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HIDEO KANEKO, SADAO HIROTA
1984 Volume 32 Issue 5 Pages
1683-1690
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Dielectric relaxation due to the interfacial polarization of emulsions of water in a hydrophobic colloidal silica-oil gel without any surfactant (denoted as W/ (S·O) emulsion, hereinafter) was investigated over a wide range of volume fraction of the dispersed aqueous phase having various electric conductivity values at frequencies ranging from 10 kHz to 3 MHz. The observed values of the limiting electric conductivities at high frequencies, k
h, of W/ (S·O) emulsion (ε
p3'=78.32, k
p3'=20.09×10
-6〓/cm) are compared with the values predicted by Wagner's theory [K.W. Wagner, Arch. Elektrotech. (Berlin), 2, 371 (1914)]. The observed values for the case of finely dispersed particles were a little larger than the theoretical values. The values of limiting electric conductivities at low frequencies, k
l, could not be obtained because they were too small to be determined by the present apparatus. The observed values of the relaxation frequency, f
0, of the W/ (S·O) emulsion showed a good agreement with Wagner's theoretical curve regardless of the dispersed particle size. In W/ (S·O) emulsions containing two kinds of dispersed particles having different electric conductivities, the parameter, α, for the distribution of relaxation frequencies as determined from complex plane plots (Cole-Cole plots) became larger than zero, even though the particles were homogeneously dispersed. From the present and previous studies [H. Kaneko and S. Hirota, Chem. Pharm. Bull., 31, 5, 1445 (1983)], it is considered that new dielectrics are formed by particle aggregation, and the new dielectrics produce a dielectric anomaly at the interface layer of the aggregated particles.
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BUNJI UNO, YOSHIO MATSUHISA, KENJI KANO, TANEKAZU KUBOTA
1984 Volume 32 Issue 5 Pages
1691-1698
Published: May 25, 1984
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In order to confirm and to extend the scope of the equation
1, 3E
UVho→lu=aF+bR+c, presented by us in the foregoing paper, the polarographic half-wave reduction (E
red1/2) and oxidation (E
oxd1/2) potentials in nonaqueous media and the electronic spectra of 4-substituted azobenzenes have been analyzed. Although the equation was originally derived for π-π
* type HOMO→LUMO transitions with the same character in a series of substances, in this paper we have theoretically verified that the equation is also applicable to the n-π
* bands of conjugated systems. The singlet n-π
* and π-π
* bands of 4-substituted azobenzenes and the triplet n-π
* bands of 4, 4'-disubstituted benzophenones were employed to examine the above equation. The results were reasonable, and are discussed from the viewpoint of molecular orbital theory.
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TOMOHISA NAGAMATSU, MASAKAZU KOGA, FUMIO YONEDA
1984 Volume 32 Issue 5 Pages
1699-1708
Published: May 25, 1984
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Ethyl 2, 3, 4, 8-tetrahydro-3-methyl-2, 4-dioxopyrido [2, 3-d] pyrimidine-6-carboxylates (IV) and their bis-compounds (VI) were synthesized by the condensation of 6-alkyl-or 6-aryl-amino-3-methyluracils (II) and appropriate ethyl 3-chloro-2-formylprop-2-enoates (III) in dimethylformamide. Hydrolysis of the esters IV and VI with base resulted in a novel rearrangement of a substituent (R
2) at the 7-position onto the 6-substituent to give the corresponding 6-acyl-1, 2, 3, 4, 7, 8-hexahydro-3-methyl-2, 4, 7-trioxopyrido [2, 3-d] pyrimidines (VII) and their bis-compounds (X). The mechanism of the rearrangement is discussed.
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MASAYOSHI ITO, TSUTOMU IWATA, KIYOSHI TSUKIDA
1984 Volume 32 Issue 5 Pages
1709-1716
Published: May 25, 1984
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Retinoidal ylidenebutenolides (XVIa, b and XVIIa, b) and their homologues have been synthesized in several steps starting from β-cyclocitral (IIIa) or 3-methoxy-β-cyclocitral (IIIb). The spectral characteristics of the 4-ylidenebutenolides (II) are described in comparison with those of methyl all-(E)-retinoate (XX).
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KOICHI KAWASAKI, MITSUKO MAEDA, HIROMI TAMURA, SUMIKO OHASHI, TETSUHIK ...
1984 Volume 32 Issue 5 Pages
1717-1723
Published: May 25, 1984
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Various tetra-and pentapeptides with Cys and Ser (Thr, Tyr, His) at the N-and C-terminals, respectively, were synthesized as model peptides of the apoprotein of cytochrome P-450. The optical spectra of the synthetic peptide-hemin complexes were measured and the results are discussed.
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HIDEHISA ASADA, TOSHIO MIYASE, SEIGO FUKUSHIMA
1984 Volume 32 Issue 5 Pages
1724-1728
Published: May 25, 1984
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Three new melampolide-type sesquiterpene lactones have been isolated from the methanol extract of Ixeris tamagawaensis KITAM. (Compositae) in addition to luteolin-7-glucoside, and the known sesquiterpene 8-desoxyurospermal A. The structures of the new compounds were elucidated from the spectral data and some chemical transformations.
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HIROMI KOBAYASHI, HIROKO KARASAWA, TOSHIO MIYASE, SEIGO FUKUSHIMA
1984 Volume 32 Issue 5 Pages
1729-1734
Published: May 25, 1984
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Two new iridoids, named cistanin and cistachlorin, were isolated together with four known compounds, D-mannitol, β-sitosterol, succinic acid and β-sitosterol-β-D-glucoside from the whole plant of Cistanche salsa (C.A. MEY.) G. BECK (Orobanchaceae). The structures of cistanin and cistachlorin were determined as I and II, respectively, on the basis of chemical and spectral data. Compounds I and II are non-glycosidic iridoids ; possessing an ether structure of the type (C-1)-O-(C-10), and II also has a chlorohydrin moiety.
