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Volume 33, Issue 12
Displaying 1-50 of 73 articles from this issue
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BUNJI UNO, KENJI KANO, TOMONORI KONSE, TANEKAZU KUBOTA, SANAE MATSUZAK ...1985 Volume 33 Issue 12 Pages 5155-5166
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe half-wave reduction potentials (Ered1/2) of aromatic polynuclear p-quinones are negative shifted with increasing π-electron conjugation, although the Ered1/2 values of usual organic substances are positive shifted with the above structure change. The main reason for this exceptional behavior of the p-quinones has been discussed in detail by applying the composite system method (linear combination of molecular orbitals (LCMO) approximation). For example, after dividing naphthoquinone into benzoquinone and cis-butadiene we consider the mutual interaction between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the former and those of the latter. It was concluded that the interaction between the LUMO of the former and the HOMO of the latter plays an important role. so that the LUMO of benzoquinone is destabilized by going to naphthoquinone, leading to the negative shift of Ered1/2 value.View full abstractDownload PDF (986K) -
HIDEO KANEKO, SADAO HIROTA1985 Volume 33 Issue 12 Pages 5167-5177
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe dielectric relaxation due to the interfacial polarization of emulsions of either polyol or aqueous solutions of polyol in a hydrophobic colloidal silica-oil gel (P/(S·O) emulsions) was investigated over a wide range of volume fractions of the dispersed phase at frequencies ranging from 10 kHz to 3MHz. P/(S·O) emulsions without surfactant showed dielectric relaxation, and the limiting dielectric constants at high and low frequencies, εh, εl, limiting dielectric conductivity at high frequency, Kh, and relaxation frequency, fo, were shown to satisfy the equations given by Wagner's theory4) up to a dispersed phase fraction as high as 0.6. In P/(S·O) emulsions without surfactant, the absence of any particle aggregation was ascertained by microscopic observation. When the polyol was diglycerin, several dispersed phases with different dielectric constants were obtained at different mixing ratios of water and diglycerin. It was found that the values of εl changed markedly on the addition of surfactant, increasing as the dielectric constant of the dispersed phase, εp, became larger. In P/(S·O) emulsions with surfactant, particle aggregation was found by microscopic observation. The fo values of P/(S·O) emulsions with particle aggregation were smaller than in those without particle aggregation, in spite of the increase in electric conductivity of the dispersed phase brought about by the addition of a surfactant. It should be noted that the magnitude of the dielectric anomaly1) varies with the magnitude of εp even if the added amount of surfactant is the same.View full abstractDownload PDF (1025K) -
TOSHIKI TANAKA, TAKESHI OISHI1985 Volume 33 Issue 12 Pages 5178-5183
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDeoxyribonucleotides containing 2'-deoxyadenosine at the 3'-terminal, i.e., a heptadeoxyribonucleotide, d-GATTCTA, two pentadecadeoxyribonucleotides, d-A15, d-AATGAGAAGCAACGA and a nonadecadeoxyribonucleotide, d-AGAATCTCGTTGCTTCTCA, were synthesized on a polystyrene polymer support by using the phosphotriester method. Dimer blocks (3) were coupled for elongation in the 5'-direction by using 1-mesitylenesulfonyl-3-nitro-1H-1, 2, 4-triazole as the activating reagent. A 3% trichloroacetic acid solution in dichloromethane was used for the detritylation process without causing any detectable depurination. 5'-O-Phosphorylated heptanucleotide and pentadecanucleotide were successfully joined by using deoxyribonucleic acid ligase in the presence of a template.View full abstractDownload PDF (613K) -
TSUTOMU KAMIYAMA, SABURO ENOMOTO, MASAMI INOUE1985 Volume 33 Issue 12 Pages 5184-5189
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMercaptobenzoic acids and mercaptopyridines were synthesized by using mercaptylation of halogeno compounds with elemental sulfur in the presence of molten salts (NaOH-KOH). This procedure was also applied to the preparation of selenoaryl compounds by using elemental selenium. Based on the behavior of the molten salts and sulfur, Na2S and K2S were considered to be the active species for the mercaptylation.View full abstractDownload PDF (543K) -
MAKOTO TAKEMURA, KUNIO HIGASHI, HIROYUKI FUJIWARA, MAKOTO SATO, MINORU ...1985 Volume 33 Issue 12 Pages 5190-5196
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe Pummerer reaction of the thienamycin-type cyclic vinylogous sulfide (4) and sulfoxide (5) was studied. When the sulfide (4) was treated with tert-BuOCl and MeOH in the presence of Ag2O, an additive-type Pummerer reaction took place to produce 17 instead of the normal rearranged product (6). The sulfoxide (5), on treatment with Ac2O, (CF3CO)2O, and 2, 4, 6-collidine, underwent an intramolecular additive-type Pummerer reaction to give the bicyclic compound (19) as a main product. In the reaction of the alkoxysulfonium salt (25) with 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), Pummerer-type rearrangement took place, giving the methoxy compound (6) in poor yield.View full abstractDownload PDF (743K) -
TAKEHIRO SANO, YOSHIE HORIGUCHI, KAZUHIKO TANAKA, YOSHISUKE TSUDA1985 Volume 33 Issue 12 Pages 5197-5201
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEliminative ring expansion of 4-acetoxy (or mesyloxy)-2-azabicyclo [3.2.0] heptan-3-ones (7) yielded 1, 5-dihydro-2H-azepin-2-ones (dihydro-2-azatropones) which, on DDQ oxidation, afforded the 2H-azepin-2-ones (2-azatropones, 9). In contrast to azatropolones, the 2-azatropones were stable to protic solvents. However, irreversible solvolytic changes were observed in both acidic and basic media.View full abstractDownload PDF (543K) -
TOHRU HINO, KOICHI HASUMI, HITOSHI YAMAGUCHI, MIKIO TANIGUCHI, MASAKO ...1985 Volume 33 Issue 12 Pages 5202-5206
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of the indolyl anion of Nb-methoxycarbonyltryptamine (4) with 2-chloro-2-methyl-3-butyne (2) gave the 3a-(1, 1-dimethylpropargyl) pyrrolo [2, 3-b] indole (6) along with the allene derivative (7) and Na-(1, 1-dimethylpropargyl) tryptamine (8). Partial reduction of 6 gave the 3a-(1, 1-dimethylallyl) derivative (10), which rearranged to the 2-(1, 1-dimethylallyl) tryptamine (11) and the Na-(3, 3'-dimethylallyl) tryptamine (12) on acid treatment. On the other hand, acid treatment of 6 gave the 2-(1, 1-dimethylpropargyl) tryptamine (14) in poor yield.View full abstractDownload PDF (634K) -
