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Volume 34, Issue 8
Displaying 1-50 of 72 articles from this issue
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AKIRA MIYAMAE, SHIGETAKA KODA, YUKIYOSHI MORIMOTO1986 Volume 34 Issue 8 Pages 3071-3078
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe crystal and molecular structure of nilvadipine, 5-isopropyl-3-methyl-2-cyano-6-methyl-4-(3-nitrophenyl)-1, 4-dihydro-3, 5-pyridinedicarboxylate, was elucidated by X-ray structural analysis. The dihydropyridine ring adopted a boat-type conformation with the phenyl ring attached to the pseudo-axial position. Each carbonyl double bond in the ester side chains was conjugated with a neighboring double bond of the dihydropyridine ring to form a plane involving the ester group. Nonbonding interaction between the two rings was reduced by puckering of the dihydropyridine ring, lengthening of the exocyclic bond at the pseudo-axial position and twisting of the phenyl ring, keeping the meta-nitro group away from the bulky isopropyl ester group. The nuclear Overhauser effects observed in chloroform solution suggest free rotation of the phenyl ring at the pseudo-axial position about the exocyclic bond.View full abstractDownload PDF (706K) -
HIDENOBU OHMORI, HATSUO MAEDA, CHIHIRO UEDA, HIROTERU SAYO, MASAICHIRO ...1986 Volume 34 Issue 8 Pages 3079-3086
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSElectrochemical transformation of five N-nitrosopiperidines and N-nitrosodibutylamine to the corresponding N-nitramines has been investigated in acetonitrile at -30°C. The nitramines are formed by the reaction of the radical cations, generated by one-electron transfer from the nitrosamines, either with dissolved oxygen (path 1) or with water which is contaminating or deliberately added to the medium (path 2) : the former is an overall one-electron process, and the latter is a two-electron process. The radical cations derived from N-nitroso-2, 2, 6, 6-tetramethylpiperidine and N-nitroso-2, 2, 6, 6-tetramethyl-4-piperidone give the nitramines exclusively via path 2, while the reaction of those from N-nitroso-2-ethylpiperidine and N-nitrosodibutylamine proceeds via path 1. Contributions of both pathways are suggested for the radical cations from N-nitrosopiperidine and N-nitroso-2, 6-dimethylpiperidine. It is proposed that path 2 becomes feasible when the radical cation exhibits a certain degree of stability as revealed by the observation of reversible character in the cyclic voltammetry of the parent nitrosamine.View full abstractDownload PDF (888K) -
YESOOK KIM, KATSUNOSUKE MACHIDA1986 Volume 34 Issue 8 Pages 3087-3096
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA model potential consisting of the exp-6 type dispersion and exchange repulsion terms, the Lippincott type hydrogen bond stretching terms and the electrostatic interaction terms between fixed atomic charges was applied for elucidation of the vibrational spectra of aspirin crystal. The frequencies of the optically active inter- and intramolecular normal modes were calculated. The proposed potential reproduced the factor group splittings between the infrared (IR) and Raman frequencies and the lattice vibrational frequencies equally well. The IR spectra of aspirin and its -COOD analogue were simulated by using the calculated normal frequencies and a simple charge flux model.View full abstractDownload PDF (790K) -
MASAYOSHI KUBO, HIROSHI SASAKI, TOHRU ENDO, HEIHACHIRO TAGUCHI, ITIRO ...1986 Volume 34 Issue 8 Pages 3097-3101
