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YUTAKA SAITO, JUNICHI ODO, YOSHIMASA TANAKA
1981 Volume 29 Issue 4 Pages
907-912
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The infrared spectra of [bis-(L-asparaginato) copper (II)] n and its isotopic complexes containing copper and hydrogen isotopes have been measured in the region between 4000 and 200 cm
-1. By referring to the isotope shifts on
63Cu and
65Cu substitution, two bands at 359 and 318 cm
-1 have been assigned to metal-ligand stretching vibrations. The frequency shifts on N, N'-deuteration revealed that the Cu-N stretching frequency is larger than the Cu-O stretching frequency.
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HIROSHI KASHIWAGI, SABURO ENOMOTO
1981 Volume 29 Issue 4 Pages
913-917
Published: April 25, 1981
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The formation of stable free radicals was observed by means of ESR spectroscopy not only on heating but also on UV irradiation of powdered saccharides at room temperature in air. Among saccharides used here, the number of free radicals was largest in the powdered disaccharides. On the other hand, free radicals of glucose were obtained by UV irradiation, but not by heating. The number of free radicals was found to increase initially after heating or after irradiation, and then became almost constant. This constant value of the number of free radicals was found to increase with increase of the heating temperature or heating time, or with increase in the duration of irradiation. The ESR spectra of saccharides were not affected by oxygen, but were found to change gradually under conditions of high humidity. Moreover, a hysteresis effect was observed between the number of free radicals and the water content in UV-irradiated potato starch. Free radicals were found to be stable when suspended in benzene, but they were destroyed by kneading the saccharides in water or alcohols.
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HIDEAKI UMEYAMA, SETSUKO NAKAGAWA
1981 Volume 29 Issue 4 Pages
918-925
Published: April 25, 1981
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The energetics of proton transfers in the methanethiol-imidazole-formic acid complex were analyzed from a quantum chemical point of view in order to elucidate the nature of the enzymatic reaction of papain and the electronic structure in the active site. Methanethiol, imidazole and formic acid were used as models of the side chains of Cys 25, His 159 and Asp 158. The calculations were performed within the closed-shell-LCAO-ab initio MO method by using a 4-31G basis set. The hydrogen-bonding structure including the anion form of the methanethiol, the cation form of the imidazole and the anion form of the formic acid was the most stable of the various hydrogen-bonding structures. This result is in good agreement with experiments on the electronic structure in the active site of papain, and it supports the mechanism of the enzymatic reaction proposed by Angelides and Fink.
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TOSHIHIKO OZAWA, AKIRA HANAKI
1981 Volume 29 Issue 4 Pages
926-928
Published: April 25, 1981
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The stability of the superoxide ion, O
2-, prepared by the electric reduction of O
2 in acetonitrile, was examined. The superoxide is decomposed, dismutated, rapidly in aqueous solutions to produce O
2 and H
2O
2, and the rate depends on the water content and/or the acidity of the medium. The addition of HCl over 10
-3M significantly accelerates the dismutation, while O
2- is stabilized relatively in alkaline solutions. The addition of H
2O
2 markedly stimulated the decomposition of O
2- to form a hydroxyl radical, ·OH, which was identified by ESR spectrometry.
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KOJI OKAMOTO, MASAHIDE NOJI, TAZUKO TASHIRO, YOSHINORI KIDANI
1981 Volume 29 Issue 4 Pages
929-939
Published: April 25, 1981
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Platinum (II) complexes of the type [PtX (1, 3-diamine)] (X=Cl
2, SO
4, (NO
3)
2, oxalato, D-glucuronato, and D-gluconato ; 1, 3-diamine=2-(aminomethyl) cyclohexylamine, 2, 4-pentanediamine, 1, 3-butanediamine, and 1, 3-diphenyl-1, 3-propanediamine isomers) were prepared, and their antitumor activity against leukemia L1210 was tested according to the protocol recommended by the National Cancer Institute for the evaluation of Pt analogs. A large number of long-term survivors was observed with certain analogs, though the therapeutic indices were not large. Among the platinum (II) complexes tested so far, trans-l- and cis-l-2-(aminomethyl) cyclohexylamine platinum (II) complexes showed marked antitumor activity, while 1, 3-diphenyl-1, 3-propane diamine platinum (II) complexes were almost inactive because of their low solubility in water. The structures of the complexes are discussed on the basis of the circular dichroism (CD) and
13C-nuclear magnetic resonance (NMR) spectral data. The structure of the cis-l-2-(aminomethyl) cyclohexylamine complex was much more flexible than that of the trans-l-2-(aminomethyl) cyclohexylamine complex, and the cyclohexane ring and the chelate ring of the latter lie in a common plane. The coplanarity of trans-2-(aminomethyl) cyclohexylamine and the flexibility of cis-2-(aminomethyl) cyclohexylamine may allow them to approach the target DNA relatively easily.
