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Teruo MAKINO, Osamu YAMASHITA, Atsumi KAZAMA, Fumio UEDA
Article type: Article
1968 Volume 37 Issue 2 Pages
135-142
Published: February 25, 1968
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The determination of vitamins A and E in their mixed preparations was examined. Hydrolysis of the samples was carried out in ethanolic potassium hydroxide by addition of antioxidants such as hydroquinone, pyrogallol or their mixtures. The unsaponifiable fraction was extracted with ether in usual method. The extracted vitamins A and E were assayed by hydrogenation method described in previous paper. The results obtained using the proposed procedure on a variety of preparations containing vitamins A and E were almost quantitative.
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Toru ADACHI, Yukio NAKAJI, Masato ASAHINA
Article type: Article
1968 Volume 37 Issue 2 Pages
143-146
Published: February 25, 1968
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Temporary increase of NAD content in the mouse liver after intraperitoneal injection of nicotinamide or nicotinic acid is wellknown. The increase of NAD content after intraperitoneal injection of α-tocopherylnicotinate was the same degree in case of the injection of nicotinic acid and less than nicotinamide. However, the maximum value of NAD content was attained at 12 hours after administration of the compound, and considerably higher than the normal value even after 24 hours. This fact shows that α-tocopherylnicotinate has more lasting action for the biosynthesis of NAD than nicotinic acid and nicotinamide.
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Choten INAGAKI, Nobuhiko ARAKAWA, Yachiyo ATSUMI, Haruyasu OTA
Article type: Article
1968 Volume 37 Issue 2 Pages
147-151
Published: February 25, 1968
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Palmitoyl- and dipalmitoyl-ascorbic acids in bile salt solution have been found to be hydrolyzed readily by the homogenate of pancreas, liver and intestine but the ratio of hydrolysis of these esters varies with changes of their micellar compositions in the reactive system. There have also been found considerable differences about both of the extent and the rate on hydrolysis of these esters on the same ratio of their micellar composition, or even on the simulated human intestinal content with respect to Na^<+>(0.15M), bile salt (0.04M), pH (6.3) and temperature (37℃). From these results it may be partially explained that there is a great difference in the body retention or availability between palmitoyl ascorbic acid and dipalmitoyl ascorbic acid, as shown in our previous report.
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Choten INAGAKI, Nobuhiko ARAKAWA, Nobuko SUZUKI, Yuriko SAGO, Kazuko N ...
Article type: Article
1968 Volume 37 Issue 2 Pages
152-158
Published: February 25, 1968
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The antiscorbutic activities of ascorbic acid derivatives, such as benzoyl, ethoxycarbonyl, and 6-monoester or 2,6-diester of C_4,C_8,C_<12> and C_<16> fatty acids were compared with that of L-ascorbic acid in guinea pigs of about 200g by the oral administration of 1.0mg ascorbic acid equivalent. It has been shown that ethoxycarbonyl derivatives was little effective and benzoyl derivative was effective in some degree, on the other hand, that fatty acid derivatives were considerably effective. Among them 6-monoesters have been shown to be more effective than 2,6-diesters. Especially, octanoyl and lauroyl drivatives were more effective than butyryl derivative in 6-monoesters. These results come to good coincidence with those of enzymatic hydrolysis. Though it can be inferred the above aspects, considering from the ability of the micelle formation between bile salt and these ascorbic acid derivatives, further investigations on the hydrolytic enzymatic system and the permeability of cell membrane would be expected.
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Yoshikazu SAHASHI, Takao SUZUKI, Shoichi MASUSHIGE, Nobuyoshi SUZUKI
Article type: Article
1968 Volume 37 Issue 2 Pages
159-164
Published: February 25, 1968
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At first, analytical investigations were performed for the separation and identification of 3-[2'-methyl-4'-aminopyrimidyl-(5')]-methyl-4-methyl-5-β-chloroethylthiazolium (chlorothiamine). The chlorothiamine was possibly estimated by the application of the paper chromatography, followed by the ordinary thiochrome method. In case of pure chlorothiamine added to poultry urine or feces, the method was found to be available for the desired recovery of the compound, yielding 98〜102% in feces, 98〜103% in urine. Then, the metabolic fate of chlorothiamine was investigated by poults fitted an artificial anus with cannula. When ^<35>S-chlorothiamine was orally administered, urinary excretion of ordinary thiamine was continued for 24 hours, while that of chlorothiamine for 12 hours. The recovery of ^<35>S (cpm) was seen to be 82% in urine and 18% in feces, whereas the recoveries of ^<35>S-chlorothiamine were 24% in urine and 5.4% in feces. From the data, it could not be realized that chlorothiamine may be convertible to the ordinary thiamine in vivo.
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Chikataro KAWASAKI, Hiroshi YOKOYAMA, Gun-ichi KURATA, Tatsuo SAKAI, T ...