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HIROAKI NISHIMURA, GENICHIRO NONAKA, ITSUO NISHIOKA
1984 Volume 32 Issue 5 Pages
1735-1740
Published: May 25, 1984
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A gallotannin (1) and two ellagitannins (2 and 3) containing a salidroside (p-hydroxyphenethyl alcohol 1-O-β-D-glucoside) core have been isolated from the bark of Quercus stenophylla MAKINO (Fagaceae). On the basis of chemical and spectroscopic evidence, their structures have been elucidated unequivocally as 2", 3", 4", 6"-tetra-O-galloyl salidroside (1), 2", 3"-di-O-galloyl-4", 6"-(S)-hexahydroxydiphenoyl salidroside (2) and 3"-O-galloyl-4", 6"-(S)-hexahydroxydiphenoyl salidroside (3).
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HIROAKI NISHIMURA, GENICHIRO NONAKA, ITSUO NISHIOKA
1984 Volume 32 Issue 5 Pages
1741-1749
Published: May 25, 1984
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By a combination of adsorption and partition chromatography, eight new proto-quercitol gallates (compounds 1-8) have been isolated from the tannin fraction of the bark of Quercus stenophylla MAKINO (Fagaceae). Their structures have been characterized mainly by
1H-NMR examinations combined with the spin-decoupling techniques as 4, 5-di-O-gallate (1), 3, 4, 5-tri-O-gallate (2), 2, 4, 5-tri-O-gallate (3), 1, 4, 5-tri-O-gallate (4), 1, 3, 5-tri-O-gallate (5), 1, 3, 4, 5-tetra-O-gallate (6), 1, 2, 4, 5-tetra-O-gallate (7) and 1, 2, 3, 4, 5-penta-O-gallate (8) of proto-quercitol (desoxyinositol).
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HIROAKI NISHIMURA, GENICHIRO NONAKA, ITSUO NISHIOKA
1984 Volume 32 Issue 5 Pages
1750-1753
Published: May 25, 1984
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A new class of ellagitannins (1 and 2) possessing a proto-quercitol moiety has been isolated from the bark of Quercus stenophylla MAKINO (Fagaceae), and their structures have been characterized from the chemical and spectroscopic evidence as 1, 5-di-O-galloyl-3, 4-(S)-hexahydroxydiphenoyl proto-quercitol (1) and 5-O-galloyl-3, 4-(S)-hexahydroxydiphenoyl protoquercitol (2).
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HIDEO YAMAGUCHI, SYUNJI NAKAJIMA, MASAO ARIMOTO, MARIKO TANOGUCHI, TOS ...
1984 Volume 32 Issue 5 Pages
1754-1760
Published: May 25, 1984
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Two kinds of 4-aryltetralin type lignans, β-peltatin-A methyl ether (I-A) and β-peltatin-B methyl ether (I-B), were synthesized from desoxypodophyllotoxin (DPT), which is available in large quantities from the seeds of Hernandia ovigera L. (Hernandiaceae). The syntheses were achieved via demethylene-DPT (IV), 8-bromo-demethylene-DPT (V) and 8-bromo-DPT (VI). Methylenation of V was carried out successfully by using cesium fluoride and methylene iodide in DMF. Compound I-B was readily obtained by the reaction of VI with cuprous iodide and sodium methoxide in the presence of pyridine. Synthesis of I-A was only achieved by the reaction of lithiated VI with nitrobenzene at-100°C in the presence of tetramethylethylene diamine, and I-A was obtained in low yield, together with I-B.
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Fused 1, 3-Oxazine Derivatives. Synthesis of 2H-1, 3-Oxazino [5, 6-b]-quinoxaline-2, 4 (3H)-diones (1-Oxaalloxazines), 2H-1, 3-Oxazino-[6, 5-b] quinoline-2, 4 (3H)-diones (5-Deaza-1-oxaalloxazines), and 2H-Pyrido [3, 2-e]-1, 3-oxazine-2, 4 (3H)-diones
MOTOI YOGO, KOSAKU HIROTA, YOSHIFUMI MAKI, SHIGEO SENDA
1984 Volume 32 Issue 5 Pages
1761-1769
Published: May 25, 1984
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Reactions of 6-anilino-3-methyl-2H-1, 3-oxazine-2, 4 (3H)-diones (1) with triethyl orthoformate, N, N-dimethylformamide dimethyl acetal, diethyl azodicarboxylate, and dimethyl acetylene-dicarboxylate were carried out with the aim of synthesizing fused-ring 1, 3-oxazine derivatives 3-Methyl-2H-1, 3-oxazino [6, 5-b] quinoline-2, 4 (3H)-dione (3-methyl-5-deaza-1-oxaalloxazine) (2) and 3-methyl-2H-1, 3-oxazino [5, 6-b] quinoxaline-2, 4 (3H)-dione (3-methyl-1-oxaalloxazine) (8) were obtained by the reactions of the 6-anilinooxazine (1a) with triethyl orthoformate and diethyl azodicarboxylate, respectively. Treatment of 1a with dimethyl acetylenedicarboxylate gave methyl 3-methyl-2, 4, 7-trioxo-8-phenyl-3, 4, 7, 8-tetrahydro-2H-pyrido [3, 2-e]-1, 3-oxazine-5-carboxylate (9a) as well as methyl 1-methyl-2, 5-dioxo-1, 2, 5, 10-tetrahydrobenzo [b] [1, 8] naphthyridine-4-carboxylate (10) as a ring transformation product. The 6-(p-anisidino)-(1b) and the 6-(3, 4-xylidino)-oxazine (1c) also gave the corresponding pyrido [3, 2-e]-1, 3-oxazines (9b) and (9c).
