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MITSUNORI WASHITAKE, YASUJI TAKASHIMA, SHIGEO TANAKA, TOSHIO ANMO, ICH ...
1980 Volume 28 Issue 10 Pages
2855-2861
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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In order to establish an in vitro method for determining drug release from ointments, the drug permeability and the drug release from ointments were investigated using egg shell membrane and isopropyl myristate (IPM)-containing membrane, and the results were compared with the in vivo results. The results of the permeation of salicylic acid at various pH values showed that egg shell membrane behaved as a dialysis membrane in the same way as cellulose membrane, while IPM-containing egg shell membrane behaved as a partition membrane in the same way as polyamide lipoid membrane. In the release experiments with betamethasone 17-valerate from various ointments, the release from hydrophilic ointment was substantial, followed by that from absorption ointment, and that from white vaseline was the least. These results were correlated with those of in vivo vasoconstrictor assay. Although macrogol ointment showed high drug release, since it changed into a solution due to the diffusion of water from receptor solution, the vasoconstrictor activity was lower than those of the other ointments.
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KATSUMI ITOH, YOSHIKAZU OKA
1980 Volume 28 Issue 10 Pages
2862-2867
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The synthesis of 7, 8-dihydroxy-1, 2, 3, 4, 5, 6-hexahydro-2, 6-methano-3-benzazocin-1-ol (6) was undertaken in an attempt to confirm the hypothesis that an equatorial conformation of the amino group in 2-amino-5, 6-dihydroxy-1, 2, 3, 4-tetrahydro-1-naphthalenol derivatives (1) might be essential for the β-adrenoceptor activity. 4-(2, 3-Dimethoxyphenyl) cyclohexanone (13) which was prepared via several steps from 2, 3-dimethoxyphenylacetonitrile (7), was led to a tetralone derivatives (17) by oxime formation, Beckmann rearrangement, hydrolysis and cyclization, by way of 14, 15, and 16. Compound 6 was derived from 17 by a five-step sequence of reactions. The β-adrenoceptor activity of 6, in which the amino moiety is fixed in an axial conformation, proved to be about one-thousandth of that of l-isoproterenol.
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HIDEMICHI FUKAWA, KUNIO SUZUKI, MINORU SEKIYA
1980 Volume 28 Issue 10 Pages
2868-2873
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The formic acid reduction of 1, 1'-benzylidenedipiperidine (1) was kinetically investigated by the carbon dioxide trapping method. Rate data gave the rate equation, v=k
obs [1] [HCOOH]. The initial mono- and diprotonation of 1 occur in equilibrium, and monoprotonated form is proposed to be an intermediate for the reduction to 1-benzylpiperidine. The isotope effect value (2.69) and the negative ρ substituent effect (similar to that of the formic acid reduction of N-benzylideneaniline) suggest that the reduction of 1 involves the same intermediate step of decarboxylation of the formic acid ester of the α-amino alcohol.
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HIDEAKI UMEYAMA, SETSUKO NAKAGAWA, TOMOKO NOMOTO
1980 Volume 28 Issue 10 Pages
2874-2883
Published: October 25, 1980
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Simulation of the enzymatic reaction of dogfish M
4 lactate dehydrogenase (LDH) was performed. In the enzymatic reaction from L-lactate to pyruvate, the structure in which the proton transfer from L-lactate to His 195 is coupled with the hydride transfer from L-lactate to NAD
+ was simulated. In the reverse reaction, the structure in which the proton transfer from His 195 to pyruvate is coupled with the hydride transfer from NADH to pyruvate was also simulated. Since the proton of His 195 approaches the carbonyl oxygen of pyruvate from the π direction of the pyruvate plane in the simulation, the electronic structure and the reactivity of pyruvate were studied from a quantum chemical point of view, using the ab initio LCAO MO method. When the carbonyl carbon of pyruvate is attacked by the hydride ion of NADH, the total π electron density of the carbonyl oxygen of pyruvate increases substantially. Therefore, the proton of His 195 attacks the carbonyl oxygen of pyruvate from the π direction. Moreover, the pyruvate-Arg 171 complex having two nearly parallel hydrogen bonds is more easily attacked by hydride than complexes having other conformations.
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TSUNEMATSU TAKEMOTO, YOSHIHIKO INAMORI, YOSHIAKI KATO, MAYURI KUBO, KA ...
1980 Volume 28 Issue 10 Pages
2884-2891
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The physiological activities of streptothricin antibiotics were investigated, taking racemomycin-D as a representative of the group. It was found that racemomycin-D has insecticidal activity, fish-toxicity and inhibitory activity on plant growth. Firstly, racemomycin-D showed a weak but broad-spectrum insecticidal activity against the adults of Blattella germanica, Musca domestica, Nilaparvata lugens, Laodelphax striatella, and Plutella xylostella. A rather strong insecticidal effect on Culex pipiens molestus larvae was found, with mortalities of 90% and 15% at 10 ppm and 2 ppm, respectively. Though racemomycin-D showed no insecticidal effect against the larvae of Spodoptera litura, it showed inhibitory activity on feeding at a concentration of 300 ppm. Secondly, racemomycin-D was toxic to all the fish species examined, i. e., Misgurnus anguillicaudatus, Carassius auratus, and Oriziae latipes. Among these, racemomycin-D showed particularly strong toxicity against C. auratus with a TLm of 3.7 ppm (after 48 hr). Thirdly, racemomycin-D showed strong inhibitory activity on the growth of Brassica campestris L. subsp. Napus Hook fil et Anders var. nippo-okifera, Arctium Lappa L., Petrocelium sativum, and Raphanus sativus L. var. acanthiformis at a concentration of 500 ppm (with an inhibitory ratio of 0.1, relative to 1.0 for the control group).