SHINICHI NINOMIYA, YUTAKA KAWAZOE1985 Volume 33 Issue 12 Pages 5207-5213
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA simple method for the evaluation of the chemoselectivit of alkylating agents toward pyridine in aqueous media is proposed. The analytical method involves the evaluation of the relative rate of quaternization of pyridine with respect to the rate of hydrolysis in aqueous buffer (pH 6.0), i.e., the evaluation of chemoselectivity toward pyridine in competitive nucleophilic attacks of a given alkylating agent on the nitrogen of pyridine versus the oxygen functions in phosphate buffer containing a large excess of pyridine. The term Spy is tentatively defined as log {(N/(1-N)) × [H2O]/[py]}, where N is the molar fraction consumed for pyridine quaternization after the complete consumption of the given alkylating agent, and [H2O] and [py] are the concentrations of water and pyridine, respectively. Spy correlated linearly with the substrate constant (s) defined by Swain and Scott : s=0.163Spy+0.209 (r=0.995, n=8) at 37°C in 4% acetone-containing 1/15 M phosphate buffer (pH 6.0). The dependences of the chemoselectivity on the reaction temperature and the acetone content of the medium are briefly discussed.View full abstractDownload PDF (624K) -
ISAO KITAGAWA, MOTOMASA KOBAYASHI, TATSUYA INAMOTO, MASAKO FUCHIDA, YO ...1985 Volume 33 Issue 12 Pages 5214-5224
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo antifungal lanostane-type triterpene oligosides, named echinosides A (11) and B (9), were isolated from the sea cucumber Actinopyga echinites (JAEGER) collected in Okinawa Prefecture. On the basis of chemical and physicochemical evidence, the structures of echinosides A and B have been elucidated respectively as 3-O-[β-D-3-O-methylglucopyranosyl (1→3)-β-D-glucopyranosyl-(1→4)-β-D-quinovopyranosyl (1→2)-β-D-(4-O-sodiosulfonato) xylopyranosyl]-3β, 12α, 17α, 20 (S)-tetrahydroxy-lanost-9 (11)-en-18, 20-olide (11) and 3-O-[β-D-quinovopyranosyl (1→2)-β-D-(4-O-sodiosulfonato) xylopyranosyl]-3β, 12α, 17α, 20 (S)-tetrahydroxylanost-9 (11)-en-18, 20-olide (9). The antifungal activities of echinosides and allied compounds are discussed.View full abstractDownload PDF (1089K) -
TADASHI OKAWARA, TETSURO YAMASAKI, KIMITOSHI SATO, HIROYUKI MIYAZAKI, ...1985 Volume 33 Issue 12 Pages 5225-5230
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reactions of p-toluenesulfinic acid (1) with dialkoxy disulfides (2), dialkoxy sulfides (6), diamino disulfides (8), diamino sulfides (9), and diamino sulfoxides (15) were examined and found to give di-p-toluenesulfonyl disulfide (3), di-p-toluenesulfonyl sulfide (4), amino p-toluenesulfonyl disulfides (10), amino p-toluenesulfonyl sulfides (13), and p-toluenesulfinamides (16), respectively.View full abstractDownload PDF (563K) -
NOBUTOSHI TANAKA, TAKAO MURAKAMI, HIROSHI WADA, ALICIA B. GUTIERREZ, Y ...1985 Volume 33 Issue 12 Pages 5231-5238
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom the fronds of Pronephrium triphyllum HOLLT., three new glycosides, named triphyllins A, B and C, were isolated. Their structures were determined as (2R, 4S)-5, 7-di-β-D-glucosyloxy-6-hydroxymethyl-4'-methoxy-8-methylflavan-4-ol, (2R, 4S)-5, 7-di-β-D-glucosyloxy-4'-hydroxy-6-hydroxymethyl-8-methylflavan-4-ol and (2S)-7-β-D-glucosyloxy-5-hydroxy-4'-methoxy-6-methoxymethyl-8-methylflavanone, respectively, on the basis of spectral data and chemical correlations.View full abstractDownload PDF (844K) -
KAZUO KOIKE, TAICHI OHMOTO1985 Volume 33 Issue 12 Pages 5239-5244
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe carbon-13 nuclear magnetic resonance chemical shift assignments for several canthin-6-one alkaloids isolated from Ailanthus altissima SWINGLE and Picrasma quassioides BENNET, made on the basis of two-dimensional 13C-1H chemical shift correlation, 13C-1H heteronuclear couplings, and long-range selective 1H decoupling experiments, are reported.View full abstractDownload PDF (494K) -
JUNICHI KUNITOMO, YOHKO MIYATA, MEGUMI OSHIKATA1985 Volume 33 Issue 12 Pages 5245-5249
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS4-Hydroxycrebanine (2), a natural product from Stephania sasakii HAYATA, was synthesized via 1-(6'-bromo-2', 3'-dimethoxybenzyl)-4-hydroxy-2-methyl-6, 7-methylenedioxy-1, 2, 3, 4-tetrahydroisoquinoline (17), which was obtained by Bobbitt's modification of the Pomeranz-Fritsch cyclization of N-[2-(6'-bromo-2', 3'-dimethoxyphenyl)-1-(3, 4-methylenedioxy phenyl) ethyl] aminoacetaldehyde diethyl acetal (12). Irradiation of the compound (17) with the cis relationship of C1-H and C4-H gave dl-4-hydroxycrebanine (2) and its isomer (2a). The stereostructures of the two isomers were established firmly by direct comparison of the proton nuclear magnetic resonance spectra.View full abstractDownload PDF (628K) -
YOSHIMOTO NAKASHIMA, YUTAKA KAWASHIMA, MASAKAZU SATO, SHIGERU OKUYAMA, ...1985 Volume 33 Issue 12 Pages 5250-5257
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAs part of a series of studies on furo [3, 2-b] indole derivatives, 4-alkoxycarbonyl-2-morpholinocarbonylfuro [3, 2-b] indole derivatives were synthesized, and their analgesic and anti-inflammatory activities were examined using the acetic acid writhing method in mice and the carrageenin edema method in rats. Some of these derivatives, particularly 4-isopropoxycarbonyl-2-morpholinocarbonyl-6-trifluoromethylfuro [3, 2-b] indole, showed pronounced pharmacological activities. The structureactivity relationships are discussed.View full abstractDownload PDF (760K) -
SHIGERU KOBAYASHI, MASARU KIHARA, KAZUYOSHI YUASA, YASUHIRO IMAKURA, T ...1985 Volume 33 Issue 12 Pages 5258-5263
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo novel alkaloids, leucotamine (1) and O-methylleucotamine (2), with a 3R-hydroxybutyryl group, and another new alkaloid, 3-O-acetylungiminorine (3), were isolated from leaves of Leucojum asetivum (Amaryllidaceae) together with five known alkaloids. O-Methylleucotamine (2) and 3-O-acetylungiminorine (3), as well as four known bases, were also isolated from bulbs of this plant. The stereochemistries of the new compounds 1, 2 and 3 were established on the basis of chemical and spectral data.View full abstractDownload PDF (664K) -