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSBesides three known flavonoid glycosides, a new monoterpene glucoside named schizonepetoside C (3) was isolated from the spikes of Schizonepeta tenuifolia BRIQ. (Labiatae), as an amorphous powder. The structure of 3 was established as (1S, 4E)-9-O-β-D-glucopyranosyl-p-menth-4(8)-en-3-one by chemical methods and spectral analyses.View full abstractDownload PDF (545K) -
YUTAKA KAWAHATA, SUGURU TAKATSUTO, NOBUO IKEKAWA, MASATSUNE MURATA, SA ...1986 Volume 34 Issue 8 Pages 3102-3110
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOxetin (1a), a unique antibiotic having an oxetane ring, and its three stereoisomers (1b, 1c, and 1d) were synthesized from the known aldehyde (6) by utilizing a highly regio- and stereoselective epoxide ring-opening reaction. The biological activities of these oxetin stereoisomers were compared.View full abstractDownload PDF (952K) -
MAMORU SUZUKI, SADAO MAEDA, KAZUO MATSUMOTO, TOHRU ISHIZUKA, YOSHIO IW ...1986 Volume 34 Issue 8 Pages 3111-3120
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of 2-substituted 4-(3-thienyl)imidazoles (6, 11, and 14) was synthesized and evaluated for antiinflammatory activity. Among them, 6g, 14a, and 14g exhibited strong activity, comparable to that of ibuprofen. The acute toxicity and the ulcerogenicity were low as compared with those of standard acidic antiinflammatory agents. The structure-activity relationships are discussed.View full abstractDownload PDF (873K) -
YOSHIHIRO NITTA, YASUSHI ARAKAWA1986 Volume 34 Issue 8 Pages 3121-3129
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSCation exchange resin (SO3H) is a highly selective dealkylation reagent for mixed esters of phosphorus oxyacids bearing primary and secondary alkyl groups. The desired products which were produced by dealkylation of the secondary alkyl group were obtained in high yields under anhydrous and mild conditions.View full abstractDownload PDF (1025K) -
SACHIKO TSUKAMOTO, KOJI HAYASHI, KOH KANEKO, HIROSHI MITSUHASHI1986 Volume 34 Issue 8 Pages 3130-3134
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe carbamoyl derivatives of enantiomeric mixtures of methyl α- and β-cymaropyranosides were resolved by high-performance liquid chromatography (HPLC).View full abstractDownload PDF (526K) -
TOSHIO SUZUKI, ETSUKO SATO, KATSUO UNNO, TETSUJI KAMETANI1986 Volume 34 Issue 8 Pages 3135-3141
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTotal synthesis of (-)-antirhine (5) has been achieved from a potentially useful chiral synthon, (3R)-[3-hydroxy-(E)-prop-1-enyl]cyclopentanone (2) [derived from (R)-1, 2-isopropylideneglyceraldehyde (1)], via the β, γ-unsaturated aldehyde (12), which was obtained by mild hydrolysis of the α-cyano-N, N-dimethylaminocyclopentanone (11).View full abstractDownload PDF (725K) -
HARUKO TAKECHI, SUMIKO TATEUCHI(nee OYADOMARI), MINORU MACHIDA, YOSHIH ...1986 Volume 34 Issue 8 Pages 3142-3152
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhotocyclization of succinimides with an N-acyl group in the side chain gave bi- and tricyclic phyrrolo[1, 2-a]pyrazines, some of which were converted to tricyclic amines by reduction. The stereochemistry of pyrrolo[1, 2-a]pyrazine derivatives is discussed on the basis of the results of X-ray analysis and carbon-13 nuclear magnetic resonance spectroscopy.View full abstractDownload PDF (936K) -
KAZUO SATO, TAKASHI UEDA, SOJI SUGAI1986 Volume 34 Issue 8 Pages 3153-3158
