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Volume 29, Issue 1
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SETSUKO NAKAGAWA, HIDEAKI UMEYAMA, KAZUO KITAURA, KEIJI MOROKUMA1981 Volume 29 Issue 1 Pages 1-6
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMany investigations on the reaction mechanism of carboxypeptidase A (CPA) have shown that the zinc ion and Glu 270 in the active site are important in the catalytic reaction with a peptide substrate. X-Ray crystallographic studies of native CPA showed that the zinc ion is coordinated to His 69, Glu 72, His 196, and one water molecule and that the Zn-coordinated water molecule forms a hydrogen bond with Glu 270. The zinc-water-Glu 270 system of native CPA was analyzed by the ab initio SCF-LCAO-MO method. Some ligands of zinc are included in the MO calculations as point fractional charges. The results show that the Zn-coordinated water molecule acts as a proton donor to Glu 270, and that the electrostatic effect of Zn2+ and its ligands and the electron delocalization between Zn2+ and the water play a significant role in lowering the barrier height of proton transfer. We consider that the carbonyl group of the substrate, without breaking the hydrogen bond between Glu 270 and the Zn-coordinated water molecule, points towards a fifth coordination site slightly away from Zn2+, and that the water molecule itself is modified by its connection to Glu 270 in a way that favors the reaction.View full abstractDownload PDF (720K) -
HIROSHI TERADA, KEIKO KITAGAWA, YUKO YOSHIKAWA, FUJIO KAMETANI1981 Volume 29 Issue 1 Pages 7-14
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe partition of 2, 4-dinitrophenol (DNP) between n-octanol and water was studied under various conditions. It was found that DNP is transferred to the organic phase in three forms : in the neutral form, in the form of an ion-pair complex with cations in the aqueous phase, and directly in the anionic form. The values of the ion-pair partition coefficient, the ion-pair complex formation constants of the DNP anion with K+ and the n-butyltrimethylammonium ion, and the partition coefficients of the neutral and anionic forms of DNP, indicated that upon partition at pH 7, most DNP is present in n-octanol in the form of the ion-pair complex with the quaternary ammonium ion, and the relative amount of the neutral form of DNP in n-octanol is about the same as that of the ion-pair with K+. Above pH 8, direct transfer of the DNP anion to n-octanol became significant, while the transfer of the neutral form of DNP became very small. These results are discussed in relation to the uncoupling activity of DNP in mitochondria.View full abstractDownload PDF (857K) -
TSUTOMU KAMIYAMA, SABURO ENOMOTO, MASAMI INOUE1981 Volume 29 Issue 1 Pages 15-24
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe catalytic hydroalkylation of benzene over palladium and fused salt (NaCl-AlCl3) was examined under hydrogen pressure. The combination catalyst of palladium and fused salt showed good activity for hydroalkylation, providing cyclohexylbenzene as the main product, with a small amount of bicyclohexyl. With 0.24% palladium supported on alumina, suitable reaction conditions were : a temperature of 120-140°, and a reaction time of 5-10 hr in the presence of fused salt (NaCl-AlCl3 ; molar ratio 1 : 1). Under these conditions, the yields of cyclohexylbenzene and bicyclohexyl were 54.7 and 5.1%, respectively. This catalyst system was applied to the hydroalkylation of toluene, xylenes and trimethylbenzenes. Based on the behavior of the fused salt, we suggest that NaAlCl4 represents an active species in the hydroalkylation reaction.View full abstractDownload PDF (832K) -
TAKAAKI OHKUMA, YUTAKA KIRINO, TAKAO KWAN1981 Volume 29 Issue 1 Pages 25-28
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe chemical and photochemical stabilities of 2-methyl-2-nitrosopropane (NtB), phenyl N-tert-butyl nitrone (PBN), 5, 5-dimethylpyrroline-N-oxide (DMPO), and 2, 5, 5-trimethylpyrroline-N-oxide (TMPO) in aqueous solutions were examined and the feasibility of their use as spin traps was evaluated. NtB has a poor solubility in water. The dissociation of dimeric NtB to its active monomeric form is slow and is accompanied by complicated decomposition reactions even in the dark. PBN is subject to hydrolysis in strongly acidic solutions, the rate constant being 90 M-1 hr-1. DMPO and TMPO were found to be stable to hydrolysis and fairly inert to photolysis. These results, together with other findings, led us to conclude that DMPO may be the first choice and PBN the second as a spin trap to be used in aqueous solutions.View full abstractDownload PDF (575K) -
YUTAKA KIRINO, TAKAAKI OHKUMA, TAKAO KWAN1981 Volume 29 Issue 1 Pages 29-34
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSpin trapping with 5, 5-dimethylpyrroline-N-oxide (DMPO) of various radicals was carried out in aqueous solutions and the ESR parameters for the spin adduct radicals were determined. Comparison of hyperfine coupling constants obtained in aqueous solutions and in benzene revealed that considerable solvent effect exists. For the radical obtained by the addition of a hydroxyl radical to DMPO, the hyperfine coupling constant was found to depend on the basicity of the solution. This phenomenon was analyzed in terms of the acid dissociation equilibrium of the hydroxyl proton of the adduct radical, and the pK value was determined to be 12.96.View full abstractDownload PDF (642K) -