Article type: Article
1968 Volume 37 Issue 2 Pages
165-169
Published: February 25, 1968
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Formation of desthiothiamine (IV) and the diazepine compound (V) from thiamine in its alkaline solution was demonstrated by means of paper partition chromatography. Thiamine-HCl with equimolar glycine in a trimolar NaOH solution at 30℃ for 48 hours evolved the highest amount of H_2S than in an equi-, di- or tetramolar NaOH solution, but at the absence of glycine evolution of H_2S was greatly decreased. When the above desulfurization of thiamine with or without glycine was carried out at 100℃ for 3 hours, the amount of evolved H_2S was remarkably increased. The presence of glycine increased formation of desthiothiamine, but decreased extremely formation of the diazepine compound. Desthiothiamine was obtained from the diazepine compound by heating its acetate buffer solution (pH5.0) on boiling water bath for 10 hours. This conversion was not effected by addition of glycine. Thiamine was also fomed from the diazepine compound by saturation of H_2S in its acetate buffer solution (pH5.0) at 90℃.
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Kunihei INAZU, Shigeyo NAKANISHI, Ryuichi YAMAMOTO
Article type: Article
1968 Volume 37 Issue 2 Pages
170-174
Published: February 25, 1968
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In the presence of isoniazid methanesulfonate sodium (I), decomposition of thiamine in solution was shown to proceed at an increased rate with a decrease in acidity through a maximum at pH 5-5.5. Activation energy for this reaction was found to be 20.7kcal/mole. Isolation of the main reaction product, 1-(2-methyl-4-amino-5-pyrimidyl) methyl-4-sulfo-methylhydrazinocarbonyl pyridinium chloride, showed that thiamine was decomposed by the replacement reaction of the thiazole moiety of thiamine with I in the presence of bisulfite from I. In addition, a replacement reaction product of thiamine, 1-isonicotinyl-2-(2-methyl-4-amino-5-pyrimidyl) methyl hydrazine (II) was obtained. However, the yield of II was low when compared with the result of the reaction of thiamine with isoniazid in the presence of bisulfite. This may be attributable to the small degree of dissociation of I. The results obtained with these experiments and those previously reported, suggest that such N-methanesulfonate compounds as sulpyrine and I may affect the stability of thiamine in a similar manner.
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Kunihei INAZU, Shigeyo NAKANISHI, Ryuichi YAMAMOTO
Article type: Article
1968 Volume 37 Issue 2 Pages
175-181
Published: February 25, 1968
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The effect of N-methanesulfonate compounds such as sulpyrine and isoniazid methanesulfonate sodium (I) on the stability of four typical thiamine derivatives of the thiol-type was examined. Thiamine disulfide in solution was easily decomposed by these N-methanesulfonate compounds to give thiamine, thiamine-S-sulfonic acid, 2-methyl-4-aminopyrimidyl-5-methanesulfonic acid, 4-methyl-5-β-hydroxyethylthiazole, and the corresponding replacement reaction products of thiamine. The stability of thiamine propyldisulfide was also affected in a similar manner, whereas O, S-bisbenzoylthiamine and O, S-bisethoxycarbonylthiamine were not decomposed by sulpyrine and I. The decomposition products indicated that the disulfide derivatives were reductively decomposed by bisulfite from N-methanesulfonate compounds, and that thiamine resulting from the decomposition of the disulfides was successively decomposed through the replacement reaction with N-methanesulfonate compounds. Results were also obtained which indicated that thiamine-S-sulfonic acid derived from the disulfides changed slightly into thiamine when heated for a long period at pH 5 and 80℃. Instability of thiamine disulfide in the presence of I was markedly decreased when formaldehyde, a dissociation product of I, was added to the system.
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Kenji MASUKAWA, Kiichiro FURUSAKI, Tadashi UEDA, Hiroaki MONAKA, Kenta ...
Article type: Article
1968 Volume 37 Issue 2 Pages
182-189
Published: February 25, 1968
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Ultraviolet spectral studies of pyridoxal-homocysteine (PAL-HCySH) in methanol were carried out at various media. The absorption bands were assigned and then the equilibria among the various molecular species in the methanol were found. Dissociation constants obtained by spectrophotometric method showed pKa_1=2.5,pKa_2=5.2,and pKb=2.8. Pyridoxal (PAL) is rapidly decomposed by exposure to light, particulary in neutral aqueous solution, while PAL-HCySH is relatively stable in the solution. Photodecomposition of PAL-HCySH would occur in the aqueous solution, because of the decomposition of PAL produced by the hydrolysis. The decomposition would be avoided in methanol, though the PAL was rapidly inactivated by exposure to light in alkaline methanol solution. PAL and PAL-HCySH in solid state were not decomposed by sunlight.
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Chentung CHEN, Tadao AOYAGI, Tomizo MORI
Article type: Article
1968 Volume 37 Issue 2 Pages
190-196
Published: February 25, 1968
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The distribution of isobutyroylthiamine disulfide (iBuTDS) in the thiamine deficient rats with oral administration of small and large doses has been investigated histochemically by thiochrome fluorescent technique. It was observed that iBuTDS was incorporated into the various organs in much more amounts and mainly distributed in hepatic parenchymal cells, intestinal mucosa and muscle, cardiac muscle and cerebral nerve cells, comparing with the cases of thiamine hydrochloride. In cerebral nerve cells, the uptake of iBuTDS was gradually increased until 20 hours.
