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SHUNICHI HATA, KOJI MIZUNO, SUIICHI TOMIOKA
1968 Volume 16 Issue 1 Pages
1-5
Published: January 25, 1968
Released on J-STAGE: March 31, 2008
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In a previous paper, it was reported that the photodecomposition of menadione in aqueous solution was inhibited by the formation of the complex with various electron donors, and it was suggested that the complex formation among them might be attributed to charge-transfer force. The relationship between the structure of the complex in electronic aspect and the rate of stabilization were investigated by a molecular orbital method described in this paper. As a result, it was concluded that suppression of the photodecomposition of menadione with various electron donors is due to the charge transfer complex formation among them.
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TEISUKE OKANO, KANETO UEKAMA, KEN IKEDA
1968 Volume 16 Issue 1 Pages
6-12
Published: January 25, 1968
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The anomalous phenomena with respect to solubility and coloration, which are observed when aminopyrine is combined with either benzoic acid or salicylic acid, have been studied by solubility method, refractometry, and spectrophotometry, and the following findings have been obtained from the experimental data : (1) a formation of chargetransfer complexes of 1 : 1 molar ratio between aminopyrine and either benzoic acid or salicylic acid were presumed, (2) from the comparative study of pyrazolone derivatives, it was concluded that 4-amino or 4-substituted amino moiety on the pyrazolone portions was found to be indispensable for the complex formation, and (3) as there were considerable differences between stability constants obtained by solubility method and those obtained from Benesi-Hildebrand plots, it was presumed that charge-transfer force might not be a sole driving force of the interaction.
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NORIO TAKASUGI, KOICHI NAKAMURA, TAIZO HAYASHI, NOBUTAKA TSUNAKAWA, YA ...
1968 Volume 16 Issue 1 Pages
13-16
Published: January 25, 1968
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1) In situ and in vitro absorption experiments of nalidixic acid from the gastrointestinal tracts of rats were studied. 2) Results obtained from both methods were in favor of pH-partition hypothesis. Namely, absorption rate of unionized form of nalidixic acid was faster than that of ionized form of nalidixic acid. 3) Absorption rate of nalidixic acid in situ was faster than that of its drug in vitro by ten times. This might be due to the volume of solution, the length of the intestine and other physiological conditions of rats.
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HISAO YAMAMOTO
1968 Volume 16 Issue 1 Pages
17-19
Published: January 25, 1968
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1-(p-Chlorobenzoyl)-2-methyl-5-methoxy-3-indolylacetic acid, a potent antiinflammatory drug, was directly prepared from N
1-(p-chlorobenzoyl)-p-methoxyphenyl-hydrazine hydrochloride and levulinic acid in excellent yield by the new method. The recrystallization of 1-(p-chlorobenzoyl)-2-methyl-5-methoxy-3-indolylacetic acid from solvents gave crystals of polymorphism -α, β, and γ-types.
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TETSUJI KAMETANI, SEIICHI TAKANO, FUJINORI SASAKI, KAZUYA YAMAKI
1968 Volume 16 Issue 1 Pages
20-24
Published: January 25, 1968
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Reductive dealkylation of 1-(4-benzyloxybenzyl)-3, 4-dihydro-6, 7-dimethoxyiso-quinoline (I) with lithium and liquid ammonia gave mainly isococlaurine (II) together with coclaurine (IV) as by-product, which were characterized as their tribenzoate, respectively. Furthermore, reductive methylation of II with formalin and sodium borohydride, followed by methylation with methyl iodide, afforded (±)-lotusine iodide (VII). Furthermore, synthesis and optical resolution of 6-acetoxy-1-(4-benzyloxybenzyl)-1, 2, 3, 4-tetrahydro-2-methylisoquinoline (XII) was carried out to give our expected (+)-N-methylisococlaurine (VI), which was converted into the methiodide (VII), followed by treatment with sliver chloride, to give (-)-lotusine chloride (VIII). The total syntheses of (±)-isococlaurine and (±)-/(-) lotusine halides have been accomplished.
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MICHIYA KIMURA, MASAHIKO TOHMA, ITSUO YOSHIZAWA, HIROTOSHI AKIYAMA
1968 Volume 16 Issue 1 Pages
25-33
Published: January 25, 1968
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The structures of the steroidal saponins, convallasaponin-A (II), -B (IX), glucoconval-lasaponin-A (I) and-B (VIII), which were isolated from the flowers of Convallaria keisukei MIQ., Japanese lily of the valley, were studied and they were elucidated as convallagenin-A-(3)-α-L-arabopyranoside, convallagenin-B-(5)-α-L-arabopyranoside, convallagenin-A-(3)-β-D-glucopyranosyl (1→2
arab)-α-L-arabopyranoside, convallagenin-B-(3)-β-D-glucoypranoside, (5)-α-L-arabopyranoside, respectively.