MICHIYA KIMURA, TOSHIKI MUTO1981 Volume 29 Issue 1 Pages 35-42
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSEpoxidation and allylic oxidation of cholesteryl acetate were studied with tert-butyl hydroperoxide (tBuOOH) in the presence of molybdenum complexes. 1. Among the acetylacetonates of various transition metals, MoO2 (acac)2 was unique in that it greatly facilitated the formation of an epoxide as well as its further conversion to the B-nor-5-carboxaldehyde. Since similar results were obtained in the presence of Mo (CO)6 or MoCl5, the effect seems to be independent of the valency and the ligand of the molybdenum catalyst. 2. The reactions using Mo (CO)6 were carried out in various solvents, and it was found that epoxidation or allylic oxidation occurred almost exclusively in benzene or in tert-butyl alcohol (tBuOH), respectively. The reaction probably proceeds by a radical mechanism in tBuOH, but not in benzene. In acetonitrile as a solvent, on the other hand, homolytic and heterolytic decomposition of tBuOOH seemed to occur simultaneously.View full abstractDownload PDF (816K) -
RIKIO OHUCHI, KENYU SHIBATA, NOBUAKI YAMAKOSHI, HIROMU MORI1981 Volume 29 Issue 1 Pages 43-50
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIt was found that the reaction of lead tetraacetate with 3β-hydroxy steroids of the 5α-series gave the corresponding 3β, 19-oxido steroids. Only poor yields were obtained in the cases of 3β-hydroxy steroids having no substituent at C-5 (5α-H). Substitution at the 5α-position by an electronegative group such as halogen or acetoxyl enhanced the yield of the 3β, 19-oxido compound. The best result was obtained when a steroid was heated with lead tetraacetate in benzene in the presence of calcium carbonate and a trace of benzoyl peroxide.View full abstractDownload PDF (905K) -
HIROSHI HARA, OSAMU HOSHINO, BUNSUKE UMEZAWA1981 Volume 29 Issue 1 Pages 51-54
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTreatment with conc. hydrochloric acid of p-quinol acetates (1) obtained from 7-hydroxy-1, 2, 3, 4-tetrahydroisoquinolines (4) gave the corresponding 8-chloro-7-hydroxy-1, 2, 3, 4-tetrahydroisoquinolines (5) in good yields. Similarly, by using conc. hydrobromic acid or 38% hydriodic acid, 8-bromo (6)- or 8-iodo-corypalline (7) was obtained.View full abstractDownload PDF (456K) -
HEIHACHIRO TAGUCHI, ITIRO YOSIOKA, KAZUO YAMASAKI, ILHYUK KIM1981 Volume 29 Issue 1 Pages 55-62
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new glucoside, named gastrodioside, was isolated from the tubers of Gastrodia elata BLUME. (Orchidaceae) and its structure was elucidated as bis (4-hydroxybenzyl)-ether mono-β-D-glucopyranoside (6). 4-Hydroxybenzaldehyde (1), 4-hydroxybenzyl alcohol (2), 4-hydroxybenzyl methyl ether (3, possibly an artifact), 4-(4'-hydroxybenzyloxy)benzyl methyl ether (4), bis (4-hydroxybenzyl) ether (5), 4-(β-D-glucopyranosyloxy) benzyl alcohol (7) and tris [4-(β-D-glucopyranosyloxy)benzyl] citrate (parishin, 8) were also isolated. This is the first time that compounds 4 and 5 have been isolated from natural sources.View full abstractDownload PDF (987K) -
MASAYUKI OYA, JUNZOH MATSUMOTO, HIDEO TAKASHINA, JUNICHI IWAO, YOSHIHI ...1981 Volume 29 Issue 1 Pages 63-70
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of mercaptoacylamino acids was synthesized and screened as angiotensin I-converting enzyme inhibitors. The inhibitory activities of these compounds were compared with that of (2S)-1-[(2S)-3-mercapto-2-methylpropanoyl] proline. The structureactivity relationship of the compounds is discussed.View full abstractDownload PDF (775K) -
MASAMI MORI, SETSUZO TEJIMA1981 Volume 29 Issue 1 Pages 71-75
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSelective tosylation of 1, 6-anhydro-4', 6'-O-benzylidene-β-maltose (1) with 4.2 molar equivalents of tosyl chloride (TsCl) in pyridine at 0°yielded 5 tosylates, which were designated 2 to 6 in order of decreasing Rf value on thin-layer chromatography. After column chromatography on silica gel, compounds 2-6 were separated and identified as the 2, 2', 3, 3'-tetratosylate (2, 2%), 2, 2', 3-tritosylate (3, 15%), 2, 2', 3'-tritosylate (4, 10%), 2, 2'-ditosylate (5, 67.7%), and 2'-monotosylate (6, 1.7%), respectively. Selective tosylation of 5 with 8 molar equivalents of TsCl in pyridine at 0°afforded 2 (9.3%), 3 (17.3%), and 4 (24.7%), together with 5 (39.3%). Compound 5, the major product of the selective tosylation of 1, is a valuable intermediate in the chemical modification of maltose.View full abstractDownload PDF (760K) -
TOSHIO SUZUKI, AKIKO TOMINO, KATSUO UNNO, TETSUJI KAMETANI1981 Volume 29 Issue 1 Pages 76-81
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA general method for the stereoselective synthesis of the potential intermediates (11), (12), (20), and (21) for the Rauwolfia alkaloid reserpine (1) and its analogs starting from furan and benzyl furfuryl ether is described.View full abstractDownload PDF (724K) -
TAKASHI NAKAGAWA, MASARU KOBAYASHI, KOJI HAYASHI, HIROSHI MITSUHASHI1981 Volume 29 Issue 1 Pages 82-87