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAcylation of 3-methyl-3-isoxazolin-5-one (2a) with acyl chlorides was investigated. 2-Acyl-3-methyl-3-isoxazolin-5-ones 5 and 5-acyloxy-3-methylisoxazoles 6, which were prepared from 2a and acyl halides, underwent acyl-transfer reaction in the presence of 4-(N, N-dimethylamino)-pyridine or potassium carbonate to give 4-acyl-5-hydroxy-3-methylisoxazoles 4. By using this reaction, 4-(2, 4-dichlorobenzoyl)-5-hydroxy-3-methylisoxazole (4h), which can be viewed as a bioisostere of the herbicidal compound, 4-(2, 4-dichlorobenzoyl)-1, 3-dimethyl-5-hydroxypyrazole (1a), was synthesized.View full abstractDownload PDF (568K) -
MASAYUKI MURASE, EIICHI KOTANI, KOUSUKE OKAZAKI, SEISHO TOBINAGA1986 Volume 34 Issue 8 Pages 3159-3165
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSOxidative aryl-aryl coupling reactions of phenols and phenol-ethers utilizing tris(2, 2'-bipyridyl)iron(III) perchlorate, Fe(bpy)3(ClO4)3·3H2O, and some iron(III) solvates, Fe(ClO4)3·9H2O in acetonitrile (AN), Fe(AN)3(ClO4)3, FeCl3 in AN, Fe(ClO4)3, in Ac2O, and FeCl3 in Ac2O, were explored. The structures of the solvates of FeCl3 in AN and Ac2O were clarified to be Fe(AN)6(FeCl4)3 and Fe(Ac2O)3(FeCl4)3, respectively.View full abstractDownload PDF (680K) -
HOU-WEI LUO, JIANG JI, MEI-YU WU, ZHONG-GEN YONG, MASATAKE NIWA, YOSHI ...1986 Volume 34 Issue 8 Pages 3166-3168
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFurther study on the constituents of Salvia miltiorrhiza BUNGE (Labiatae) afforded a novel seco-abietanoid named tanshinlactone. The structure of tanshinlactone was characterized on the basis of spectral data. The biogeneses of tanshinlactone and a related compound are discussed.View full abstractDownload PDF (338K) -
TETSUJI KAMETANI, TETSUYA TOYA, MASAYOSHI TSUBUKI, KEN-ICHI KAWAI, TOS ...1986 Volume 34 Issue 8 Pages 3169-3174
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe A, B, C-ring system of a triterpene, pollinastanol, was stereoselectively constructed by intramolecular γ-alkylation of the β, γ-unsaturated ketone prepared from the thermal cycloaddition product of a benzocyclobutene derivative as a key reaction.View full abstractDownload PDF (628K) -
KEIICHI NOMURA, KOUSUKE OKAZAKI, KOHZO HORI, EIICHI YOSHII1986 Volume 34 Issue 8 Pages 3175-3182
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReaction of lithiated 3-cyano-1(3H)-isobenzofuranone (7) with 5-substituted 2-furfuralacetones 6a-c and subsequent O-methylation of the resulting naphthohydroquinones afforded 2-acetyl-3-furylnaphthalenes 8a-c in good yields. Annulation of the dialkoxyphthalides 12a, b with 6a could also be carried out to give 13a, b. The 5-tert-butoxy-2-furyl compounds were stereoselectively transformed into (1R*, 3R*, 4R*)-pyrano-γ-lactones 16a, 18a, b in high yields by a modification of the Kraus method (LiAlH4 reduction followed by treatment of the product carbinol with p-toluenesulfonic acid (TsOH) in acetonitrile and then with 1, 8-diazabicyclo[5.4.0]undec-7-ene in toluene at low temperatures). The 5-methoxy-2-furyl compound 9b also afforded 16a stereoselectively in one step (treatment with TsOH), but this compound was less effective as a substrate of the pyrano-γ-lactone annulation since a side reaction leading to the spiro-γ-lactone 17 became significant. The 5-phenylthio compound 9c failed to give 16a under a variety of conditions.View full abstractDownload PDF (956K) -
TOHRU KIKUCHI, SHIGETOSHI KADOTA, SATOKO MATSUDA, HISASHI SUEHARA1986 Volume 34 Issue 8 Pages 3183-3201
