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HIDEAKI UMEYAMA, AKIRA IMAMURA, CHIKAYOSHI NAGATA
1975 Volume 23 Issue 12 Pages
3045-3055
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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From the results of molecular orbital study on the effects of substituents on the proton transfer from Ser-195 to His-57 in the "charge relay system"of α-chymotrypsin, the acylation step is thought to be as follows : (1) the carbonyl carbon of the substrate approaches to the oxygen of Ser-195 in the "charge relay system" ; (2) after the proton of Ser-195 is transferred to N
■2 of His-57 by the trigger of the interaction between the oxygen of Ser-195 and the carbonyl carbon of the substrate, the oxygen of Ser-195 covalent-bonds with the carbonyl carbon of the substrate ; (3) acyl-Ser-195 rotates by 120 degrees around the serine C
α-C
β bond. The rotation of acyl-Ser-195 must be accompanied with the deeper movement of the aromatic part of the substrate in the pocket of α-chymotrypsin. Moreover, it was shown that a significant role in accelerating the proton transfer from Ser-195 to His-57 was played by the interaction between the oxygen of Ser-195 and carbonyl carbon of substrate, not by two hydrogen bonds between the carbonyl oxygen and the backbone-NH-groups of Gly-193 and Ser-195.
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MASANORI NAGATA, SUMIKO MIYAKOSHI, HIROSHI TAKEZAWA, KATSUHIDE MATOBA, ...
1975 Volume 23 Issue 12 Pages
3056-3061
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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3, 4-Dimethoxyphenethyl hydrazine (III), reacting with ethyl γ-oxopimelate, was converted into the hydrazone (IV), which was reduced to the corresponding hydrazine (V). V was then subjected to the intramolecular ring closure to afford (VI), which showed dimorphism. VI was subjected to the Bischler-Napieralski reaction accompanied with the reduction to afford the titled compound (VIII), which was also obtained by the Bischler-Napieralski ring closure of V followed by the reduction and the ring closure to furnish the D-ring of the diazasteroid. The stereochemistry of VIII was discussed based on its nuclear magnetic resonance data and its mercuric acetate oxidation.
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MASASHI KUROZUMI, NAOKI NAMBU, TSUNEJI NAGAI
1975 Volume 23 Issue 12 Pages
3062-3068
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Investigations were made to prepare the inclusion compounds of the non-steroidal antiinflammatory drugs and additionally other slightly water soluble drugs with α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD) in solid powdered form by the freeze-drying and the coprecipitation methods. The freeze-drying method was successful in obtaining the inclusion compounds of all the test drugs with β-CD and also some of them with α-CD by obtaining their aqueous solutions with addition of aqueous ammonia before the process, with a very good yield compared with the usual coprecipitation method. The drugs included by the coprecipitation method seemed to have fittable molecular sizes. The result showed that the coprecipitation method might be originally inferior to the freeze-drying method in obtaining the inclusion compounds of drugs in powdered form. It was shown by X-ray diffractometry that the inclusion compounds obtained by the freeze-drying method were amorphous. Clear differences in infrared (IR) absorption spectroscopy and differential calorimetry were observed between the inclusion compounds and the physical mixtures of drug/β-CD.
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TAEKO TANAKA, KAZUMI TANEDA, HIROSHI KOBAYASHI, KATSUHIKO OKUMURA, SHO ...
1975 Volume 23 Issue 12 Pages
3069-3074
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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In order to examine the possibility of utilizing liposomes as drug carriers, the fate of
14C-inulin and
131I-insulin entrapped in negatively or positively charged liposomes after intravenous injection was investigated in rats. The clearance rate from plasma of
14C-inulin entrapped in liposomes was faster than that of free
14C-inulin, and decreased with the increase of the liposomal concentration. Further, liposome-entrapped drugs were recovered mainly in the liver, especially in Kupffer cells, as well as the spleen, and such hepatic accumulation was reduced by pretreatment with methyl palmitate to a great extent. From these results, it appears that the large proportion of drugs entrapped in liposomes is delivered into the RES intact and their distribution pattern depended on the liposomal surface properties, but not on the kind of drugs entrapped.