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThree new minor cembrane-type diterpenes, sarcophytol-C, sarcophytol-D, and sarcophytol-E, were isolated from the lipid extract of the soft coral, Sarcophyton glaucum Q. et G., collected in southern Japan. Their structures were characterized on the basis of spectral evidence and degradative studies by ozonolysis.View full abstractDownload PDF (803K) -
KINICHI IMAI, MITSUHIKO MANO, TAKUJI SEO, TOSHIMI MATSUNO1981 Volume 29 Issue 1 Pages 88-97
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS1, 6-Dihydro-6-oxo-2-pyrazinecarboxylic acid 4-oxide (1) has been synthesized by two different methods. The first is a hydrolysis of methyl 6-chloro-2-pyrazinecarboxylate 4-oxide, which was in turn obtained from methyl 6-chloro-2-pyrazinecarboxylate by reaction with m-chloroperbenzoic acid. The second is an oxidation of 6-hydroxymethyl-2 (1H)-pyrazinone 4-oxide with nickel peroxide. Compound 1 was converted to amine salts, esters and amides. 6-Methoxy, 6-mercapto and 1-alkyl derivatives were also prepared. The compounds prepared were tested for anticoccidial activity in chickens against Eimeria tenella and marked activity was seen with compound 1 and amine salts of 1. The activity of 1 was counteracted by the simultaneous administration of an equal weight of orotic acid or adenine.View full abstractDownload PDF (975K) -
HIROSHI YAMANAKA, SHIGERU OGAWA, SHOETSU KONNO1981 Volume 29 Issue 1 Pages 98-104
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction of 4-chloro-2, 6-dimethylpyrimidine 1-oxide (II) with ethyl cyanoacetate and malononitrile under basic conditions gave the expected condensation products, while the reaction of II with methylene ketones failed. On the other hand, 2, 6-dimethyl-4-phenylsulfonylpyrimidine (X) smoothyl reacted not only with the above active methyl compounds but also with methylene ketones such as acetone, acetophenone and cyclohexanone.View full abstractDownload PDF (854K) -
TETSUJI KAMETANI, KOJI SUZUKI, HIROSHI KUROBE, HIDEO NEMOTO1981 Volume 29 Issue 1 Pages 105-109
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCyclization of the olefinic β-hydroxy selenide (5) with various catalysts was carried out to give the cyclic compound (9) which was converted to safranal (19) via the olefinic alcohol (14), the diolefinic alcohol (16), and the aldehyde (17).View full abstractDownload PDF (697K) -
AKIRA TANAKA, TOSHINAO USUI1981 Volume 29 Issue 1 Pages 110-115
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS2-Substituted 3-(5-nitro-2-furyl) quinoxaline 1, 4-dioxides (Va-g) were prepared by the reaction of benzofurazan 1-oxide with α-aryl- or α-(2-furyl)-β-(5-nitro-2-furyl)-vinylamines and aryl or 2-furyl 5-nitro-2-furfuryl ketones. It was found that primary enamines, as well as tertiary enamines, are useful in this reaction. One-pot synthesis of 2-(2-furyl)-3-(5-nitro-2-furyl) quinoxaline 1, 4-dioxide (Va) from 2-[β-(5-nitro-2-furyl) ethynyl] furan was examined, and afforded Va in 11% yield. Compounds Va-g were subjected to antibacterial activity tests and some of them showed activity at 6.25-25μg/ml (minimal inhibitory concentration).View full abstractDownload PDF (618K) -
USHIO SANKAWA, HIDEAKI OTSUKA, YOSHITOMO KATAOKA, YOICHI IITAKA, AKIO ...1981 Volume 29 Issue 1 Pages 116-122
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCyclo-alkannin and cycloshikonin were formerly considered to be derivatives of hydroanthraquinone 3. However, chemical and spectral investigation revealed that cycloalkannin possesses no secondary hydroxyl group. Thus, the structure of cyclo-alkannin leucoacetate (8) was determined by X-ray analysis, by the direct method ; the final R index with hydrogen atoms except for those of methyl groups was 0.065. The cyclization of alkannin and shikonin is a reaction between the hydroxyl group and double bond and does not involve the formation of a carbocyclic ring. In 1H-NMR both alkannin and cyclo-alkannin show two singlet signals arising from the protons of the aromatic and quinonic rings. The absence of coupling and lower chemical shift values suggests delocalization of the quinonic ring so that these compounds can be regarded as consisting of tautomeric structures (10, 11). The results of antitumor tests on alkannin and cycloalkannin derivatives (6, 7, 8, 10, 11) are also reported.View full abstractDownload PDF (771K) -
NORIYUKI OOKAWA, YUKINOBU IKEYA, HEIHACHIRO TAGUCHI, ITIRO YOSIOKA1981 Volume 29 Issue 1 Pages 123-127
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThree new dibenzocyclooctadiene lignans, named acetyl (1)-, angeloyl (2)- and caproylbinankadsurin A (3), were isolated from the fruits of Kadsura japonica DUNAL (Schizandraceae). Their absolute structures were elucidated by chemical and spectral studies.View full abstractDownload PDF (673K) -
TATSUO HAMADA, YOHMEI OKUNO, MASAYUKI OHMORI, TAKAO NISHI, OSAMU YONEM ...1981 Volume 29 Issue 1 Pages 128-136
