Chemical and Pharmaceutical Bulletin
Online ISSN : 1347-5223
Print ISSN : 0009-2363
ISSN-L : 0009-2363
29 巻, 2 号
選択された号の論文の54件中1~50を表示しています
  • 梅山 秀明, 工藤 貴子, 中川 節子
    1981 年 29 巻 2 号 p. 287-292
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The heat of complex formation of H3PBH3 was calculated to be -15.3 kcal/mol by double zeta ab initio LCAO MO SCF calculations ; this is very similar to the experimental values for (CH3)3PB(CH3)3 and (CH3)3PBF3. The origin of complex formation of H3PBH3 was elucidated by energy decomposition methods. The order of contributions is ES-(41%)>CT (37%)> PL (22%). The d atomic orbitals on phosphorus play a role in increasing the polarization energy upon complex formation. The barrier to internal rotation of H3PBH3 was calculated to be 2.4 kcal/mol, which is in very good agreement with the experimental value of 2.47kcal/mol. The exchange repulsion and the charge transfer energy related to the staggered form contribute to the barrier to internal rotation. The change of the charge transfer energy corresponds to the difference of the barrier heights between H3PBH3 and H3SiCH3. The energies of complex formation of F3PBH3 and (CH3)3PBH3 were calculated, to investigate the origin of the barrier to internal rotation.
  • 湯川 栄二, 香野 敬喜, 小野 行雄, 上田 陽
    1981 年 29 巻 2 号 p. 293-300
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A quantum chemical method for prediction of the specific atom of 1, 2, 3, 4-tetrahydronaphthalene or indane at which hydroxylation will occur most easily in liver microsomes is presented. The interaction energy changes of a binary system composed of the hydrocarbon and O2 caused by changes of the mutual spatial arrangement between the hydrocarbon and O2 were calculated by the CNDO/2 method. The theoretical predictions were found to coincide very well with the reported experimental results.
  • 香野 敬喜, 小川 千穂子, 下村 由紀子, 矢野 弘重, 上田 陽
    1981 年 29 巻 2 号 p. 301-307
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The interaction between imidazole and p-benzoquinone in acetonitrile was investigated at both low temperature (below 0°) and room temperature. The step of formation of the charge-transfer complex between two intact molecules could not be detected. Instead, the two compounds were found to react with each other fairly quickly at room temperature to form 2, 5-bis (imidazol-1-yl) hydroquinone, 2, 3-bis (imidazol-1-yl) hydroquinone and hydroquinone.
  • 田村 眞造, 尾能 満智子
    1981 年 29 巻 2 号 p. 308-317
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The hydrolysis of acyl derivatives of malonaldehyde dianil was examined. Alkaline hydrolysis of 1-(N-acetyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (V) in aqueous ethanol gave simply 1-(p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (malonaldehyde dianil of p-toluidine) (VI) and acetic acid. Hydrolysis of 1-(N-benzoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (VII) in aqueous dioxane in the presence of equimolar amounts of acetic acid and sodium acetate gave β-(p-toluidino) acrolein (VIII), β-(N-benzoyl-p-toluidino) acrolein (XIII) and N-benzoyl-p-toluidine. A small amount of β-(p-toluidino) crotonaldehyde (II) was obtained by hydrolysis of 1-(N-benzoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-butene (IX). The buffer-catalyzed hydrolysis reaction of VII was followed by measuring the PMR spectrum of the reaction solution to elucidate the sequence of the reaction process.
  • 大塚 栄子, 若林 利明, 田中 正治, 田中 俊樹, 押柄 和幸, 長谷川 明, 池原 森男
    1981 年 29 巻 2 号 p. 318-324
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    2'-and 3'-O-(o-Nitrobenzyl) derivatives of uridine, cytidine, adenosine and guanosine were synthesized by treatment of uridine, N-benzoylcytidine, N-benzoyladenosine and N-isobutyrylguanosine, respectively, with o-nitrophenyldiazomethane followed by isolation and deblocking. 3'-O-(o-Nitrobenzyl) guanosine is a novel compound. By using N-acylated nucleosides, separation of the 2'-and 3'-substituted isomers on silica gel became feasible and these compounds were useful intermediates for the synthesis of oligoribonucleotides. Some physical properties of these compounds were studied by ultraviolet, nuclear magnetic resonance, circular dichroism and the 2'-substituted isomers were found to have more stacked structures than the 3'-isomers.
  • 福田 直通, 今村 成子, 斉藤 英子, 野原 稔弘, 川崎 敏男
    1981 年 29 巻 2 号 p. 325-335
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Three oligoglycosides of 18-norspirostane derivatives, Ty-2, Ty-3, and Ty-4, along with two steroidal compounds, Tm and Tj, were isolated from the underground parts of Trillium kamtschaticum PALL. These five compounds and two other compounds, Th and Tz acetate, which had been obtained previously but remained unidentified, were characterized as follows. Ty-2, mp 235-240°(dec.), [α]D-110° : deapio-trillenoside A (II) (named trillenoside B). Ty-3, mp 182-185°(dec.), [α]D-98.7° : 3, 21-di-O-acetyl-24-epitrillenogenin 1-O-(2', 3', 4'-tri-O-acetyl-α-L-rha·pyr)-(1-2)-α-L-ara·pyranoside (IV) (epitrillenoside C-PA). Ty-4, mp 226-230°(dec.), [α]D-105°; 21-deoxytrillenoside A (VII) (deoxytrillenoside A). Tm, mp 326-329°(dec.), [α]D-99.4° : 24β-hydroxypennogenin (V). Tj, mp 205-212°(dec.), [α]D-66.5° : prototype compound (VIII) of pennogenin 3-O-β-chacotrioside. Th, mp 194-200°(dec.), [α]D-90° : prototype compound (IX) of pennogenin 3-O-α-L-rha·pyr-β-chacotrioside. Tz acetate : crude ecdysterone triacetate (X). This is the first report of the natural occurrence of these compounds, except for IX and X ; the occurrence of IV is particularly interesting. VIII and IX had been expected to coexist with the corresponding pennogenin glycosides.