TOZO FUJII, MASASHI OHBA1985 Volume 33 Issue 12 Pages 5264-5269
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to establish the structure of the Alangium alkaloid demethylcephaeline, chiral syntheses of the two possible alternative structures, (-)-9-demethylcephaeline (1) and (-)-10-demethylcephaeline (2), have been accomplished through a "cincholoipon-incorporating route." The synthesis of (-)-2 started with an initial condensation of the tricyclic acid (-)-12b, prepared from the ester (-)-11b by alkaline hydrolysis, with 3-benzyloxy-4-methoxyphenethylamine and proceeded through the intermediates (-)-13b, (+)-15b, and (-)-14b. The 1'-epimers (-)-18b and (-)-17 were also produced in this reaction sequence. A parallel sequence of conversions starting with (+)-15a afforded (-)-1 via the intermediate (-)-14a, together with the 1'-epimer (-)-16 via (-)-18a. Unfortunately, however, lack of a sufficient amount of natural (-)-demethylcephaeline for a detailed and direct comparison precluded identification of either (-)-1 or (-)-2 with this alkaloid, leaving its chemistry incomplete.View full abstractDownload PDF (699K) -
TAKESHI KATO, AKIRA INADA, YUTAKA MORITA, HIROSHI MIYAMAE1985 Volume 33 Issue 12 Pages 5270-5277
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe crystal structure of meso 1, 3 ; 1', 3'-tetramethylleucoisoindigo was determined by X-ray analysis. A comparative proton nuclear magnetic resonance study on the meso and racemic isomers of leucoisoindigos showed a characteristic high field shift of one set of aromatic protons, H (5)'s, in the meso isomers.View full abstractDownload PDF (630K) -
HIROYUKI ISHIBASHI, SUZUMI HARADA, KAZUMI SATO, MASAZUMI IKEDA, SHUJI ...1985 Volume 33 Issue 12 Pages 5278-5283
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHeating of the N-(3-oxo-1-cyclohexene-1-yl)-α-(methylsulfinyl) acetamides 7a-c with p-toluenesulfonic acid in 1, 2-dichloroethane gave the 3, 5, 6, 7-tetrahydro-3-methylthio-1H-indole-2, 4-diones 9a-c. Compound 9b, when heated in 85% phosphoric acid at 80°C, underwent further cyclization to afford the 7-(methylthio) erythrinan-1, 8-dione 14 and the 6, 7-didehydroerythrinan-1, 8-dione 15 in 53 and 15% yields, respectively. Refluxing of 9b in 99% formic acid gave 15 in 43% yield. Double cyclization of 7b to 14 and 15 was achieved by refluxing in 99% formic acid in 7 and 47% yields, respectively. In marked contrast, treatment of 9c with formic acid resulted in the formation of the 1, 3-dihydro-4-hydroxy-2-methylthio-2H-indol-2-one 16 and the 3, 5, 6, 7-tetrahydro-1H-indole-2, 4-dione 17 in 47 and 16% yields, respectively.View full abstractDownload PDF (603K) -
SETSUO SAITO, YUSHIN NAKAMURA, YUTAKA MORITA1985 Volume 33 Issue 12 Pages 5284-5293
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOptically active diphenylphosphine derivatives, (1R, 3R, 4S, 5R, 6R)-6-cyano-5-diphenylphosphino-3, 4-O-isopropylidene-2-oxabicyclo [3.2.0] heptane-3, 4-diol (15) and its reduction product (17), were prepared by the cyclization of 12 or 13, which was obtained from a common sugar, D-glucose. These phosphines were used as ligands in the rhodium complex-catalyzed asymmetric hydrogenation of prochiral olefins. The rhodium complex catalyst which was constructed with 2 mol of 15 and 1 mol of rhodium (cyclooctene)2Cl (20) worked efficiently for the asymmetric hydrogenation of α-acetamidocinnamic acid (18) and itaconic acid (24) with 91.6% ee-(S) and 69.6% ee-(R), respectively. On the other hand, the rhodium complex constructed with 1 mol of 17 and 1 mol of 20 was less effective than that of 15, giving 39.0% ee-(R) in the reaction with 18. Methyl esters of 18 and 24 were also hydrogenated using the complex of 15.View full abstractDownload PDF (940K) -
YOSHIO HANO, HIDEAKI KOHNO, MASATO ITOH, TARO NOMURA1985 Volume 33 Issue 12 Pages 5294-5300
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThree new 2-arylbenzofuran derivatives named mulberrofurans K, N, and O were isolated from the extract of the Chinese crude drug "Sang-Bai-Pi" (Japanese name "Sohakuhi"), the root bark of Morus sp. (Moraceae). The structures of mulberrofurans K, N and O were shown to be 1, 2, and 3, respectively, on the basis of spectral and chemical evidence. Mulberrofurans K and O are optically active and may be regarded biogenetically as Diels-Alder type adducts of chalcone derivatives and a dehydroprenyl-2-arylbenzofuran derivative. Furthermore, mulberrofuran K seems to be derived from the Diels-Alder type adduct by intramolecular ketalization.View full abstractDownload PDF (755K) -
YOSHIO OKADA, YUKO TSUDA, NAOKI TENO, YOKO NAGAMATSU, UTAKO OKAMOTO, N ...1985 Volume 33 Issue 12 Pages 5301-5309
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSStereoisomers of specific chromogenic substrates for various enzymes were synthesized by a conventional solution method. Among them, Suc-L-Tyr-D-Leu-D-Phe-pNA was found to be an effective and specific inhibitor of α-chymotrypsin. However, Suc-L-Tyr-D-Leu-D-Phe-Pipe did not show any inhibitory effect on α-chymotrypsin. The role of the pNA moiety of the above stereoisomer was investigated, and it was found that the pNA moiety participated in binding with some part of the enzyme, resulting in the manifestation of the inhibitory activity.View full abstractDownload PDF (900K) -
HIROYUKI ISHIBASHI, MASAZUMI IKEDA, HONGDAE CHOI, HIROKO NAKAGAWA, YUK ...1985 Volume 33 Issue 12 Pages 5310-5315
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFriedel-Crafts reaction of the phenylacetates 5a, b with ethyl α-chloro-α-(methylthio) acetate (1) in the presence of stannic chloride gave the α-methylthio-1, 4-benzenediacetates 7a, b. The reactions of biphenyl, diphenylmethane, and diphenyl ether with an excess amount of 1 gave directly the corresponding disubstituted products 10a-c. Desulfurization of 7a, b and 10a-c gave the corresponding diacetates 8a, b and 11a-c. Methyl 4-(2-oxopropyl) phenylacetate (14) was prepared by reaction of methyl phenylacetate with α-chloro-α-(methylthio)acetone (2) followed by desulfurization of the resulting product. Methyl 2-(2-furyl)propionate (19) reacted with 2 in the presence of zinc chloride to give the 2, 5-disubstituted furan 20, whose desulfurization gave methyl 2-[5-(2-oxopropyl)-2-furyl]propionate (21).View full abstractDownload PDF (606K) -