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAlthough N-chloroacetyl derivatives of benzylamines (2, 8) and anilines (21, 25, 29) disappeared quite rapidly when irradiated with a high pressure mercury lamp, no photocyclization to six- and five-membered lactams occurred. Measurements of fluorescence quenching and disappearance quantum yields of N-chloroacetyl-(3, 4-dimethoxylphenyl)-alkylamines having various lengths of alkyl chain revealed that the shorter the alkyl chain is, the more efficient the exciplex formation is. Therefore, the failure of photocyclization seemed to be due to trans conformation of amide bonds in the benzylamine and aniline derivatives. Introduction of an alkyl group on the amide nitrogen changed the stable conformation of amides from trans to cis, and hence N-alkyl-N-chloroacetylbenzylamines (11, 13, 15, 17, 19) readily gave the corresponding 1, 2, 3, 4-tetrahydroisoquinolin-3-ones (12, 14, 16, 18, 20) on irradiation. Oxindoles (36, 38, 40, 41, 43, 46) were similarly synthesized by photocyclization of N-alkyl-N-chloroacetylanilines (35, 37, 39, 42, 45).View full abstractDownload PDF (1095K) -
MASAHIKO TOHMA, YUKO NAKATA, HIROMI YAMADA, TAKAO KUROSAWA, ISAO MAKIN ...1981 Volume 29 Issue 1 Pages 137-145
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDeuterium-labeled ursodeoxycholic acid (UDCA-d2) was synthesized from cholic acid by heterogeneous catalytic reduction of the 11, 12-unsaturated bile acid with deuterium gas. A new method for the simultaneous determination of UDCA, UDCA-d2, related bile acids and cholesterol in human bile has been developed by gas chromatography-mass fragmentography of the methyl ester trimethylsilyl ether derivatives. The glycine conjugate of 5β-chol-3-en-24-oic acid was prepared from lithocholic acid and used as an internal standard. Calibration plots gave a good linear relationship over the range of 100-500 ng of each compound, and their recoveries (95-99%) relative to the internal standard suggested that the present method is sufficiently accurate for the practical analysis of these bile acids in human bile. The method was applied to investigate the fate of UDCA-d2 orally administered to a patient with complete bile fistula.View full abstractDownload PDF (941K) -
MAMORU SUGIURA, SHINOBU HAYAKAWA, YOSHIMASA ITO, KAZUYUKI HIRANO1981 Volume 29 Issue 1 Pages 146-149
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe optimal reaction conditions and kinetic properties of glucose dehydrogenase were studied in order to develop a method for serum glucose determination. The Km value for glucose of this enzyme was influenced by the medium pH and ionic strength. Suitable conditions for the use of glucose dehydrogenase in rate assay and end point assay were identified. These methods showed very good reproducibility and were essentially unaffected by other reducing agents in the serum. The values obtained by these methods showed excellent correlations with those obtained with the hexokinase method. The present methods are rapid, simple and accurate.View full abstractDownload PDF (514K) -
YUKINORI KAWAHARA, MASAFUMI HISAOKA, YASUSHI YAMAZAKI, AKIKO INAGE, TA ...1981 Volume 29 Issue 1 Pages 150-157
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA new procedure has been established for the determination of captopril [1-(D-3-mercapto-2-methyl-1-oxopropyl)-L-proline] in biological fluids. Captopril was trapped with p-bromophenacyl bromide or N-(4-dimethylamino-3, 5-dinitrophenyl) maleimide (DDPM), then the addition products were separated and determined by high-performance liquid chromatography (HPLC) on a reversed-phase column. The disulfides, metabolic products derived from captopril and excreted in the urine, were reduced with tributylphosphine to captopril which in turn was trapped with DDPM. These adducts were separated and determined by HPLC. The method provided quantitative results for captopril levels of 5-2000 ng/ml of whole blood and 0.1-100μg/ml of urine with satisfactory accuracy and precision.View full abstractDownload PDF (826K) -
SATORU IKENOYA, MASAHIRO TAKADA, TERUAKI YUZURIHA, KOUICHI ABE, KOUICH ...1981 Volume 29 Issue 1 Pages 158-164
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA high performance liquid chromatographic method with both an ultraviolet spectrometric detector (UVD) and an electrochemical detector (ECD) has been developed for the simultaneous determination of reduced and oxidized ubiquinones in biological materials. This method is based on extraction from animal tissues or mitochondrial fractions with ethanol-n-hexane mixture, followed by quantitation on a reversed-phase column with UVD and ECD. The detection limits by ECD or UVD were 100pg, 2ng, 150pg and 2ng for ubiquinol-9, ubiquinone-9, ubiquinol-10 and ubiquinone-10, respectively. The persentages of reduced ubiquinones (ubiquinols) to total ubiquinones were 41.6, 32.4 and 45.2% for guinea pig heart, rat heart and heart mitochondrial fraction of guinea pig, respectively, with added succinate as a substrate.View full abstractDownload PDF (770K) -
TOMOO TANAKA, KUNIYUKI TANAKA, MORIO NAKAYAMA, MASAHIKO CHIKUMA, HISAS ...1981 Volume 29 Issue 1 Pages 165-169
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSNew water-soluble chelating agents, azothiopyrine sulfonates, which possess mercapto and azo groups as a chelate-forming site and a sulfonic acid group as a functional group providing water-solubility, were prepared. Their acid dissociation constants and chelate formation with metal ions were determined by a spectrophotometric method.View full abstractDownload PDF (625K) -
HIROSHI HOSODA, YASUO SAKAI, TOSHIO NAMBARA1981 Volume 29 Issue 1 Pages 170-175