  • 南條 勝美, 鈴木 邦夫, 関屋 実
    1981 年 29 巻 2 号 p. 336-343
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The present paper describes the enantioface-differentiaing epoxidation of alkylidenemalononitriles with molecular oxygen, catalyzed by chiral tertiary amines. In the light of the by-product formation, the reaction path was concluded to involve intermolecular nucleophilic attack of a hydroperoxide intermediate catalyzed by a chiral tertiary amine. A similar epoxidation was demonstrated with cumylhydroperoxide in the presence of nicotine.
  • 小笹 茂, 藤岡 靖弘, 塚田 真千代, 伊夫伎 英一
    1981 年 29 巻 2 号 p. 344-355
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Eight new linear octiphenyls containing two or three kinds of linkage were synthesized by the Ullmann homo-coupling reaction of iodoquaterphenyl. Among them, five compounds were alternatively synthesized by the Kharash-type Grignard cross-coupling of biphenylylmagnesium bromide and diiodoquaterphenyl or of terphenylylmagnesium iodide and diiodoquaterphenyl in the presence of bis (acetylacetonato) nickel (II). Spectral studies proved that the octiphenyls thus prepared displayed highly characteristic infrared, ultraviolet, and nuclear magnetic resonance spectra. Empirical Huckel molecular orbital calculations of the longest wavelength absorption bands of the octiphenyls were also performed. The calculated and observed wavelengths were in rather good agreement, except for the cases of two compounds.
  • 佐藤 良博, 園田 よし子
    1981 年 29 巻 2 号 p. 356-365
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Starting from lanosteryl acetate (1b), we synthesized twelve lanosterol analogs (cf. Chart 1-3 ; 9, 11, 14, 16, 18a, 19, 26, 27a, 28, 29, 30, 32) with different sizes of side chain and 20-iso-24-dihydrolanosterol (37), for biological studies. The analogs have shorter side chains than 1b except for the 24-ethylidene derivative (19) and 37. 20-Iso-24-di-hydrolanosterol (37) was prepared via 20-iso-22-dehydro-24-dihydrolanosterol [obtained by the Wittig reaction of 20R, S-aldehyde mixture (6, 33) with isoamyl triphenylphosphonium iodide, followed by column chromatographic separation].
  • 高畑 廣紀, 石倉 稔, 永井 克昌, 永田 正典, 山崎 高応
    1981 年 29 巻 2 号 p. 366-369
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The reaction of methyl valerolactim (1) with cyclic β-aminoester (6) afforded only 1, 9-diazasteroid (14), whereas that of methyl valerothiolactim (2) with 6 led to the cyclic diamide (12) together with 14. The latter reaction, followed by iodination and reduction, gave 5, 9-diazasteroid (17).
  • 小笹 茂, 藤岡 靖弘, 岡田 基文, 和泉 裕美, 伊夫伎 英一
    1981 年 29 巻 2 号 p. 370-378
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A Kharash-type Grignard cross-coupling reaction of phenyl-d5-magnesium bromide and an appropriate diiodo compound in the presence of bis (acetylacetonato) nickel (II) was successfully employed for the syntheses of twelve new decadeuterated polyphenyls, each of which has phenyl-d5 rings at both termini. On the basis of the nuclear magnetic resonance spectra of the deuterated and normal polyphenyls, close correlations between the apparent signal patterns of phenylene groups and the structures of the adjacent groups became apparent. The mass spectral studies revealed that the deuterated polyphenyls containing o-linkage (s) were less stable to electron bombardment than those containing no o-linkage. Inspection of the ultraviolet spectra of the deuterated polyphenyls showed that the isotope effect in their K-bands was hardly detectable.
  • 米田 文郎, 中川 敬士, 野口 みつ子, 樋口 昌嗣
    1981 年 29 巻 2 号 p. 379-385
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Treatment of 3-methyl-6-(1-methylhydrazino) uracil (I) with phenacyl bromides in ethanol afforded the corresponding 3-aryl-4, 8-dihydro-1, 6-dimethylpyrimido [4, 5-c]-pyridazine-5, 7 (1H, 6H)-diones (3-aryl-4, 8-dihydro-4-deazatoxoflavins) (II) and 3-aryl-1, 7-dimethyl-6, 8-dioxo-1, 4, 6, 7, 8-pentahydropyrimido [4, 3-c]-as-triazines (III). Oxidation of II with diethyl azodicarboxylate gave the corresponding 3-aryl-4-deazatoxoflavins (IV) in quantitative yields. The reaction of aryl aldehyde N-methyl-N-(3-methyluracil-6-yl)-hydrazones (VII) with triethyl orthoformate in dimethylformamide also gave the corresponding 3-aryl-4-deazatoxoflavins (IV). Compounds IV thus obtained oxidized alcohols under alkaline conditions in the dark to yield the corresponding carbonyl compounds, while they themselves were hydrogenated to compounds II. Under certain conditions, these oxidations were automatically recycled to give the corresponding carbonyl compounds in more than 100% yields.
  • 堀 孝子, 吉田 長作, 村上 昭八, 木羽 泰男, 竹野 隆恒, 中野 譲二, 津田 久嗣, 才川 勇
    1981 年 29 巻 2 号 p. 386-389
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Degradation products of 1-(2-chloroethyl)-3-(4-substituted-2, 3-dioxo-1-piperazinyl)-alkyl-1-nitrosourea in aqueous solution were investigated. Among them, a symmetrical urea derivative, 1, 3-bis [4-(4-ethyl-2, 3-dioxo-1-piperazinyl) butyl] urea (3c), was found to have antitumor activity. A synthetic unsymmetrical urea derivative, 1-[2-(4-ethyl-2, 3-dioxo-1-piperazinyl) ethyl]-3-methylurea (4a), also showed antitumor activity against Ehrlich carcinoma (solid form).