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MASAYUKI OYA, JUNZOH MATSUMOTO, HIDEO TAKASHINA, TOSHIO WATANABE, JUNI ...
1981 Volume 29 Issue 4 Pages
940-947
Published: April 25, 1981
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The synthesis and structure-activity relationship of a series of mercaptoacylamino acids are described. These compounds were tested for antihypertensive activity. When the compounds were screened as angiotensin I-converting enzyme inhibitors in vitro, N-(2-mercaptopropanoyl)-L-cysteine-a (7a) and N
2-(2-mercaptopropanoyl)-L-tryptophan-a (20a) were found to be 10 and 20 times more active than tiopronin, respectively.
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TETSUO SEKIYA, HIDETOSHI HIRANUMA, MASAYUKI UCHIDE, SHUNSUKE HATA, SHU ...
1981 Volume 29 Issue 4 Pages
948-954
Published: April 25, 1981
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4-Amino-2-methylthiopyrimidine derivatives (4) were synthesized by the cyclization of 3-cyano-2-methylisothiourea (2) with ketones (3). Oxidation of 4 produced 4-amino-2-methylsulfinyl or 2-methylsulfonylpyrimidine derivatives (7 or 8). Amination of 7 or 8 gave hypoglycemic 2-(1-piperazinyl) pyrimidines (1). Compounds 4 were converted to 4 (3H)-pyrimidinone derivatives (12). Derivatives 1 were also synthesized via 12.
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NOBUKO SAKURAI, OSAMU KIMURA, TAKAO INOUE, MASAHIRO NAGAI
1981 Volume 29 Issue 4 Pages
955-960
Published: April 25, 1981
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Two new xylosides were isolated from the underground part of Cimicifuga japonica-24-O-acetylhydroshengmanol xyloside (2), C
37H
60O
11, mp 235-237°, [α]
22D+6.6°and 22-hydroxycimigenol xyloside (3), C
35H
56O
10·H
2O, mp 282-284°, [α]
17D+17.7°. The xyloside (2) afforded, on acid hydrolysis in aq. methanol, cimigenol (4) and isodahurinol (5). Enzymatic hydrolysis of 2 afforded its genuine aglycone 24-O-acetylhydroshengmanol (8), C
32H
52O
7, mp 200-202°, [α]
26D+9.0°. The xyloside (2) and its genin (8) showed a mutarotation. When treated at room temperature with sulfuric acid in aq. methanol, 2 changed firstly into 25-O-acetylcimigenol xyloside (6) and finally into cimigenol xyloside (7). On the basis of chemical and spectral data, the structure of 24-O-acetylhydroshengmanol xyloside (2) was proposed to be (23R, 24S)-3β, 15α, 16ξ, 25-tetrahydroxy-24-acetoxy-16, 23-epoxy-9, 19-cyclolanostane 3-O-β-D-xylopyranoside. Another glycoside (3) showed, in its
13C-nuclear magnetic resonance (NMR) spectrum, a pattern of chemical shifts very similar to that of cimigenol xyloside (7), but a downfield shift of C-22 by 44.2 ppm was observed, suggesting oxygenation of C-22 in the glycoside (3). The xyloside (3) afforded, on both acidic and enzymatic hydrolyses, its aglycone (13), C
30H
48O
6, mp 274-276°, [α]
19D+45.0°. Huang-Minlon reduction of a diketo derivative (15) of 13 provided a didesoxy compound (16), C
30H
48O
4, mp 202.5-203.5°, which was identical with the 3-desoxy derivative of cimigenol. The stereochemistry of the hydroxyl group at C-22 of 13 was assigned as R on the basis of its NMR spectrum. The structure of 22-hydroxycimigenol xyloside (3) was established as (22R)-22-hydroxycimigenol 3-O-β-D-xylopyranoside.
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KUNIZO ARAI, KIKUO MASUDA, NORIKI KIRIYAMA, KEIICHI NITTA, YUZURU YAMA ...
1981 Volume 29 Issue 4 Pages
961-969
Published: April 25, 1981
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Eleven kinds of bisindolyl-dimethoxyl-p-benzoquinones, "asterriquinones A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, C-1, C-2, and D"were isolated from Aspergillus terreus IFO 8835, and their structures were determined. Asterriquinone D had the basic structure, and the others were substituted with dimethylallyl group (s) in the indole ring.
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KENICHIRO INOUE, YOSHIO TAKEDA, TAKAO TANAHASHI, HIROYUKI INOUYE
1981 Volume 29 Issue 4 Pages
970-980
Published: April 25, 1981
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Geniposide (9) was chemically converted into 10-hydroxyloganin (3a), which is presumed to be a precursor for secologanin (2). The stereoisomers 8a, 18a and 19a were also prepared. The absolute configurations of these four compounds were determined on the basis of chemical reactions and NMR measurements.