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NOBUO KUNISHIGE, KUNIO KAWAMURA, MASAYUKI MUROI, TOYOKAZU KISHI
1975 Volume 23 Issue 12 Pages
3075-3080
Published: December 25, 1975
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Macrolide antibiotic producing organisms produce usually several homologous components. A quantitative analysis of these components has not been reported because of their physicochemical similarity. A method for quantitative analysis of a mixture of macrolide components was established by the use of thin-layer chromatography and ultraviolet (UV) absorption spectrometry. 9-Propionylmaridomycin which has no absorption maximum in UV and visible region was converted into its thiosemicarbazone exhibiting an absorption maximum at 271nm. The thiosemicarbazones formed are separated by silica gel thin-layer chromatography using a solvent system of hexane-isopropyl ether-EtOH-H
2O (1 : 4 : 3 : 2). The composition ratio of each component was calculated from the absorbance of each extract of separated fraction. By this method recovery rate was almost quantitative.
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AKIRA ITO, RIEKO TAKAHASHI, YOSHIHIKO BABA
1975 Volume 23 Issue 12 Pages
3081-3087
Published: December 25, 1975
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Benzyloxycarbonyl (Cbz)-amino acid esters were reduced to the corresponding α-aminoaldehydes with diisobutylaluminum hydride. Comparison of specific rotation of the Cbz-aminoalcohols, which were derived from the aldehydes by sodium borohydride reduction, with that of the optically pure material showed that chromatography on a silica gel caused marked racemization in the Cbz-α-aminoaldehyde through keto-enol tautomerism. Cbz-S-Bzl-cysteinal was liable to racemize to a great extent. On the other hand, little racemization occurred in Cbz-N
G-nitroargininal. This fact might be accounted for the characteristic cyclic carbinolamine structure of the argininal derivative. The semicarbazones prepared from the crude Cbz-α-aminoaldehydes could be reproduced to the initial aldehydes without racemization. These semicarbazones might be used as good starting materials in peptide aldehyde synthesis.
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TSUGIO SHIMAMOTO, YASUAKI OGAWA
1975 Volume 23 Issue 12 Pages
3088-3094
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The interaction of methyl p-hydroxybenzoate (MP) with polyoxyethylene dodecyl ethers having a variety of numbers of oxyethylene units in the homogeneous chain was investigated by ultrafiltration and nuclear magnetic resonance spectrometry. The results obtained suggested the existence of two kinds of interaction mechanisms between the preservative and the nonionic surfactant micelle. The binding parameters in each class were calculated using a multiple regression technique. In the primary class of sites, the interaction obeyed the form of the Langmuir type adsorption and the bound molecules of MP were probably located at the interface of the hydrocarbon core and the polyoxyethylene mantle of the micelles. Moreover, in the second class of sites, the interaction could be described as a simple partition between the micelles and the aqueous phase and the preservative molecules seemed to be situated in the polyoxyethylene mantle.
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TAKAKO YOKOZAWA, HACHIRO SENO, HIKOKICHI OURA
1975 Volume 23 Issue 12 Pages
3095-3100
Published: December 25, 1975
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A single intraperitoneal administration of the extract (fraction 4) from the roots of Panax ginseng C.A. MEYER increased the incorporation of labeled precursor into total lipid of liver and epididymal adipose tissue in rats. A maximum increase in both tissues was found 4 hr after the treatment, but the response curve to ginseng extract was not the same. In addition, accumulation of lipid was observed in adipose tissue, showing a maximum increase 6 to 8 hr after the treatment with fraction 4. In contrast, the concentration of serum triglycerides was slightly decreased after treatment with fraction 4. Further, reduction of blood sugar level and liver glycogen content by ginseng extract administration was observed. Based on these results, the metabolic interrelation induced by ginseng extract was discussed.
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MASATOSHI YAMATO, KUNIKO HASHIGAKI, JUNICHI UENISHI, IKUKO YAMAKAWA, N ...
1975 Volume 23 Issue 12 Pages
3101-3105
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Structural modification of the ethylene moiety (B-moiety) of β-(3-hydroxy-4-methoxyphenyl) ethylbenzene (1), which constitute an essential part of phyllodulcin molecule, was attempted to make the relationship between structure and sweet taste clearer, and compounds (3), (4), (5), (6), (7), and (8) were synthesized. The compound (5) had strong sweet taste, 6 had faint sweet taste and 3, 4, 7, and 8 were tasteless. On the base of these data, the taste of these compound was discussed in the connection with the favored conformation of them.