  • 大本 太一, 小池 一男, 坂本 曜子
    1981 年 29 巻 2 号 p. 390-395
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    1-Acetyl-4-methoxy-β-carboline (I), canthin-6-one (VIIIa), 1-methoxycanthin-6-one (VIIIb), and canthin-6-one-3N-oxide (IXa), and three new alkaloids, 1-(2'-hydroxyethyl)-4-methoxy-β-carboline (IIa), 1-(1', 2'-dihydroxyethyl)-4-methoxy-β-carboline (IIIa), and 1-methoxycanthin-6-one-3N-oxide (IXb), were isolated from the root bark of Ailanthus altissima SWINGLE (Simaroubaceae). The structures of IIa, IIIa, and IXb were elucidated by spectroscopic and chemical studies.
  • 十一 元晴, 藤谷 ゆかり, 安東 良子
    1981 年 29 巻 2 号 p. 396-401
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Total syntheses of 'abnormal-type' erythrinan alkaloids, (±)-coccolinine (1), (±)-isococculidine (2), (±)-coccuvinine (3) and (±)-cocculidine (4), are described. Mondon's glyoxylic ester synthesis was successfully applied in these syntheses. The key intermediate, 16-ethoxycarbamido-2, 15-dimethoxyerythrinan-7, 8-dione (7), was obtained by condensation of 3-ethoxycarbamido-4-methoxyphenylethylamine (5) with ethyl 4-methoxycyclohexanone-2-glyoxylate (6), followed by treatment with phosphoric acid. The ethoxycarbamido group at the C16 position was effectively employed as a regiospecific para-directing group in the isoquinoline ring closure.
  • 大和 正利, 橋垣 国子, 池田 雅夫, 大竹 英俊, 田坂 賢二
    1981 年 29 巻 2 号 p. 402-405
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    1'-Alkylspiro [isochroman-3, 4'-piperidin]-1-ones (2) and 1'-alkylspiro [isochroman-4, 4'-piperidines] (4 and 5) were prepared and examined for analgesic activity. Several of the 4-spiro compounds (3, 4, and 5) were found to have analgesic activity as potent as that of aminopyrine, while the 3-spiro compounds (2) were inactive. Further pharmacological studies revealed that several of these compounds inhibited the histamine release induced by compound 48/80 from isolated rat peritoneal mast cells.
  • 佐藤 晋, 赤岩 明, 藤本 善徳, 石黒 正路, 池川 信夫
    1981 年 29 巻 2 号 p. 406-415
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A stereoselective synthesis of demethylgorgosterol (2) is described. Alkylation at the C-22 position of the steroidal 23-aldehyde (5) was achieved by Claisen rearrangement of the piperidine enamine to give the (22S)-22-aldehyde (10a) predominantly. Compound 10a was transformed to the 22-hydroxymethyl-24-aldehyde mesylate (15a). When the mesylate was treated with potassium t-butoxide, the 22, 23-cyclopropyl 24-aldehyde (19a) was obtained in high yield. An isopropyl group was introduced at the C-24 position by means of the Grignard reaction and subsequently the hydroxy group was oxidized to provide the 24-ketone (25a). Wittig reaction of 25a followed by hydroboration and then LiAIH4 reduction of the mesylate gave 2, which was identical with the natural compound in all physical properties. Three other epimers, the (22R, 23R, 24S)-isomer (32), (22S, 23S, 24R)-isomer (34) and (22S, 23S, 24S)-isomer (35), were prepared by the same procedure. These four isomers can be separated by gas-liquid chromatography on a glass capillary column coated with OV-17.
  • 阿部 フミ子, 山内 辰郎
    1981 年 29 巻 2 号 p. 416-420
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Teikaside A, one of the pregnane glycosides of Trachelospermum asiaticum (Apocynaceae), was isolated and its structure was determined to be 3-O-(β-D-digitalosyl)-20-O-(β-D-glucosyl-β-D-sarmentosyl)-3β, 17α, 20α-trihydroxy-5α-pregn-6-ene. In view of the structural similarity to the glycosides in Bei-Wujiapi, which are known to induce the potentiation of the nerve growth factor, similar physiological activity is expected in teikaside A.
  • 森 雅美, 手島 節三
    1981 年 29 巻 2 号 p. 421-425
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The new reducing disaccharide 4-O-α-D-altropyranosyl-D-glucopyranose (12) was synthesized by isomerization of secondary hydroxyl groups in the non-reducing part of maltose. Treatment of 1, 6-anhydro-4', 6'-O-benzylidene-2, 2'-di-O-tosyl-β-maltose (2) with methanolic sodium methoxide at room temperature gave the corresponding monoepoxide (3) in 90% yield, in which the oxirane ring is located in the reducing part of maltose. When the reaction was performed at boiling temperature, the diepoxide (5) having α-D-mannopyranosyl-D-mannopyranose configuration was obtained in 77% yield. Compound 5 was also obtainable from 2 in 79% yield. Heating a mixture of 5 and excess potassium hydroxide resulted in trans-diaxial cleavage of both oxirane rings, and 2, 3-di-O-acetyl-1, 6-anhydro-4-O-(2, 3-di-O-acetyl-4, 6-O-benzylidene-α-D-altropyranosyl)-β-D-glucopyranose (6) was isolated in 81.4% yield after acetylation of the cleavage product. Compound 6 was also obtainable from 2 in 59% yield. The disaccharide 12 was prepared as a hygroscopic amorphous powder after removal of the protecting groups of 6 as follows ; debenzylidenation, acetylation, acetolysis, and deacetylation.
  • 杉浦 衛, 加藤 憲二, 足立 哲夫, 伊藤 吉将, 平野 和行, 沢木 [シュン]二
    1981 年 29 巻 2 号 p. 426-429
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    We have established new colorimetric methods for the assay of adenosine deaminase, purine nucleoside phosphorylase and guanase activities in serum, based on the formation of hydrogen peroxide with xanthine oxidase as a coupling enzyme. [chemical formula] The proposed methods were found to be precise and convenient. Under the assay conditions, the mean levels of adenosine deaminase, purine nucleoside phosphorylase and guanase activities in the sera of normal subjects were 5.8±2.2 I. U./1, 3.7±2.1 I. U./1 and 0.5±0.3 I. U./1, respectively.