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Akira MINATO, Seiyu HIROSE, Toshio AMMO, Eiichi FUJIHIRA, Katsuhiko NI ...
Article type: Article
1968 Volume 37 Issue 2 Pages
197-203
Published: February 25, 1968
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The distribution and excretion of O-isobutyroylthiamine disulfide-^<35>S (iBuTDS-^<35>S) in male Wistar rats were studied, comparing with those of thiamine-HCl-^<35>S. The oral administration of iBuTDS-^<35>S raised the initial radio activity in blood and liver 2 to 3 times over than of thiamine-HCI-^<35>S, and later on until 72 hrs.maintained higher level of ^<35>S in various organs tested. In an earier time, the urinary excretion of iBuTDS-^<35>S was inferior to that of thiamine-HCl-^<35>S. No significant difference between iBuTDS-^<35>S and thiamine-HCl-^<35>S was found in fecal excretion, but it was observed that large amounts of ^<35>S were secreted in bile after the intravenous injection of iBuTDS-^<35>S.
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Chikataro KAWASAKI, Yoshio ITO, Masaharu OGAWA
Article type: Article
1968 Volume 37 Issue 2 Pages
204-208
Published: February 25, 1968
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When the alcohol solution of retinoic acid was mixed with Tyrode's, Locke's or Krebs・Ringer bicarbonate solution, significant decrease of retinoic acid content was observed. The decrease of retinoic acid content was due to the combined effect of calcium and bicarbonate concentrations in these physiological solutions at pH 8.3. It was also found that the decrease did not occure on addition of antioxidants to the reaction mixture or under the anaerobic conditions. At the presence of Ca^<2+> in veronal or borate buffer at pH 8-9 and also in combination of CaCl_2,BaCl_2 or MgCl_2 with bicarbonate, retinoic acid was quickly destroyed. These results suggested catalytic oxidation of retinoic acid by metal ions at the suitable ranges of pH. Retinol or retinal was shown to be more resistant to similar degradation experiments, while the stability of retinoic acid to KMnO_4,HClO, H_2O_2 and other oxidizing agents was proved to similar to that of retinol.
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Chikataro KAWASAKI, Tomio ICHIKAWA
Article type: Article
1968 Volume 37 Issue 2 Pages
209-212
Published: February 25, 1968
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When papain was incubated with thiamine propyldisulfide (TPD) in increasing concentrations, its enzymatic activity was inhibited proportionally to the thiamine released from TPD. Determination of thiol radicals of TPD-ihibited papain by p-(bis-nitrophenyl) disulfide (PNPD) also indicated decrease of PNPD-values in correspondence with enzymatic activity of the papain. The activity of TPD-inhibited papain, when incubated with ICH_2COOH, was completely destroyed but the thiol radicals detected by PNPD were always demonstrated to the extent of 45-50% of the papain-SH value. When papain was incubated with ICH_2COOH and TPD, thiamine was hardly released and thiol radicals detected by PNPD were also demonstrated to 47% of the papain-SH. When papain was denatured by urea in increasing concentrations, the thiamine released from TPD in its incubation with TPD, was proportional to the enzymatic activity of urea-denatured papain, while the radicals detected by PNPD were always demonstrated. That the thiamine released from TPD in the incubation of papain with TPD was shown to be a good index of the enzymatic activity.
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Chikataro KAWASAKI, Tomio ICHIKAWA
Article type: Article
1968 Volume 37 Issue 2 Pages
213-216
Published: February 25, 1968
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Papain, after its incubation with thiamine propyldisulfide (TPD) at pH 7.4,37℃ for 1 hour, was repeatedly precipitated by satulated NaCl solution and the precipitated papain was proved to be inactive, unless cysteine was added. TPD-inactivated papain was shown to be S-propylmercapto-papain by means of paper chromatography. S-Propylmercapto-papain was also isolated from TPD-inhibited papain by fractionated filtration through Sephadex G-25 column. S-Propylmercapto-papain was shown to be more resistant to the reaction with ICH_2-COOH or H_2O_2 but less resistant to heat-inactivation than papain.
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[in Japanese], [in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
217-
Published: February 25, 1968
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[in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
217-
Published: February 25, 1968
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[in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
217-218
Published: February 25, 1968
Released on J-STAGE: February 10, 2018
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[in Japanese], [in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
218-219
Published: February 25, 1968
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[in Japanese], [in Japanese], [in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
219-220
Published: February 25, 1968
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[in Japanese], [in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
220-
Published: February 25, 1968
Released on J-STAGE: February 10, 2018
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[in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
221-
Published: February 25, 1968
Released on J-STAGE: February 10, 2018
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[in Japanese], [in Japanese], [in Japanese], [in Japanese], [in Japane ...
Article type: Article
1968 Volume 37 Issue 2 Pages
221-
Published: February 25, 1968
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[in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
221-222
Published: February 25, 1968
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[in Japanese], [in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
222-223
Published: February 25, 1968
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[in Japanese], [in Japanese]
Article type: Article
1968 Volume 37 Issue 2 Pages
223-
Published: February 25, 1968
Released on J-STAGE: February 10, 2018
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