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KENICHIRO INOUE, YOSHIO TAKEDA, TAKAO TANAHASHI, HIROYUKI INOUYE
1981 Volume 29 Issue 4 Pages
981-990
Published: April 25, 1981
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Administration of various
3H labeled compounds, deoxyloganic acid (6), loganin (1), 10-hydroxyloganin (3) and 7-epi-10-hydroxyloganin (5) to Lonicera morrowii and A dina pilulifera suggested that, unlike the first two compounds, neither 3 nor 5 was a precursor of secologanin (2). This conclusion was supported by dilution analysis of 3 and 5 carried out during the same experiments.
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KUNIZO ARAI, SAKAE SHIMIZU, YASUHISA TAGUCHI, YUZURU YAMAMOTO
1981 Volume 29 Issue 4 Pages
991-999
Published: April 25, 1981
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Demethylation of asterriquinones (AQ, bisindolyl-dimethoxyl benzoquinones) was investigated in connection with the determination of their structures and studies of their antitumor activity. Usually, the demethylation proceeded smoothly with KOH, but several types of side reactions were observed with acidic reagents.
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TOHRU ENDO, HEIHACHIRO TAGUCHI, ITIRO YOSIOKA
1981 Volume 29 Issue 4 Pages
1000-1004
Published: April 25, 1981
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A new flavanone glucoside, plantagoside (1) was isolated from the seeds of Plantago major var. japonica NAKAI (Plantaginaceae) together with aucubin, geniposidic acid, acteoside and syringin. The structure of plantagoside was elucidated to be 1 on the basis of chemical and spectral evidence.
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KUNIZO ARAI, SAKAE SHIMIZU, YUZURU YAMAMOTO
1981 Volume 29 Issue 4 Pages
1005-1012
Published: April 25, 1981
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Seven colorless metabolites related to asterriquinones and one colorless compound of another type were isolated from Aspergillus terreus IFO 8835, and their chemical structures were determined.
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MASAKO NAKAGAWA, SHIRO KATO, SHIGEHIRO KATAOKA, SHINICHI KODATO, HIDEY ...
1981 Volume 29 Issue 4 Pages
1013-1026
Published: April 25, 1981
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The isolation, structure determination, and reactivity of the tricyclic labile hydroperoxides 10 and 2 obtained by dye-sensitized photooxygenation of L-, D-, and DL-tryptophan and Nb-methoxycarbonyltryptophan ester are reported. The tricyclic hydroperoxide 10, under appropriate conditions, was easily convertible to formylkynurenine. Plausible mechanisms for these transformations are discussed.
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TSUKASA TAKAMURA, TAKU CHIBA, SETSUZO TEJIMA
1981 Volume 29 Issue 4 Pages
1027-1033
Published: April 25, 1981
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The title branched tetrasaccharide (18) is the core structure of more complex oligosaccharides of human milk. A synthesis of 18 was achieved. Stirring of the acetylated oxazoline derivative of GlcNAc (6 mol eq.), 1, 6-anhydro-2, 2', 3, 4'-tetra-O-benzyl-β-lactose (7, 1 mol eq.), and p-toluenesulfonic acid in 1, 2-dichloroethane at 60-65°for 48 hr under nitrogen afforded products consisting of the corresponding tetrasaccharide (major) contaminated with by-products and trisaccharide (minor). The former was purified by debenzylation followed by acetylation to isolate the desired tetrasaccharide as the acetylated 1, 6-anhydro-β-derivative (15) in 81.7% yield based on 7. The protecting groups of 15 were removed by acetolysis and de-O-acetylation, and 18 was obtained as hygroscopic fine needles in 69% yield from 15. The latter was isolated in 16% yield by column chromatography and assigned as O-2-acetamido-3, 4, 6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl-(1→6)-O-2, 4-di-O-benzyl-β-D-galactopyranosyl-(1→4)-1, 6-anhydro-2, 3-di-O-benzyl-β-D-glucopyranose.
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MORIO IKEHARA, JUNKO IMURA
1981 Volume 29 Issue 4 Pages
1034-1038
Published: April 25, 1981
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2'-Deoxy-2'-fluoroguanosine (VII) was synthesized starting from 8, 2'-anhydro-8-oxy-9-β-D-arabinofuranosylguanine (8, 2'-O-cycloguanosine) (I). Compound I was protected at 2-NH
2 with an isobutyryl group and at 3'- and 5'-OH with tetrahydrofuranyl groups. The protected compound III was derivatized to the arabino nucleoside V and thence converted to VII by treatment with trifluoromethanesulfonyl chloride and tetra-n-butylammonium fluoride. The resulting 2'-deoxy-2'-fluoroguanosine showed a 3'-endo favored conformation.