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TETSUJI KAMETANI, SHIROSHI SHIBUYA, CHIHIRO KIBAYASHI
1968 Volume 16 Issue 1 Pages
34-38
Published: January 25, 1968
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The mass spectra of several kinds of 10, 11-dihydrodibenz [b, f] oxepine derivatives (I-VII) were investigated and the characteristic fragmentation patterns were revealed.
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HIROSHI HIKINO, YOJIRO SAKURAI, SEIICHIRO NUMABE, TSUNEMATSU TAKEMOTO
1968 Volume 16 Issue 1 Pages
39-42
Published: January 25, 1968
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Curcumenol, C
15H
22O
2, a new sesquiterpenic constituent of zedoary, Curcuma zedoaria (Zingiberaceae), has been shown to be represented by formula I on the basis of the following evidence. Chemical and physico-chemical properties of curcumenol and its derivatives indicate that curcumenol has a secondary methyl, a vinylic methyl on a trisubstituted double bond in which the carbon bearing a vinyl hydrogen is a to a quaternary carbon, an isopropylidene, and a hemiketal linkage whose carbon terminal is carrying no hydrogen. The carbon skeleton and the location of the hemiketal system have been established by the transformation to S-guaiazulene (V) and to the five-membered ring ketones (VII and VIII), respectively.
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HIROSHI HIKINO, KUNIO ITO, KEITARO AOTA, TSUNEMATSU TAKEMOTO
1968 Volume 16 Issue 1 Pages
43-51
Published: January 25, 1968
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Isopatchoul-9-en-5α-ol (VII) was hydrogenated using nickel catalyst in methanol to give 10α (H)-isopatchoulan-5α-ol (XII). Dehydration of the alcohol (XII) formed 10-epi-cyperene (IV) which on oxidation yielded 10-epi-cyperotundone (V). The alcohol (VII) was converted into 9α-acetoxy-10α (H)-isopatchoul-4-ene (XVII) via 10α (H)-isopatchoulane-5α, 9α-diol (XIV) by known methods. Hydrolysis of the unsaturated acetate (XVII) afforded 10α (H)-isopatchoul-4-en-9α-ol (XIX) which was oxidized to yield isopatchoul-4-en-9-one (XXI). Wolff-Kishner reduction of the ketone (XXI) furnished cyperene (III) which on oxidation gave cyperotundone (I) and patchoulenone (II).
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HIROSHI HIKINO, KEITARO AOTA, TSUNEMATSU TAKEMOTO
1968 Volume 16 Issue 1 Pages
52-55
Published: January 25, 1968
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From nutgrass, Cyperus rotundus (Cyperaceae), a new sesquiterpenic ketol has been isolated as the acetate and named sugeonol whose stereostructure I has been deduced from the following evidence. Spectral determinations of sugeonol and its acetate (II) indicate the presence of a 2-methyl-3-substituted-cyclopent-2-enone system. Chemical and physico-chemical properties of its derivatives (III and IV) have established that the hydroxyl group of sugeonol is situated at the γ-position of the α, β-unsaturated ketone system and in another cyclopentane ring. Oxidation of sugeonol with selenium dioxide has given the trione (VI) derived from cyperotundone (V) establishing the skeleton of sugeonol. The coupling constant between the C-6 and C-7 hydrogens shows the C-6 hydroxyl to be α-oriented.
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MASAO TOMITA, YOSHIAKI AOYAGI, YOSHIRO SAKATANI, KAZUYOSHI FUJITANI
1968 Volume 16 Issue 1 Pages
56-61
Published: January 25, 1968
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During the course of the studies for synthesis of II, the Ullmann reaction product of 8-bromoarmepavine, Bischler-Napieralski reaction of amide XI was carried out. Characterization of the product was effected by metallic sodium-liquid ammonia fission reaction. It was found that the isoquinoline ring-closure of such an amide formulated as XVIII occurred onto both o-and p-positions to the phenoxyl grouping, that is, the direction of the ring-closure was unexpectedly affected by substituent borne on 4-position of the phenoxyl grouping.