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TOSHIO KINOSHITA, YUTAKA SASADA, MITSUAKI WATANABE, SUNAO FURUKAWA
1980 Volume 28 Issue 10 Pages
2892-2899
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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6-Methyl-5-methylthio-2-[2(1H)-quinolylidene] methyl-1, 3-oxazin-4-one (1) was treated with acid to give 4-methyl-5-methylthio-3-[2(1H)-quinolylidene] pyridine-2, 6 (1H, 3H)-dione (2) in good yield. Similarly, 2-aminopyridine derivatives (7a-e) were obtained by the reaction of 1 with various amines. On the thermolysis of 1, 3-methylthio-2-[2 (1H)-quinolylidene]-3, 5-dioxohexanitrile (12) was obtained. When 1 was treated with trifluoroacetic anhydride, a trifluoroacetyl group was introduced at the active methine moiety of 1. No ring conversion occurred in the reaction of 6-methyl-5-methylthio-2-[2 (1H)-quinolylidene-2-quinolyl] methyl-1, 3-oxazin-4-one (13) with various reagents, whereas ring cleavage of the 1, 3-oxazine ring of 13 was observed. Dimethylsulfonium acetyl-N-phenylcarbamoylmethylide (18) was treated with quinoline 1-oxide and acetyl chloride to give 4-methyl-3-methylthio-1-phenyl-5-[2 (1H)-quinolylidene] pyridine-2, 6 (1H, 5H)-dione (20) instead of the 1, 3-oxazin-4-one derivative (19).
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HIROSHI HIKINO, CHOHACHI KONNO, HIROSHI TAKATA, MITSURU TAMADA
1980 Volume 28 Issue 10 Pages
2900-2904
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Since the traditional usage of an Oriental medicine "mao", consisting of Ephedra herbs, suggests that it may possess antiinflammatory activity, a crude drug preparation, the aerial part of E. intermedia, was subjected to bioassay for antiinflammatory activity by two methods. The methanol extract was found to be active. The extract was fractionated in monitoring the antiinflammatory activity, resulting in the isolation of (+)-pseudoephedrine as the active principle. The antiinflammatory effects of ephedrine analogs were determined by four assay methods ; pseudoephedrine exhibited the strongest activity in the Whittle method, the carrageenin paw edema method in mice, and the fertile egg method.
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MASAHIRO NAKANO, MASAHIKO KOUKETSU, YUHKO NAKAMURA, KAZUHIKO JUNI
1980 Volume 28 Issue 10 Pages
2905-2908
Published: October 25, 1980
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The use of agar beads for sustained release of a urinary tract disinfectant was examined in vivo. Agar beads containing dispersed sulfamethizole were administered to five healthy volunteers, and the rate of excretion of the drug in urine was determined for pharmacokinetic analysis. The results indicated that agar beads should be useful for the preparation of sustained release dosage forms.
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HIROKAZU TANIGUCHI, TOMOHIKO YOSHIDA, YURIKO ADACHI, SABURO NAKANO
1980 Volume 28 Issue 10 Pages
2909-2914
Published: October 25, 1980
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A new fluorometric method for determination of the chloride ion was established. Chloride reacted with 2-(5-nitro-2-furyl) benzothiazole in 60% sulfuric acid upon ultraviolet irradiation to form 2-(5-chloro-2-furyl) benzothiazole, which gave intense violet fluorescence with an excitation maximum at 375 nm and emission maximum at 422 nm. Chloride could be determined in the range of 0.1-10μg/ml by measuring the fluorescence intensity. This method can be applied to the determination of chloride in tap water.
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MINEO SANEYOSHI, MANAMI MOROZUMI, KENJIRO KODAMA, HARUHIKO MACHIDA, AK ...
1980 Volume 28 Issue 10 Pages
2915-2923
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Enzymatic selective dephosphorylation of 1-β-D-arabinofuranosylcytosine 3', 5'-diphosphate (1) with nuclease-3'-nucleotidase P
1 at 60° for 24 hr gave 1-β-D-arabinofuranosylcytosine 5'-phosphate (Ara CMP) (2) in good yield. The acylation of both N
4- and the 2', 3'-hydroxyl groups of 2 followed by coupling with various alcohols and phenols in the presence of 2, 4, 6-triisopropylbenzenesulfonyl chloride and subsequent alkaline hydrolysis afforded the title compounds (4). The resulting 32 kinds of Ara CMP alkyl or aryl esters were examined to determine their biological activities, such as antiviral activity against herpes simplex type 1 in cultured human embryonic lung fibroblast cells, growth inhibitory activity against mouse leukemic L5178Y cells in culture and antileukemic activity against L-1210 in mice. Ara CMP esters were active in these assay systems.