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TSUNEO ITOH, HARUO OGURA, KYOICHI A. WATANABE, NORIO KAWAHARA
1981 Volume 29 Issue 4 Pages
1039-1043
Published: April 25, 1981
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Bis-6, 6'-(1, 3-dialkyluracilyl) sulfides (3) were synthesized by coupling of 6-chloro-1, 3-dialkyluracil (1) and 1, 3-dialkyluracil-6-mercaptide (2). Compounds (3) were found to undergo photochemical cyclization, giving rise to three types of isolable products with novel ring systems, namely, 1, 3, 6, 8-tetraalkyl [1, 4] dithiino [2, 3-d ; 5, 6-d'] dipyrimidines (4), 1, 3, 6, 8-tetraalkylthiopheno [2, 3-d ; 4, 5-d'] dipyrimidines (6) and the dihydro derivatives (8) of the latter. These compounds were fully characterized by 'H-NMR, mass spectral and elemental analyses. A plausible mechanism for this photocyclization of 3 to 6 and to 8 has been proposed.
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HIROSHI YAMANAKA, TAKAO SAKAMOTO, TAKAYUKI SHIRAISHI
1981 Volume 29 Issue 4 Pages
1044-1048
Published: April 25, 1981
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The reaction of isoquinoline 2-oxide with diketene afforded three products whose structures were assigned as 2, 6-dimethyl-3-(1-isoquinolyl)-4-pyrone (II), 4-methyl-2-oxo-2H-benzo [α] quinolizine (III), and 1-acetonyl-4-acetoxy-2-acetyl-1, 2-dihydroisoquinoline (IV), respectively.
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HIROSHI YAMANAKA, TAKAYUKI SHIRAISHI, TAKAO SAKAMOTO, HITOMI MATSUDA
1981 Volume 29 Issue 4 Pages
1049-1055
Published: April 25, 1981
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The addition reaction of diketene in formic, acetic or propionic acid to isoquinoline afforded 1-acetonyl-2-acyl-1, 2-dihydroisoquinoline (II) in satisfactory yields. Though no reaction of this type was observed to occur in quinoline, isoquinoline-like N-heteroaromatic compounds such as phthalazine and 1, 6-naphthyridine underwent similar addition reactions to give the corresponding dihydro-acetonyl compounds. The above product II was easily convertible to benzoquinolizine derivatives.
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HIROSHI YAMANAKA, TAKAYUKI SHIRAISHI, TAKAO SAKAMOTO
1981 Volume 29 Issue 4 Pages
1056-1062
Published: April 25, 1981
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Acetic anhydride reacted with isoquinoline (IV) itself under reflux to give an addition product, whereas quinoline did not react with acetic anhydride under the same conditions. The structure of the product was determined to be 2-acetyl-1, 2-dihydroisoquinoline-1-acetic acid (V) by means of chemical reactions. Active methylene (or methyl) compounds were observed to react with IV competitively to give the corresponding 1, 2-dihydroisoquinolines when they were heated with IV in acetic anhydride.
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HIROKI TAKAHATA, YOSHINORI OHNISHI, HIROYUKI TAKEHARA, KAZUKO TSURITAN ...
1981 Volume 29 Issue 4 Pages
1063-1068
Published: April 25, 1981
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The intramolecular N-alkylation of β-bromopropionamides (1) under phase transfer conditions afforded monocyclic N-substituted β-lactams (2) in high yields. In a similar manner, cyclization by N
1-C
4 bond formation gave 4-benzoyl-2-azetidinones (4) from 3-benzoyl-3-bromopropionanilides (3).
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TETSUZO KATO, NOBUYA KATAGIRI, AKIHIRO WAGAI
1981 Volume 29 Issue 4 Pages
1069-1075
Published: April 25, 1981
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Heating of methylquinolines (1, 3, 6, and 12) with phosphorus pentachloride in phosphoryl chloride gave the corresponding trichloromethylquinoline derivatives (2, 4, 9, and 14). Similar treatment of 4-chloro-2-methyl-3-nitroquinoline (16) gave 4-chloro-2-dichloromethyl-3-nitroquinoline (17), 4-chloro-3-nitro-2-trichloromethylquinoline (18), and 3, 4-dichloro-2-cyanoquinoline (19). The reaction of 2-trichloromethylquinolines (2, 9, and 18) with trimethyl phosphite gave the corresponding methylated products, 2-(1, 1-dichloroethyl) quinolines (21, 24, and 27). However, 4-trichloromethylquinolines (4 and 14) reacted with trimethyl phosphite under similar conditions to give 4-dichloromethylquinolines (23 and 13).
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TSUKASA TAKAMURA, TAKU CHIBA, SETSUZO TEJIMA
1981 Volume 29 Issue 4 Pages
1076-1082
Published: April 25, 1981
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1, 6-Anhydro-4', 6'-O-benzylidene-3'-O-tosyl-β-lactose was converted into 1, 6-anhydro-2, 2', 3-tri-O-benzyl-4', 6'-O-benzylidene-β-lactose (3) in 74.1% yield by benzylation followed by detosylation. Condensation of 3 with 2, 3, 4-tri-O-acetyl-α-L-fucopyranosyl bromide in benzene-nitromethane in the presence of mercuric cyanide and molecular sieves gave the corresponding trisaccharide derivatives (6 and 11) bearing α- and β-L-fucopyranosyl linkages in 37.1 and 43.1% yields, respectively. Compounds 6 and 11 were isolated by column chromatography on silica gel. The title sugars (10 and 15) were prepared in 4 steps from 6 and 11, respectively ; hydrogenolytic removal of the benzylidene and benzyl groups, acetylation, cleavage of the 1, 6-anhydro-β-ring to β-acetate, and deacetylation.