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HAJIME KATAYAMA, MITSUKO OHKOSHI, KIMIYOSHI KANEKO
1984 Volume 32 Issue 5 Pages
1770-1779
Published: May 25, 1984
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The amino-Claisen rearrangements of 9-unsubstituted and 9-substituted N-allyljulolidinium halides were investigated. The former compounds can be regarded as aniline derivatives in which the two ortho sites are occupied. In the latter compounds, the two ortho positions and the para position are all blocked. N-Allyljulolidinium halides rearranged into 9-allyljulolidine. However, 9-substituted N-allyljulolidinium halides gave 8-allyl-9-substituted julolidines. This meta rearrangement constitutes the first reported example of meta amino-Claisen rearrangement. The reaction pathways can be rationalized in terms of a combination of [3, 3] and [1, 2] sigmatropic rearrangements.
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SEITARO SAEKI, SACHIKO KONDO, TAKAAKI HAYASHI, MASATOMO HAMANA
1984 Volume 32 Issue 5 Pages
1780-1789
Published: May 25, 1984
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The 1-oxido-4-pyridyl radical generated by the reaction of 4-aminopyridine 1-oxide with amyl nitrite reacted smoothly with aromatic hydrocarbons, including five-membered heterocycles, i.e. thiophene, furan and pyrrole, to give the arylated products when acetic acid was used as the solvent. The relative rates of reaction with the 1-oxido-4-pyridyl radical indicated that this radical is electrophilic, and this finding was supported by a comparison of molecular orbital energy levels. 2-Aminopyridine 1-oxide also undergoes a similar reaction.
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TAKASHI YOSHIDA, TSUTOMU HATANO, TAKUO OKUDA, M.USMAN MEMON, TETSURO S ...
1984 Volume 32 Issue 5 Pages
1790-1799
Published: May 25, 1984
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The
13C nuclear magnetic resonance (
13C-NMR) spectra of hydrolyzable tannins, in which D-glucopyranose takes the
4C
1 conformation, have been analyzed and the
13C resonances of the glucose carbons fully assigned. The peak sequences of carbons in glucose are different among several types of hydrolyzable tannins, reflecting differences of the acyl (galloyl, hexahydroxy-diphenoyl and dehydrohexahydroxydiphenoyl) groups, as found upon comparison of penta-O-galloyl-β-D-glucose (1), casuarictin (7), tellimagrandin II (13) and isoterchebin (15). The additive character of galloylation and hexahydroxydiphenoylation shifts can be used for locating the positions of the acyl groups. The substituents and substitution mode at C-1 and C-2 of glucose in these tannins can be deduced from the diagnostic
13C chemical shift of the anomeric carbon. The
13C resonances of the dimeric hydrolyzable tannins were assigned on the basis of the data for their monomeric units.
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YASUNOBU AKIYAMA, SHOKO TAKEBAYASHI, TOMOMI KAWASAKI, MASANORI SAKAMOT ...
1984 Volume 32 Issue 5 Pages
1800-1807
Published: May 25, 1984
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The reaction of ethyl cyanoformate (1a) with phenylcadmium bromide (3a) gave ethyl benzoate (4), ethyl 2-phenyl-2-oxoacetate (5a), and 2-ethoxycarbonyl-2, 4-diphenyl-3-imidazolin-5-one (6). In the presence of zinc chloride, the addition of 3a to the cyano group of 1a occurred to give only 5a. The similar reaction of 1a with other organocadmium reagents (3b-f) in the presence of zinc chloride gave the corresponding α-ketoesters (5b-f) in moderate yields. The reactions of 1a with other organometallic reagents, e.g. phenylmagnesium (2a), -zinc (8) and-mercuric bromide (9) in the presence or in the absence of zinc chloride were examined. Furthermore, the addition of phosphonium ylide 13a to the cyano group of 1a in the presence of stannic chloride occurred exclusively to give the phosphonium salt 14. The results are discussed in terms of the hard and soft acids and bases (HSAB) principle.
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TAKAO MURAKAMI, NOBUTOSHI TANAKA, TSUYOSHI KIMURA, TADASHI NOGUCHI, YA ...
1984 Volume 32 Issue 5 Pages
1808-1814
Published: May 25, 1984
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From the fronds of Plagiogyria euphlebia (KUNZE) METT. 4-O-p-coumaroyl-D-glucose and its related compound, plagiogyrin A were isolated. The structural formula II has been assigned to plagiogyrin A by chemical and spectroscopic analysis. The absolute stereochemistry has been determined at C-5 by the application of modified Horeau's method.
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TAKAO MURAKAMI, NOBUTOSHI TANAKA, TADASHI NOGUCHI, YASUHISA SAIKI, CHI ...
1984 Volume 32 Issue 5 Pages
1815-1821
Published: May 25, 1984
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From the fronds of Plagiogyria matsumureana MAKINO, besides fern-9 (11)-ene and astragalin, plagiogyrin A (I) and B (II) were isolated. The structure and the absolute configuration of plagiogyrin B were determined mainly by spectroscopic methods and chemical transformation to plagiogyrin A. The biosynthetic origin of I and II is probably 4-O-p-coumaroyl-D-glucose, followed by a condensation of the C
6-C
3 unit with the 3-dehydroglucose moiety.
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TETSURO FUJITA, YOSHIHISA TAKAISHI, HIDEKI MORITOKI, TADASHI OGAWA, KY ...