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SHIGERU KOBAYASHI, MASARU KIHARA, TETSURO SHINGU, KEIJI SHINGU
1980 Volume 28 Issue 10 Pages
2924-2932
Published: October 25, 1980
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Pretazettine (1), which shows antileukemic activity, was obtained by conversion of tazettine (2) to 3-epitazettadiol (3) [whose structure was confirmed by its cyclization to deoxypretazettine (4)], followed by manganese dioxide oxidation of 3. The transformation of 2 to 1 confirmed the stereochemistry of pretazettine (1).
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MASASHI TOMODA, KAZUYO SHIMADA, YUKO SAITO, MICHIKO SUGI
1980 Volume 28 Issue 10 Pages
2933-2940
Published: October 25, 1980
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A representative mucilage, named Okra-mucilage F, has been isolated from the immature fruits of Abelmoschus esculentus MOENCH (=Hibiscus esculentus L. ; Okra). The final preparation was homogeneous as determined by ultracentrifugal analysis, cellulose acetate membrane electrophoresis, and gel chromatography. Its water solution gave an intrinsic viscosity value of 30.1. It was composed of partially acetylated acidic polysaccharide and protein in a ratio of approximately 8.1 : 1.0, and its molecular weight was estimated to be about 1700000. Analysis of component sugars, together with reduction and methylation, and partial degradation studies showed that the polysaccharide moiety in the mucilage possesses a main chain having the repeation structure (1→4)-O-α-(D-galactopyranosyluronic acid)-(1→2)-O-α-L-rhamnopyranose, and that half the L-rhamnose residues in the main chain have branches composed of 4-O-β-D-galactopyranosyl D-galactopyranose at position 4.
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SATORU IKENOYA, OSAMU HIROSHIMA, MASAHIKO OHMAE, KIYOSHI KAWABE
1980 Volume 28 Issue 10 Pages
2941-2947
Published: October 25, 1980
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A high performance liquid chromatography (HPLC) procedure with an electrochemical detector (ECD) has been developed for the analysis of fatty acids, bile acids and prostaglandins. These carboxylic acids were converted to p-hydroxyanilides by reaction with p-aminophenol in the presence of 2-bromo-1-methylpyridinium iodide and triethylamine. The anilides were oxidized in a two-electron process and analyzed by reversed-phase HPLC-ECD. The detection limits were 0.5, 2 and 2ng for stearic acid, chenodeoxycholic acid and prostaglandin F
2a, respectively. The method was applied to the determination of free fatty acids in guinea pig plasma and bile acids in human bile.
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MASANORI KUROYANAGI, SEIGO FUKUSHIMA, KUNITOSHI YOSHIHIRA, SHINSAKU NA ...
1980 Volume 28 Issue 10 Pages
2948-2959
Published: October 25, 1980
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Thirteen aromatic compounds, having C
6-C
4, C
6-C
8-C
6 or C
6-C
10 carbon skeletons, were isolated from the rhizomes of a Thai medicinal plant, Zingiber cassumunar. Eight compounds were new among these, and their structures were elucidated as 6, 7, 8, 9, 10, 11, 12, and 13 by chemical and spectral methods. The structures were confirmed by
13C-NMR spectroscopy.
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KUNIO KOBAYASHI, TAKAFUMI SAKOGUCHI, MASAKO KIMURA, KUNIO HAITO, AKIRA ...
1980 Volume 28 Issue 10 Pages
2960-2966
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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In order to characterize the amplifying effect of bovine serum albumin (BSA) on the optical density in the color reaction for the determination of xanthurenic acid (XA) using 4-aminoantipyrine (4-AAP), the interactions of XA with native and modified BSA were examined by equilibrium dialysis. BSA was modified with hydrogen peroxide (H
2O
2), p-chloromercuribenzoic acid (PCMB) and 2-hydroxy-5-nitrobenzyl bromide (HNBB). Binding of XA with BSA was confirmed by gel filtration of a mixture containing BSA and XA on a Sephadex G-150 column. The amount of bound XA increased dose-dependently in proportion to the BSA concentration in the mixture. Scatchard plots for the interaction of XA with BSA at pH 4.0, 5.7, 7.4 and 10.0 were obtained. The plots indicated two classes of XA-binding sites on BSA at pH 5.7 and 7.4, but gave a simple straight line with disappearance of the primary binding site at pH 4.0 and 10.0. The binding capacity (n
2K
2) in the secondary binding site decreased linearly with increasing pH of the solution from 4.0 to 10.0, suggesting that the binding force was electrostatic. The standard free energy change (ΔG
o2), standard enthalpy change (ΔH
o2) and entropy change (ΔS
o2) were-5.3 kcal/mol, -4.2 kcal/mol and 3.6 entropy units at pH 7.4, respectively. The temperature dependence of the secondary binding affinity (K
2) was large, suggesting that the association was not ionic. consequently, these results indicate that the secondary association may involve both electrostatic and hydrophobic interactions. Any modifications of cysteine, methionine and tryptophan residues on the BSA molecule destroyed the primary binding site, and the secondary binding site was also slightly affected ; thus, it is speculated that both binding sites may be associated with regions around these three amino acid residues on the BSA molecule. In conclusion, although the relationship between the coloration and the interaction of XA with BSA must be examined more closely, the present results suggest that the binding of XA to BSA contributes substantially to the amplification of the optical density in the color reaction of XA using 4-AAP.