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MASAO TOMITA, KAZUYOSHI FUJITANI, YOSHIAKI AOYAGI
1968 Volume 16 Issue 1 Pages
62-69
Published: January 25, 1968
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The cyclobisamide IV was synthesized by intramolecular condensation of an ω-amino acid XIII or its corresponding p-nitrophenyl ester. Bischler-Napieralski cyclization of IV followed by NaBH
4 reduction and N-methylation gave a mixture of N-methyltetrahydroisoquinolines, from which dl-cycleanine (XIV), the diastereoisomer of cycleanine (XV), and a structural isomer of cycleanine (XVII) were isolated in crystalline state. The structural elucidations of the products were effected by IR, NMR, and mass spectral comparisons with the natural base. The structure of the isomeric product XVII was further proved by sodium-liquid ammonia cleavage reaction which afforded XVIII as the bisected product.
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MASAO TOMITA, KAZUYOSHI FUJITANI, YUKIO MASAKI, YASUKO OKAMOTO
1968 Volume 16 Issue 1 Pages
70-75
Published: January 25, 1968
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A synthesis of dl-cuspidaline and dl-4'-O-methylberbamunine was carried out through Bischler-Napieralski reaction followed by separation of the diastereoisomers. The configuration of each racemic diastereoisomer was ascertained by NMR comparisons with the bases of known absolute configuration.
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KEIZO INOUE, SHOSHICHI NOJIMA
1968 Volume 16 Issue 1 Pages
76-81
Published: January 25, 1968
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Bis (dipalmitoyl D, L-α-glycerylphosphoryl)-1, 3-glycerol disodium salt (I) was synthesized by the condensation of the silver salt of dipalmitoyl D, L-α-glycerophosphoric acid benzyl ester (XI) with 1, 3-diiodopropanol benzyl ether, followed by debenzylation with sodium iodide and hydrogenolysis with palladium black. Bis (dipalmitoyl D, L-α-glycerylphosphoryl)-1, 5-pentanediol disodium salt (III), bis (dipalmitoyl D, L-α-glycerylphosphoryl)-1, 4-butanediol disodium salt (IV), bis (dipalmitoyl D, L-α-glycerylphosphoryl)-1, 2-ethanediol disodium salt (VI) and bis (dipalmitoyl D, L-α-glycerylphosphoryl) methanediol disodium salt (VII) were synthesized similarly by the condensation of the silver salt (XI) with alkyl diiodide or dibromide, followed by debenzylation with sodium iodide. Bis (benzylphosphoryl)-1, 3-propanediol disodium (X) was synthesized by condensation of silver dibenzyl phosphate with alkyl diiodide, followed by debenzylation with sodium iodide.
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YASUO INUBUSHI, HISASHI ISHII, BOMPEI YASUI, MASASHI HASHIMOTO, TAKASH ...
1968 Volume 16 Issue 1 Pages
82-91
Published: January 25, 1968
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Serratinine, one of major alkaloids of Lycopodium serratum THUNB. var. Thunbergii MAKINO, is a tetracyclic new alkaloid possessing an expanded formula, C
10H
15(〓CH-OH)(〓CH-OH)(〓CH-CH
3)(-COCH
2-) (-N-). On the basis of chemical and spectroscopic data, the partial structure (C) for serratinine was proposed.
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YASUO INUBUSHI, HISASHI ISHII, BOMPEI YASUI, MASASHI HASHIMOTO, TAKASH ...
1968 Volume 16 Issue 1 Pages
92-100
Published: January 25, 1968
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On the basis of chemical and spectroscopic evidence, the plane structure for serratinine was completly established as the formula (I).
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YASUO INUBUSHI, HISASHI ISHII, BOMPEI YASUI, TAKASHI HARAYAMA
1968 Volume 16 Issue 1 Pages
101-112
Published: January 25, 1968
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The stereochemistry of serratinine containing its absolute configuration (E) has been established. The tentative biogenesis of serratinine from lycodoline type alkaloid has been also proposed.
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MASASHI TOMODA, SHOKO KATO
1968 Volume 16 Issue 1 Pages
113-116
Published: January 25, 1968
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The main oligosaccharide fraction obtained from the water extract of the tuberous roots of Ophiopogon japonicus KER-GAWLER var. genuinus MAXIMOWICZ was purified by the gel filtration on Sephadex G-25, and separated into three oligosaccharides. They were a heptasaccharide composed of one glucose unit and six fructose units, a hexasaccharide composed of one glucose unit and five fructose units, and a pentasaccharide composed of one glucose unit and four fructose units. Methylation and periodate oxidation studies showed that the each oilgosaccharide possesses the structure consisted of a chain of 2→1 linked D-fructofuranose units having a D-glucopyranose residue, joined by a type of sucrose bond, on the end.