1H-NMR and
13C-NMR spectral data of 10, 15, and the intermediates are also described.
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Studies on Tetrahydroisoquinolines. XIX. Synthesis of (±)-Isothebaine, (±)-1-Hydroxy-2, 9-dimethoxy-, (±)-1-Hydroxy-2, 10-dimethoxy-, and (±)-2, 10-Dimethoxy-aporphines, (±)-2, 6-Dimethoxyhomomorphinandienone, and (±)-1-Hydroxy-2, 10-dimethoxyhomoaporphine
HIROSHI HARA, OSAMU HOSHINO, TETSUO ISHIGE, BUNSUKE UMEZAWA
1981 Volume 29 Issue 4 Pages
1083-1087
Published: April 25, 1981
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The title alkaloids and two related aporphines have been prepared in considerable yields by trifluoroacetic acid treatment of the corresponding p-quinol acetates.
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KOICHI YASUMURA, KENJI OKAMOTO, SHINICHI SHIMAMURA, HARUAKI YAJIMA
1981 Volume 29 Issue 4 Pages
1088-1095
Published: April 25, 1981
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The docosapeptide, H-Arg-Pro-Val-Lys-Val-Tyr-Pro-Asn-Gly-Val-Gln-Glu-Glu-Thr-Ser-Glu-Gly-Phe-Pro-Leu-Glu-Phe-OH, corresponding to positions 18 to 39 of ostrich ACTH (ostrich-type corticotropin-like intermediate lobe peptide, ost-CLIP), was synthesized, using 1M trifluoromethanesulfonic acid-thioanisole in TFA as a deprotecting reagent.
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HIDETAKA YUKI, TAKEO OHMURA, HIDEKI KAWASAKI, TAKEHIKO YAJIMA, KIMITOS ...
1981 Volume 29 Issue 4 Pages
1096-1100
Published: April 25, 1981
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The chemical structure of the color reaction product, 2-amino-5, 6-dimethyldihydro-3H-1, 2, 4-triazine-3-one (3a), obtained from the reaction of urea with diacetylmonoxime (DAM) and thiosemicarbazide (TSC) in 10% sulfuric acid in methanol was elucidated. The ethyl and p-tolyl derivatives (3b and 3c) of 3a were also obtained from the reactions of ethyl- and p-tolylurea with DAM and TSC, along with 1, 1'-disubstituted-5, 4'-dimethly-2, 2'-dioxo-4, 5'-diimidazolylmethanes. 3a and its derivatives, 3b and 3c, develop a red color immediately in acidic media and are thought to be the main products of the color reaction of urea, ethylurea and p-tolylurea, respectively, with DAM in the presence of TSC. A reaction mechanism is proposed.
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TOSHIHIKO OZAWA, AKIRA HANAKI
1981 Volume 29 Issue 4 Pages
1101-1105
Published: April 25, 1981
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The rate constants for the thiol-disulfide exchange, k
SH, and for the thiolate iondisulfide exchange, k
s-, between biologically relevant aminothiols, i.e., cysteine, cysteamine and penicillamine, and 5, 5'-dithiobis (2-nitrobenzoic acid), Ellman's reagent, in aqueous solutions were determined by a spectrophotometric method. The apparent rate constant, k
1', increases with increase of pH under the experimental conditions used. The value of k
s-, approximately 2×10
5 M
-1S
-1 except for penicillamine, appears to be independent of the pK
a (SH), and k
SH is three orders of magnitude smaller than k
s-. The thiolate ion-disulfide exchange in penicillamine is one order of magnitude slower than in the other aminothiols. The results of the kinetic study indicate that one of the sulfur atoms of disulfide is attacked by the thiolate anion with subsequent cleavage of the S-S bond.
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TOSHIO AMANO, FUMIKO KASAHARA, HIDEO NAKAMACHI
1981 Volume 29 Issue 4 Pages
1106-1114
Published: April 25, 1981
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The diastereomeric isomer ratio of 3, 3, 5-trimethylcyclohexyl DL-mandelate (cyclandelate) was examined by various physico-chemical methods. Capillary gas chromatography and
13C nuclear magnetic resonance spectroscopy showed that the bulk of cyclandelate which had been determined by proton magnetic resonance to have an isomer ratio of 73 : 27 was actually a mixture of nearly equal amounts of the two isomers. The reason for the difference in the results was studied in detail by an analysis of the physical properties of solid solutions of the isomers.