1984 Volume 32 Issue 5 Pages
1822-1828
Published: May 25, 1984
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Two new peptide antibiotics, hypelcins A and B, were isolated from Hypocrea peltata, which is antagonistic to Lentinus edodes. Hypelcins A and B are linear peptides which include nine or ten residues of the abnormal amino acid α-aminoisobutyric acid (Aib) and an amino alcohol, L-leucinol. Hypelcin A was confirmed to be an amide of hypelcin B by chemical conversion. Hypelcin A showed antifungal and antibacterial activities, and contractile action on guinea pig ileum.
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MASAHITO OCHIAI, TATSUZO UKITA, EIICHI FUJITA, SHINICHI TADA
1984 Volume 32 Issue 5 Pages
1829-1839
Published: May 25, 1984
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Organosulfur compounds on treatment with butyllithium in tetrahydrofuran followed by tributylstannylmethyl iodide 1 afforded olefins. The reaction was found to proceed via the destannylsulfurization of the initially formed β-stannyl organosulfur compounds. Thus, allyl 2-pyridyl sulfides 2 or allyl phenyl sulfones 12 were converted into 1, 3-dienes 4. Compounds 13 and 15 were converted into the olefins 14 and 17. Furthermore, the reaction was applied to the synthesis of α-substituted vinyl sulfides 24 and allene 27. The stereochemistry of the double bond is discussed.
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DENICHI MOMOSE, KAZUO IGUCHI, TOSHIKAZU SUGIYAMA, YASUJI YAMADA
1984 Volume 32 Issue 5 Pages
1840-1853
Published: May 25, 1984
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Reaction of various types of organic halides with a monovalent cobalt complex, chlorotris (triphenylphosphine) cobalt (I) is described. Reaction of benzylic monohalides, dihalides and trihalides with CoCl (Ph
3P)
3 gave a coupling product with formation of a carbon-carbon single bond, double bond and triple bond, respectively, under mild and non-basic conditions. Dehalogenation of non-benzylic vicinal dihalides with the reagent took place cleanly to give an olefin in high yield. Reductive coupling of allylic halides using the reagent afforded regioselectively a 1, 5-diene with retention of the stereochemistry of the carbon-carbon double bond of the allylic halides used. By using this reaction, (E, E, E, E)-squalene was stereospecifically synthesized from (E, E)-farnesyl bromide. Reaction of halohydrins with CoCl (Ph
3P)
3 gave exclusively a ketone in the presence of an amine or olefin through an alkylcobalt intermediate. A 1, 2-hydrogen shift is involved in this reaction.
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TOSHIYUKI OKUTOME, HIROYUKI KAWAMURA, SEIZO TAIRA, TOYOO NAKAYAMA, SHI ...
1984 Volume 32 Issue 5 Pages
1854-1865
Published: May 25, 1984
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Guanidino-ester derivatives were synthesized and evaluated for inhibitory activities against trypsin, plasmin, kallikrein, thrombin and Cl esterase, as well as on in vitro complement-mediated hemolysis. Among the compounds synthesized, phenyl α-ethyl-p-guanidinocinnamate (IVg) and phenyl α-propyl-p-guanidinocinnamate (IVh) exhibited potent and selective Cl esterase inhibition (IC
50 : 7×10
-6 and 6×10
-6 M, respectively) and 6-methyl-3-pyridyl α-ethyl-p-guanidinocinnamate (IVi) markedly suppressed complement-mediated hemolysis (86% inhibition at 1×10
-3M).
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YOSHIYUKI KIMURA, HIROMICHI OKUDA, KAZUKO MORI, TAKUO OKUDA, SHIGERU A ...
1984 Volume 32 Issue 5 Pages
1866-1871
Published: May 25, 1984
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The effects of several kinds of extracts from the herb Geranium thunbergii and of geraniin, the main components of tannin of this herb, on liver injury produced in rats by feeding peroxidized oil were investigated. The acetone-water and water extracts, and also geraniin, were found to reduce lipid peroxide concentrations in the serum and liver of the animals with liver injury. These extracts and geraniin were also found to reduce the levels of serum cholesterol, glutamic oxaloacetic transaminase (GOT) and glutamic pyruvic transaminase (GPT) in the peroxidized oil-treated rats.
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YEOLIK SUNG, KAZUO KOIKE, TAMOTSU NIKAIDO, TAICHI OHMOTO, USHIO SANKAW ...
1984 Volume 32 Issue 5 Pages
1872-1877
Published: May 25, 1984
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Cyclic adenosine monophosphate (cAMP) phosphodiesterase inhibitors present in Picrasma quassioides BENN. were identified as 1-methoxycarbonyl-β-carboline, 4, 5-dimethoxycanthin-6-one and 5-hydroxy-4-methoxycanthin-6-one. The structure-inhibitory activity relationships were studied in 31 derivatives of β-carboline, 2 dimeric derivatives of β-carboline and 12 derivatives of canthin-6-one. β-Carboline derivatives with a methoxycarbonyl group and canthin-6-one derivatives with a methoxyl group generally had a strong inhibitory effect on cAMP phosphodiesterase.