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFour new methylsterols, cyclonervilasterol, 24-epicyclonervilasterol, dihydrocyclonervilasterol, and 24-epihihydrocyclonervilasterol, were isolated from the methylsterol fraction of Nervilia purpurea SCHLECHTER by reversed-phase high-performance liquid chromatography. The structures 2a, 3a, 5a, and 6a were proposed for these compounds, respectively, based on chemical evidence and two-dimensional nuclear magnetic resonance spectroscopy including INADEQUATE (Incredible Natural Abandance Double Quantum Transfer Experiment).View full abstractDownload PDF (1559K) -
GIICHI GOTO, KENJI KAWAKITA, TETSUYA OKUTANI, TAKUICHI MIKI1986 Volume 34 Issue 8 Pages 3202-3207
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA series of N-hydroxyamino acids and their esters (9a, b, d-k) coupled with N-hydroxyglycinamide (9c) were synthesized through facile preparations of N-furfurylidenealkoxy (and hydroxy) carbonylalkylamine N-oxides (7a, b, d-g) and N-furfurylidenecarbamoylmethylamine N-oxide (7c) followed by hydrolysis. The method was applied to the syntheses of emimycin (1) and hadacidin monosodium salt (2b).View full abstractDownload PDF (632K) -
YOSHIKI KASHIWADA, GEN-ICHIRO NONAKA, ITSUO NISHIOKA1986 Volume 34 Issue 8 Pages 3208-3222
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA chemical examination of high-quality commercial rhubarb (Choukichio : ?? ?? ?? ) has led to the isolation and characterization of eight flavan-3-ol glucosides and three proanthocyanidin glucosides, together with several known compounds, i.e., (+)-catechin 5-O-β-D-glucopyranoside (1), (+)-catechin 7-O-β-D-glucopyranoside (2), procyanidin B-2 8-C-β-D-glucopyranoside (3) and procyanidin B-2 6-C-β-D-glucopyranoside (4). On the basis of chemical and spectroscopic evidence, the former compounds were characterized as (+)-catechin 3'-O-β-D-glucopyranoside (5), (+)-catechin 4'-O-β-D-glucopyranoside (6), (+)-catechin 7, 3'-di-O-β-D-glucopyranoside (7), (+)-catechin 5, 3'-di-O-β-D-glucopyranoside (8), (+)-catechin 3', 4'-di-O-β-D-glucopyranoside (9), (+)-catechin 5, 4'-di-O-β-D-glucopyranoside (10), (+)-catechin 8-C-β-D-glucopyranoside (11), (+)-catechin 6-C-β-D-glucopyranoside (12), procyanidin B-3 7-O-β-D-glucopyranoside (13), procyanidin B-1 8-C-β-D-glucopyranoside (14) and procyanidin B-1 6-C-β-D-glucopyranoside (15).View full abstractDownload PDF (1388K) -
HIROAKI NISHIMURA, GEN-ICHIRO NONAKA, ITSUO NISHIOKA1986 Volume 34 Issue 8 Pages 3223-3227
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo novel tannins, stenophynins A and B, isolated from the bark of Quercus stenophylla MAKINO (Fagaceae), have been characterized on the basis of chemical and spectroscopic evidence as (+)-catechin 8-C-β-D-[2", 3" : 4", 6"-bis(S)-hexahydroxydiphenoyl]-glucopyranoside (1) and (+)-catechin 8-C-β-D-[2", 3"-(S)-hexahydroxydiphenoyl-6"-galloyl]-glucopyranoside (2), respectively.View full abstractDownload PDF (623K) -
KAZUO KOIKE, TAICHI OHMOTO, KOREHARU OGATA1986 Volume 34 Issue 8 Pages 3228-3236
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe structure and absolute configuration of picrasidine F, which was isolated from the root bark of Picrasma quassioides BENNET, has been confirmed by an X-ray crystal structure analysis of its hydrochloride (1).View full abstractDownload PDF (676K) -
YOSHIKI KASHIWADA, GEN-ICHIRO NONAKA, ITSUO NISHIOKA1986 Volume 34 Issue 8 Pages 3237-3243