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MASAAKI KAI, TETSURO MIURA, KAZUYA KOHASHI, YOSUKE OHKURA
1981 Volume 29 Issue 4 Pages
1115-1120
Published: April 25, 1981
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A new fluorimetric method for the precise and rapid determination of guanidino compounds with benzoin is described. This is based on their reaction in an aqueous potassium hydroxide solution with benzoin (dissolved in methylcellosolve), in the presence of β-mercaptoethanol and sodium sulfite, while the pH of the reaction mixture is maintained at 9.2 after the reaction. This method requires heating at 100° for only 10 min. The excitation and emission maximum wavelengths of the fluorescence from these compounds are at around 325 and 435 nm, respectively. The method is simple, selective for guanidine and monosubstituted guanidino compounds (including peptides with one or two arginyl residues) and sensitive ; almost all the compounds can be determined at concentrations as low as 40-170 pmol/ml.
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ATSUO NAGAMATSU, SHINJI SOEDA
1981 Volume 29 Issue 4 Pages
1121-1129
Published: April 25, 1981
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The specific limited proteolysis of human plasminogen by human granulocyte elastase results in the cleavage of three peptides from the heavy chain of plasminogen. These three peptides bind to lysine- and fibrin-Sepharose. The remainder of the molecule possesses a molecular weight of 38000 and represents a fully activatable plasminogen lacking the lysine binding site (s) in the heavy chain. Upon treatment of this low molecular weight form of plasminogen with urokinase, esterolytic, fibrinolytic and amidolytic activities appear. The low molecular weight form of plasmin consists of two disulfide-linked polypeptide chains with molecular weights of approximately 25000 and 13000. The kinetic parameters of hydrolysis of synthetic substrates by the low molecular weight form of plasmin and native plasmin, respectively, are similar. Furthermore, the inhibitions of the two enzymes by several inhibitors of the hydrolysis of Blue Dextran-fixed fibrin are identical. The initial rate of activation with urokinase is about two times faster for the low molecular weight form of plasminogen than for native plasminogen, and the activation of native plasminogen by urokinase is inhibited by plasma α
2-antiplasmin, whereas the activation of the low molecular weight form of plasminogen is not. Urokinase-induced clot lysis is inhibited efficiently by α
2-antiplasmin, but the inhibitory effect of α
2-antiplasmin is removed by heavy chain fragments containing lysine binding site (s), which are obtainable from plasminogen by limited elastase digestion. Urokinaseinduced fibrinolytic activity of plasma is promoted by human granulocyte elastase in an apparently time-dependent manner. The findings further indicate that the lysine binding site (s) in the heavy chain of plasmin (ogen) are of great importance in relation to the rate of its reaction with α
2-antiplasmin.
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TSUNEHIRO KITAGAWA, TAKURO SHIMOZONO, TADAOMI AIKAWA, TOYOKICHI YOSHID ...
1981 Volume 29 Issue 4 Pages
1130-1135
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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TAIJU KURAMOTO, KENJI KIHIRA, NAOKO MATSUMOTO, TAKAHIKO HOSHITA
1981 Volume 29 Issue 4 Pages
1136-1139
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The total structure of 5β-bufol sulfate, which is the major bile salt of the toad, Bufo vulgaris formosus, was elucidated as the 26-sulfate ester of 5β-cholestane-3α, 7α, 12α, 25, 26-pentol on the basis of
13C-NMR. This method can thus be used for determination of the location of the sulfate ester group in bile alcohol sulfates.
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HARUHISA UEDA, NAOKI NAMBU, TSUNEJI NAGAI
1981 Volume 29 Issue 4 Pages
1140-1146
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The permeation of sulfonylureas through cellulose and dimethylpolysiloxane membranes was investigated as part of a series of pharmaceutical studies on sulfonylureas. In the case of cellulose membrane, the permeability decreased with increase in the molecular volume of sulfonylureas. The activation energy of permeation was close to that of diffusion of usual organic medicinals in water. The effect of pH on the permeation was negligibly small under the conditions used in this study. These results suggested that the permeation of sulfonylureas through cellulose membrane proceeds by diffusion through pores. In the case of dimethylpolysiloxane membrane, at pH 2, the permeability constants, P, of tolbutamide, chlorpropamide, glyclopyramide and tolazamide were 16.15, 5.13, 2.33 and 0.95×10
-8 cm
2·sec
-1, respectively, and the diffusion constants of the four drugs were all calculated to be (14.92±1.39)×10
-7 cm
2·sec
-1. The results for tolbutamide indicate that the rate of permeation of sulfonylureas through the membrane is pH-dependent because only the undissociated species can permeate through the membrane.