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SHIGEO YAMAMOTO, TERUAKI KOBAYASHI, YASUO SUEMOTO, MASAMI MAKITA
1984 Volume 32 Issue 5 Pages
1878-1884
Published: May 25, 1984
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Our previous method for the determination of acetylpolyamines in human urine by gas chromatography has been improved. A urine sample fortified with the internal standard (monoacetylnorspermidine) was directly treated with ethyl chloroformate in an alkaline medium, thereby converting the acetylpolyamines to the N-ethoxycarbonyl derivatives. After extraction of the resulting derivatives with chloroform, the combined extract was applied to a silica gel minicolumn to remove interfering substances. The derivatives of acetylpolyamines thus isolated were determined by gas chromatography with nitrogen-selective detection under temperature-programmed conditions. Calibration curves for acetylpolyamines were linear over the range of 0.2-10 nmol examined. The sensitivity of this method is over 100-fold higher than that of the previous method, so that the acetylpolyamines in human urine could be accurately determined in a sample as small as 200 μl. The use of a nitrogen-selective detector and concomitant procedural modifications greatly reduced the time required for analysis.
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ITSUO YOSHIZAWA, MASAYUKI KAMEYAMA, KAZUHIRO WATANABE
1984 Volume 32 Issue 5 Pages
1885-1890
Published: May 25, 1984
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The preparation and antigenic properties of estradiol 17-sulfate-bovine serum albumin conjugate in which the hapten is linked to the carrier protein through the C-6 position on the steroid nucleus are described. Antibody raised against antigen in the rabbit possessed extremely high specificity to estradiol 17-sulfate, exhibiting no significant cross-reactions with other estrogen sulfates except estriol 17-sulfate (0.2%), and no cross-reactions with free estrogens, their glucuronides, or other related steroids (<0.001%).
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SHINICHI MIYAIRI, HIROAKI SHIOYA, MITSUTAKA EBIHARA, HIROSHI HOSODA, T ...
1984 Volume 32 Issue 5 Pages
1891-1897
Published: May 25, 1984
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The N-succinimidyl esters of various glycine-conjugated bile acid 3-hemisuccinates and 3-hemiglutarates have been prepared for use in immunoassay. Unconjugated bile acids were condensed with p-nitrophenol to form the activated esters. Subsequent reaction with 2, 2, 2-trichloroethyl glycinate provided the glycine-conjugated trichloroethyl esters. On treatment with succinic anhydride and glutaric anhydride in pyridine, the glycine-conjugated bile acids were led to the 3-hemisuccinates and 3-hemiglutarates, respectively. Condensation of these half esters with N-hydroxysuccinimide was effected by the use of water-soluble carbodiimide to provide the N-succinimidyl esters. Elimination of the protecting group in the side chain was achieved by reduction with zinc dust in tetrahydrofuran-potassium dihydrogen phosphate solution, yielding the desired haptens.
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AKIRA TAKADATE, MITSURU IRIKURA, YOSHIKO OHKUBO, SHUJIRO GOYA, MASAKI ...
1984 Volume 32 Issue 5 Pages
1898-1903
Published: May 25, 1984
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The effects of pH, chloride ion, and fatty acids on the interaction between methacycline (MTC) and human serum albumin (HSA) were fluorometrically examined. The fluorescence intensity and binding constant (K) of MTC-HSA complex increased with pH from 6.4 to 8.4, suggesting that MTC binding to HSA is significantly affected by conformational change of HSA in this pH range. Chloride ion effectively displaced MTC from its binding site when HSA was in the basic conformation. The binding affinity of MTC for fatty acid-free HSA depended upon the concentration of fatty acids (oleic and palmitic acids) at physiological pH. Specific binding sites for MTC on HSA were also examined in connection with Sudlow's classification. It was found that the primary binding site of MTC on HSA is site 1.
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AKIRA TAMURA, TAKASHI SATO, TATSUZO FUJII
1984 Volume 32 Issue 5 Pages
1904-1911
Published: May 25, 1984
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Invagination or crenation of human erythrocytes induced by pretreating the cells with an invaginator or crenator was reversed by treatment with phospholipase A
2 (from bee venom) or phospholipase C (from Clostridium perfringens), respectively, under non-hemolytic conditions. In this study, flurbiprofen and lysophosphatidylcholine were used as crenators, and chlorpromazine and cepharanthine were used as invaginators. Crenation or invagination induced by pretreating the erythrocytes with phospholipase A
2 or phospholipase C, which attacks mainly phosphatidylcholine in the outer layer of the membrane lipid bilayer, was also reversed by treatment with an invaginator or crenator, respectively. We also found that pretreatment of the erythrocytes with any of the drugs tested does not significantly affect the susceptibility of the cells to the phospholipases, and also that pretreatment of the erythrocytes with any of the phospholipases used does not affect the binding of the drug to the cells. Thus, the findings suggest that the shape change of human erythrocytes induced by amphiphilic drugs occurs through a mechanism similar to that by which the shape change due to partial hydrolysis of the outer layer phospholipids by phospholipase action occurs, possibly through a change in the lipid bilayer balance of the membrane.
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YOSHIHIRO SATO, YOSHIKO SONODA
1984 Volume 32 Issue 5 Pages
1912-1918
Published: May 25, 1984
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Starting from 3β-acetoxy-25, 26, 27-trinorlanost-8-en-24-al (1), eight lanosterol analogs (10-17) with longer side chains side chains than that of lanosterol were synthesized by Wittig reaction followed by catalytic hydrogenation. Cholesterol biosynthesis was examined in rat hepatic subcellular preparation (S
10) incubated with [24-
3H]-lanosterol in the presence of each of the eight lanosterol analogs. Some of the analogs (10 and 12) caused slight inhibition, but 16 and 17 showed no inhibitory effect. The structure-inhibitory activity relationship of lanosterol analogs on cholesterol biosynthesis from lanosterol is discussed.
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AKIRA KONO, YASUHIRO HARA, SETSURO SUGATA, YOSHIKAZU MATSUSHIMA, TOHRU ...