  • 杉浦 衛, 加藤 憲二, 足立 哲夫, 伊藤 吉将, 平野 和行
    1981 年 29 巻 2 号 p. 430-432
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A colorimetric method for the assay of xanthine oxidase activity, based on the production of hydrogen peroxide, is described. [chemical formula] The precision, accuracy, sensitivity and specificity of the method were found to be satisfactory for the rapid and reliable determination of xanthine oxidase activity.
  • 狐塚 寛, 小山 又次郎, 興津 知明
    1981 年 29 巻 2 号 p. 433-437
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The murexide reaction was investigated to clarify the mechanism of the coloration, with caffeine as a model compound. From the reaction mixture of caffeine with hydrogen peroxide and hydrochloric acid, 1-hydroxy-5, 7-dimethyl-2, 4, 6-trioxo-1H, 5H, 7H-oxazolo-[4, 5-d] pyrimidine (yellow oil) (I) and 1, 3, 7-trimethyl-2, 6, 8-trioxo-9-hydroxy-1H, 3H, 7H-xanthine (red powder) (II) were isolated, and these two compounds were shown to be responsible for the murexide reaction of caffeine. Compound I was regarded as a key intermediate, since its purple coloration with dil. ammonia was similar to that of caffeine developed by the murexide reaction. The absorption maximum of II corresponds to that of the red-colored solution obtained from the reaction of caffeine with hydrogen peroxide and hydrochloric acid.
  • 市川 哲生, 寺田 弘
    1981 年 29 巻 2 号 p. 438-444
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The second derivative spectra of N-acetyl ethyl esters of tryptophan, tyrosine and phenylalanine were measured with various values of derivative wavelength difference, Δλ, at pH 7 and 13. The second derivative spectra of tryptophan at pH 7 and 13 were very similar at and Δλ, as were those of phenylalanine. However, the derivative spectrum of tyrosine at pH 13 was quite different from that at pH 7 ; at pH 7 there were two peaks and troughs between 270 and 300nm, whereas at pH 13, these spectral bands were not present but there were broad positive and negative spectral bands, due to acid dissociation of the phenolic-OH group. A method for the quantitative determination of these amino acids was developed on the basis of the spectral properties of the three aromatic amino acids. This method should be suitable for determining the amounts of these three aromatic amino acid residues in proteins.
  • 田中 共生, 田中 邦幸
    1981 年 29 巻 2 号 p. 445-450
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Azothiopyrine and methyl-azothiopyrine were synthesized as new chelating agents which form stable chelates with some metal ions at the mercapto and azo groups. Azothiopyrines are unusually stable in solution because of a strong intramolecular hydrogen bond between the mercapto and azo groups. The chelates of azothiopyrines with nickel (II), cobalt (II), copper (II), zinc (II), cadmium (II), mercury (II), Palladium (II) and silver (I) were prepared in a neutral or slightly acidic medium, and characterized by elementary analysis, and visible and ultraviolet absorption spectroscopy. The metal chelates are stable, insoluble in water, and extractable into some organic solvents, and the excess azothiopyrines can be removed by extraction with sodium hydroxide solution without decomposition of the metal chelates. Azothiopyrines may be applicable to extraction spectrophotometric determination of such metal ions as palladium (II), mercury (II), copper (II), nickel (II) and cobalt (II), in view of the high molar extinction coefficients of the chelates.
  • 広島 修, 池谷 理, 大前 雅彦, 河部 靖
    1981 年 29 巻 2 号 p. 451-455
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Electrochemical detection was applied to high-performance liquid chromatography (adsorption chromatography). The column eluate was mixed with methanol-ethanol mixture containing NaClO4 as a supporting electrolyte and analyzed with an electrochemical detector. We applied this method to the determination of tocopherol isomers (TP) in wheat germ oil and phylloquinone isomers (PK) in rat plasma. The limits of detection were 1 ng and 10 ng for TP and PK, respectively. The present method can be applied to the determination of small amounts of geometricalisomers or stereoisomers
  • 早川 尭夫, 谷本 剛, 木村 俊夫, 川村 次良
    1981 年 29 巻 2 号 p. 456-462
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    In order to investigate the functional role of the region around the A and B rings of 20-oxo-steroids in the interaction with the binding site of 20β-hydroxysteroid dehydrogenase, kinetic studies were made using 28 kinds of steroids which differed in the nature of the substituent, and in the shape and electronic character of the region around the A and B rings. Structural changes in the A ring of steroids, such as reduction of pregn-4-ene derivatives to the corresponding 5α- or 5β-pregnane derivatives, introduction of a further double bond into the A ring, and change of the 5α-series to 5β-series or change in the configuration and size of the substituent at C-3 caused only small changes in the apparent Km and Vmax values. It is suggested that the region around the A ring is of little significance in the interactions between a steroid molecule and the enzyme. It seems unlikely that the electronic character and shape of the B ring affect the steroid-enzyme interaction, since introduction of a C-5/C-6 double bond scarcely changed the kinetic constants. Neither a nonpolar (methyl group) nor a polar (hydroxyl group) substituent at the C-6 α-position (equatorial) produced any appreciable changes in the kinetic constants. Further, a 6-methyl group and a 9α-fluoro group (axial) did not cause any marked changes in the kinetic constants. On the other hand, introduction of a hydroxyl group at the C-6 β-position (axial) or removal of the 10β-methyl group caused a marked increase in the apparent Km. These findings suggest that recognition of the steroid moiety by the enzyme may involve the 10β-methyl group and the region around the β-side of the B ring. The nature of the interaction of these regions of the steroid with the enzyme may be hydrophobic, since a polar 6β-hydroxyl group had a marked repulsive effect on the steroid binding site of the enzyme, while a 10β-methyl group increased the binding affinity of the steroid.