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MASAAKI MORI, YOSHIFUMI NARUSE, HIROSHI KOZUKA
1981 Volume 29 Issue 4 Pages
1147-1150
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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Nine metabolites of 2, 4-dinitrotoluene (2, 4-DNT) in rat urine were detected by thin-layer chromatography (TLC) after repeated oral administration to male Wistar rats. These metabolites, 2-amino-4-nitrotoluene (2A4NT, M-I), 4-amino-2-nitrotoluene (4A2NT, M-II), 2, 4-diaminotoluene (2, 4-DAT, M-III), 2, 4-dinitrobenzyl alcohol (2, 4-DNB, M-IV), 2-amino-4-nitrobenzyl alcohol (2A4NB, M-V), 4-amino-2-nitrobenzyl alcohol (4A2NB, M-VI), 2-nitro-4-acetylaminotoluene (2N4AAT, M-VII), 2-amino-4-acetylaminotoluene (2A4AAT, M-VIII) and 2-amino-4-acetylaminobenzoic acid (2A4AAB, M-IX), were identified by comparison of ultraviolet (UV) and mass spectral data with those of authentic samples. The probable metabolism of 2, 4-DNT in rats is discussed on the basis of these results.
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MASAHIRO HATA, NAOKI NAMBU, TSUNEJI NAGAI
1981 Volume 29 Issue 4 Pages
1151-1155
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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In order to assess the suitability of chlorhexidine for dental use, we investigated the effects of various factors such as temperature, pH, inorganic ions (F
-, Ca
2+, Sr
2+, Na
+) and polymers (mucin, bovine serum albumin, polyvinylpyrrolidone) on the adsorption of chlorhexidine gluconate (CHG) from aqueous solution by hydroxyapatite (HAP). The adsorption isotherms were of Langmuir type at low equilibrium concentration. The amount adsorbed was of the order of 10
-7 mol/g, and was a little higher at 10°than at 37°. With the addition of inorganic ions such as Ca
2+, Sr
2+ and Na
+, the amount of CHG adsorbed decreased. These results indicated that the adsorption involves electrostatic forces, and is a physical adsorption. Fluoride had an interesting effect on the adsorption. When the concentration of F
- was low (0.01 M), the amount adsorbed was higher, while when the concentration was high (0.1 and 0.25 M), the amount adsorbed was lower. This phenomenon might be a result of the formation of CaF
2 on the surface of HAP. Polymers such as mucin and bovine serum albumin increased the adsorption of CHG by HAP. This might be due to the strong binding of CHG with these polymers. On the other hand, polyvinylpyrrolidone had no significant effect on the adsorption.
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KIYOSHI IKEDA, YOSHIYASU TERAO, MINORU SEKIYA
1981 Volume 29 Issue 4 Pages
1156-1159
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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Reaction of silyl enol ethers of ketones and aldehydes with 1, 3, 5-trialkylhexahydro-1, 3, 5-triazines in the presence of acetyl chloride and titanium tetrachloride afforded α-N-alkylacetamidomethylated carbonyl compounds. Thus, the reaction provides a convenient, general method for introduction of the N-alkylacetamidomethyl moiety at a position α to a carbonyl group.
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ATSUKO NOSE, TADAHIRO KUDO
1981 Volume 29 Issue 4 Pages
1159-1161
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The reduction of aromatic nitro compounds with the sodium borohydride-nickelous chloride system was examined. Aromatic nitro compounds afforded primary amines in high yield without by-products. Similarly, nitroso-, azoxy-, azo- and hydroxylaminobenzene were reduced with sodium borohydride-nickelous chloride to give aniline.
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SHIRO URANO, SHINJU YAMANOI, MITSUYOSHI MATSUO
1981 Volume 29 Issue 4 Pages
1162-1165
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The reactivity of some tocopherols (vitamin E) with the methyl radical was examined. When the methyl radical was generated from dimethyl sulfoxide by the action of hydrogen peroxide in the presence of ferrous sulfate, either β-tocopherol or γ-tocopherol reacted with it to give the corresponding methyl ether and 2, 5, 5, 7, 8-pentamethyl-2-(4, 8, 12-trimethyltridecyl) chroman-6 (5H)-one in Iow yields. Tocol afforded only a small amount of its methyl ether. On the other hand, 5, 7-dimethyltocol was converted to its methyl ether and 2, 5, 5, 7-tetramethyl-2-(4, 8, 12-trimethyltridecyl) chroman-6 (5H)-one in 9 and 38% yields, respectively. Taken with the previous data on α-tocopherol, these results indicate that the radical scavenging abilities of tocopherols against the methyl radical are in the following order : α-tocopherol≥5, 7-dimethyltocol>β-tocopherol=γ-tocopherol≥tocol.
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YOSHIHISA OKAMOTO, TOSHIO KINOSHITA
1981 Volume 29 Issue 4 Pages
1165-1169
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The reaction of 3-substituted-4-amino-1H-1, 5-benzodiazepines (1a, b) with sodium borohydride afforded deaminated compounds (4a, b and 6a, b). On the other hand, acyclic amidines were converted by treatment with sodium borohydride to the corresponding secondary amines (13) under the same conditions.