1984 Volume 32 Issue 5 Pages
1919-1921
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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A thymidine phosphorylase preparation was partially purified from human liver tumor tissues (poorly differentiated adenocarcinoma). The substrate specificity of the enzyme was investigated with eleven pyrimidine nucleosides. Thymidine and 2'-deoxyuridine were good substrates, while uridine, 3'-deoxyuridine, 5'-deoxyuridine, and 2', 3'-dideoxy-3'-hydroxy-methyluridine were not. Uridines substituted at the 5-position by a cyano, bromo, or chloro group were also phosphorolyzed by the enzyme, but the activity for 5-fluorouridine was much lower. 5'-Deoxy-5-fluorouridine was also cleaved. Either a 5-substituent or a 2'-deoxy structure seems to be essential for a good substrate.
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HSINGCHU HSU, JUN WATANABE
1984 Volume 32 Issue 5 Pages
1922-1928
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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A two-period crossover study was carried out to determine the rate and the extent of bioavailability of rabbit muscle creatine phosphokinase (CPK) after intramuscular administration to six male rabbits. The plasma profile of CPK after intramuscular administration (500 U/kg body weight in 0.8 ml of 2% rabbit serum albumin solution into the vastus lateralis muscle) showed a plateau around 4-12 h. Intravenous administration of CPK was performed at doses of 300 and 500 U/kg body weight. The mean clearance/body weight and Vd
ss/body weight were 0.00604±0.00094 l/h/kg (mean±S.D., n=6) and 5.32±1.47%, respectively. The mean residence time (MRT
im) and mean absorption time (MAT
im) of CPK after intramuscular administration were 20.7±4.2 and 11.9±5.1 h, respectively. Since MAT
im was long relative to MRT
im, the rate of bioavailability was slow and the residence time distribution appeared to be skewed. The value of MAT
im/MRT
im, reflecting the contribution of moment of input function to the plasma activity of CPK, was 55.4±11.6%. The variance of residence time (VRT
im) and variance of absorption time (VAT
im) were 608±107 and 505±122h
2. The results imply that the aborption and disposition of CPK after intramuscular administration were rather complicated. The mean fraction of CPK absorbed was 0.311±0.149. Presumably, the incomplete access of CPK to the systemic circulation was due to extravascular inactivation.
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KAZUHIRO TSUKADA, SEIGO UEDA, RYUZO OKADA
1984 Volume 32 Issue 5 Pages
1929-1935
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Liposomal encapsulation of drugs by a reverse-phase evaporation vesicle (REV) method was carried out, and the relation between the in vitro release rates and the lipophilicity of drugs was investigated. Anti-tumor drugs such as carboquone (CQ), nimustine (ACNU), nimustine hydrochloride (ACNU-HCl), cytosine arabinoside (Ara-C), 5-fluorouracil (5-FU) and related compounds were used as model drugs. Encapsulation of the drugs in liposomes was concluded to have no relation with the partition coefficients of the drugs, whereas the in vitro release rate was highly correlated to the partition coefficient and it was evident that the drug was released more slowly when the partition coefficient was lower. Therefore, to achieve sustained release of a drug by means of liposomal encapsulation, it would be necessary to decrease the partition coefficient of the drug by converting it into the hydrochloride form, as in the case of ACNU, or by forming the sodium salt of the drug, if the drug has a carboxylic acid group.
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TSUTOMU TAKAI, KOZO TAKAYAMA, NAOKI NAMBU, TSUNEJI NAGAI
1984 Volume 32 Issue 5 Pages
1936-1941
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Dissolution profiles of griseofulvin (GRF) dispersed in water-soluble polymers were investigated by the paddle method, and large differences in dissolution behavior were observed with different kinds of polymers. The quantitative relationship of dissolution behavior with several properties of the polymers was investigated by the application of multiple regression analysis. It was found that the degree of crystallinity of GRF, the wetting of samples, the solubility or insolubility of water-soluble polymers in methanol, the viscosity of polymer solution and the dissolution rate of polymers were important in the analysis of dissolution mechanisms and prediction of dissolution profiles of GRF from these systems.
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TSUTOMU TAKAI, KOZO TAKAYAMA, NAOKI NAMBU, TSUNEJI NAGAI
1984 Volume 32 Issue 5 Pages
1942-1947
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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A computer optimization technique was applied to obtain griseofulvin (GRF)/hydroxypropyl cellulose (HPC) solid dispersions which provide a high dissolution rate and good stability of dissolution properties. The amounts of HPC and methanol were selected as independent variables in the regression analysis (methanol was used for the preparation of the solid dispersions). Concentrations of GRF dissolved in the dissolution medium at each sampling time were selected as dependent variables for deciding the optimum formulation. These dissolution characteristics were predicted quantitatively by using the best combination of independent variables. The physical meaning of the regression equation for each dissolution characteristic was defined by the application of contour graphs. Two hundred mg of GRF, 2 g of HPC and 125 ml of methanol was predicted to be the optimum for the preparation of GRF/HPC solid dispersions. Experimental results with this optimized solid dispersion agreed well with the predictions.
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TERUO MURAKAMI, YUMI SASAKI, RYOKO YAMAJO, NOBORU YATA
1984 Volume 32 Issue 5 Pages
1948-1955
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The rectal absorption of sodium ampicillin in the presence of various bile salts, such as dehydrocholate, dihydroxycholate, trihydroxycholate, and their glycine and taurine conjugates, was investigated using the in situ rat rectal loop method. A marked but variable absorptionpromoting effect was observed with dihydroxycholate, whereas trihydroxy and triketo bile salts did not enhance the rectal absorption of sodium ampicillin. These results suggest that the promoting efficacy of bile salts for rectal absorption of sodium ampicillin depends upon their chemical structures and/or their physicochemical properties. Solubilizing activity, hemolytic activity, lipophilicity and calcium ion sequestration capacity of the bile salts were measured in vitro, and the relations between promoting efficacy and physicochemical properties were investigated. The bile salts having higher hemolytic activity, higher lipophilicity, and higher values of lipophilicity (Rm value)×calcium ion sequestration capacity showed higher promoting effects on rectal absorption of sodium ampicillin.