TOZO FUJII, MASASHI OHBA, SHIGEAKI AKIYAMA1985 Volume 33 Issue 12 Pages 5316-5327
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSNew syntheses of the ipecac and Alangium alkaloids possessing the 9, 10-dimethoxy- and 8-hydroxy-9, 10-dimethoxybenzo [a] quinolizidine skeletons (types 1 and 2) have now become possible through generally applicable routes starting from 3-acetylpyridine (5). The routes involve the mercuric acetate-edetic acid oxidation of the 3-acetylpiperidine derivatives 9a, b or the alkaline ferricyanide oxidation of the quaternary salts (26a, b and 27a, b) of 3-acetylpyridine equivalents, Wolff-Kishner reduction of the acetyl group or reductive desulfurization of the thioketal group, sulfenylation-dehydrosulfenylation of the lactams 12a, b, Michael reaction of the α, β-unsaturated lactams 15a, b, and de-ethoxycarbonylation of the Michael adducts 16a, b as the main operations.View full abstractDownload PDF (1316K) -
TOSHIHIKO NAITO, CHIKARA KANEKO1985 Volume 33 Issue 12 Pages 5328-5331
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS1, 2-Dihydrocyclobut [c] isoquinoline was synthesized through photochemical 2+2 cycloaddition of 3-methoxyisoquinolin-1 (2H)-one to 1, 1-dichloroethylene.View full abstractDownload PDF (552K) -
AKIRA SHIOZAWA, YOSHIYA KOGO, YUHICHIRO ICHIKAWA, CHIKARA KOMURO, MICH ...1985 Volume 33 Issue 12 Pages 5332-5340
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe quantitative structure-activity relationships (QSAR) between the molecular structures and antivertigo activities of 6-[2-(4-aryl-1-piperazinyl) ethyl]-5, 6, 7, 8-tetrahydro-1, 6-naphthyridines were investigated. The effects of the ortho-, meta-, and para-substituents on the phenyl ring of the arylpiperazine moiety were examined by means of regression analysis using various physicochemical parameters related to these substituents. The results showed that only the parameters concerning the ortho-substituent were statistically significant. Namely, the relative activity depended on both Fortho (Swain-Lupton field effect constant of the ortho-substituent) and I (indicator variable for the presence of an ortho-alkoxy group and an ortho-dimethylamino group). Thus, regression analysis for only the ortho-substituted compounds was examined and afforded a result similar to that described above. Further, the net atomic charge calculated by the molecular orbital method besides free energy-related substituent parameters was used as electronic parameters of the ortho-substituents on the phenyl ring for this QSAR analysis. For the ortho-substituted compounds alone, the potency correlated well with the net atomic charge on the first atom of the ortho-substituent (Qortho), while the correlation for all the compounds (ortho-, meta-, and parasubstituents) was slightly lower than that for the ortho-substituted compounds alone. It was found that increase in the negative net atomic charge on the first atom of the ortho-position increased the relative activity. The correlation between Qortho and Fortho and I was examined and the role of I is discussed in connection with hydrogen bond-forming ability. The interaction between the arylpiperazine moiety in the compound and a putative receptor is discussed based on the QSAR analysis.View full abstractDownload PDF (848K) -
EISHIN KATO, KOJI YAMAMOTO, TOSHIO BABA, TOSHIO WATANABE, YOICHI KAWAS ...1985 Volume 33 Issue 12 Pages 5341-5350
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSVarious mono-and dithiazolidinecarboxylic acids were synthesized by acylation of (4R)-4-thiazolidinecarboxylic acids and tested for aldose reductase inhibitory activity in vitro. (2R, 4R)-3-(8-Carboxyoctanoyl)-2-(3-nitrophenyl)-4-thiazolidinecarboxylic acid (13) and (2R, 2'R, 4R, 4'R)-3, 3'-azelaoylbis [2-(3-nitrophenyl)-4-thiazolidinecarboxylic acid] (24) showed the most potent activity among them.View full abstractDownload PDF (822K) -
TAKUO KOSUGE, MASAMI YOKOTA, KIYOSHI SUGIYAMA, TOSUKE YAMAMOTO, TAKAKI ...1985 Volume 33 Issue 12 Pages 5351-5354
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe methanol extract of the root of Angelica pubescens MAXIM. was fractionated, and, by following the inhibitory activities on rat hind paw edema induced by carrageenan and on writhing induced by acetic acid in mouse, the active principle was isolated and identified as osthol.View full abstractDownload PDF (444K) -
TAKUO KOSUGE, MASAMI YOKOTA, KIYOSHI SUGIYAMA, TAKAKI MURE, HIROYO YAM ...1985 Volume 33 Issue 12 Pages 5355-5357
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAnti-inflammatory and analgesic principles were isolated from the methanol extract of the whole herb of Pyrola rotundifolia L., based on bioassays of the inhibitory activities on carrageenaninduced hind paw edema in rats and on acetic acid-induced writhing in mice. The principles were identified as ursolic acid and chimaphilin.View full abstractDownload PDF (385K) -
YOSHIAKI WATANABE, SHUICHI SANADA, YOSHITERU IDA, JUNZO SHOJI1985 Volume 33 Issue 12 Pages 5358-5363
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSix homoisoflavonoidal compounds, tentatively named NE-I (1), NE-II (2), NE-III (3), NE-IV (4), NE-V (5) and NE-VI (6), were isolated from the ether-soluble fraction of the subterranean part of Ophiopogon ohwii OKUYAMA (Liliaceae) and four homoisoflavonoidal compounds, tentatively named JE-I (7), JE-II (8), JE-III (9) and JE-IV (10), were isolated from that of O. jaburan (KUNTH) LODD. NE-I and NE-II were identified as compound I (1) and compound II (2), respectively, which had been isolated by Kaneda et al. from an Ophiopogonis Tuber imported from China. NE-III, NE-IV and NE-V were identified as methylophiopogonanone A (3), methylophiopogonanone B (4) and methylophiopogonone A (5), respectively. The structures of NE-VI, JE-I, JE-II, JE-III and JE-IV were elucidated to be 5, 7-dihydroxy-6, 8-dimethyl-3-(2-hydroxy-3, 4-methylenedioxybenzyl) chromone (6), 3, 5-dihydroxy-7-methoxy-6-methyl-3-(4-hydroxybenzyl) chroman-4-one (7), 5-hydroxy-7-methoxy-6-methyl-3-(3, 4-dihydroxybenzyl) chromone (8), 5, 7-dihydroxy-6-methyl-3-(4-hydroxybenzyl) chromone (9), and 5, 7-dihydroxy-3-(4-hydroxybenzyl) chromone (10), respectively.View full abstractDownload PDF (678K) -
KAZUHIKO SAGARA, YUJI ITO, TOSHIYUKI OSHIMA, MASANARI KAWAURA, TETSUO ...1985 Volume 33 Issue 12 Pages 5364-5368