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA sensitive enzyme immunoassay for urine 6β-hydroxycortisol has been developed. Enzyme labeling of 6β-hydroxycortisol was accomplished by the N-succinimidyl ester method. The use of N-succinimidyl ester of 6β-hydroxycortisol 21-hemisuccinate and β-galactosidase in an appropriate molar ratio provided a conjugate suitable for enzyme immunoassay. Antiserum was prepared by immunization with the 6β-hydroxycortisol 21-hemisuccinate-bovine serum albumin conjugate in the rabbit. Sufficient sensitivity and improved specificity of the assay system could be obtained by the selective blocking of less specific antibodies. The quantitation limit of 6β-hydroxycortisol was approximately 10 pg, which is comparable to that of radioimmunoassay. The intra- and inter-assay coefficients of variation for 6β-hydroxycortisol in human urine were 5.9-8.1% and 2.8-12.3%, respectively.View full abstractDownload PDF (707K) -
YASUMASA KOYAMA, YOSHITAKA YAZAWA, FUMIO KATO, SABURO YAMAGISHI1981 Volume 29 Issue 1 Pages 176-180
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBrevibacterium sulfureum is capable of carotenoid synthesis when grown under illumination, but not in the dark. The carotenogenesis consists of two steps, an initial photochemical reaction and a series of metabolic reactions (dark reactions) which lead to carotenoid synthesis de novo. Inhibition experiments with chloramphenicol showed that the dark metabolic reactions include the process of de novo synthesis of carotenogenic enzymes. These results show B. sulfureum to be a typical photochromogen.View full abstractDownload PDF (681K) -
HIROTERU SAYO, MIKIO HOSOKAWA1981 Volume 29 Issue 1 Pages 181-187
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe enzymic activities of various preparations of catalase were determined. Catalase C-100, which is a twice-crystallized preparation, showed the highest catalatic activity, whereas C-40, which is a lyophilized preparation, showed the highest N-demethylase activities towards aminopyrine. The ethyl hydroperoxide (EHP)-supported peroxidatic activity towards methanol increased in parallel with the increase in the catalatic activity. On the other hand, the order of increasing N-demethylase activities towards aminopyrine was not the same as that of increasing catalatic activity. Treatment with alkali followed by neutralization increased the N-demethylase activities of C-40 and C-100 and decreased both the peroxidatic activity towards methanol and the catalatic activity. When the alkali-treated catalase solution was neutralized and allowed to reconstitute, the increased levels of N-demethylase activities only slightly decreased with time up to 2 hr. The decreased peroxidatic activity towards methanol was restored nearly completely, whereas only 7.6% of the original catalatic activity of C-40 was restored after reconstitution for 24 hr. Gel chromatographic experiments showed that treatment with alkali results in the dissociation of catalase into subunits, and that the recombination of the subunits takes place fairly rapidly on neutralization of the alkali-treated catalase. The present results suggest that catalase molecules with a loosely combined quaternary structure, which are formed by lyophilization or by treatment with alkali followed by neutralization, are capable of catalyzing the organic hydroperoxide-supported N-demethylation of aminopyrine, whereas they cannot decompose hydrogen peroxide efficiently.View full abstractDownload PDF (846K) -
YOKO TSUMURA, KEIKO MURAKOSO, SHOHEI KAGAWA, AKIRA MATSUOKA1981 Volume 29 Issue 1 Pages 188-193
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effect of alloxan on pancreatic islets of the rat was studied by following the change in the incorporation of uridine diphospho (UDP) D-[U-14C] galactose into glycoproteins (chloroform/methanol-insoluble fraction) and glycolipids (chloroform/methanol-soluble fraction). Islets exposed to either alloxan or alloxan plus D-glucose anomers (16.7 mM) at 37° for 5 min, were incubated in a medium containing UDP-[U-14C] galactose at 37°for 120 min. The incorporation of UDP-[U-14C] galactose into glycoproteins and glycolipids was unaffected by 1.25 mM alloxan, but was slightly reduced by 6.25 mM alloxan. Alloxan at 31.2 mM severely inhibited the incorporation. The combination of alloxan (31.2 mM) plus the α anomer abolished the inhibitory effect of alloxan to a considerable extent, while the β anomer provided no protection against the action of alloxan. The label distribution on polyacrylamide gel electrophoresis of islets incubated with UDP-galactose was similar to that obtained after labeling with galactose oxidase and NaB3H4. In conclusion, the present data indicate that pancreatic islets of the rat can transfer galactose from UDP-galactose on the plasma membrane and that the α anomer of glucose is more effective than the β anomer in overcoming the inhibitory effect of alloxan.View full abstractDownload PDF (663K) -
TERUYOSHI YOKOYAMA, TSUNEO UMEDA, KOJI KURODA, TSUTOMU KURODA, SHOZO A ...1981 Volume 29 Issue 1 Pages 194-199