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAlong with the previously reported phenylbutanone glucosides, i.e., lindleyin (7), isolindleyin (8) and 4-(4'-hydroxyphenyl)-2-butanone 4'-O-β-D-glucopyranoside (9), three new related compounds (1, 2 and 3) have been isolated from a rhubarb of high quality (commercial name : ?? ?? ?? ). The structures of 1-3 were established on the basis of chemical and spectroscopic data to be 4-(4'-hydroxyphenyl)-2-butanone 4'-O-β-D-(2", 6"-di-O-galloyl)-glucopyranoside (1), 4-(4'-hydroxyphenyl)-2-butanone 4'-O-β-D-(2"-O-galloy-6"-O-cinnamoyl)-glucopyranoside (2) and 4-(4'-hydroxyphenyl)-2-butanone 4'-O-β-D-(2"-O-galloyl-6"-O-p-coumaroyl)gluocopyranoside (3). In addition, 3, 4', 5-trihydroxystilbene 4'-O-β-D-(2"-O-galloyl)-glucopyranoside (4), gallic acid 3-O-β-D-glucopyranoside (5) and gallic acid 4-O-β-D-glucopyranoside (6) have been newly isolated.View full abstractDownload PDF (749K) -
SHIGETOSHI KADOTA, SATOKO KANOMI(nee MATSUDA), TAKEHIKO SHIMA, TOHRU K ...1986 Volume 34 Issue 8 Pages 3244-3248
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo novel methylsterols, cyclohomonervilasterol and neocyclonervilasterol, were isolated from the methylsterol fraction of Nervilia purpurea by repeated preparative high-performance liquid chromatography. The structures 1 and 2 are proposed for these compounds, respectively.View full abstractDownload PDF (478K) -
MASATAKE NIWA, SEIKO OTSUJI, HIROSHI TATEMATSU, GUO-QUAN LIU, XIANG-FA ...1986 Volume 34 Issue 8 Pages 3249-3251
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSTwo C-3/C-3"-biflavanones, chamaejasmine (1) and isochamaejasmin (2), were isolated from the roots of Stellera chamaejasme L. (Thymelaeaceae) and their stereostructures were elucidated on the basis of spectral and chemical evidence. Chamaejasmine was found to be a mixture of (-) and (+) forms (68 : 32) by high-performance liquid chromatographic analysis with a column for optical resolution.View full abstractDownload PDF (445K) -
KAZUO OGAWA, TADAFUMI TERADA, YOSHIYUKI MURANAKA, TOSHIHIRO HAMAKAWA, ...1986 Volume 34 Issue 8 Pages 3252-3266
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMany 2-oxoalkyl arenesulfonate derivatives having straight or branched alkyl chains of different lengths, 2-oxoalkyl bis-arenesulfonate derivatives, and alkyl arenesulfonate derivatives having a ketal moiety at the 2-position on the alkyl chain were synthesized, and their esterase-inhibitory activities, as well as hypolipidemic activities, were evaluated.Among these compounds, 1-(2, 4, 6-trimethylbenzenesulfonyloxy)-2-dodecanone (III-1u), and 1-(2, 3, 4, 6-tetramethylbenzenesulfonyloxy)-2-hexanone (III-1w), -2-octanone (III-1x) and -2-decanone (III-1y) exhibited potent esterase-inhibitory activities (IC50=3×10-10, 2×10-10, 2×10<-10> and 3×<-11>M, respectively). However, the sulfonate (XV) having a ketal moiety on the alkyl chain and the bis-sulfonate (XVI) exhibited low inhibitory activities toward esterase in comparison with III and XII. Most of the compounds III and some of the compounds XII exhibited potent hypolipidemic activities corresponding to more than 50% lipid-lowering effect (plasma triglyceride and cholesterol ester) in vivo. The structure-activity relatioinships of these compounds are discussed.View full abstractDownload PDF (1183K) -
YUTAKA KAWASHIMA, MASAKAZU SATO, YUICHI HATADA, SHIGERU OKUYAMA, FUSAO ...1986 Volume 34 Issue 8 Pages 3267-3272
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESS4, 6-Disubstituted N-(3-piperidinopropyl)furo[3, 2-b]indole-2 carboxamide derivatives possess analgesic and antiinflammatory activities. To understand how substituents affect the biological activities, the quantitative structure-activity relationships of 26 compounds were analyzed by the adaptive least-squares method. For analgesic activity, the steric effect of the substituent at the 6th position in terms of the STERIMOL length and width parameters needs to be augmented to obtain higher activity. For antiinflammatory activity, an electron-donating effect of the substituent at the 6th position seems to be favorable. On the other hand, the physicochemical factors relating to the role of the 4-substituent were not clarified. A similar correlation was obtained by Hansch analysis of analgesic ED50 values of 21 derivatives in mice.View full abstractDownload PDF (539K) -