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KUNIO NAKANISHI, AKIO OGATA, MIKIO MASADA, TANEKAZU NADAI
1984 Volume 32 Issue 5 Pages
1956-1966
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The effect of nonsteroidal anti-inflammatory drugs (NSAIDs) on the permeability to marker drugs, sulfanilic acid and creatinine, was investigated in rat rectum using the in situ perfusion technique. Indomethacin (IM), phenylbutanone (PB), diclofenac sodium (DF), and aspirin (ASA) were used as NSAIDs. The permeability-enhancing effect increased in the following order : ASA<PB<DF<IM. The effects were reversible. No marked histological changes were observed and, furthermore, protein release from the rectal mucosa was not increased. On the other hand, there was a good correlation between the permeability-enhancing effect and the NSAID amount accumulated in the rectum. Consequently, it is suggested that the accumulation of NSAID in the rectum plays and important role in the enhancement of the rectal permeability to drugs.
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YORISHIGE IMAMURA, ELIORAMON LOO, HISASHI ICHIBAGASE
1984 Volume 32 Issue 5 Pages
1967-1972
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The effect of chloral hydrate (CH) on the in vivo and in vitro binding of sulfamethoxazole (SMX) to plasma proteins was investigated in rabbits. CH clearly reduced the in vivo binding of SMX to plasma proteins. On the other hand, CH had no effect on the in vitro binding of SMX to plasma proteins. CH was found to indirectly reduce the in vivo plasma protein binding of SMX through the formation of trichloroacetic acid (TCA), which is a major metabolite of CH. In addition, CH was found to indirectly reduce the in vivo plasma protein binding of SMX by causing a significant increase in the plasma concentration of N
4-acetylsulfamethoxazole (N
4-AcSMX), which is the major metabolite of SMX and which markedly reduces the in vitro binding of SMX to plasma proteins. These results lead us to conclude that both TCA and N
4-AcSMX play an important role in the in vivo protein binding interaction betwen SMX and CH in rabbits.
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KAZUICHI HAYAKAWA, TOSHIHIKO OGAI, YOSHIAKI IRIKURA, MOTOICHI MIYAZAKI ...
1984 Volume 32 Issue 5 Pages
1973-1979
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Changes in the distributions and chemical forms of biological metals, copper, iron, zinc, calcium and magnesium, produced by the administration of clioquinol in rabbits were investigated. Single administration caused a decrease in plasma zinc and excretion into urine of a large amount of iron (this may have originated from iron-binding proteins such as hemoglobin). Multiple administrations increased plasma copper, which was mainly bound to ceruloplasmin. Decrease in copper in the kidney, increase in copper in the cerebrum and increase in zinc in both the kidney and liver were also observed after multiple administrations.
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HISAYUKI KANAMORI, NAOHIDE KINAE, MASARU SAITO, ISAO TOMITA
1984 Volume 32 Issue 5 Pages
1980-1986
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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When a mixture of 2-furaldehyde (I) and L-tryptophan dissolved in 0.1 M phosphate buffer (pH 7.0) was kept at 37°C for 4 weeks, a browning reaction gradually occurred. The reaction mixture after treatment with nitrite at pH 4.0, was mutagenic to S. typhimurium TA100 in the absence of S9 mix. The browning solution was fractionated by applying high-performance liquid chromatography (HPLC) and thin-layer chromatography (TLC), and two 1-furyl-β-carboline derivatives were isolated. They were compound A, (1R, 3S)-1-(2-furyl)-1, 2, 3, 4-tetrahydro-9H-pyrido [3, 4-b] indole-3-carboxylic acid, and compound B, (1S, 3S)-1-(2-furyl)-1, 2, 3, 4-tetrahydro-9H-pyrido [3, 4-b] indole-3-carboxylic acid. These compounds had similar mutagenic potency toward S. typhimurium TA 100 without metabolic activation after treatment with nitrite.
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MORIO KIYOZUMI, SHOJI KOJIMA
1984 Volume 32 Issue 5 Pages
1987-1991
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The mechanism of the stimulatory effect of chelating agents, such as DL-penicillamine and citric acid, on the biliary excretion of cadmium in rats was studied. The results of Sephadex G-75 gel filtration of liver soluble fraction of rats administered cadmium with or without these chelating agents indicated that the chelating agents significantly depressed the binding of cadmium to a high molecular weight protein of liver tissue. The cumulative biliary excretion of DL-penicillamine and citric acid in a 9 h period after administration were about 1% and about 0.04% of the dose, respectively. It is suggested that the stimulatory effect of DL-penicillamine on the biliary excretion of cadmium was due to the formation of DL-penicillamine-cadmium complex, and that citric acid depressed the binding of cadmium to high molecular protein in the liver cytosol, resulting in enhanced biliary excretion of cadmium.
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YUICHI HASHIMOTO, KOICHI SHUDO
1984 Volume 32 Issue 5 Pages
1992-1994
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Isomers of dinitropyrenes (1, 3-, 1, 6-, and 1, 8-dinitropyrenes) uncontaminated by the other isomers were prepared from the corresponding diaminopyrenes by oxidation, or nucleophilic substitution with nitrite after diazotization.
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YASUMITSU TAMURA, JUNICHI UENISHI, HONGDAE CHOI, JUNICHI HARUTA, HIROY ...