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MASATOSHI YAMATO, TADATAKA ISHIKAWA, TOSHIO KOBAYASHI
1980 Volume 28 Issue 10 Pages
2967-2971
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The C
(1)-position of 1-ethoxyisochroman (3) is very susceptible to attack by various nucleophilic reagents. Reaction of 3 with various alcohols, such as benzyl alcohols, N, N-dimethylaminoethanol and ethyl lactate, gave corresponding 1-alkoxyisochromans (5, 7, 8, and 9). Reaction of 3 with phenols, such as phenol and methyl p-hydroxybenzoate, gave 1-(hydroxyphenyl) isochromans (11, 12, 13, and 16). Some monoalkoxybenzenes were unreactive with 3 but 1, 3-dimethoxybenzene gave corresponding 1-(dimethoxyphenyl) isochromans (14 and 15). Reaction of 3 with an emanine such as 1-morpholino-1-cyclohexene gave 2-(1-isochromanyl)-1-(4-morpholino) cyclohexene, which was hydrolyzed to give 2-(1-isochromanyl) cyclohexanone (17). Reaction of 3 with ketones, i. e., cyclohexanone and ethyl acetoacetate, gave 17 and ethyl α-(1-isochromanyl) acetoacetate (18), respectively.
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TAKUSHI KURIHARA, TSUTOMU TANI, HIROMI IMAI, KEIKO NASU
1980 Volume 28 Issue 10 Pages
2972-2979
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The reactions of ethyl 3-ethoxymethylene-2, 4-dioxovalerate (1a) and ethyl ethoxy-methyleneoxaloacetate (1b) with indole analogs (2, 14, 17-19) are described. Treatment of 1a, b with 2 in ethanol followed by refluxing in acetic anhydride afforded 3, 4, 10-trisubstituted pyrimido [1, 2-a] indoles (4a, b). Hydrogenation or nucleophilic addition of 4a, b was found to occur on the pyrimidine ring in a 1, 4-fashion. Compounds 1a, b were also reacted with 14 in ethanol under ice cooling to give the 3, 4-disubstituted 9H-pyrimido-[2, 3-b] indoles (15a, b) directly. Indole (17) or 2-methylindole (18) reacted with 1a (or 1b) to give a mixture of 3-indolylmethylene derivatives (20a, b and 21a, b) and tris-(3-indolyl)-methanes (23 and 24).
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TOSHIHIKO HASHIMOTO, TAIICHIRO WATANABE, YOICHI KAWANO, TERUO TANAKA, ...
1980 Volume 28 Issue 10 Pages
2980-2986
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Several β-hydroxy-α-halogeno-α-amino acid derivatives (3-5) were prepared from tert-butyl N-benzylideneglycinate (1) and α-haloketones or an α-haloaldehyde for utilization in the synthesis of 4, 5-dihydro-6H-1, 3-thiazine derivatives (7 and 12). An alternative thiazine synthesis starting from tert-butyl glycinate (13) was found to proceed stereoselectively, giving rise to 12a. The two thiazine derivatives 7 and 12a were converted into cephalosporin derivatives (10 and 17, respectively) by reaction with azidoacetyl chloride. The 7-azido-3-methylcephem derivative (17) was further led to 7-aminodeacetoxycephalosporanic acid (7-ADCA, 22).
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YAEKO KONDA, MASAYUKI ONDA, ATSUSHI HIRANO, SATOSHI OMURA
1980 Volume 28 Issue 10 Pages
2987-2993
Published: October 25, 1980
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Oxaline (1) has been isolated from Penicillium species Fg-234 and the structure of the compound (2) obtained by treatment of 1 with hydrochloric acid is deduced on the basis of spectral data. Neoxaline (9) isolated from Aspergillus japonicus Fg-551 has a structural framework similar to that of 1.
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AKIRA SHIRAHATA, MASANORI YOSHIOKA, MISAO MATSUSHITA, ZENZO TAMURA
1980 Volume 28 Issue 10 Pages
2994-3001
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Antigens of 3-O-methylcatecholamines (metanephrine, normetanephrine, 3-methoxy-tyramine) were prepared, keeping the methoxyl and hydroxyl groups of the benzene ring and the side chain intact. Rabbits were immunized with the metanephrine antigen and sufficient antiserum to develop a specific radioimmunoassay of metanephrine was obtained. The detection limit of metanephrine in the radioimmunoassay was 0.03 pmol. The radioimmunoassay was useful for the measurement of urinary metanephrine and of rat liver catechol-O-methyltransferase activity.
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NAOKI TAKEUCHI, HIDEO NAKAGAWA, SEISHO TOBINAGA
1980 Volume 28 Issue 10 Pages
3002-3006
Published: October 25, 1980
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The intramolecular condensation reaction of 8-phenyl-7-octene-2, 4, 6-trione (1) gave 10, which was subsequently transformed into the aromatic compounds 12 and 15. On the other hand, the intermolecular condensation reaction of 8-phenyl-2, 4, 6-octanetrione (2) afforded 17 and 18.