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AKIRA ITO, RIEKO TAKAHASHI, CHIEKO MIURA, YOSHIHIKO BABA
1975 Volume 23 Issue 12 Pages
3106-3113
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Some of the leupeptin Ac-LL analogs, in which the argininal moiety was replaced by aromatic aminoaldehydes, were synthesized starting from benzyloxycarbonyl-α-amino-aldehyde semicarbazones derived from benzyloxycarbonyl amino acid esters by the reduction with diisobutylaluminum hydride. The racemization of the aldehyde part of the purified analogs was examined using the analytical ion exchange chromatography of diastereomers produced by the condensation of L-aspartic acid with aminoalcohols, which were obtained by the sodium borohydride reduction of the synthesized peptide aldehydes followed by acid hydrolysis. The results demonstrate that racemization occurs only to a limited extent, when these starting materials are used and careful purifications of the products are carried out.
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HIROTERU SAYO, AYAKO MORIMOTO
1975 Volume 23 Issue 12 Pages
3114-3118
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Anodic oxidation of benzenesulfon-p-anisidide (I) was investigated by cyclic voltammetry and controlled potential electrolysis at a glassy-carbon electrode in aqueous acetonitrile solution. I showed a single anodic wave below pH 7, and two anodic waves above pH 7.5. Electrolysis of I at pH 3.9 gave a coulometric n-value of two, and p-benzoquinone and benzenesulfonamide were obtained. Electrolysis of I at pH 10.5 and the potential of the first wave gave an n-value of about one, and N, N'-dibenzenesulfonyl-N-(4'-methoxy-phenyl)-5-methoxy-o-phenylenediamine (IV) was obtained. The formation of IV was interpreted in terms of a head-to-tail coupling of the free radical of I.
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SHORYO HAYASHI, TAKASHI SAKAGUCHI
1975 Volume 23 Issue 12 Pages
3119-3124
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Effects of 3, 7-dimethyl-1-(5-oxo-hexyl)-xanthine (BL 191) on lipolysis in rat epididymal adipose tissue were investigated by comparison with those of theophylline. BL 191 blocked the activity of phosphodiesterase in the 105000×g supernatant prepared from rat epididymal adipose tissue, and the type of inhibition was noncompetitive with the K
i value of 2.1mM. Furthermore, BL 191 elicited a dose-dependent lipolytic response, as did theophylline, and the response increased 1, 3-fold and about 3-fold over the basal activity at 2mM and 5mM, respectively. BL 191 as well as theophylline potentiated the lipolytic action of epinephrine and increased adenosine 3', 5'-monophosphate (cyclic 3', 5'-AMP) levels in adipose tissue. BL 191, in a concentration producing no effects by itself (10
-4M), together with epinephrine (10
-6M) caused a 38-fold increase in cyclic 3', 5'-AMP levels and an about 5-fold increase in lipolytic effecs.
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YASUO NAKAMOTO, MITSURU HASHIDA, SHOZO MURANISHI, HITOSHI SEZAKI
1975 Volume 23 Issue 12 Pages
3125-3131
Published: December 25, 1975
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The enhanced delivery into lymph of bleomycin was studied by the intraperitoneal and intramuscular injection of oil emulsified preparations. A comparison of concentration of bleomycin in thoracic duct lymph showed that W/O emulsion was the most effective and followed by O/W emulsion. An application of spray drying powder was also attempted to the enhanced delivery, and the lymph concentration was increased as compared with the injection of the aqueous solution although lower than O/W liquid emulsion. A measuring of binding to oil particles indicated that approximately 40% of bleomycin was bound to the particles of O/W liquid emulsion and of reconstituted emulsions prepared from drying products. Furthermore the clearance rates of bleomycin from the muscle were delayed about one half by W/O, O/W and reconstituted emulsion. The possible mechanism of enhanced delivery into lymph was discussed in this paper.
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KENGO ARAKI, SHINRO TACHIBANA, MIKIO UCHIYAMA, TERUMI NAKAJIMA, TADASH ...
1975 Volume 23 Issue 12 Pages
3132-3140
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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A new active peptide xenopsin was obtained from the skin of Xenopus laevis, possessing a potent contractile activity on rat stomach strip in vitro. The amino acid sequence of xenopsin has been found to be pyrGlu-Gly-Lys-Arg-Pro-Trp-Ile-Leu-OH. The contractile responses on a rat stomach strip were proportional to the peptide doses. This peptide also had a moderate contractile activity on guinea-pig ileum but the response was not reproducible. Intravenous injection of this peptide lowered arterial blood pressure of the anesthetized rat but a prompt and intense tachyphylaxis was observed. Xenopsin and several of its analogous peptides were synthesized and their biological activities were determined. Essential sequence that displayed the activity was Arg-Pro-Trp-Ile-Leu-OH. In addition to xenopsin and caerulein, it was confirmed that the skin of Xenopus laevis contained biological active amines, serotonin, buffotenidine, and N-methylserotonin.