SHIN-ICHI NINOMIYA, FEN-ZHI LIU, HIROAKI NAKAGAWA, KOHFUKU KOHDA, YUTA ...1986 Volume 34 Issue 8 Pages 3273-3278
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSN-Trialkylsilymethyl- and N-trialkylgermylmethyl-N-nitrosoureas, which are analogues of N-neopentyl-N-nitrosourea, were synthesized and tested for cytotoxicity to leukemia L1210 cells. Rates, activation energies, and entropies of activation of the hydrolytic activation of these derivatives were determined. The chemoselectivity and partition properties were also determined in terms of the Swain-Scott's substrate constant and logk', respectively. In aqueous media, all the Si- and Ge-containing nitrosoureas examined underwent hydrolysis accompanied by the ready cleavage of the Si-C or Ge-C bond to give methanol. From these nitrosoureas, the corresponding diazoalkanes were synthesized and reacted with a carboxylic acid in benzene containing alcohols. The results indicated that the Ge-C bond is more susceptible to hydrolysis than the Si-C bond. More lipophilic dimethylphenylsilyl and -germyl derivatives were more toxic to L-1210 than the crresponding trimethyl derivatives.View full abstractDownload PDF (635K) -
KEISO NAKAYAMA, HIROKO FUJINO(nee KIMATA), RYOJI KASAI, YOHKO MITOMA, ...1986 Volume 34 Issue 8 Pages 3279-3283
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSMukurozi-saponins Y1 and Y2, bisdesmosides from pericarps of Sapindus mukurossi, greatly increased the water solubilities of the co-occuring monodesmosides. The mode of solubilizing properties of these saponins were investigated. The bisdesmosides also increased the solubilities of Yellow OB and Progesterone in phosphate buffer.View full abstractDownload PDF (568K) -
RYOJI KASAI, KAZUHIRO MATSUMOTO, SHIGENORI TANIYASU, OSAMU TANAKA, JEU ...1986 Volume 34 Issue 8 Pages 3284-3289
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe experimental details of the isolation and structural determination of chiisanoside (1), a new 3, 4-seco-lupane type triterpene glycosyl ester, from leaves and stem bark of Acanthopanax chiisanensis are described. From leaves of this plant, two homologous glycosyl esters, named isochiisanoside and its methyl ester (2 and 3), were also isolated. Their structures were elucidated on the basis of chemical and spectral data and confirmed by the derivation of these compound from 1.View full abstractDownload PDF (735K) -
NAOTAKA UCHIYAMA, TERUKAZU TAKANO, SHIZUKO SAITO, HIROAKI MORIKAWA, MA ...1986 Volume 34 Issue 8 Pages 3290-3297
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA simple and sensitive method for the determination of forphenicinol (L-(3-hydroxy-4-hydroxymethylphenyl)glycine) and its metabolites (M-1-M-5) in human serum and urine has been developed by means of gas chromatography-mass spectrometry with selected ion monitoring.Forphenicinol (FPL) and M-2 (3-hydroxy-4-hydroxymethylbenzylamine) were quantified at the same time as the trimethylsilyl (TMS) derivatives. M-1 (α-(3-hydroxy-4-hydroxymethylphenyl)-α-oxoacetic acid) was methoximated, and then analyzed simultaneously with M-3 (3-hydroxy-4-hydroxymethylbenzoic acid) and