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new, simple and precise method using ion-pair high-performance liquid chromatography was developed for the determination of glycyrrhizin in Glycyrrhizae Radix. A reversed-phase system was used, consisting of an ODS column with water and methanol (45 : 55) containing 5mM tetra-n-butylammonium hydroxide and adjusted to pH 6.0 by phosphoric acid as the mobile phase. A peak (peak I) which had the same retention time as glycyrrhizin in the established ion-suppression method was separated by the ion-pair method. The analytical results of glycyrrhizin measured by this method were lower by 6.2% to 10.8% than those obtained by the ion-suppression method.View full abstractDownload PDF (544K) -
KAZUHIKO SAGARA, YUJI ITO, MITSUHARU OJIMA, TOSHIYUKI OSHIMA, KEIICHI ...1985 Volume 33 Issue 12 Pages 5369-5374
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new, simple and precise method using ion-pair high-performance liquid chromatography was developed for the determination of alkaloids in Corydalis Tuber and Anchusan-to dry extract, i.e., tetrahydrocolumbamine, glaucine, tetrahydropalmatine, corydaline, columbamine, coptisine, palmatine, berberine and dehydrocorydaline. Reversed-phase systems with an octadecylsilane chemically bonded silica gel column using a mixture of sodium dodecyl sulfate, 0.05M tartaric acid and acetonitrile (0.5 : 62 : 38) and a mixture of sodium dodecyl sulfate, Britton-Robinson buffer (pH 3.0) and acetonitrile (0.5 : 56 : 34) as the mobile phases were suitable for the separation of tertiary alkaloids and quaternary alkaloids, respectively, in Corydalis Tuber.View full abstractDownload PDF (587K) -
YASUHIKO KASAI, SHIGETAKA HOSHINO, YASUKO SUZUKI, HIROSHI YAMADA1985 Volume 33 Issue 12 Pages 5375-5379
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA method was developed for the determination of 1-ethyl-, 1-isopropyl-, and 1-cyclohexyl-3-(3-dimethylaminopropyl) carbodiimide perchlorates. Benzoic acid and hydroxylamine perchlorate were coupled at 20°C for 40min in ethanolic medium by using the above carbodiimide perchlorates (0.25 to 7.5mM) at pH 5.5. Ferric perchlorate in ethanolic perchloric acid was added to the benzohydroxamic acid formed. The absorbance of the resultant ferric benzohydroxamate was measured at 550nm vs. the blank solution. This method is more sensitive than that using hydroxamate formation via carboxylic acid anhydride, or than the oxalic acid or cyanide method, and is simpler than the method using aniline or barbiturates or aconitic acid.View full abstractDownload PDF (525K) -
KENICHIRO NAKASHIMA, TAIJI ANDO, TAKAKO NAKAMIZO, SHUZO AKIYAMA1985 Volume 33 Issue 12 Pages 5380-5384
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA rapid, sensitive, and selective high-performance liquid chromatographic method has been developed for the quantification of lipoperoxides (malondialdehyde, MDA) in biological fluids (rat plasma and human serum) with visible detection of 1, 3-diphenyl-2-thiobarbituric acid (DPTBA) condensate. The assay was linear up to 500 pmol per assay tube of MDA. The lower limit of detection of MDA was 10pmol per tube (S/N>2). and the coefficient of variation at the 50pmol/tube level was 2.6% (n=5). A linear relationship was obtained between the peak height and the amount of rat plasma or human serum (10-100μl). A comparison of the DPTBA-high-performance liquid chromatographic method with the thiobarbituric acid-colorimetric one was made for normal human sera. The correlation coefficient (r) was 0.954 with 18 samples. The method is simple and useful for routine assay of trace amounts of lipoperoxides in body fluids.View full abstractDownload PDF (514K) -
YOSHIKAZU FUJITA, ITSUO MORI, KINUKO FUJITA, SHOKO KITANO, TAKESHI TAN ...1985 Volume 33 Issue 12 Pages 5385-5392
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA color reaction of 1, 2-diphenols, such as catecholamines (CA), caffeic acid and gocypol, utilizing colored complex formation among a 1, 2-diphenol, an organic reagent and a metal ion was studied, and suitable conditions for the spectrophotometric determination of 1, 2-diphenols [as norepinephrine (NE), a CA] with phenylfluorone and iron (III) were established. The optimum pH range for the formation of colored complexes in the presence of polyoxyethylene monolauryl ether was pH 8.9-9.9. In the case of NE, the method could be used to determine up to ca. 10μg/10ml, and the apparent molar absorptivity at 630nm was 1.7×105dm3mol-1cm-1. This method was applied to the assay of CA in commercial pharmaceutical preparations. A detection test for CA on a spot plate was also examined.View full abstractDownload PDF (636K) -
HIROSHI HOSODA, WATARU TAKASAKI, SACHIKO AIHARA, TOSHIO NAMBARA1985 Volume 33 Issue 12 Pages 5393-5398
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEnzyme labeling of a steroid with alkaline phosphatase by the N-succinimidyl ester method was investigated. The activated ester of 4-hydroxytestosterone 4-hemiglutarate was treated with alkaline phosphatase to give a labeled antigen. Various molar ratios of steroid to enzyme, ranging from 5 to 200, were employed. The loss of enzymic activity was less than 20% under the coupling conditions used. Satisfactory immunoreactivities with an anti-testosterone antiserum in the enzyme immunoassay procedure were obtained with the labeled antigens prepared at molar ratios higher than 20. The effect of steroid/enzyme molar ratio in the labeling on the sensitivity of the testosterone assay was then examined. It was found that the sensitivity of the assay is significantly influenced by the molar ratio, and a higher ratio results in a decrease in assay is significantly influenced by the molar ratio, and a higher ratio results in a decrease in assay sensitivity. A doserespared at a molar ratio of 30. The active ester method proved to be useful for the preparation of alkaline phosphatase-labeled antigens as well as for β-galactosidase and horseradish peroxidase labelings, because of its simplicity and excellent reproducibility.View full abstractDownload PDF (676K) -
TOSHIKO KUBOTA, SHUICHI MIYAURA, HIDEO ISONO1985 Volume 33 Issue 12 Pages 5399-5403