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HIROSHI HOSODA, KOUWA YAMASHITA, TOSHIO NAMBARA
1975 Volume 23 Issue 12 Pages
3141-3145
Published: December 25, 1975
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The titled compounds (1, 2) have been prepared from estrone by the new synthetic routes. Introduction of a hydroxyl group into the 15α-position was readily attained by hydroboration of the 14, 15-or 15, 16-double bond with diborane and subsequent oxidation of the organoborane with alkaline hydrogen peroxide. In the preparation of 1 the dimethyl-tert-butylsilyl function was conveniently employed for the purpose of protecting the 3, 17β-hydroxyl groups.
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NAOKI KAMO
1975 Volume 23 Issue 12 Pages
3146-3150
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Relation between the activity and mobility of small ions in charged membrane is derived theoretically using a cell model, where each macro-ion attached to the membrane matrix is assumed to be located at the center of individual cell. The result obtained shows that the mobilities of small ion are linearly proportional to the activity coefficient of the corresponding ion species in the membrane. This conclusion is consistent with the experimental results reported in a previous series of papers.
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TAKAJI KOYAMA, TAKASHI HIROTA, FUMIKO YAGI, SHINJI OHMORI, MASATOSHI Y ...
1975 Volume 23 Issue 12 Pages
3151-3153
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Condensation of 1-tetralone (I) with trisformylaminomethane gave 5, 6-dihydrobenzo- [h] quinazoline (II) which was dehydrogenated with sulfur to benzo [h] quinazoline (III). Condensation of 2-tetralone (IV) with formamide or trisformylaminomethane gave 5, 6-dihydrobenzo [f] quinazoline (V) which was dehydrogenated with sulfur to benzo [f] quinazoline (VI).
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KIYOMI KIKUGAWA, ISAKO KAWADA, MOTONOBU ICHINO
1975 Volume 23 Issue 12 Pages
3154-3161
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Treatment of cytidine (I) with sulfuryl chloride in acetonitrile and pyridine gave 2, 2'-anhydro-5, 5'-dichloro-5'-deoxy-1-β-D-arabinofuranosylcytosine (II) as a main product, which was subsequently converted into 5, 5'-dichloro-5'-deoxy-1-β-D-arabinofuranosylcytosine (III). The reaction of 1-β-D-arabinofuranosylcytosine (IX) with the reagent afforded 2, 2'-anhydro-5, 5'-dichloro-5'-deoxy-1-β-D-lyxofuranosylcytosine (XII). Uridine (XIV) was converted into 2, 2'-anhydro-5, 5'-dichloro-5'-deoxy-1-β-D-arabinofuranosyluracil 3'-O-chlorosulfate (XVI), which upon heating in water was transformed into 5, 5'-dichloro-5'-deoxy-1-β-D-lyxofuranosyluracil (XVII). Treatment of I with the reagent in hexamethylphosphoroamide gave poly-sulfated derivatives of I.
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HIROMI TERAUCHI, AKEMI YAMASAKI, SHOJI TAKEMURA
1975 Volume 23 Issue 12 Pages
3162-3169
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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In order to confirm the orientation of the addition of N, N-dibromobenzenesulfonamide (DBBS) to olefins, the reactions of DBBS with asymmetric alkenes and α, β-unsaturated carboxylic acid esters were examined. The additions of DBBS to alkenes proceeded by Markownikoff's fashion, and those to the unsaturated esters gave the products which have bromines at α-carbons and sulfonamido groups at β-positions. The reactions of DBBS with 1-methylcyclohexene, 2, 3-dimethyl-1-butene, and 1, 1-dimethyl-1-butene gave I, III, and IV, respectively. The reactions of DBBS with methyl methacrylate, methyl acrylate, and methyl crotonate gave V and VI, VIII and IX, and XI and XII, respectively.
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SADAO NISHIGAKI, MISUZU ICHIBA, SHINOBU FUKAZAWA, MICHIKO KANAHORI, KA ...