  • 三羽 信比古, 高柳 博一, 鈴木 章
    1981 年 29 巻 2 号 p. 463-471
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A method for the efficient further purification of two active forms of urokinase (UK) [EC. 3. 4. 21. 31] from partially purified human urinary UK was established by serial column chromatography on Sephadex G-100, Sephadex G-75, and SP-Sephadex C-50. According to Ferguson plots two active forms showed molecular weights of 5.5×104 (H-UK) and 3.6×104 (H-UK). Both UK forms were shown to be homogeneous by SDS-polyacrylamide gel electrophoresis, gel gradient electrophoresis, and Ouchterlony's double immunodiffusion method. Amino acid analysis showed that there was no marked difference in composition between H- and L-UK. The specific activity of H-UK was 1.2×105 IU/mg protein, which exceeds the highest specific activity that has ever been obtained by other investigators, and that of L-UK was 1.52×105 IU/mg protein. These results suggest that this serial column chromatography procedure is effective for the purification of H-UK, which is known to be a pharmacologically advantageous form. As judged by isotachoelectrophoresis, H-UK contained five subforms with pI values of 8.7, 8.9, 9.1, 9.2, and 9.4, and L-UK contained the same number of subforms with pI values of 7.5, 8.3, 8.8, 9.4 and 9.7. The pI values of the subforms with the highest specific activity were 9.4 for H-UK and 8.3 and 8.8 for L-UK. Judging from the dissimilarity in the pI values of UK preparations obtained so far by other investigators and ourselves, we consider that the subforms of UK obtained after purification do not correspond to the forms present in vivo, but are artifacts of the purification procedures used.
  • 三羽 信比古, 小畑 雄司, 鈴木 章
    1981 年 29 巻 2 号 p. 472-475
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    pH-stability curves and heat inactivation of the MW 55000 form (H-UK) and MW 36000 form (L-UK) of human urinary urokinase [EC 3. 4. 21. 31] were investigated by measurements of plasminogen activator activity. L-UK was distinctly more stable than H-UK (in terms of activity) on incubation at pH 6.8-9.6 or on heat treatment at temperatures above 60°. The ranges of pH 8.2-9.0 and 5-37°, were favorable for both H-UK and L-UK.
  • 川村 次良, 谷本 剛, 福田 秀男, 早川 尭夫
    1981 年 29 巻 2 号 p. 476-484
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    In order to investigate the functional role of the region around the C and D rings in the interaction of steroids with the binding site of 20β-hydroxysteroid dehydrogenase, kinetic measurements were made for 34 kinds of steroids which differed in the nature of substituents, and in the shape and electronic character of the region around the C and D rings. Introduction of an oxo group at C-11 increased the apparent Vmax, apparent Km and II (Km/Vmax) values 2- to 9-, 13- to 195-, and 2- to 30-fold, respectively. Introduction of a hydroxyl group at the C-11β-position markedly increased the apparent Km (58- to 119-fold) and II (164- to 256-fold) values, but decreased the apparent Vmax value to one-half to one-third. An 11α-hydroxyl group caused an increase in the apparent Km value similar to that caused by an 11β-hydroxyl group, but the degree of decrease in the apparent Vmax value was rather lower. Esterification of the 11α-hydroxyl group led to a decrease in the apparent Km value (0.3-fold) without any significant change in the Vmax value. It is suggested that a binding interaction may occur between the region around C-11 of the steroid and the enzyme-coenzyme complex ; the interaction is probably hydrophobic in nature. A substituent at C-16 had an inhibitory effect on the hydrogen transfer stage since it resulted in loss of the substrate activity or a marked decrease in the Vmax value (to about 1%) and an increase in the Km value (23-fold). Introduction of a C-16/C-17 double bond, which caused a change in the configurational relationship between the 17β-side chain and the D ring, markedly decreased the apparent Vmax value (to one-thirtieth) and increased the apparent Km value (43-fold). Introduction of a hydroxyl group at C-18 had a marked effect on the kinetic constants, though the extent of the effect depended on the substituent at C-21. The steric and polar properties of the substituent at C-18 seem to be important factors in the interaction of the steroid with the binding site of the enzyme, and indirectly in that with the catalytic site. The features of the interaction between 20β-hydroxysteroid dehydrogenase and 20-oxo-steroids, as deduced from the results of the present and previous studies, are discussed.
  • 松井 勝彦, 福田 清美, 亀田 幸雄
    1981 年 29 巻 2 号 p. 485-489
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Amino groups of alanine dehydrogenase from Bacillus natto KMD 1126 were modified by treatment with 2, 4, 6-trinitrobenzenesulfonic acid (TNBS) ; this resulted in loss of the enzyme activity with pseudo first order kinetics. However, sulfhydryl groups were not modified by TNBS, and the circular dichroism spectrum of the TNBS-modified enzyme was identical with that of the native enzyme. Complete inactivation was obtained upon modification of 5 amino groups per subunit of the enzyme. However, a plot of log [reciprocal of the half-time of inactivation] versus log [concentration of TNBS] suggested that one amino group has an essential role in the catalysis. Protection against inactivation by TNBS was not observed on the addition of nicotinamide adenine dinucleotide or its reduced form.
  • 日合 奨, 横山 弘臣, 大浦 彦吉
    1981 年 29 巻 2 号 p. 490-494
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The effect of β-escin on plasma adrenocorticotropin (ACTH) and corticosterone levels in rat plasma was determined by radioimmunoassay and by the competitive protein binding method. Intraperitoneal administration of β-escin induced increases of plasma ACTH and corticosterone in rats. The increase of plasma corticosterone was accompanied by a transient increase of plasma glucose and a transient decrease of plasma immunoreactive insulin. Hexamethonium partially suppressed the escin-induced corticosterone secretion, but diphenhydramine did not.