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NAOKI TAKEUCHI, SEISHO TOBINAGA
1980 Volume 28 Issue 10 Pages
3007-3012
Published: October 25, 1980
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A biogenetic-type synthesis of a dihydroisocoumarin, 3, 4-dihydro-8-hydroxy-3-phenylisocoumarin (1), from trans-cinnamaldehyde (13) modelled on the polyketide mode of biosynthesis is described.
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NAOKI TAKEUCHI, MASAYUKI MURASE, KAZUE OCHI, SEISHO TOBINAGA
1980 Volume 28 Issue 10 Pages
3013-3019
Published: October 25, 1980
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A biogenetic-type synthesis of (±)-phyllodulcin (2), a sweet principle of Hydrangea serrata SERINGE var. thunbergii SUGIMOTO, from 3-(3-benzyloxy-4-methoxyphenyl)-2-propenal (7) modelled on the polyketide mode of biosynthesis is described.
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KAZUYUKI WACHI, ATSUSUKE TERADA
1980 Volume 28 Issue 10 Pages
3020-3028
Published: October 25, 1980
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New rearrangement modes in the reaction of 4-chloro-2, 2-dimethyl-2H-1, 3-benzoxazine (1) with various α- and/or γ-substituted pyridine N-oxides are described. The benzoxazine moiety was introduced into the side chain and/or β-position of the pyridine ring, in addition to the α-position. possible mechanism of the reactions are discussed.
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OSAMU OGAWA, YUTAKA KAWAZOE, HIROYUKI SAWANISHI
1980 Volume 28 Issue 10 Pages
3029-3034
Published: October 25, 1980
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Treatment of carcinogenic and mutagenic 4-(N-hydroxy-N-methylamino) quinoline 1-oxide with acetic anhydride gave 4-(N-acetoxy-N-acetoxymethylamino) quinoline and 4-(N-acetoxy-N-methylamino) quinoline as the main products, with evolution of methane and carbon dioxide. This reaction is discussed in relation to the carcinogenicity and mutagenicity.
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HIROSHI HOSODA, HIROKO YOSHIDA, YASUO SAKAI, SHINICHI MIYAIRI, TOSHIO ...
1980 Volume 28 Issue 10 Pages
3035-3040
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The effects of the combination of antiserum and enzyme-labeled steroid and of the molar ratio of steroid to enzyme in the preparation of the conjugate on sensitivity and specificity in enzyme immunoassay of testosterone have been investigated. The enzyme labeling of testosterone was carried out by the N-succinimidyl ester method. Six testosterone derivatives were covalently linked to β-galactosidase at various molar ratios. The anti-testosterone antiserum used was that raised against the 4-O-hemiglutaroyl 4-hydroxytestosterone-bovine serum albumin conjugate. Immunological properties of the conjugate in both homologous and heterologous systems were examined. The number of steroid molecules incorporated per enzyme molecule markedly influenced the sensitivity in enzyme immunoassay. Cross-reactivity was also tested with 10 kinds of closely related steroids. The effect of site heterology on specificity was more significant than that of bridge heterology.
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YOSHIHISA MIZUNO, TAKESHI ENDO, AKIRA TAKAHASHI, ATSUKO INAKI
1980 Volume 28 Issue 10 Pages
3041-3048
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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A number of alkylating agents of the 4-substituted pyridine N-oxide series, such as (4-nitro-, 4-methylthio-, or 4-methoxy-2-picolyl 1-oxide) halide, have been prepared. Treatment of 2', 3'-O-(dibutylstannylene) uridine or 2', 3'-O-(dibutylstannylene) adenosine with the alkylating agents afforded the corresponding 2'-O- and 3'-O-(4-substituted 2-picolyl 1-oxide) nucleosides. 2'-O-(4-Nitro-2-picolyl 1-oxide) uridine was converted to the 4-methoxy-2-picolyl derivative on treatment with methanolic sodium methoxide at 60°. However, it was found that the treatment of adenosine with sodium hydride in DMF, followed by alkylation with (4-methoxy-2-picolyl 1-oxide) chloride gave a more satisfactory yield (56.4%) of 2'-O-(4-methoxy-2-picolyl 1-oxide) adenosine. 2'-O-(4-Methylthio-2-picolyl 1-oxide) adenosine could be similarly prepared in 36.7% yield. 4-Methoxy-2-picolyl protection was removable under milder conditions than 2-picolyl 1-oxide protection. Phosphorylation of 17 with phosphoryl chloride in triethyl phosphate gave the corresponding 5'-phosphate in 57.8% yield.
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FUMIO YONEDA, KINSHIRO TSUKUDA, KAZUO SHINOZUKA, FUMITOSHI HIRAYAMA, K ...
1980 Volume 28 Issue 10 Pages
3049-3056
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Treatment of aryl-bis (6-anilino-3-methyluracil-5-yl) methanes, which were prepared by the condensation of 6-anilino-3-methyluracils with arylaldehydes, with diethyl azodicarboxylate (DAD) in the presence of sulfolane led to the formation of the corresponding 10-arylprimido [4, 5-b] quinoline-2, 4 (3H, 10H)-diones (10-aryl-5-deazaflavins). Heating of the methanes alone in sulfolane without DAD gave the corresponding 5-aryl-5-deazaalloxazines. The oxidizing abilities of the 10-aryl-5-deazaflavins thus obtained were examined from both kinetic and synthetic viewpoints. The oxidations of benzyl alcohol and benzylamine by these 5-deazaflavins have been shown to recycle automatically, and more than 100% yield of benzaldehyde (based on the 5-deazaflavins) was obtained.