1975 Volume 23 Issue 12 Pages
3170-3177
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The reaction of nalidixic acid (1) with thionyl chloride afforded 1-ethyl-1, 4-dihydro-4-oxo-7-trichloromethyl-1, 8-naphthyridine-3-carboxylic acid (2) in high yield. Several 7-N-substituted carbamoyl-(3-47) and 7-(5-substituted benzimidazol-2-yl)-1-ethyl-1, 4-dihydro-4-oxo-1, 8-naphthyridine-3-carboxylic acids (48-52) were prepared by treatment of 2 with appropriate amine and o-phenylenediamine, respectively. Alkaline treatment of 2 provided unexpected 7-hydroxy derivative (54), while the action of conc. sulfuric acid gave 3, 7-dicarboxylic acids (53). The in vitro antibacterial activity and structural requirements of these compounds for broad spectrum activity were also discussed.
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KATSUHIKO NAGAHARA, KANAME TAKAGI, TAKEO UEDA
1975 Volume 23 Issue 12 Pages
3178-3183
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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La benzamidoxime et quelques uns de ses derives conduisent, par chauffage pendant une heure dans l'ethanol, avec des anhydrides isatoiques a des N-(amino-2 benzoyl) benzamidoximes. Lorsqu'on prolonge le temps de chauffage de la reaction, on obtient un melange de N-(amino-2 benzoyl) benzamidoximes et d'(amino-2 phenyl)-5 phenyl-3 oxadiazoles correspondants. La presence de base dans le milieu reactionnel favorise la transformation des benzamidoximes en oxadiazoles. Si l'on realise les memes reactions en presence d'ethylate de sodium, on n'observe que la formation d'oxadiazoles. Les structures des composes obtenus sont determinees principalement par les etudes spectroscopiques infrarouges, de resonance magnetique nucleaire et de masse.
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SHUNJI NARUTO, ATSUSUKE TERADA
1975 Volume 23 Issue 12 Pages
3184-3188
Published: December 25, 1975
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Bischler-Napieralski reaction of N-(2-indol-4-ylethyl) acetamide (II) gave pyridoindole (III) and azepinoindole (IV), N-(2-indol-5-ylethyl) acetamide (V) afforded pyridoindoles (VI and VII), N-(2-indol-6-ylethyl) acetamide (XIII) gave pyridoindoles (XIII and XIV) and N-(2-indol-7-ylethyl) acetamide (XIX) yielded pyridoindole (XX). These reactivity of indole was supported by calculated charge density with CNDO/2.
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AKIRA TAHARA, MASAYUKI SHIMAGAKI, MASAYOSHI ITOH, YOSHIHIRO HARIGAYA, ...
1975 Volume 23 Issue 12 Pages
3189-3202
Published: December 25, 1975
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The steroidal D-rings (31 and 37), along with 32 and 38, were synthesized by the use of a part or whole of the carbon units of the isopropyl group of l-abietic acid (1), via oxidation of 18 or 20 with Tl (ONO
2)
3, or addition reaction of 20 with 1, 1-dichloroethylene, and modifications of the functionality, followed by Friedel-Crafts cyclization. Cyclization to the 14-position (formation of 31 or 37) in 30 or 35 was always predominant over that to the 12-position (formation of 32 or 38). In attempts for functionalization of the isopropyl group with Pb (OAc)
4, 9, a hopeful intermediate to syntheseze quinoid diterpenes, was obtained via 3, 4, 5 and 6. RuO
2 reduction of 6 and successive Pb (OAc)
4 oxidation to 17 is also described.
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KOUICHI YOSHIOKA, GIICHI GOTO, HIROSHI MABUCHI, KENTARO HIRAGA, TAKUIC ...
1975 Volume 23 Issue 12 Pages
3203-3207
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The mixture of enol acetates (II and III) of 16-acetyl-estrone-3-methyl ether underwent hydrogenolysis under high pressure (100kg/cm
2) of hydrogen in the presence of Raney Ni to form the 16β-ethyl-17β-ol compound (X) in high yield. The mechanism of hydrogenolysis was discussed. This facile and stereoselective introduction of 16β-ethyl and 17β-hydroxy groups was applied to the synthesis of 16β-ethyl-19-nortestosterone (TSAA-291, XIX), which shows strong antiandrogenic activity.
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MICHIO KIMURA, TAKESHI NAKAJIMA, TOSHIO ATSUMI, YOSHIHIKO KOGA, HISAO ...