M-4 (hydroxyterephthalic acid) after trimethylsilylation. On the other hand, M-5 (L-N-acetyl(3-hydroxy-4-hydroxymethylphenyl)glycine) was hydrolyzed enzymatically with acylase to convert it into FPL and determined as the TMS derivative.In serum, the calibration range for FPL was 0.02-5 μg/ml. As for urine, the calibration curves were linear in the ranges of 0.04-10 μg/ml for FPL, 0.1-10 μg/ml for M-1, M-3, M-4, and M-5, and 0.4-100 μg/ml for M-2.The metabolic fate of FPL in man was investigated after a single oral dose (50 mg) of FPL to each of five healthy volunteers. In the serum, unchanged FPL was found but no metabolites were detected. The serum FPL levels were followed and analyzed pharmacokinetically. In the urine, unchanged FPL and its five metabolites (M-1-M-5) were detected and quantified; M-2 and M-5 were the major urinary metabolites.View full abstractDownload PDF (727K) -
MASATAKA ISHIBASHI, MASAHIRO ITOH, KOUWA YAMASHITA, HIROSHI MIYAZAKI, ...1986 Volume 34 Issue 8 Pages 3298-3305
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe gas chromatographic-mass spectrometric properties of diethylhydrogensilyl cyclic diethylsilylene derivatives of hydroxypregnanes were studied. Pregnanes with a sterically hindered 11β-hydroxyl group were smoothly silylated with a new silylating agent, N, O-bis(diethylhydrogensilyl)-trifluoroacetamide, under mild conditions. The mass spectra of these derivatives were characterized by the appearance of the intense molecular ion peak, which provides convenient and reliable confirmation of the molecular weight of these hydroxypregnanes. The most characteristic fragment ions were those at m/z 185 for 17, 20-diols and at m/z 287 for 17, 20, 21-triols, which were produced by cleavage at the C(13)-C(17) and C(15)-C(16) bonds with hydrogen atom transfer. This indicates that all of the major fragmentations are directed by the cyclic diethylsilylene group. Another fragmentation common to the spectra was the successive loss of diethylhydrogensilanol from the molecular ion. A remarkable difference in the appearance of peaks was observed between DEHS-DES derivatives of a 17α, 20α, 21-triol and its 20β-isomer. Structures are proposed for some of these fragment ions.View full abstractDownload PDF (769K) -
MACHIKO MATSUBARA, HISATORA KURODA1986 Volume 34 Issue 8 Pages 3306-3311
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFour polusaccharides were extracted with acetic acid from conidia of a pea brown spot-causing fungus, Mycosphaerella pinodes. Fraction II-I showed activity to induce accumulation of pisatin, a phytoalexin. Its molecular weight was about 45000, and it was composed of α-1, 2-linked mannose and α-1, 4- and α-1, 6-linked glucose. The sugar chains were branched with α-1, 4, 6-linkages and the non reducing terminal was glucose.View full abstractDownload PDF (636K) -
TSUTOMU MIMURA, YASUTAKA MAKINO, HIROSHI NAKAJIMA, MASARU OKABE, YASUH ...1986 Volume 34 Issue 8 Pages 3312-3319
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSA substance showing gastric secretion-inhibitory activity in rats was purified from defatted cell wall of brewer's yeast cells through extraction by autoclaving in distilled water, pepsin digestion, fractionation with ethanol, diethyl aminoethyl-Sephadex A-50 column chromatography and gel filtration on a Sepharose 6B column. The substance, named SP-I, markedly decreased gastric juice secretion in pylorus-ligated rats when administered intraperitoneally or intravenously at a dose of 2.5 mg/kg. SP-I reduced Shay ulceration by 81% (25 mg/kg×2, i.p.), aspirin ulceration by 56% (25 mg/kg, i.p.) and phenylbutazone ulceration by 82% (25mg/kg, i.p.). It was also shown that the decreases of hexosamine and sialic acid contents in gastric mucosa caused by aspirin administration in pylorus-ligated rats were significantly recovered by the administration of SP-I. SP-I, a new peptide-mannan (95% mannan, 3% peptide), showed a homogeneous pattern in ultracentrifugal analysis, and its molecular weight was estimated to be several hundred thousand daltons.View full abstractDownload PDF (997K) -