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe gastrointestinal absorption of 6-mercaptopurine (6-MP) polymorphs was studied in rabbits, and their absorption kinetics were analyzed. Form III of 6-MP was absorbed more efficiently from the gastrointestinal tract than form I. It was found that the absorption kinetics after oral administration of 6-MP could be satisfactorily accounted for by a two-compartment model with two consecutive first-order input steps. Form III had an extent of bioavailability about 1.5 times greater than that of form I. This result may be attributed to a difference of K1 and/or Ka between the polymorphic forms I and III.View full abstractDownload PDF (614K) -
MAKOTO TANIGUCHI, MASAHIRO NAKANO1981 Volume 29 Issue 1 Pages 200-204
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe hydrolysis and permeation of trichloroethyl phosphate were examined in vitro by using everted sacs of rat intestine. The concentration of trichloroethanol was higher in serosal solutions than in mucosal solutions at a high concentration of the phosphate ester whereas the opposite was the case at a low concentration of the ester at pH 7.4. The concentration of trichloroethanol in serosal solutions differed in different regions of the small intestine. The phosphate ester permeated into serosal solutions as such at pH 3.5. Therefore the ester is expected to permeate into serosal solutions as such and then to be hydrolyzed at a high concentration of the phosphate ester at pH 7.4. Percentage losses of the phosphate ester from the intestinal loop in situ differed slightly in different regions of intestinal tracts. The ester is expected to be hydrolyzed in the intestinal lumen before absorption under normal conditions, or be absorbed as such when present at a high concentration.View full abstractDownload PDF (621K) -
EIHEI FUKUOKA, SHINTARO KIMURA, MIDORI YAMAZAKI1981 Volume 29 Issue 1 Pages 205-212
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA direct measuring method for the liquid penetration rate into tablets was devised and compared with the usual powder method. The effect of the diameter and shape of tablets on the penetration rate was examined by using a two-dimensional model and confirmed to be negligible in practice. Directly compressed tablets of several powders used as excipients were tested as samples. The weight variation of tablets had little effect on penetration. Since the penetration rate depends on the compression pressure, all tablets were prepared at a constant pressure of 215 kg/cm2. Both in the present method and in the usual powder method most samples were in conformity with Washburn's equation, but the rate constants (K) were considerably different in the two methods. The results for crystalline cellulose could be described by such an equation in the case of the powder method but not in the case of the tablet method. The reason is considered to be the swelling of tablets and the accompanying generation of cracks. In this case, an L vs. t plot showed good linearity instead of an L2 vs. t plot. The penetration patterns of crystalline cellulose tablets were also different from those of the other samples. Most of the tablets were not disintegrated after completion of penetration ; calcium carbonate, lactose and crystalline cellulose were exceptions.View full abstractDownload PDF (755K) -
KANETO UEKAMA, FUMITOSHI HIRAYAMA, TORU WAKUDA, MASAKI OTAGIRI1981 Volume 29 Issue 1 Pages 213-219
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe rates of hydrolysis of prostacyclin (PGI2) and its methyl ester (PGI2Me) in aqueous solution were significantly retarded by α-, β-, and γ-cyclodextrins (α-, β-, and γ-CyDs), and showed characteristic saturation kinetics and competitive inhibition. The deceleration effects of CyDs on the hydrolysis of PGI2Me were about 3 times larger than those on the hydrolysis of PGI2. The importance of the spatial relationship between the host and guest molecules was reflected in the kinetically determined stability constant (Kc) for these inclusion complexations. To elucidate the deceleration mechanism of the CyDs, the effects of pH, solvent and temperature on the hydrolysis rate were studied. The protolytic dissociation of the terminal carboxylic acid moiety of PGI2 was suppressed by the binding to CyDs, depending upon the magnitude of the Kc value. Thermodynamic activation parameters suggested that the deceleration mechanism of CyDs in the case of PGI2 was somewhat different from that for PGI2Me, which may be due to different modes of inclusion.View full abstractDownload PDF (687K) -
KEITO BOKI, SEIKI TANADA, KAZUOKI MATSUMOTO1981 Volume 29 Issue 1 Pages 220-224
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAdsorption isotherms of hydrogen sulfide on zeolite and activated carbon were obtained by a gravimetric method at 20° and 30°in order to elucidate the thermodynamic properties of adsorption of hydrogen sulfide in micropores of zeolite and activated carbon. The Dubinin-Astakhov equation could be applied to these adsorption isotherms. The net differential heat of adsorption q and the differential molar entropy of adsorption ΔS were calculated from the adsorption isotherms by using the following equations : q=E [(ln ao/a)1/n+αT/n (ln ao/a)1/n-1] and ΔS=-αE/n (ln ao/a)1/n-1. In all cases, q decreased with increasing degree of filling of micropores. It was considered that the micropores of zeolite and activated carbon are successively filled with hydrogen sulfide from the smallest pores to the largest ones. The differential molar entropy of adsorption became smaller with increase in the degree of filling. This entropy change suggests that hydrogen sulfide molecules are compactly filled in the micropores at the final stage of filling.View full abstractDownload PDF (551K) -