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSRat brain glutathione S-transferases (GSTs) were studied and compared with rat hepatic GSTs in order to elucidate the mechanisms of detoxication of xenobiotics in the brain. In rat brain, the diethylaminoethyl (DEAE)-cellulose-bound fraction contained more glutathione S-transferase (GST) activity than the DEAE-cellulose-unbound fraction under conditions of 10mM Tris-HCl, pH 8.0. The group of GSTs in the DEAE-cellulose-bound fraction was found to be resolved into at least three peaks. The GST in the main peak was partially purified by Sephadex G-75 and CM-52 column chromatography. The activity was eluted as a single peak on Sephadex G-75 gel filtration, and did not bind to a CM-52 column (10mM potassium phosphate, pH 6.7). The molecular weight of the GST in the main peak was about 44000 daltons, and the enzyme consisted of YnYn (Yn subunit : M, 24500) subunits as determined by SDS/polyacrylamide gel electrophoresis. The GST activities of this main peak were inhibited by antiserum raised against peak II (YbYb subunits : Yb subunit, M, 25000) in the DEAE-cellulose-bound fraction of rat liver.View full abstractDownload PDF (556K) -
TARO OGISO, MASAHIRO IWAKI, TOSHIHIKO TAKAGI, ITSUKO HIRAI, TOKIKO KAS ...1985 Volume 33 Issue 12 Pages 5404-5412
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSHuman erythrocytes were separated into fractions of different age by centrifugation. The effect of some drugs on the separated cells, the levels of some components and enzymes in the cells and the fatty acid composition of membrane phospholipids were estimated to obtain insight into the lifespan of the cells. The bottom (old) cells were relatively more sensitive to the drugs, and aged cells pretreated with chlorpromazine had an increased osmotic fragility and increased viscous properties compared with the top (young) cells, although the differences were relatively small. Significantly lower levels of antioxidant, glutathione and tocopherol, and decreased activities of enzymes (superoxide dismutase, glutathione peroxidase and catalase) involved in peroxide metabolism were observed in old cells as compared with young ones. The proportion of arachidonic acid and the unsaturated/saturated ratio of fatty acids of phospholipids in old cells were significantly lower than those of young cells. The treatment of cells with hydrogen peroxide in vitro produced a dramatic decrease in the proportions of polyenoic fatty acids in all cell fractions, although the decrease in arachidonic acid was less in old cells. The causal relationships among these changes and the lifespan of erythrocytes are discussed.View full abstractDownload PDF (1147K) -
YASUKO KOZAKI, KUNIO YOKOTA, SACHIKO TAKESUE, YOSHIKI TAKESUE1985 Volume 33 Issue 12 Pages 5413-5418
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe addition of Triton X-100 to isolated rabbit intestinal microvilli induced proteolysis of some microvillar proteins. The proteolysis, which was conspicuous in actin, was inhibited by ethylenediamine N, N, N', N'-tetraacetic acid (EDTA) effectively at pH 7.0 but partially at pH 8.6. Phosphoramidon and phenylmethylsulfonyl fluoride showed no inhibitory effect. When microvilli solubilized by Triton X-100 were concentrated, trehalase, a microvillar membrane enzyme, became subject to limited proteolysis, which was also almost completely inhibited by EDTA at pH 7.0. These results show that on solubilization of intestinal microvilli with detergent, care must be taken to avoid induced proteolysis. Most of such proteolysis can be prevented by EDTA at pH 7.0.View full abstractDownload PDF (740K) -
TAKASHI ABIKO, HIROSHI SEKINO1985 Volume 33 Issue 12 Pages 5419-5427
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDeacetyl-thymosin α11 was synthesized by successive azide condensations of seven peptide fragments, Boc-(1-3)-NHNH2, Boc-(4-7)-NHNH2, Boc-(8-11)-NHNH2, Boc-(12-16)-NHNH2, Boc-(17-22)-NHNH2, Boc-(23-26)-NHNH2 and Boc-(27-29)-NHNH2, with H-(30-35)-OBzl, followed by deprotection with hydrogen fluoride in the presence of anisole and thioanisole. An increase of E-rosette-forming cells was obtained after incubation of peripheral blood from a rheumatoid arthritis patient with the synthetic deacetyl-thymosin α11. This synthetic deacetyl-thymosin α11 was approximately equal in potency to our synthetic deacetyl-thymosin α1 in cases of rheumatoid arthritis.View full abstractDownload PDF (983K) -
TAKAYUKI FUNAKOSHI, SHOZO SHOJI, SATOSHI HAYATA, YUKIHO KUBOTA1985 Volume 33 Issue 12 Pages 5428-5436
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe amino acid sequences of the amino-and carboxyl-terminal regions of carboxypeptidase CUa were determined to be Ala-Val-Glu-Leu-His-Phe-Ile-His-Asn-and-Arg-His-Met-Glu-Pro-(Ala, Asp, Lys)-Gly-Thr-Ser, respectively. The enzyme was inactivated with the incorporation of 1 mol of 3H-labeled diisopropylfluorophosphate (DFP) per mol of enzyme, and this reagent was found to react with a serine residue in the active site of the enzyme. The primary structure around this reactive serine residue was determined to be Asp-Val-Ala-Gly-Tyr-Asp-Ser-Glu-Trp-Ile-Gln-Leu-Arg-Val-Pro-Cys-Glu-Gly-Asp-Ser-Gly-Gly-Glu-Leu-Asp-Lys-Glu-Gly-Met-Ala-Pro-Asn-Gly-Ile-Val-Ser-Asp-Ala-Leu-Phe-Thr-Ser-Arg (Ser, reactive serine) by sequence analysis of two radioactive peptides released from [3H] DFP-treated carboxypeptidase CUa on tryptic digestion and cyanogen bromide cleavage.View full abstractDownload PDF (866K) -
KIYOMI KIKUGAWA, KAORI TAKAYANAGI, SHIGENOBU WATANABE1985 Volume 33 Issue 12 Pages 5437-5444
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe interaction of components of peroxidized lipids with polylysine, as a model of protein, was investigated by evaluating the fluorescence and cross-links produced. Treatment of polylysine with 1/3 molar excess malonaldehyde at pH 7.5 gave modified polylysines containing 1, 4-dihydropyridine-3, 5-dicarbaldehyde residues that fluoresced at 398nm (excitation maximum) and 470nm (emission maximum). The amount of the fluorescent residues was estimated to be less than 0.2% of the ε-amino groups. Most of the malonaldehyde was incorporated into the ε-amino groups as nonfluorescent aminopropenal residues (22%) which exhibited an absorption maximum at 280nm and were reactive to 2-thiobarbituric acid. These residues are unstable and might produce cross-links by reacting with unmodified ε-amino groups. Reaction of polylysine with hydroperoxylinoleic acid, acetaldehyde or n-hexylaldehyde produced cross-linked polylysines which exhibited much weaker fluorescence with excitation maxima at 340-360nm and emission maxima at 410-430nm. Studies of the characteristics of fluorescence of these modified polylysines revealed that the fluorophore in the hydroperoxide-modified polylysine was distinguishable from that of the malonaldehydemodified polylysine. It is likely that the fluorophores and cross-links in the hydroperoxide-and the monofunctional aldehyde-modified polylysines were formed by different mechanisms from those involved in the case of malonaldehyde.View full abstractDownload PDF (836K) -