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MITSUHIKO MANO, TAKUJI SEO, KINICHI IMAI
1980 Volume 28 Issue 10 Pages
3057-3063
Published: October 25, 1980
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Hydrolysis of 1, 6-dihydro-6-oxo-2, 3-pyrazinedicarbonitrile (4) gave sodium hydrogen 1, 6-dihydro-6-oxo-2, 3-pyrazinedicarboxylate (6), which was converted to methyl 1, 6-dihydro-6-oxo-2-pyrazinecarboxylate (10) and methyl 4, 5-dihydro-5-oxo-2-pyrazine-carboxylate (12) via a sequence of reactions including decarboxylation and esterification. Although the synthesis of 4, 5-dihydro-5-oxo-2-pyrazinecarboxylic acid 1-oxide (2) from 12 was unsuccessful, its 6-methyl derivative 3 was synthesized from the 5-methyl analog of 4.
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NOBUO IKOTA, TAKAYUKI SHIOIRI, SHUNICHI YAMADA
1980 Volume 28 Issue 10 Pages
3064-3069
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Two coupling reagents for peptide synthesis, diphenyl phosphorazidate (DPPA) and diethyl phosphorocyanidate (DEPC), were tested using the solid-phase method. The reactivities of DPPA and DEPC were examined by coupling Boc-Ile with Gly-resin. In a comparison of these reagents with DCCD, these reagents showed higher reactivity than DCCD in DMF. The N-Boc derivative of melanocyte release inhibiting hormone was synthesized in good yield by the solid-phase method using these reagents. Racemization during fragment condensation on the polymer support was examined by coupling Boc-Gly-L-Ala with Leu-resin (Izumiya test).
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NOBUTOSHI TANAKA, HARUKA MAEHASHI, SUMIE SAITO, TAKAO MURAKAMI, YASUHI ...
1980 Volume 28 Issue 10 Pages
3070-3077
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Six new compounds were isolated from the methanol extract of Arachinoides standishii OHWI. Chemical and physicochemical studies showed their structures to be 1-(2, 4, 6-trimethoxyphenyl)-but-trans-2-en-1-one (I), 5, 7-dimethoxy-2-methylchromanone (II), 2-ethyl-5, 7-dimethoxychromanone (III), 5-hydroxy-dimethoxy-2-methyl-chromanone (IV), 3-β-D-allosyloxy-1-(2-hydroxy-4, 6-dimethoxyphenyl)-butan-1-one (V) and 8-carboxy-6-hydroxy-2, 5-dimethyl-2a, 3, 4, 5-tetrahydroacenaphthene (VI). Compound VI, named ryomenin, is the first sesquiterpene reported to possess a tetrahydroacenaphthene skeleton.
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ISAO KITAGAWA, TOSHIYUKI KAMIGAUCHI, HIDENOBU OHMORI, MASAYUKI YOSHIKA ...
1980 Volume 28 Issue 10 Pages
3078-3086
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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In the course of studies aimed at finding a new selective cleavage method for the glucuronide linkage in glucuronide-saponins, an electrolytic oxidation reaction has been found to be useful as an initial reaction for the desired selective cleavage method. The new cleavage method comprises an anodic oxidation of glucuronide-saponin, by which the carboxyl function is converted to an acetoxyl moiety, and a subsequent alkali treatment. It has also been found that the anodic oxidation causes selective oxidation of axial hydroxyl groups and allylic oxidation in the sapogenol moiety.
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YASUNORI MORIMOTO, MASAYUKI AKIMOTO, KENJI SUGIBAYASHI, TANEKAZU NADAI ...
1980 Volume 28 Issue 10 Pages
3087-3092
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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To examine the possibility of utilizing albumin microspheres containing 5-fluorouracil (5-FU) as a drug carrier, the antitumor activity of albumin microsphere-entrapped 5-FU against Ehrlich ascites carcinoma and solid tumor in mice was studied. After intraperitoneal injection of microsphere-entrapped 5-FU into Ehrlich ascites-bearing mice, the 5-FU level in the ascites was very high compared with that after injection of the free drug. The suppressive effect of microsphere-entrapped 5-FU on tumor growth in ascites-bearing mice was significantly higher than that of the free drug. After multiple-shot administration of microsphere-entrapped 5-FU to ascites-bearing mice, the increase in life-span was over 50% compared with a control. The therapeutic effect of microsphere-entrapped 5-FU on Ehrlich solid tumor after intratumoral injection was also studied. 5-FU level in the tumors of mice was significantly higher after intratumoral injection of microsphere-entrapped 5-FU than when the free drug was administered. The injection of microsphere-entrapped 5 FU, which was slowly released from the albumin microspheres in the solid tumor, caused a higher suppression of tumor growth at the inoculation site than administration of the free drug at the same dose. These results suggest that albumin microspheres containing 5-FU may represent an effective system for drug delivery, with prolonged action.
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IKUE KANEKO, YOSHIKAZU TAKEUCHI, YUMIKO YAMAOKA, YUMIKO TANAKA, TOMOAK ...