TADASHI KIHO, CHIHIRO HARA, SHIGEO UKAI1981 Volume 29 Issue 1 Pages 225-228
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe locations of O-acetyl groups in the acidic polysaccharides AC and BC isolated from the fruit bodies of Tremella fuciformis BERK were determined by employing an improved procedure. The results indicated that the O-acetyl groups in AC and BC are located at positions 4, 6, and both 4 and 6 of a part of the mannose residues, and at positions 2, 4, and both 2 and 4 of a part of the glucuronic acid residues. AC and BC differ significantly in that the amount of the O-acetyl groups linked to the mannose residues in BC was higher than that in AC. Our improved procedure should be widely applicable for determining the locations of O-acyl groups on acidic polysaccharides.View full abstractDownload PDF (539K) -
SHOICHI KANATOMO, TETSUKO HASE, SOTOO NAGAI1981 Volume 29 Issue 1 Pages 229-232
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMethods for the synthesis of 5-carboxy-6-methyluracil (9), which is expected to be useful as an intermediate for the preparation of sparsomycin analogs, were investigated. A new route that leads to 9 from cyanoacetylurea (5) via 2-cyano-3-oxobutanoylurea (6a), 5-cyano-6-methyluracil (7a), and 5-carbamoyl-6-methyluracil (8), was developed. The total yield from 5 to 9 was 20.7%.View full abstractDownload PDF (466K) -
KENJI SUZUKI, YUSUKE SASAKI, NOBUYOSHI ENDO, YUICHI MIHARA1981 Volume 29 Issue 1 Pages 233-237
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOptically pure diketopiperazines were obtained in good yields when dipeptide esters were refluxed in 2-butanol containing 0.1 M acetic acid for 3 hours. When prolyl-amino acid ester was used as the starting material, 1 to 2 M acetic acid was the most effective concentration.View full abstractDownload PDF (616K) -
HARUO SAIKACHI, TOKUJIRO KITAGAWA, AKIHIRO NASU, HIDEAKI SASAKI1981 Volume 29 Issue 1 Pages 237-244
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe kinetics of the thermal Curtius rearrangement of benzoheteroaroyl azides, i.e., 2-benzofuroyl azide (2), 2-benzothenoyl azide (4), 2-indolecarbonyl azide (6), 2-, 3-, 4-, 5-, 6-, and 7-quinolinecarbonyl azides (8, 10, 12, 13, 14, and 15), and 1- and 2-naphthoyl azides (17 and 18), in toluene were studied by infrared spectrophotometry to determine how the annelation of the benzene ring to side b of 2-furoyl, 2-thenoyl, and 2-pyrrolecarbonyl azides (1, 3, and 5) and 2-, 3-, and 4-pyridinecarbonyl azides (7, 9, and 11) affects the rearrangement and its rate. The annelation effect slightly promotes the rearrangement ; the effect on the thiophene ring and pyrrole ring is greater than that on the furan ring, and the effect on the pyridine ring of 4-pyridinecarbonyl azide (11) is greater than that on the pyridine ring of 2- and 3-pyridinecarbonyl azides (7 and 9).View full abstractDownload PDF (809K) -
KATSUMI TABEI, ETSUKO KAWASHIMA, TETSUZO KATO1981 Volume 29 Issue 1 Pages 244-249
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe reaction of N-hydroxyacetoacetanilide derivatives (1a-g) with hydroxylamine in aqueous ethanol gave 3-methyl-4-arylhydrazono-5-isoxazolones (3a-g). When ethanol or chloroform was used as the reaction medium, the reaction of N-hydroxyacetoacetanilide (1a) with carbonyl reagents gave N-phenylhydroxylamine derivatives and five-membered heterocycles such as 3-methyl-5-isoxazolone or 3-methyl-5-pyrazolone derivatives. The mechanism of the formation of these products is discussed.View full abstractDownload PDF (701K) -
The Chemistry of Indoles. XII. A Facile Route to 5-Nitroisocoumarins and Methyl Indole-4-carboxylateMASANORI SOMEI, YOSHIO KARASAWA, TOSHIYA SHODA, CHIKARA KANEKO1981 Volume 29 Issue 1 Pages 249-253
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA convenient synthesis of 5-substituted isocoumarin derivatives, such as 5-nitroisocoumarin (2), 5-aminoisocoumarin (8), 3, 4-dihydro-3-methoxy-5-nitroisocoumarin (3), and 5-amino-3, 4-dihydro-3-methoxyisocoumarin (10), from 2-methyl-3-nitrobenzoic acid (1) is reported. Several synthetic routes to methyl indole-4-carboxylate (9) from methyl 2-methyl-3-nitrobenzoate (4) directly or via these isocoumarins (8 and 10) are also presented.View full abstractDownload PDF (655K) -
HIDEJI ITOKAWA, KEIICHI SUTO, KOICHI TAKEYA1981 Volume 29 Issue 1 Pages 254-256
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPachypodol, ombuine, apigenin, rhamnetin, apigetrin and a new flavone, apigenin 7-O-β-D (-6"-p-coumaroyl)-glucoside, were isolated from the aerial part of patchouli, Pogostemon cablin (Labiatae). These compounds were identified by analysis of various spectral data.View full abstractDownload PDF (463K) -
NORITO KANEDA, TADAYUKI KURAISHI, KAZUO YAMASAKI1981 Volume 29 Issue 1 Pages 257-259
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFrom a crude drug, toad cake (Bufonis Venenum), a new bufogenin was isolated and its structure was elucidated as 20, 21-epoxyresibufogenin by spectral analysis, mainly by 13C-NMR spectroscopy.View full abstractDownload PDF (430K) -