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MINORU KUBOTA, OSAMU NAGASE, HARUAKI YAJIMA
1981 Volume 29 Issue 4 Pages
1169-1171
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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MASAYOSHI YAMAGUCHI, TAKEO YAMAMOTO
1981 Volume 29 Issue 4 Pages
1172-1175
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The effects of fasting and thyroparathyroidectomy on bile calcium excretion in rats were investigated. The bile calcium excretion in rats fasted for 24 hr decreased slightly in comparison with that of fed rats. A single intraperitoneal administration of calcium chloride (4.0 mg Ca/100 g) to fed rats produced a remarkable elevation of bile calcium excretion, while a significant increase was not observed in fasted rats. On the other hand, thyroparathyroidectomy caused a significant reduction of bile calcium excretion in both fed and fasted rats. This reduction was much more pronounced in fasted rats than in fed rats. In thyroparathyroidectomized rats, a single intraperitoneal administration of calcium chloride (4.0 mg Ca/100 g) in both fed and fasted rats did not produce a significant elevation of bile calcium excretion. These results suggest that the bile calcium excretion is regulated by dietary calcium, as well as by the thyroid and parathyroid glands.
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YUJI KUROSAKI, TOSHIKIRO KIMURA, SHOZO MURANISHI, HITOSHI SEZAKI
1981 Volume 29 Issue 4 Pages
1175-1179
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The stability of liposomal enzymes and the encapsulation efficiency of reverse-phase evaporation vesicles (REV) were investigated in comparison with those of the original small multilamellar liposomes (SML), by using elastase as a model-enzyme. The encapsulation efficiency of REV was greatly superior to that of SML. In addition, REV retarded the inactivation of elastase in the neutral pH region, as did SML. Therefore the REV method should be useful for the preparation of carriers to encapsulate not only elastase but also other macromolecules. However, at lower pH, pH 2.63, where elastase was rapidly inactivated, REV accelerated the inactivation of the enzyme, although SML retarded it, as at neutral pH. Thus, since liposomes prepared by different methods have significantly different physicochemical properties, further and more precise studies on the methods of preparation are required.
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SUMIE YOSHIOKA, HIROYASU OGATA, TOSHIO SHIBAZAKI, AKIRA EJIMA
1981 Volume 29 Issue 4 Pages
1179-1181
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The analgesic effects of the decomposition products of sulpyrine, N-[2-(5-hydroxymethyl-2, 3, 4, 5-tetrahydro-2, 3, 4-trihydroxy) furyl] methyl-N-methylantipyrine (MAAG) and antipyrinyl-4-peroxide (AP), which were reported by us previously, were determined by measurement of the inhibition of writhing caused by the injection of acetic acid into male mice, and compared with the effects of sulpyrine and antipyrine. MAAG and AP showed 62% and 48% of the potency of sulpyrine, respectively, in spite of having hydrophilic substituents. It is suggested that the analgesic effects of these compounds are intrinsic to the compounds themselves.
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TAKAHARU MIZUTANI, KAORUKO WAGI, YOSHIE TERAI
1981 Volume 29 Issue 4 Pages
1182-1183
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The amounts of diazepam adsorbed on silicone-coated glass surfaces (100m
2) were 0.39mg in 5% dextrose in water, 0.37mg in lactated Ringer's solution, and 0.46mg in Ringer's solution. The amounts of diazepam bound on non-coated glass surfaces were much lower (4-23μg/100m
2) in the same solutions.
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GENICHRO NONAKA, YOUKO MATSUMOTO, ITSUO NISHIOKA
1981 Volume 29 Issue 4 Pages
1184-1187
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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A novel hydrolyzable tannin named trapain has been isolated from Trapa japonica FLEROV. (Oenotheraceae), and the structure has been established as II on the basis of the spectroscopic and chemical evidences.
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SACHIKO YAMADA, MASAYUKI OHMORI, HIROAKI TAKAYAMA, TATSUO SUDA, YOSHIK ...
1981 Volume 29 Issue 4 Pages
1187-1188
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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The synthesis of 25-hydroxy-24-oxovitamin D
3 is described. The compound is identical in all respects with the natural product.
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ISAO KITAGAWA, MOTOMASA KOBAYASHI, TATSUYA INAMOTO, TOHRU YASUZAWA, YO ...
1981 Volume 29 Issue 4 Pages
1189-1192
Published: April 25, 1981
Released on J-STAGE: March 31, 2008
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Six new antifungal triterpene-oligoglycosides named stichlorosides A
1, A
2, B
1, B
2, C
1, and C
2 have been isolated from the sea cucumber Stichopus chloronotus (BRANDT). The structures of their genuine aglycones stichlorogenol (1) (for A
1, B
1, and C
1) and dehydrostichlorogenol (2) (for A
2, B
2, and C
2) have been elucidated on the bases of chemical and physicochemical evidence together with the X-ray analysis of 1. They are the first examples of lanost-7-ene type aglycones isolated from sea cucumber.
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