antioxidants, butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), were followed by using 2, 2-diphenyl-1-picrylhydrazyl (DPPH) as the hydrogen acceptor, and their relation to the synergism is discussed. The hydrogen donation to DPPH by BHA was almost complete in 10 min. DPPH and BHA were regenerated from this reaction mixture by addition of DPPH·H in the molar ratio of 2 : 1, and BHA and 2, 6-di-tert-butylquinone methide (QM) were formed by addition of BHT in the molar ratio of 1 : 1. The phenoxy radical formed from BHA was lost upon further addition of DPPH. These results suggest the formation of a stable intermediate which accepts two hydrogens from BHT to regenerate BHA, and the possible reaction processes of BHA and BHT with DPPH are shown as Chart 1 ; BHA reacts with DPPH to form the stable intermediate via its phenoxy radical, and this intermediate reacts with BHT to regenerate BHA with the enhanced oxidation of BHT to QM via its phenoxy radical. These processes may be associated with the synergism between BHA and BHT in hydrogen donation to DPPH. The amount of loss of DPPH was in fair agreement with the sum of two hydrogens donated by BHT in the enhanced oxidation to QM and hydrogens donated by BHA. The rate of decrease in DPPH concentration by BHA was about 450 times that by BHT.View full abstractDownload PDF (709K) -
MOTOME TERAO, KATSUO AOKI, YASUSHI UEKI1982 Volume 30 Issue 8 Pages 2971-2979
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe present paper is concerned with an application of the annual atmospheric temperature distribution to the shelf life prediction of pharmaceutical preparations in distribution channels. The method attempts to correct for the relatively wide variation in storage temperature by utilizing actually recorded thermal histories in the respected market. The calculated storage breakdown rates obtained by this method have been found to correlate well with actual experience.View full abstractDownload PDF (747K) -
YASUNORI MORIMOTO, YUKIYA YAMAGUCHI, KENJI SUGIBAYASHI1982 Volume 30 Issue 8 Pages 2980-2985
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe detoxication of quinine sulfate as a model drug by a multiple (water-in-oil-in-water, w/o/w) emulsion was evaluated in vitro and in vivo. In vitro drug extraction into the emulsion was determined using a dialysis system. Drug extraction into the emulsion increased with increasing volume fraction of water-in-oil (w/o) emulsion in the w/o/w system (Fw/o/w). However, when 0.01 N HCl, which has the same pH as the stomach, was selected as a continuous aqueous solution of the emulsion, quinine was hardly extracted into the emulsion regardless of the Fw/o/w values. Thus, we attempted the simultaneous use of the emulsions and an antacid (NaHCO3) in order to increase the pH in the continuous phase of the emulsion, but combined use of the antacid increased the viscosity of the system. From the viscosity data of the emulsions and further in vitro extraction data, in vivo experiments were carried out with a suitable emulsion (Fw/o/w=0.2). The blood concentration of quinine co-administered with the multiple emulsion containing the antacid in rabbits was significantly lower than that in the control. These results indicate that the use of multiple emulsions may be a promising new approach to the emergency treatment of drug overdose.View full abstractDownload PDF (647K) -
MASARU KIDO, KAZUYUKI NAKAGAWA1982 Volume 30 Issue 8 Pages 2986-2990
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe crystal structures of 5-hydroxy-3, 4-dihydro-2-quinolone (2) and 5-hydroxy-1-methyl-3, 4-dihydro-2-quinolone (3) were determined by X-ray analysis. The C (3)-C (4) bond distance of 2, 1.430 (9) A, is slightly shorter than a single bond distance. On the other hand, those of the two independent molecules of 3 found in an asymmetric unit, 1.474 (6) A and 1.516 (6) A, are normal with usual thermal parameters for the C (3) atom, probably because of the restriction of the ring puckering by compact crystal packing.View full abstractDownload PDF (456K) -
HIROSHI TAKAKU, TSUTOMU KONO1982 Volume 30 Issue 8 Pages 2991-2995
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe efficiencies of various of phosphate protecting groups in the synthesis of internucleotidic bonds by the phosphotriester approach have been studied. We found that in the coupling reaction using alkyl groups as phosphate protecting groups of internucleotidic bonds, extensive sulfonation of the 5'-hydroxyl group of nucleoside occurred, whereas when aryl groups were used in place of alkyl groups, the sulfonation did not occur.View full abstractDownload PDF (562K) -