YASUMASA HAMADA, KIYOKO ANDO, TAKAYUKI SHIOIRI1981 Volume 29 Issue 1 Pages 259-261
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAromatic α-nitroketones can be conveniently prepared from aromatic carboxylic acids and nitromethane by the action of diethyl phosphorocyanidate (DEPC) in the presence of triethylamine.View full abstractDownload PDF (429K) -
MASAAKI KATAI, TADAMASA TERAI, HARUO MEGURI1981 Volume 29 Issue 1 Pages 261-264
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTriterpenoids in the bark of Pieris japonica D. DON were investigated. Oleanolic acid acetate, ursolic acid acetate, ursolic acid, β-sitosterol, lupeol and compound A (VI), mp 262-263°, C32H50O5, were obtained. The physical properties of VI were elucidated by infrared absorption, nuclear magnetic resonance (NMR), 13C-NMR and mass spectral studies. The structure of VI is probably 3β-acetoxy-16α-hydroxy-ursan-28, 19-olide.View full abstractDownload PDF (567K) -
YUTAKA TAKEDA, NAOKI NAMBU, TSUNEJI NAGAI1981 Volume 29 Issue 1 Pages 264-267
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIndomethacin (IMC) suspended in soybean oil was microencapsulated in a gelatinacacia system by a modified phase separation method from aqueous solution. The microcapsules were hardened with formaldehyde without the use of sodium hydroxide. Average particle diameter of the microcapsules was 111μm, and the content of IMC in the microcapsules was more than 80% of the initial amount of IMC. The in vitro dissolution of IMC from the microcapsules was slower than that of intact IMC, and this indicated that the walls of the microcapsules affected the drug dissolution. The bioavailabilities in beagle dogs of the IMC microcapsules and of a soybean oil suspension of IMC administered in capsules were larger than that of intact IMC.View full abstractDownload PDF (496K) -
YURIKO KATO, MAYUMI KOHKETSU1981 Volume 29 Issue 1 Pages 268-272
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effect of the polymorphic form of amobarbital on its bioavailability was examined by measurement of the dissolution rate and in vivo absorption of two forms (Form I and Form II). The dissolution rate of Form II was faster than that of Form I. In in vivo absorption experiments using rabbits, two crystal forms of amobarbital were administered orally and the resulting blood level-time curves were compared with the dissolution rates. It appeared that the polymorphic form of the drug appreciably affected the absorption process from the digestive tract. Hydroxyamobarbital was confirmed to be the main metabolite of amobarbital.View full abstractDownload PDF (547K) -
HISAKAZU SUNADA, AKINOBU OTSUKA, YASUKO TANAKA, YOSHIAKI KAWASHIMA, HI ...1981 Volume 29 Issue 1 Pages 273-276
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo-dimensional agglomerates having various degrees of packing were formed by successive addition of uniform discs to a core by means of a Monte Carlo simulation procedure. Whether cohesion between discs occurred or not was determined by comparing the pseudo-random number generated at every collision with the cohesion probability P. The figures of agglomerates formed by this simulation method appear very similar to those of real agglomerates observed under a microscope. The void fraction of agglomerates and the average coordination number were calculated.View full abstractDownload PDF (668K) -
KENICHI SASAKI, SHINOBU FURUSAWA, GIICHI TAKAYANAGI1981 Volume 29 Issue 1 Pages 276-279
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effect of prior administration of aminophylline, caffeine, or propranolol on the antitumor activity of 6-mercaptopurine (6-MP) or 6-mercaptopurine riboside (6-MPR) against Ehrlich solid tumor in ddY male mice was studied. These three drugs each weakened the action of 6-MP but had less effect on the action of 6-MPR. Considering the variation in the activities of hypoxanthine-guanine phosphoribosyltransferase and xanthine oxidase, we suggest that higher doses of aminophylline and propranolol may promote the conversion from 6-MP to biologically inactive thiouric acid or hypoxanthine rather than to biologically active thioinosinic acid.View full abstractDownload PDF (539K) -
TOMIHISA OHTA, HIROSHI HIKINO1981 Volume 29 Issue 1 Pages 280-282
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structure of lyoniatoxin, a diterpenoid from the leaves of Lyonia ovalifolia var. elliptica, has been revised to I on the basis of 13C NMR evidence, providing a typical example of the use of the long-range 13C-1H spin decoupling technique for the structural elucidation of isoprenoid natural products.View full abstractDownload PDF (444K) -
ISAO KITAGAWA, MOTOMASA KOBAYASHI, MANABU HORI, YOSHIMASA KYOGOKU1981 Volume 29 Issue 1 Pages 282-285
Published: January 25, 1981
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOn the basis of chemical and physicochemical evidence, the structures of four triterpenoidal oligoglycosides, bivittoside A, B, C, and D from the sea cucumber Bohadschia bivittata MITSUKURI, have been elucidated as 6, 8, 9, and 10, respectively. A new homoannular dienic sapogenol was isolated as the acetate and the highly strained structure (4a) has been elucidated.View full abstractDownload PDF (452K)
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