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HIDEO KANO, IKUO ADACHI
1968 Volume 16 Issue 1 Pages
117-125
Published: January 25, 1968
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Nine bicyclic isoxazolines (IVa-g and Va-b) were prepared by 1, 3-dipolar cycloaddition of nitrile oxides to the following heterocyclic olefins : 2, 3-and 2, 5-dihydrofurans, 5-methyl-2, 3-dihydrofuran, 2, 3-dihydropyran, and N-acetyl-2-piperidein. Acid-catalized cleavage of IVa-d gave the corresponding 4-substituted 3-phenylisoxazoles (VIa-c and IIIg). Nine 4-aminoalkyl-3-phenylisoxazoles (IIIa-i) were prepared for pharmacological testings in comparison with those of 3- and 5-aminoalkyl analogs (I and II). Base-catalized cleavage of the adducts (IVa-c and Va) was also investigated and in some cases the lactones (XIIa and XIIb) were obtained besides the isoxazoles (VIa and VIb). In this connection the Hofmann reactions of the bicyclic isoxazoline-3-carbon-amides (IVe'and IVf') were studied.
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TOSHIO NAMBARA, MOTOHIKO KATO, REIKO IMANARI, TOSHIHIRO KUDO, nee IMAI
1968 Volume 16 Issue 1 Pages
126-130
Published: January 25, 1968
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The synthesis and Zimmermann reaction of some androsten-16-ones having double bond in ring A and/or B were described. These 16-oxosteroids showed weak Zimmermann color as compared with saturated androstan-16-one, probably due to long-range conformational effect. The structure of Zimmermann complex derived from 3β-hydroxy-androst-5-en-16-one was also discussed.
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AKIO HOSHI, KAZUO KURETANI
1968 Volume 16 Issue 1 Pages
131-135
Published: January 25, 1968
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The terephthalic acid (TPA) in the tissues of rat was assayed with radioactive terephthalic carboxyl-
14C acid. Two groups were fed the diet supplemented with 0.5% of TPA for one and three days respectively, and TPA content in each tissue was determined. No difference was found between the groups. TPA per unit weight or volume, in kidney and liver was higher than in plasma but in the rest of the tissues was lower (8-10 μg in plasma, 40-50 in kidney, 16-23 in liver, and 0.4-4.8 in the other tissues). A single dose of TPA was distributed rapidly in the tissues within 2 hr, and the ratios of TPA contents in the tissues showed the same tendency as the above case. The maximum contents of TPA in the tissues were observed within 2 hr after administration, while in brain after 8 hr. In the both cases, three-day feeding of the TPA diet and single oral administartion, a little amount of TPA was found after 24 hr only in several tissues. It already disappeared in more than half of the tissues. The biological half-lives of TPAs in the tissues, 1.2-3.3 hr, were calculated from the result of single oral administration. It is concluded that terephthalic acid is rapidly eliminated from the tissues and not accumulated in any of them.
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REIKO YANAI, KAZUO KURETANI
1968 Volume 16 Issue 1 Pages
136-141
Published: January 25, 1968
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The reductase and demethylase activities of rat liver fed the p-dimethylaminoazobenzene (DAB) diet with or without 2.5% disodium terephthalate (Na
2TPA) were measured to clarify the participation of terephthalic acid (TPA) in DAB metabolism. Male rats of Wistar strain were fed the three different experimental diets for 2 or 4 weeks, which were supplemented with 0.06% DAB, with 2.5% Na
2TPA and 0.06% DAB, or with 2.5% Na
2TPA (DAB, TPA plus DAB or TPA diets, respectively). Although neither reductase nor demethylase activities were increased by the TPA diet feeding, they were maintained by TPA plus DAB diet when compared with the notable decrease by DAB feeding. From these findings, it was suggested that Na
2TPA did not activate these enzymes, but prevented the decline of their activities induced by DBA. The effects of two TPA derivatives, dimethyl terephthalate (DMT) and β-hydroxyethyl terephthalate (BHET), on these enzyme systems were also studied. DMT elevated the reductase activity only when it supplemented the basal diet. BHET fairly increased the reductase activity when it was given with DAB. Both derivatives were not superior to Na
2TPA in their efficacies. Furthermore, the content of protein bound aminoazo dyes in the liver of rat fed DAB plus TPA or BHET (but not DMT) were much lower than the content on the DAB diet feeding. The potentiating effect of TPA on DAB metabolism may be supported by this result.