1984 Volume 32 Issue 5 Pages
1995-1997
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Diclofenac, a potent antiinflammatory agent, was prepared by acid-catalyzed cyclization of N-(2, 6-dichlorophenyl)-α-(methylsulfinyl) acetanilide or of α-chloro-N-(2, 6-dichlorophenyl)-α-(methylthio) acetanilide followed by desulfurization and hydrolysis of the resultant 1-(2, 6-dichlorophenyl)-3-(methylthio) oxindole.
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TADAYUKI KURAISHI, TSUYOSHI KIMURA, TAKAO MURAKAMI, YASUHISA SAIKI, CH ...
1984 Volume 32 Issue 5 Pages
1998-2000
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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4-O-p-Coumaroyl-D-glucose (I) and its 2-O-acetyl derivative (II) were isolated from the fronds of Plagiogyria euphlebia (KUNZE) METT. and Microlepia speluncae L., respectively. The latter compound is new, and the structure II was determined mainly by spectroscopic methods.
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SUGURU TAKATSUTO, NOBUO IKEKAWA
1984 Volume 32 Issue 5 Pages
2001-2004
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Brassinolide analogues, (22R, 23R, 24R)-2α, 3α, 22, 23-tetrahydroxy-B-homo-7-oxa-5α-ergostan-6-one (24-epibrassinolide) (10) and (22S, 23S, 24R)-2α, 3α, 22, 23-tetrahydroxy-B-homo-7-oxa-5α-ergostan-6-one (9), were synthesized from brassicasterol (3a) in five steps and with ca. 20% overall yield. The key steps are the direct formation of (22E, 24R)-3α, 5-cyclo-5α-ergost-22-en-6-one (4) from brassicasterol mesylate (3b), the acid-catalyzed rearrangement of 4 to (22E, 24R)-5α-ergosta-2, 22-dien-6-one (6), and the Baeyer-Villiger oxidation of the tetrahydroxy 5α-ergostan-6-ones 7 and 8.
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TAKAO SAKAMOTO, HIROSHI YOSHIZAWA, HIROSHI YAMANAKA
1984 Volume 32 Issue 5 Pages
2005-2010
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The condensation of 2, 4 (2, 6)-dimethylpyrimidines (7a-c), but not 6-methoxy-2, 4-dimethylpyrimidine (7d), with benzaldehyde in the presence of zinc chloride occurred at the 4 (6)-methyl group predominantly. In contrast, the reaction of 7d under the same conditions gave 6-methoxy-4-methyl-2-styrylpyrimidine (17) as the main product. Similar site-selectivity in the oxidation of the dimethylpyrimidines with selenium dioxide was found.
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HISAYUKI TANIZAWA, SHIZUO TODA, YASUYUKI SAZUKA, TOSHIO TANIYAMA, TERU ...
1984 Volume 32 Issue 5 Pages
2011-2014
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Antioxidative components in the leaves of green tea (Thea sinensis L.) were examined by using our evalution method based on the air oxidation of linoleic acid. l-Epicatechin showed the strongest activity, its 50% inhibitory concentration (IC
50 : 3.54×10
-3%) was nearly equal to that of butylated hydroxyanisole (BHA).
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YOSHIHIKO INAMORI, YOSHIAKI KATO, MAYURI KUBO, YOSHIO WAKU, KEIZO HAYA ...
1984 Volume 32 Issue 5 Pages
2015-2019
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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It was previously reported that deoxypodophyllotoxin (I) shows strong insecticidal activity against several kinds of insects, including the 5th instar larvae of silkworm, B. mori. In the present work, in order to clarify the mechanisms of insecticidal action of I, histopathological examination of the fat body, the skin, the Malpighian tubules, and the ventriculus of intoxicated silkworm larvae was carried out and destruction of the epidermal cells was noted. No abnormality of the Malpighian tubules or the ventriculus in the treated larvae was found. Although the fat body cells were also destroyed, the extent of destruction was almost the same both in the administered group and in a fasted group. Therefore, it is unlikely that the primary site of action of I is the fat body cells.
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MASATOSHI MIYAKE, TOSHIAKI NISHIHATA, NORIKO WADA, EMIKO TAKESHIMA, AK ...
1984 Volume 32 Issue 5 Pages
2020-2025
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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Ethylacetoacetate enamines of phenylalanine and phenylglycine enhanced the rectal absorption of macromolecular drugs such as lysozyme and heparin in rabbits. Glycerine-1, 3-diacetoacetate, 1, 2-isopropylideneglyceryl-3-acetoacetate and ethylacetoacetylglycolate also enhanced the rectal absorption of lysozyme and heparin. Lysozyme is a basic compound and heparin is an acidic compound, so the non-surfactant adjuvants used in this study can promote the rectal absorption of macromolecular compounds irrespective of their electrochemical properties. The coadministration of calcium ion inhibited the adjuvant action, so complex formation of the adjuvant with calcium ion may occur, reducing the efficacy of these compounds as adjuvants.
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KENJI MATSUYAMA, HIDEYUKI SAWAHARA, ATSUKO NODA, SHIGERU GOTO, SADAO I ...
1984 Volume 32 Issue 5 Pages
2026-2029
Published: May 25, 1984
Released on J-STAGE: March 31, 2008
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The effect of environmental temperature on the elimination of theophylline was examined by using four male rabbits kept at 15 or 30°C. The rabbits kept at 30°C showed a decrease in the elimination of plasma theophylline compared with those at 15°C. The elimination rate of theophylline from rabbits at 30°C was about 1.5 times slower than that at 15°C. However, no difference was observed in the volume of distribution.
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