1975 Volume 23 Issue 12 Pages
3208-3214
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The cyclization of 1-(substituted-allyl)-1, 2, 5, 6-tetrahydro-2-benzylpyridines with Lewis acid was found to give novel benzomorphans consisted of a new four-ring system. The synthesized compounds have been found to possess a potent analgesic activity with low toxicity in mice in general, and some of them are several times as potent as pentazocine. The relationships between the analgesic activity and the molecular conformation of these compounds were also suggested in this paper.
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EIJI OWADA, KATSUYUKI TAKAHASHI, TAKAICHI ARITA, RYOHEI HORI
1975 Volume 23 Issue 12 Pages
3215-3222
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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In order to clarify the renal tubular reabsorption of sulfonamides, the effects of urinary pH and urine flow rate on the renal excretion of four sulfonamides were examined in rabbits. The excretion ratio (ER) of sulfanilamide, sulfamethoxypyridazine and sulfamethizole were little or not affected by modification of the urinary pH, but that of sulfisoxazole was considerably influenced. It was also demonstrated that the ER of these sulfonamides except for sulfamethizole increased with increasing urine flow rate. Only sulfamethizole exhibited as the excretion pattern which was dependent on its plasma level. These different responses to the influencing factors may be described on the basis of their secretion characteristics, reabsorption by non-ionic diffusion and their lipoid solubility.
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MAMORU SUGIURA, AKIRA ITO
1975 Volume 23 Issue 12 Pages
3223-3227
Published: December 25, 1975
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Dextranase (EC 3.2.1.11) of Brevibacterium fuscum var. dextranlyticum was immobilized by the fixation to Sepharose 4B activated with cyanogen bromide. The specific activity of the preparation was about 30%, compared with that of native dextranase. The immobilization led to increase pH stability, although thermal stability. optimum pH and temperature were similar to that of the native enzyme, respectively. The immobilized dextranase was very stable on storage at 4°and retained more 90% of the initial activity in the 9th weeks whereas the native enzyme lost about 50% of it after 6 days later. Relative activity of immobilized dextranase on dextrans with various molecular weights decreased relatively for an increase in molecular weight. Michaelis constant (Km) of the immobilized enzyme was larger 2-5 times than that of the native enzyme on each molecular weight of dextran. Action pattern of dextranase was not effected by the immobilization. Immobilized dextranase was very stable in a column reaction and suitable for continuous enzyme reaction, and also found to keep steady activity by the repeated use. These properties of immobilized dextranase of B. fuscum were very similar to those of the immobilized enzyme of P. funiculosum.
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MASAKI OTAGIRI, KANETO UEKAMA, KEN IKEDA, SHINJI ONODERA
1975 Volume 23 Issue 12 Pages
3228-3233
Published: December 25, 1975
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The solubilization of barbiturates by chloral hydrate was investigated by solubility measurement and a molecular interaction was found to be due to the hydrogen bonding from infrared and
1H-and
13C-nuclear magnetic resonance (NMR) spectra. In water the stability constants of 1 : 2 complex, K
1 : 2' were larger than those of 1 : 1 complex, K
1 : 1. The stability constants in benzene were larger compared to those in water. For the N-methyl series K
1 : 2 values could not be obtained. The stability constants decreased with increasing of the polarity of solvent and pK
a of proton donors. It was found that chloral hydrate had the extraordinary reactivity in molecular interaction. The intensities of the OH strechting bands of chloral hydrate decreased by the addition of phenobarbital and a new band due to the hydrogen bonded OH appeared. The OH protons of chloral hydrate shifted to downfield by the addition of metharbital. Meanwhile, the
13C signals of carbonyl groups at 2-and 4-or 6-C of hexethal shifted to lower field in the presence of chloral hydrate. The former shift occurs to the farthest at the lower concentration of ligand and the latter proceeds with the increase of ligand. This may indicate that 2-carbonyl group forms the hydrogen bond with chloral hydrate preceedingly and 4-or 6-carbonyl group participates subsequently.