YOSHIE KITAMURA, HIROSHI MIURA, MICHIYASU SUGII1985 Volume 33 Issue 12 Pages 5445-5448
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAlkaloid composition and atropine esterase activity in callus and differentiated tissues from callus and from the original plant of Duboisia myoporoides were determined. Callus and differentiated shoots from callus contained no tropane alkaloids, though they contained very small amounts of anabasine and nicotine. In contrast, differentiated roots from callus contained all the kinds of alkaloids found in the original plant, i.e., atropine, scopolamine, anabasine, nornicotine and nicotine. Neither callus nor differentiated leaves showed atropine esterase activity, but differentiated roots did show atropine esterase activity. These results indicate that the root plays an important role in both tropane alkaloid biosynthesis and degradation, whereas the leaf does not.View full abstractDownload PDF (504K) -
SAI CHEONG WAN LUCY, THANGARAJAH JEYABALAN1985 Volume 33 Issue 12 Pages 5449-5457
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of the operating variables of the dish pelletiser on pellet formation and pellets so formed were studied. Pellet growth was found to be so sensitive to the amount of binding liquid incorporated, that a small variation of it could bring about changes in surface plasticity and ability to deform and coalesce through surface moisture bonds. Increasing the amount of binding liquid led to the formation of pellets with flattened facets instead of being well-rounded. Increase in agitation speed led to a reduction in the average pellet diameter. This could be due to increasing inertial forces which far exceeded the cohesive forces present in the nucleus of the pellet, thus resulting in split pellets. A longer residence time in the dish rendered the pellets more round and smooth but of lower strength. Increasing the load of charge in the pelletiser increased average pellet diameter, due to the size of the load pressing on the feed material. No definite relationship between angle of inclination of pelletiser and average pellet diameter was observed.View full abstractDownload PDF (767K) -
HIROSHI FUJIWARA, SUSUMU KAWASHIMA, YUTAKA YAMADA1985 Volume 33 Issue 12 Pages 5458-5463
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAmpicillin degradation is accelerated by some carbohydrates. The kinetics of the degradation in the presence of polyhydric alcohols (xylitol, glycerin, ethyleneglycol) was studied in alkaline solution, because these alcohol were expected to exhibit a similar accelerating effect. In these experiments, the degradation of ampicillin obeyed apparent-first-order kinetics and the rate constrants increased with increasing concentration of polyhydric alcohols. The rate constant, however, was not affected by monohydric alcohols such as ethanol, propanol, and ethyleneglycol-monomethylether. The degradation of ampicillin was accelerated only by polyhydric alcohols which have adjacent hydroxy groups. This suggests that nucleophilic attack of a hydroxy anion on the β-lactam ring became easier as a result of simultaneous hydrogen bonding among the two adjacent hydroxy groups of alcohols and the amide-carbonyl and β-lactam carbonyl group of ampicillin. The rate accelerating effect of polyhydric alcohols on the degradation of ampicillin was depressed by the addition of aldehydes. This inhibition seems to be attributable to the steric hindrance and resonance effect of Schiff's base formation between the α-amino group of ampicillin and the aldehyde.View full abstractDownload PDF (572K) -
SHIGERU ITAI, MASAMI NEMOTO, SHOZO KOUCHIWA, HIROSHI MURAYAMA, TSUNEJI ...1985 Volume 33 Issue 12 Pages 5464-5473
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of surfactant, particle size, and additives on the dissolution rate of flufenamic acid (FFA) were evaluated in relation to the time course of the available surface area (S (t) ). The ratios of S (t) generated by time t to the total S (t) generated during the dissolution process (F (t)), obtained from the dissolution rate study, were well regressed to the Weibull probability distribution functions. By using the probability parameters obtained, it was possible to elucidate the influence of these factors on the surface characteristics of FFA quantitatively. When the concentration of the surfactant employed was below the critical micelle concentration (cmc), the initial S (t) generated was significantly increased as the surfactant concentration of the dissolution medium increased. Above the cmc, however, the increase was not so marked. The micronization of particles has a significant enhancing effect on the S (t) generated when the surfactant concentration in the dissolution medium was at cmc. The influence of numerous additives on the dissolution rate of FFA and the S (t) generated is also described.View full abstractDownload PDF (782K) -
TAKASHI OHSAWA, HIROSHI MIURA, KIYOSHI HARADA1985 Volume 33 Issue 12 Pages 5474-5483
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIn order to obtain information for a formulation study of liposomes prepared by the freezing-thawing (FT) method, the influence of various water-soluble additives and conditions of preparation (such as storage temperature during the freezing process) on the properties of the liposomes was investigated using L-asparaginase (A-ase) as a model drug. Turbidity (A1%), an index of the particle size, was decreased by NaCl, CaCl2, MgCl2 and glucose, but scarcely affected by KCl, bovine serum albumin or gelatin. The encapsulation efficiency (EN%) was decreased by all additives, but to differing extents. By optical microscopic observation, the generation of large yolk phospholipid (YPL) aggregates was found during preparation without any additive, but was not observed in the presence of NaCl. In the latter case, the mixture visibly froze at below -16°C, but both EN% and A1% were low when it was stored at -20°C, whereas they increased remarkably when the storage temperature was lowered to below the eutectic point (-21°C) of NaCl. Both EN% and A1% became maximum at a certain temperature and decreased at lower temperatures, and this suggests that the cooling velocity also affects them. Based on differential scanning calorimetry measurements, unfrozen water was presumed to be present around YPL particles and the amount of this water seems to affect EN% very significantly. A schematic description of the encapsulation mechanism in the FT method is proposed.View full abstractDownload PDF (983K) -