  • 日合 奨, 横山 弘臣, 長沢 哲郎, 大浦 彦吉
    1981 年 29 巻 2 号 p. 495-499
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The effects of saikosaponin-a, -c and -d, isolated from the roots of Bupleurum falcatum L., on plasma adrenccotrcotropin (ACTH) and corticosterone concentrations in unanesthetized or pentobarbital-anesthetized rats were determined by radioimmunoassay and by the competitive protein binding method. A single dose of saikosaponin-a (5 mg/kg, i. p.) or -d (2.5 mg/kg, i. p.) significantly increased plasma ACTH and corticosterone levels 30 and 60 min after the treatment, but saikosaponin-c at a dose of 100 mg/kg had no effect. Intraperitoneal administration of saikosaponin-a or -d, but not -c, induced a transient hyperglycemia and a transient hypoinsulinemia. Dexamethasone pretreatment depressed the saponin-induced increase of both corticosterone and glucose. Treatment with hexamethonium partially depressed the saponin-induced responses in plasma corticosterone, but treatment with diphenhydramine did not.
  • 横山 弘臣, 日合 奨, 大浦 彦吉
    1981 年 29 巻 2 号 p. 500-504
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The corticosterone secretion-inducing activities of saikosaponins isolated from the roots of Bupleurum falcatum L., their artifact saponins and genuine genins were examined in rats 30 minutes after administration. Intraperitoneal administration of saikosaponin-a (1) or -d (2) increased the plasma corticosterone level maximally at a dose of 2.5 mg/kg or 1.0mg/kg, respectively. Saikosaponin-c (9) did not increase the plasma corticosterone level at a dose of 100 mg/kg. Saikogenin-F (3) and -G (4), the genuine aglycones of 1 and 2, also increased the plasma corticosterone level but their activities were 1/70 to 1/90, respectively, of those of the corresponding saponins on a molar basis. Saikosaponin-b1 (5) and -b3 (7), artifact saponins derived from 1, showed 1/8 and 1/40 of the activity of 1, respectively. Saikosaponin-b2 (6) and -b4 (8), derived from 2 through the same structural change as in the case of 1, showed 1/50 and 1/30 of the activity of 2, respectively. Oral administration of 2, which was unstable to acid, increased plasma corticosterone to a maximum level at a dose of 50 mg/kg in fed rats but did not in fasted rats.
  • 西川 嘉廣, 吉本 公浩, 西島 宗和, 福岡 文子, 池川 哲郎
    1981 年 29 巻 2 号 p. 505-513
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Selective fatty acylation of maltose was carried out by heating an equimolar mixture of the disaccharide and an appropriate acid chloride in pyridine. The resulting crude product was chromatographed to furnish two preparations, termed maltose-[mono]- and-[high]-esters ; the former preparation was an isomeric mixture of monoesters among which the 1-, 6-, and 6'-isomers were presumably predominant, and the latter consisted of di-, tri-, and poly-esters, as indicated by gas-liquid and thin-layer chromatographies. The antitumor effects of the maltose-[mono]-esters of stearic, palmitic, myristic, lauric, and caprylic acids towards Ehrlich ascites carcinoma in mice were tested by the total packed cell volume method, by intraperitoneal injection. The stearic, palmitic, and myristic esters proved to be effective, while the lauric and caprylic esters exhibited a slight effect and no effect, respectively. The antitumor effect of the maltose-[mono]-stearate upon the same tumor was compared with that of the analogous derivative of sucrose by survival bioassay (intraperitoneal administration) at various doses. Both compounds showed similar antitumor results, giving especially marked effects at the dose of 50 mg/kg/day×5. These two compounds also exerted moderate growth-inhibitory effects against solid sarcoma 180 in mice when they were administered subcutaneously ; in the case of sucrose-[mono]-stearate, intramuscular injection was also effective. The maltose-[high]-esters of stearic, palmitic, and myristic acids failed to exert marked activity upon this solid tumor by either administration route.
  • 徳久 幸子, 斉須 久美代, 成瀬 克子, 吉川 春寿, 馬場 茂雄
    1981 年 29 巻 2 号 p. 514-518
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A healthy human female was loaded with D- and L-phenylalanine (Phe)-d5 (8 mg/kg body weight), and free Phe-d5 and tyrosine (Tyr)-d4, and protein-bound Phe-d5 in the plasma were assayed by gas chromatography-mass spectrometry with selected ion monitoring. Free Phe-d5 appeared more rapidly and abundantly in the plasma and disappeared more slowly from the plasma after loading with the D-isomer than after loading with the L-isomer. The maximum concentrations were 1.5 mg/100 ml plasma at 30 min after loading with the D-isomer, and 0.1 mg/100 ml plasma at 2 hr after loading with the L-isomer. The half-lives were 3.3 and 0.5 hr for the D-isomer and the L-isomer, respectively. After loading with the D-isomer, as after loading with the L-isomer, free Tyr-d4 and protein-bound Phe-d5 were found in the plasma.
  • 平野 耕一郎, 市橋 輝久, 山田 秀雄
    1981 年 29 巻 2 号 p. 519-531
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The absorption behavior following intramuscular injection of practically waterinsoluble drugs in water-immiscible oil solution was investigated with several azo dyes and two steroids as model drugs by the local clearance method in the m. gastrocnemius of the rat. The absorption of the drug component obeyed approximately 1st order kinetics, while the absorption of the oily solvent was very slow. The injection volume (V0) influenced the absorption rate constant (k) and the correlation k∝ V0m was experimentally observed (for intact rats, m=-0.14 ; for anesthetized rats, m=-0.32). This was also the case at another injection site, the m. rectus femoris in rats. Comparison of the absorption rate of a drug in various oil vehicles showed that k was controlled predominantly by the oil/water distribution coefficient (K) and depended little on the viscosity of the vehicle. These results suggested that the release process of the drug component from the oily depot to the aqueous phase around it was the main route for absorption, and that the subsequent transport process in the aqueous phase might be rate-limiting. A plot of log k versus log K gave a straight line with a slope close to -1, but of a slightly smaller absolute value. This plot could be applied satisfactorily for estimating the absorption rate of other drug-oil systems. A guideline for predicting the absorption rate of a drug in oily suspension from the k value for its solution is presented.