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HIROKO OHTSUKA, HATSUNORI TOYOFUKU, TADASHI MIYASAKA, KIICHI ARAKAWA
1975 Volume 23 Issue 12 Pages
3234-3242
Published: December 25, 1975
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5, 6-Dihydrothiazolo [2, 3-b] thiazolium salts (1a-d) were synthesized from 2-mercapto-thiazoline and α-haloketones. The reaction of 1 with a secondary amine gave 2-aminothiazole (7a-1) with the liberation of thiirane (9) via an unstable adduct, 7a-amino-2, 3, 5, 6-tetrahydrothiazolo [2, 3-b] thiazole (8a-g). The reaction of 1 with a primary amine afforded 3-(2-mercaptoethyl)-4-thiazolin-2-imine (10) and/or its disulfide (11). The reaction of 1 with an amine was concluded to be initiated by the attack of the reagent on C-7a.
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HIROKO OHTSUKA, TADASHI MIYASAKA, KIICHI ARAKAWA
1975 Volume 23 Issue 12 Pages
3243-3253
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The reaction of 5, 6-dihydrothiazolo [2, 3-b] thiazolium salts (1) with hydroxide ion furnished disulfide of 3-(2-mercaptoethyl)-4-thiazolin-2-one (6). The reaction of 1 with hydrogensulfide ion furnished 3-(2-mercaptoethyl)-4-thiazolin-2-thione (7) and/or its disulfide (8) and with N, N-dimethyldithiocarbamate ion furnished 3-(N, N-dimethyl-dithiocarbamylethyl)-4-thiazolin-2-thione (12) whereas the reaction of 1b with thiophenolate ion afforded 3-(2-phenylthioethyl)-4-thiazolin-2-thione (18b), thiazole (21), 6b, phenyl 2-[2-(4-phenylthiazolin-2-thion-3-yl) ethylthio] ethyl disulfide (22) and phenyl 2-phenylthioethyl disulfide (23). Brief reaction mechanism of the formation of these products are discussed. The reaction of 1 is considered to be initiated by the attack of the nucleophile on the polarized >C=N< bond to form an adduct and to proceed through AE-mechanism. The elimination stage of the reaction is concluded to depend upon basicity, polarizability and other properties of the reagent to induce either the cleavage of S
7-C
7a bond, the cleavage of S
7-C
7a and N-C
5 bonds, or another attack of the reagent on C
5 or on S
7.
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HIROKO OHTSUKA, TADASHI MIYASAKA, KIICHI ARAKAWA
1975 Volume 23 Issue 12 Pages
3254-3265
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The reaction of 5, 6-dihydrothiazolo [2, 3-b] thiazolium salt (1) with the sodium salt of acetylacetone furnished 3-(2-thiazolyl)-acetylacetone (2) with elimination of thiirane and 2-acetonylidene-3-acetylthioethyl-4-thiazoline (3). The reaction of 1 with the sodium salt of ethyl acetoacetate gave ethyl 2-(2-thiazolyl)-acetoacetate (12) and the reaction of 1 with the sodium salts of ethyl cyanoacetate and malononitrile gave 2-substituted thiazole (16), 3-(2-mercaptoethyl)-thiazoline (17) and/or its disulfide (18). The tautomeric forms of 2, 12 and 16 are discussed on the basis of the structures of the methylated products and of their spectrophotometric properties.
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HIDEKO ISHIHARA, HIROH IKEZAWA, SETSUZO TEJIMA
1975 Volume 23 Issue 12 Pages
3266-3271
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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In order to reveal a difference between the enzyme mechanisms of lipase and esterase, lipase-catalyzed methanolysis was compared with esterase-catalyzed methanolysis. 1) Purified pancreatic lipase and a mold, Mucor lipase were found to catalyze methanolysis of n-alkyl n-butyrates and tri-n-butyrin in heterogeneous assay system. 2) The same partitioning ratio (A/H), irrespective of the substrate leaving group, was obtained by our experiments. This indicates formation of a common intermediate during solvolysis. It is reasonable to postulate that this intermediate is an acyl enzyme. 3) Kinetic parameters for lipase and esterase were estimated and compared with each other. Acyl-esterase was more susceptible to nucleophilic attack by methanol than acyl-lipase.
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MASUO MORISAKI, AKISUKE SAIKA, KIYOSHI BANNAI, MASAKO SAWAMURA, NOBUO ...