1980 Volume 28 Issue 10 Pages
3093-3097
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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A rapid and reliable thin-layer chromatographic (TLC) method for the quantitative analysis of ergothioneine in plasma and in various organs is presented. After extraction from biological materials with acetone/methanol (1 : 1), ergothioneine was separated by TLC and the spot corresponding to the compound with Rf 0.29 was quantified by scanning with a densitometer at 256 nm. The sensitivity of the assay was 0.05 μg/20μl of liver extract. This procedure should be useful in pharmacokinetic studies of ergothioneine in relation to its physiological role.
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MASANORI TAKAMATSU, MINORU SEKIYA
1980 Volume 28 Issue 10 Pages
3098-3105
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The reaction of 1-trichloromethyl-substituted amines with tert-butoxide has been shown to provide important entries into a number of groups of functionalized amines, i. e., 2, 2-dichlorovinylamines (which are also convertible into chloroynamines with a large excess of tert-butoxide), 2, 2-dichloroenamines, N-(α-dichloromethylbenzylidene)-amines and 2, 2-dichloroaziridines. The formation of the products in individual cases depends upon the structure of the amine substrate.
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YOSHIO SASAKI, TOSHIO TSUJIMOTO, HITOSHI TAKAI, MAKIKO SUGIURA
1980 Volume 28 Issue 10 Pages
3106-3113
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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^<13>C Substituent-induced chemical shifts (SCS) at the ipso and α positions of monosubstituted benzenes or methanes can be expressed by a linear combination of three kinds of empirical parameters, σ
i, σ
π, and ΔS°. ΔS° represents the difference of the entropy (due to the substituent) between the standard entropy S°of the substituted compound and that of the parent one. The following results were obtained. SCS
ipso=63.9·σ
i-3.9·σ
π+0.6ΔS°
+-0.4·ΔS°
-+3.8 (r=0.927, SD=4.9 ppm, n=13) SCS
α=162.1·σ
i-10.1·σ
π+1.2·ΔS°
+-0.3·ΔS°
-+2.3 (r=0.976, SD=4.9ppm, n=13) where + and - subscripts of ΔS° indicate electron-donating and -attracting groups, respectively. This treatment is also applicable for elucidation of the
13C SCS of analogous positions of many substituted aromatics and heteroaromatics, including ortho-disubstituted benzenes, and provides a reasonable and explicit chemical basis for the origin of the
13C SCS
ipso and SCS
α. The same treatment also provides an explicit chemical basis for Mulliken's electronegativity scale and the steric substituent constant, E
s.
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FULMER Y. SHEALY, MARTHA C. THORPE, WILLIAM C.JR. COBURN, JOE D. CLAYT ...
1980 Volume 28 Issue 10 Pages
3114-3117
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Comparisons of aristeromycin and the synthetic carbocyclic analog (C-Ado) of adenosine by several methods have been made because of anomalous results relating to aristeromycin that have appeared in the literature. Aristeromycin and C-Ado demonstrated the same behavior in four thin-layer chromatography and three high-pressure liquid chromatography solvent systems. Proton (100 MHz) and carbon-13 (25 MHz) nuclear magnetic resonance spectra of the two substances, determined under the same experimental conditions, are identical. Previously, comparisons of certain data had supported the identity of aristeromycin and C-Ado ; the data presented here show unequivocally that the synthetic and natural forms of the carbocyclic analog of adenosine are identical.
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TOSHIO MIYAZAKI, MOTOHIRO NISHIJIMA
1980 Volume 28 Issue 10 Pages
3118-3121
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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A water-insoluble β-D-glucan designated as OL-2, [α]
20D : -0.1° (0.5N NaOH), was isolated from a fungal crude drug, "Raigan" (dried fruiting body of Omphalia lepidescence). The results of periodate oxidation and methylation studies indicated that OL-2 possessed a highly branched structure consisting of 1, 3- and 1, 6-linked β-D-glucopyranosyl residues.
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TAKESHI MIKAMI, YOSHIO OKAWA, MINORU KADOWAKI, TATSUJI MATSUMOTO, SHIG ...
1980 Volume 28 Issue 10 Pages
3121-3123
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Chondroitin sulfate A (CSA) was found to show a strong synergistic effect with mitomycin C in combination therapy of sarcoma 180 ascites tumor implanted in dd mice. Namely, 50% of mice each implanted with 1×10
6 tumor cells of ascitic form were found to survive on combination treatment with mitomycin C (0.3 mg/kg/day, 5 times) and CSA (1 and 10 mg/kg/day, 5 times). Enhancement of acid phosphatase and β-D-glucuronidase activities of the peritoneal cells in the mice given the combination therapy was evident as compared with those of mice of the control group.
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MASAAKI KATAI, MASAYOSHI FUJIWARA, TADAMASA TERAI, HARUO MEGURI
1980 Volume 28 Issue 10 Pages
3124-3126
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Four new diterpenoids, pieristoxins H (I), I (II), J (III) and K (IV), were isolated from the leaves of Pieris japonica D. DON, together with the known diterpenoids, asebotoxin IV (XI) and VII (XII). The chemical structures of I and II were established to be 7-O-hydroxy and 14-O-lactoyl grayanotoxin III, respectively. III and IV were shown to be esters of pieristoxin G (VI), one of the most highly oxygenated grayanoids.