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GENZO OKUSA, SHOZO KAMIYA
1968 Volume 16 Issue 1 Pages
142-147
Published: January 25, 1968
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5-Pyridazinol 1-oxide was synthesized from 5-methoxypyridazine 1-oxide which was obtained from 3, 4-dichloro-5-methoxypyridazine 1-oxide. The Mannich reaction of 5-pyridazinol 1-oxide using 37% formalin and piperidine gave 6-piperidinomethyl-5-pyridazinol 1-oxide in 40% yield. Treatment of 5-pyridazinol 1-oxide with excess amounts of the reagents gave 4, 6-di (piperidinomethyl)-5-pyridazinol 1-oxide in 56% yield. The alkylaminomethylated positions in these Mannich bases were determined by NMR spectroscopy.
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TAKAYUKI NAITO, SUSUMU NAKAGAWA, KIYOSHI TAKAHASHI
1968 Volume 16 Issue 1 Pages
148-159
Published: January 25, 1968
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Preparations of 5-methyl-3-phenylisothiazole-4-carboxylic acid (Xa) and related compounds are described. 3-(Halogen-substituted phenyl)-5-methylisothiazole-4-carboxylic acids were also obtained by halogenation of 4-cyano-5-methyl-3-phenylisothiazole (VIIa), followed by hydrolysis. 5-Bromo-3-phenylisothiazole-4-carboxylic acid (XV) was prepared, and converted into the 5-methylthio derivative (XVI) which was oxidized to the corresponding sulfoxide (XVII) and sulfone (XVIII).
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TAKAYUKI NAITO, SUSUMU NAKAGAWA, KIYOSHI TAKAHASHI
1968 Volume 16 Issue 1 Pages
160-164
Published: January 25, 1968
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Nitration of 4-substituted-3-phenyliosthiazoles (I, II, III, and IV) with fuming nitric acid and sulfuric acid yielded exclusively the corresponding 3-m-nitrophenyl derivatives (VI, VII, VIII and IX), while nitration of 3-phenylisothiazole (V) gave 3-p-nitrophenylisothiazole (Xa) and 3-m-nitrophenylisothiazole (Xb). Reduction of 5-methyl-3-m-nitrophenylisothiazole-4-carboxylic acid (IX) afforded the corresponding amino derivative (VII), which was diazotized and subjected to the Sandmeyer Reaction to give the corrsponding 3-m-chlorophenyl (XIV) and 3-m-bromophenyl (XV) derivatives. Preparation of the 3-m-methoxyphenyl derivative (XVII) was also described.
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TOSHIMITSU UJIIE
1968 Volume 16 Issue 1 Pages
165-171
Published: January 25, 1968
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MASARU AOKI, HIROSHI FUKUCHI, SETSUKO NAKAYA
1968 Volume 16 Issue 1 Pages
171-176
Published: January 25, 1968
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DAISUKE SATOH, JUNKO MORITA
1968 Volume 16 Issue 1 Pages
178-180
Published: January 25, 1968
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BUNSUKE UMEZAWA, OSAMU HOSHINO, YASUO TERAYAMA
1968 Volume 16 Issue 1 Pages
180-182
Published: January 25, 1968
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HARUAKI YAJIMA, HIROKI KAWATANI
1968 Volume 16 Issue 1 Pages
182-184
Published: January 25, 1968
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AKIE NAKAMURA, MASAKO MAEDA, KAYOKO IKEGUCHI, TOSHIO KINOSHITA, AKIO T ...
1968 Volume 16 Issue 1 Pages
184-186
Published: January 25, 1968
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YUKIHIKO KAMEDA, SHOICHI KANATOMO, YUKIO KAMEDA, YOKO SAITO
1968 Volume 16 Issue 1 Pages
186-187
Published: January 25, 1968
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HIROMICHI SAEKI, TADAHIRO IWASHIGE, EIJI OHKI
1968 Volume 16 Issue 1 Pages
188-189
Published: January 25, 1968
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ITIRO YOSIOKA, ISAO KITAGAWA, KATSUHIKO HINO, AKIKO MATSUDA, YOSHIKO N ...
1968 Volume 16 Issue 1 Pages
190-193
Published: January 25, 1968
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