1975 Volume 23 Issue 12 Pages
3272-3278
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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1α-Hydroxyvitamin D
3 (20) was prepared from cholesterol (1) in ca. 1% overall yield. Hydroboration of the tetrahydropyranyl ether 2 followed by chromic acid oxidation and NaBH
4 reduction gave the 6β-ol 5. Brief treatment of its acetate 6 with acid followed by Jones oxidation gave the 6β-acetoxy-3-one (7) in 55% yield from 1. Introduction of C-1 double bond (64%) was effected by bromination of 7, followed by dehydrobromination with CaCO
3, yielding the 3-oxo-1-ene 9. Oxidation of 9 with alkaline H
2O
2 afforded the 1α, 2α-epoxide 10 (80%) and this was converted by successive 6 steps sequences to 1α-hydroxycholesterol 15 in 43% yield. The 5, 7-diene 19 was obtained from the acetate 16 in 40% yield by allylic bromination with N-bromosuccinimide, dehydrobromination with trimethyl phosphite and saponification. Ultraviolet irradiation of 19 in benzene solution followed by thermal isomerization, produced 1α-hydroxyvitamin D
3 (20) (20%).
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SHIGEHO INABA, KIKUO ISHIZUMI, TADASHI OKAMOTO, HISAO YAMAMOTO
1975 Volume 23 Issue 12 Pages
3279-3282
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The synthesis of 5-(2-pyridyl)-and 3-methyl-1, 4-benzodiazepin-2-ones by oxidative ring enlargement of the corresponding 2-aminomethyl-and 2-(1-aminoethyl) indoles is described.
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NORIKO KONDO, JUNZO SHOJI
1975 Volume 23 Issue 12 Pages
3282-3285
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The chemical structures of saponin B (I) (=chikusetsusaponin IV), C
47H
74O
18, [α]
18D -9.10° (pyridine) and saponin C (III) (=desarabinofuranosylchikusetsusaponin IV), C
42H
66O
14, [α]
18D +15.8° (MeOH), which were isolated from Panax pseudoginseng subsp. himalaicus var. angustifolius (Araliaceae), were established on the basis of physical data and chemical investigations.
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KENJI FUJIWARA, MICHIHIRO UEDA, TAMOTSU KOIZUMI
1975 Volume 23 Issue 12 Pages
3286-3287
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Explicit expression was derived for the lag time due to drug accumulation in the diffusion layer of the sink solution, which is encountered at experiments on drug release from ointments.
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TAMOTSU KOIZUMI, MICHIHIRO UEDA, MASAWO KAKEMI, HARUKO KAMEDA
1975 Volume 23 Issue 12 Pages
3288-3292
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Higuchi's equation that expresses the rate of release of medicaments from ointments containing drugs in suspension has long been used for its surprisingly simple form and convenience. If initial drug concentration is close to the solubility of the drug in the ointment base, however, accuracy of the equation is not always high. In order to improve the accuracy, explicit solution of Fick's laws with the appropriate boundary conditions was attempted.
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KAZUYO NISHIHARA, HITOSHI NAKAMURA, YUKIYA SAITOH, TOKUJI SUZUKI
1975 Volume 23 Issue 12 Pages
3293-3296
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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A simple and reliable method was devised for investigating the effect of another drug on pharmacokinetic parameters of a drug in the rat. This consists of the cannulation technique repeated after a suitable interval in the same rat. The effect of phenobarbital on the elimination of diphenylhydantoin was presented as a typical example.
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HEIHACHIRO TAGUCHI, YUKINOBU IKEYA
1975 Volume 23 Issue 12 Pages
3296-3298
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Three new schizandrin type lignans, gomisin A, B and C, were isolated from the fruits of Schizandra chinensis BAILL. (Schizandraceae) and their structures were elucidated to be I, II and III, respectively.
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HARUAKI YAJIMA, KOUKI KITAGAWA, TOMIO SEGAWA, MASUMI NAKANO, KIYOSHI K ...
1975 Volume 23 Issue 12 Pages
3299-3301
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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Neurotensin, a bovine hypothalamic principle, was synthesized in a conventional manner, after removing three different protecting groups employed ; tosyl (Tos), benzyl (Bzl) and benzyloxycarbonyl (Z), by trifluoromethanesulphonic acid.
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TADASHI YASUHARA, TERUMI NAKAJIMA
1975 Volume 23 Issue 12 Pages
3301-3303
Published: December 25, 1975
Released on J-STAGE: March 31, 2008
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The tripeptide obtained from the skin of Bombina orientalis BOULENGER was coincided to mammalian thyrotropin releasing hormone by chemical characterization of the peptide. The amount of the peptide in the skin was much higher in cocentration than in mammalian hypothalamus.
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