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YOSUKE OHKURA, MASATOSHI YAMAGUCHI, SHIRYU MIYAMOTO
1980 Volume 28 Issue 10 Pages
3127-3130
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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A sensitive phosphorimetric method for the assay of alkaline and acid phosphatases in biological materials is described. p-Nitrophenol, formed enzymatically from the substrate p-nitrophenyl phosphate, is extracted with ether and then determined phosphorimetrically in a mixture of ether and ethanolic potassium hydroxide. The method is rapid and very sensitive, and thus requires as little as 0.5-5μl of human serum or 0.1-5μg of protein of rat tissue with a detection limit for p-nitrophenol formed of as little as 10 pmol.
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CHIZUKO HAMADA, MASATAKE IWASAKI, YUTAKA MIBUCHI, KIYOSHI ZAITSU, YOSU ...
1980 Volume 28 Issue 10 Pages
3131-3134
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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A highly sensitive fluorimetric method is described for the enzymatic assay of free and total cholesterol in serum and of cholesterol in serum high-density lipoprotein. Cholesterol is oxidized by means of the cholesterol oxidase-mediated reaction to give hydrogen peroxide, which is measured by a fluorimetric technique using the peroxidase-tyramine system. Cholesterol ester is hydrolyzed by means of the cholesterol ester hydrolase-catalyzed reaction. High-density lipoprotein is separated by the dextran sulfate-Mg
2+ method. The method is simple, with good precision, and is extremely sensitive, requiring less than 1μl of serum for free or total cholesterol assay and less than 5μl of serum for high-density lipoprotein cholesterol assay.
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YOSHISUKE TSUDA, TAKEHIRO SANO
1980 Volume 28 Issue 10 Pages
3134-3137
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Three isomeric hydrogenation products of α-onocerin diacetate, onoceranediol diacetates-I, -II, and -III, were converted to the corresponding diones-I, -II, and -III, which exhibited a positive, a double humped, and a negative CD spectrum, respectively. The configurations of onocerane-I, -II, and -III were therefore elucidated as 8αH-14βH, 8αH-14αH, and 8βH-14αH, respectively.
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TAKAO MURAKAMI, HIROSHI WADA, NOBUTOSHI TANAKA, TAKASHI YAMAGISHI, YAS ...
1980 Volume 28 Issue 10 Pages
3137-3139
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The fronds of Plenasium banksiifolium (PR.) PR. contain stigmastan-3β, 5α-diol-6-one and its C
28-homolog, which are previously unreported in nature, together with the known compounds, ecdysone, ecdysterone, astragalin, stigmastan-3β, 5α, 6β-triol and its C
28-homolog.
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HARUAKI YAJIMA, KENICHI AKAJI, YORIKO HIROTA, NOBUTAKA FUJII
1980 Volume 28 Issue 10 Pages
3140-3142
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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3-Acyl derivatives obtained from the DCC condensation of N
α-protected amino acids and thiazoline-2-thione were found to be useful for peptide synthesis, in the same way as active esters.
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HISAYUKI KANAMORI, KAZUYOSHI MORIMOTO, NAOHIDE KINAE, ISAO TOMITA
1980 Volume 28 Issue 10 Pages
3143-3144
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The reaction between L-ascorbic acid and L-tryptophan in phosphate buffer (pH 7.0) at 37° for 2 months gave several reaction products of which 2 were mutagenic on S. typhimurium TA 100 in the absence of S-9 Mix. The structure of these 2 compounds were determined to be 1-(2-furyl)-pyrido [3, 4-b] indole and 1-(2-furyl) pyrido [3, 4-b] indole-3-carboxylic acid respectively by their mass spectral and
13C NMR analysis.
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GENICHIRO NONAKA, ITSUO NISHIOKA
1980 Volume 28 Issue 10 Pages
3145-3149
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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The homologous series of novel chalcan-flavan dimers, gambiriin A
1, A
2, A
3, B
1, B
2 and B
3, along with a proanthocyanidin dimer, gambiriin C (epiafzelechin-catechin), have been isolated from Gambir.
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TOSHIHIKO NAITO, CHIKARA KANEKO
1980 Volume 28 Issue 10 Pages
3150-3152
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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Irradiation of 4-hydroxy-2-quinolones (IVa and IVb) and their enolates in the presence of olefins provided intermolecular 2+2 addition products (V, VII, and VIII). The cycloaddition reactions were shown to be regioselective giving in all cases 1-substituted 1, 2, 2a, 8b-tetrahydrocyclobuta [c] quinolin-3 (4H)-ones. Base catalyzed retro aldol reaction of these cycloadducts afforded 1, 2, 3, 4, 5, 6-hexahydro-1-benzazocine-2, 6-diones (VI).
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YOSHIHISA YAMAMOTO, EIKO TOYOTA
1980 Volume 28 Issue 10 Pages
3153-3155
Published: October 25, 1980
Released on J-STAGE: March 31, 2008
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β
1 and β
2-8-Quinolinolato (triethylenetetramine) cobalt (III) chloride dihydrate, β-[Co (oxine) trien] Cl·2H
2O, have been isolated and characterized by analytical and spectroscopic methods.
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