  • 小松 曼耆, 横江 一朗, 白滝 義明
    1981 年 29 巻 2 号 p. 532-538
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Three new flavonoid compounds, named sophoraisoflavanone B (I), mp 171-172°, C26H30O6, sophorapterocarpan A (II), mp 149°, C20H20O4, and sophoracoumestan A (III), mp over 300°, C20H14O5, were isolated from the root of Sophora franchetiana DUNN (Leguminosae). Their structures were determined by chemical and spectroscopic studies.
  • 崎谷 陽子, 宮内 芳子, 杖村 由治
    1981 年 29 巻 2 号 p. 539-544
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Variations in osmotic pressure, viscosity, gastric emptying rate, and drug concentration in the gastric effluent following oral administration of quinine solutions prepared with various amounts of sucrose or sodium carboxymethyl cellulose (CMC-Na) were examined. The osmotic pressure of the gastric effluent after the administration of a hypertonic or hypotonic quinine solution tended to approach isotonicity with increase of the elapsed time after administration. In the case of a high viscosity solution, there was a gradual decrease in the viscosity of the effluent, while in the case of a low viscosity solution, little difference was seen between the original viscosity and that of the effluent during the overall time course. The solution administered was diluted in the stomach and thereafter flowed out at a definite quinine concentration. However, this concentration was varied by the effects of the added agents, sucrose and CMC-Na. In the absence of these agents, the quinine concentration of the effluent was the highest among the test solutions, and the concentration decreased markedly with increasing osmotic pressure. It was found that osmotic pressure had a greater influence on the quinine concentration of the effluent than did viscosity. The time course of the cumulative volume of effluent differed with each test solution. The ratio of quinine amount remaining in the stomach per dose versus time was expressed in terms of a biexponential expression for all the test solutions except for the most hypertonic solution. The gastric emptying rate estimated from the curves mentioned above was greatly influenced by osmotic pressure rather than viscosity, and decreased with increase increase in osmotic pressure.
  • 池北 雅彦, 守屋 寛, 小沢 誠一, 木村 和幸
    1981 年 29 巻 2 号 p. 545-553
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Fucose, mannose, galactose, N-acetylglucosamine and neuraminic acid were detected as structural sugars of the purified hog pancreatic kallikreins A and B. Kallikrein B contained roughly twice as much sugar as kallikrein A (A, 4.56 ; B, 8.40% by weight). Kallikreins A and B were further divided into 3 (A-I, A-II and A-III) and 6 (B-I, B-II, B-III, B-IV, B-V and B-VI) micro-heterogeneous components, respectively. The sugar contents of B-III and B-IV (the main micro-heterogeneous forms of B) were also about twice as much as that of A-II (one of the micro-heterogeneous forms of A). As for the content of neutraminic acid, A (more acidic than B) contained less than B. On the other hand, the contents of neutraminic acid in the micro-heterogeneous components from A and B were different from each other, and the more acidic micro-heterogeneous forms were richer in neuraminic acid. After treatment with neuraminidase, the more acidic microheterogeneous forms shifted to the positions of the less acidic ones. These observations suggested that the neuraminic acid content in the molecule was the main factor permitting the separation of the micro-heterogeneous forms by isoelectric focusing. After the reduction of kallikreins A and B with 2-mercaptoethanol, two protein bands were detected in each case on polyacrylamide gel electrophoresis. However, although staining of the carbohydrate moiety of the reduced B with PAS reagent also showed two bands identical with the protein bands, only one of the protein bands of the reduced A was stained for carbohydrate. Thus, kallikreins A and B both consist of two peptide chains, but one of the peptide chains of A has no carbohydrate moiety, whereas carbohydrate moieties are bound to both peptide chains in the case of kallikrein B. The Km values and optimum pH's of kallikreins A and B, their micro-heterogeneous forms (A-II, A-III, B-IV and B-V) and asialo-kallikreins A and B for Bz-Arg-OEt hydrolysis were closely similar. Asialo kallikreins A and B were less stable than intact sialo-A and -B at 80°during incubation for 1 hr. Thus, neuraminic acid appears not to be related to the enzymatic activity, but dose influence the stability of the enzyme molecules.
  • 梅山 秀明, 工藤 貴子
    1981 年 29 巻 2 号 p. 554-558
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Diborane as a molecular complex was studied by using a double zeta ab initio MO method and energy decomposition analyses. For diborane, a qualitatively major contribution of HOMO-LUMO transfers was reported by Yamabe et al. on the basis of configuration analyses by using a single zeta basis set. However, no quantitative work on the origin on the complex formation has been reported. In this note, we show that the charge transfer energy is the dominant contributor to the complex formation (2BH3→B2H6). The charge transfer energy and the exchange repulsion are analyzed at the molecular orbital (MO) levels.
  • 井上 謙一郎, 塩原 義則, 大川 滋紀, 井上 博之, 多賀 徹, 吉田 和代, 大崎 建次
    1981 年 29 巻 2 号 p. 558-563
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The absolute configuration at C-2 of 2-carboxy-2-prenyl-4-oxo-1-tetralone (2), a key intermediate in the biosynthesis of prenylnaphthoquinone congeners of the wood and callus tissues of Catalpa ovata, was verified to be S by X-ray crystallographic analysis of the p-bromobenzoate (8) derived from 2.
  • 安田 一郎, 竹谷 孝一, 糸川 秀治
    1981 年 29 巻 2 号 p. 564-566
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The structures of three unstable amides from the roots of Asiasarum heterotropoides MAEK. var. mandshuricum MAEK. (Aristolochiaceae) were established as (2E, 4E)-N-isobutyl-2, 4-decadienamide (pellitorine), (2E, 4E, 8Z, 10E)-N-isobutyl-2, 4, 8, 10-dodecatetraenamide and (2E, 4E, 8Z, 10Z)-N-isobutyl-2, 4, 8, 10-dodecatetraenamide by spectroscopic investigation and chemical transformation studies. (2E, 4E, 8Z, 10E)-N-Isobutyl-2, 4, 8, 10-dodecatetraenamide and (2E, 4E, 8Z, 10Z)-N-isobutyl-2, 4, 8, 10-dodecatetraenamide were identical in their chromatographic properties, but they could be identified in a mixture of both compounds by our carbon-13 nuclear magnetic resonance method, by observing the cis double bond shielding effect in comparison with the all-trans isomer.