TAKUZO HISANO, MASATAKA ICHIKAWA, KONOSUKE TSUMOTO, MASANOBU TASAKI1982 Volume 30 Issue 8 Pages 2996-3004
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBenzoxazoles, benzothiazoles and benzimidazoles having substituents on the azole and benzene nuclei were synthesized evaluated for antifungal, insecticidal and herbicidal activities. It was found that benzimidazoles tended to exhibit antifungal activity while benzothiazoles tended to show herbicidal activity. Chloro, trifluoromethyl, methoxy and ethoxy groups at the 5 position were potent substituents, and the 2-pyridyl group at the 2 position is a common structural unit. Among several active derivatives, 7-chloro-2-(2-pyridyl) benzimidazole and 2-(2-pyridyl)-5-trifluoromethylbenzothiazole exhibited significant activity against Panonycus citri.View full abstractDownload PDF (759K) -
OSAMU MIYASHITA, TOSHIHIKO KASAHARA, YOSHIKAZU WADA1982 Volume 30 Issue 8 Pages 3005-3009
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBoth optical isomers of t-6-butoxy-r-5-ethoxycarbonyl-5-fluoro-5, 6-dihydrouracil (1, TAC-278), a new candidate for use as a pro-drug of 5-fluorouracil (5-FU), have been prepared via the enantiomeric 6-(+)-and 6-(-)-α-methylbenzylamino derivatives (4).View full abstractDownload PDF (544K) -
TAKAO KONOSHIMA, KAZUYO SHIMIZU, NAOKO MUNE, TOKUNOSUKE SAWADA, YOSHIH ...1982 Volume 30 Issue 8 Pages 3010-3012
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA major triterpenoid saponin (GS-C) of the fruit capsule of Gleditsia japonica MIQ. (Leguminosae) contains eight sugar units and two monoterpenyl moieties in the molecule. It has been proved that at least one of the monoterpenyl groups is attached to the C-2 hydroxyl of the terminal L-rhamnosyl group in the C-28 oligoside portion of GS-C on the basis of upper-field shifting of the 13C nuclear magnetic resonance signal of the anomeric carbon, which was refined by means of a partially relaxed Fourier transform (PRFT) experiment.View full abstractDownload PDF (357K) -
KOZO TAKAYAMA, NAOKI NAMBU, TSUNEJI NAGAI1982 Volume 30 Issue 8 Pages 3013-3016
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDissolution profiles of ketoprofen (KPF) from solid dispersions in water-soluble polymers were investigated by the rotating disk method, and great differences in dissolution behavior were observed among different kinds of polymers. Therefore, the physicochemical nature of the polymers might play a predominant role in the dissolution of KPF from these solid dispersions. The quantitative relationship of dissolution behavior with several properties of the polymers depended on a combination of such factors as the water penetration of the compressed disk surface, pH of polymer solution and the apparent dissolution rate of polymers.View full abstractDownload PDF (453K) -
MASAHITO FUKUNAGA, YOKO KURACHI, YASUO MIZUGUCHI1982 Volume 30 Issue 8 Pages 3017-3019
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of metal compounds on nuclear mitotic cross-over, mitotic gene conversion and reversion were studied in a diploid yeast, Saccharomyces cerevisiae strain D7. All metal compounds used in these experiments had cell killing effects at concentrations of 10-2 to 10-4M. These metal compounds were classified into two groups according to their effects on strain D7. Chromium, arsenic, cadmium, cobalt and nickel compounds induced mitotic cross-over and gene conversion. Lead, mercury and zinc compounds induced mitotic gene conversion at only limited frequencies but the frequency of mitotic cross-over among the convertants was significantly higher than in the control. No increase in reversion frequencies was observed with these compounds.View full abstractDownload PDF (448K) -
TERUO TAKAHASHI, SHIGEO TOGASHI, MUNEO MORISHITA, SHIRO TAKEDA1982 Volume 30 Issue 8 Pages 3020-3023
Published: August 25, 1982
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDiphenic acid anhydride (1) is decarbonylated by prolonged heating with mercuric oxide (HgO) in acetic acid to give a diphenic anhydride-mercury compound (3). Since its infrared spectrum showed a shift of carbonyl adsorption to a very low wave number, the O-Hg linkage was considered to be in an iouic form (3'), with the carbon bonded to mercury becoming a carbonium ion. If this is the case, the compound would be expected to react with nucleophilic reagents and indeed 3 is reactive to KI, H2S and KCN.View full abstractDownload PDF (476K)