HIDEO KANEKO, SADAO HIROTA1985 Volume 33 Issue 12 Pages 5484-5494
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe dielectric relaxation due to the interfacial polarization of water-in-oil type emulsions (W/O emulsions) was investigated at frequencies ranging from 10 kHz to 3 MHz. In preparing W/O emulsions, differences of mixing or micronizing efficiency arise between bench-scale and production-scale apparatus owing to the difference of mixing or shear rate. Therefore, the size of dispersed particles can be regarded as an index of the mechanical effect arising from the mixing apparatus. Firstly, the relationship between the size of dispersed particles and the dielectric properties of W/O emulsions was investigated. It was found that 1 d after preparation, the degree of particle aggregation leveled off and became fairly steady, and the values, for W/O emulsions with coarse particles, of the limiting dielectric constant at low frequency, εl, and parameter α, indicating the distribution of relaxation frequencies, determined from complex plane plots, were greater than for those for emulsions with fine particles. The value of εl is thought to be related to the thickness of the surfactant layer between aggregated particles rather than to the size of particle clusters, but the relation becomes more ambiguous as the concentration of surfactant becomes higher. Relaxation frequency, f0, decreases with increasing particle aggregation. Secondly, in order to obtain good emulsification in the W/O emulsion, the stabilizing effects of 23 stabilizing agents upon the state of dispersion of W/O emulsion were evaluated by dielectric measurement. Primary emulsifiers for micronizing dispersed particles, such as polyoxyethylene (POE) (6) sorbitan monooleate, secondary emulsifiers for protecting interface membranes, such as phytosterol, and lipojelling additives, such as aluminum stearate, decreased the value of εl of W/O emulsions. From the present study, it was concluded that dielectric evaluation can be applied to examine the mechanical effects on emulsification and to as an aid in the selection of optimum additives and vehicles for a W/O emulsion.View full abstractDownload PDF (1462K) -
TERUTAKA TAKAHASHI, YOSHIMI SHIRAI, YASUHIKO NAKAMURA, YUKO UEZONO, HI ...1985 Volume 33 Issue 12 Pages 5495-5502
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe suitability of gastric-emptying-controlled rabbits (GEC-rabbits) as a model for estimating the bioavailability of controlled-release preparations in humans was investigated. Non-disintegrating tablets (diameter of 4.1-7.7 mm) and granules (diameter of 0.8-2.0 mm ; specific gravity of 0.90-1.85) were used as a model preparation. Six tablets and 100 granules were administered to GEC-rabbits, and the number of each dosage form remaining in the gastrointestinal tract was counted at suitable intervals. Tablets with diameters of 4.1 and 5.8 mm were randomly emptied from the stomach and the inter-animal variation was very large. Tablets with a diameter of 7.7 mm were not emptied at all even after 7 h. Granules were gradually emptied from the stomach and the profile was similar to that in humans under non-fasting conditions. The gastric emptying was strongly influenced by specific gravity, but the small intestinal transit time was not influenced by either diameter or specific gravity. The mean transit time through the small intestine (about 1.2 h) was about one-third that of humans. The results obtained in this study show that it is important to consider duration and extent of absorption in attempting to predict the bioavailability of controlled-release preparations in humans by using GEC-rabbits.View full abstractDownload PDF (788K) -
TOMONARI KUWAYAMA, TAMOTSU YASHIRO1985 Volume 33 Issue 12 Pages 5503-5510
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSChemical species of diazepam and fludiazepam in an acidic aqueous solution (0.5 N DCl) were studied by means of proton and carbon-13 nuclear magnetic resonance (13C-NMR) spectroscopy. These compounds were present in the form of a protonated iminium structure immediately after preparation of the solution and subsequently underwent slow hydrolysis of the iminium moiety to give a ring-opened benzophenone structure. The structures produced were in equilibrium with the corresponding ring-closed iminium structures. Furthermore, the benzophenone structures were present as an equilibrium mixture of rotating isomers around an amide (cis and trans isomers). The proportion of the benzophenone structure of fludiazepam in the equilibrium solution was greater than that of diazepam. The ratio of rotating isomers of the benzophenone structure that arose from fludiazepam was almost identical to that from diazepam. Assignments of the characteristic proton and carbon-13 resonances of these species and of the aromatic carbon-13 resonances of the iminium structure were carried out.View full abstractDownload PDF (739K) -
YOSHINARI HASEGAWA, MASUYUKI MORITA1985 Volume 33 Issue 12 Pages 5511-5514
Published: December 25, 1985
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe comparative antitumor effects of cisplatin were investigated against several murine tumors after i.p., i.v., and oral administrations. A single administration of cisplatin could significantly inhibit the growth of both L1210 and P388 leukemias, and EL-LP-12 tumors under the conditions used. Oral cisplatin was tested against EL-LP-12 in combination with 6 other antitumor drugs. Cisplatin was inhibitory in binary combination with mitomycin C, vinblastine, 5-fluorouracil, carmustine (BCNU), and cyclophosphamide. In particular, the drug combined with either BCNU or cyclophosphamide showed marked therapeutic synergism.View full abstractDownload PDF (440K)