  • 山口 正義, 杉井 邦好
    1981 年 29 巻 2 号 p. 567-570
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The molecular weight of calcium-binding protein (CaBP) purified from the soluble fraction of normal rat liver was estimated to be 28800 by calibrated gel filtration on Sephadex G-100. Amino acid analysis of the CaBP showed glycine and glutamic acid to be the predominant amino acids. The calcium binding constant was found to be 4.19×105M-1 by equilibrium dialysis, and there appear to be 6-7 high affinity binding sites for calcium per molecule of protein.
  • 水柿 道直, 鵜沼 恒夫, 白石 隆幸, 西巻 知子, 山中 宏
    1981 年 29 巻 2 号 p. 570-573
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    An enzyme fraction which catalyzes the reduction of N-ethylmaleimide (NEM) to N-ethylsuccinimide in the presence of reduced nicotinamide adenine dinucleotide phosphate was partially purified from Escherichia coli extracts. The apparent Michaelis-Menten constant for NEM was estimated to be 4μM. The enzyme showed a rather broad pH optimum between 7 and 8. The enzyme was 90% inhibited after being heated at 55° for 15 min, and was 94% inhibited by 1 mM p-hydroxymercuribenzoic acid.
  • 小林 邦夫, 迫口 孝文, 木村 正子, 木谷 裕子, 松岡 瑛
    1981 年 29 巻 2 号 p. 573-577
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The interactions of gliclazide, a potential hypoglycemic drug, with native and chemically modified bovine serum albumin (BSA) were studied by means of an equilibrium dialysis technique. The Scatchard plot for the interaction of gliclazide with native BSA was a hyperbola, suggesting the existence of two (or more) classes of gliclazide-binding sites on the BSA molecule (n1=0.5, K1=160×103M-1 ; n2=4.5, K2=4.4×103M-1). Total binding capacity (ΣniKi) for gliclazide-BSA binding was lower (99.8×103M-1) than that (190.7×103M-1) for tolbutamide. Modification of BSA with hydrogen peroxide, iodoacetic acid, iodoacetamide or 2-hydroxy-5-nitrobenzyl bromide lowered the binding affinity in the primary binding site or destroyed the binding site, and decreased the total binding capacity of gliclazide-BSA binding. Since the binding capacities of the primary and secondary binding sites varied upon modification of cysteine, methionine, histidine and tryptophan residues of the BSA molecule, it is possible that the binding sites are both closely associated with loops 1-4 of the BSA molecule.
  • 谷口 誠, 中野 眞汎
    1981 年 29 巻 2 号 p. 577-580
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    4-Acetamidophenyl phosphate was synthesized by a phosphorylation procedure with polyphosphoric acid to examine its properties as a prodrug of acetaminophen. Separation of the ester from the phosphorylation mixture was carried out by precipitation with organic solvents. 4-Acetamidophenyl phosphate was soluble in water, was practically tasteless, and was quickly hydrolyzed to acetaminophen by alkaline phosphatase at 37°. The ester was stable in aqueous solution at neutral and acidic pH at 37°.
  • 加藤 喜昭, 久保 真百合, 森本 一洋, 斉藤 元一, 森坂 勝昭, 稲森 善彦, 浜 一郎, 前川 孝, 真崎 博昭, 石正 力, 沢田 ...
    1981 年 29 巻 2 号 p. 580-584
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    The hematoxicity of a streptothricin antibiotic was investigated in rats by blood morphological examination by scanning electron microscopic observation of changes in the erythrocytic membrane and by means of the coil planet centrifuge (CPC) technique to detect alterations in erythrocytic membrane dysfunction. The administration of the antibiotic caused no appreciable hematological change, nor any alteration in the morphology or function of the red blood cell membrane. The results indicate that the streptothricin antibiotic has no hematotoxic potential.
  • 鈴木 美代子, 佐々木 喜男
    1981 年 29 巻 2 号 p. 585-587
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    An aqueous solution of orange II and γ-cyclodextrin forms a lyotropic mesophase at room temperature. Nuclear magnetic resonance and circular dichroism suggest that the mesophase is formed from the inclusion compound which has a 1 : 1 structure and that orange II enters γ-cyclodextrin mainly from the long axis side of the molecule. Moreover this side aligns perpendicular to the magnetic field.
  • 高村 吏, 千葉 拓, 手島 節三
    1981 年 29 巻 2 号 p. 587-590
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    Reaction of 1, 6-anhydro-2, 2', 3, 4'-tetra-O-benzyl-β-lactose (1 mol eq.) with the acetylated oxazoline of N-acetyllactosamine (5 mol eq.) gave the corresponding 1, 6-anhydro-β-tetrasaccharide (3, 24.5%) and hexasaccharides (8, 53.5%). The protecting groups of 3 and 8 were removed by the following series of reactions to provide 6'-N-acetyl-lactosaminyllactose (7) and lacto-N-neohexaose (12), respectively : debenzylation followed by acetylation, acetolysis, and de-O-acetylation. 13C-NMR spectral data for 1, 6-anhydro-β-derivatives of 7 and 12 are presented.
  • 岡本 敏彦, 首藤 紘一, 橋本 祐一, 小菅 卓夫, 杉村 隆, 西村 [ススム]
    1981 年 29 巻 2 号 p. 590-593
    発行日: 1981/02/25
    公開日: 2008/03/31
    ジャーナル フリー
    A reactive major metabolite of the mutagen, 2-amino-3-methylimidazolo [4, 5-f]-quinoline (IQ), by rat liver microsomes was 2-hydroxyamino-3-methylimidazolo [4, 5-f]-quinoline (N-OH-IQ). The synthesis and reaction with DNA of N-OH-IQ were discussed.
feedback
Top