KAZUKI MURAKAMI, SADAKI FUJIMOTO, AKIRA OHARA1986 Volume 34 Issue 8 Pages 3320-3327
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe distribution of acid phosphatases of intermediate molecular weight was determined in various rat tissues. The distribution study of intermediate-molecular-weight acid phosphatase (disignated P-II) in the subcellular fractions of rat liver and kidney indicated that P-II was localized in the mitochondrial fractions. The P-II partially purified from liver showed a pI value of 7.0 on isoelectric focusing, and the apparent molecular weight was estimated to be 40000 by Sephadex G-100 gel filtration or 44000 by sodium dodecyl sulfate-polyacrylamide disc gel electrophoresis. The enzyme catalyzed the hydrolysis of a wide variety of natural phosphomonoesters, except for phosphoproteins, phosphoserine, o-phosphocholine and thiamine monophosphate. The enzyme showed a high activity on pyridoxal phosphate, β-glycerophosphate, flavin mononucleotide and adenosine 2'-monophosphate. It was markedly inhibited by Hg2+ and Ag+, but not significantly by sulfhydryl blocking agents or by L-(+)-tartrate.View full abstractDownload PDF (789K) -
NAOHITO OHNO, KAZUYOSHI IINO, SHOZO OIKAWA, KICHIRO SATO, MASUMI OHSAW ...1986 Volume 34 Issue 8 Pages 3328-3332
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe antitumor β-glucan from the fruit body of Grifola frondosa was resolved by DEAE-Sephadex chromatography into neutral and acidic components, both of which were found to be growth-inhibitory against sarcoma 180 solid tumor inplanted in ICR male mice (Ohno et al., Chem. Pharm. Bull., 33, 1181 (1984)). In the present study, the acidic β-glucan was further fractionated by diethylaminoethyl (DEAE)-Sephadex chromatography followed by ammonium sulfate precipitation, and the resultant β-glucan subfractions were assayed for antitumor effect.The β-glucan fraction absorbed on DEAE-Sephadex A-25 was eluted with 8 M urea, an inducer of helix-random coil transition of β-1, 3-glucan. The eluted glucan fraction (fraction N (8M)) was a β-1, 3-glucan branched at the 6 position and possessing almost the same properties as those of a neutral β-1, 3-glucan obtained from the neutral fraction (fraction N (0M)). The remaining acidic β-glucan fraction was eluted with 0.45 M ammonium bicarbonate in 8 M urea (fraction A), and was further separated into a β-1, 3-glucan branched at the 6 position (fraction AP) and a β-1, 6-glucan (fracton AS) fractions by ammonium sulfate precipitation. Fraction AP showed potent antitumor activity, while that of fraction AS was quite weak. These results suggest that G. frondosa contains three kinds of acidic glucans, (1) branched β-1, 3-glucan non covalently coupled with an acidic component, (2) branched β-1, 3-glucan tightly coupled with an acidic component, and (3) acidic β-1, 6-glucan, and that the antitumor activity of the crude extracts of G. frondosa is due to both the neutral and the acidic β-1, 3-glucans.View full abstractDownload PDF (587K) -
YOSHIMITU SHIMAMORI, YASUHIRO WATANABE, YUKIO FUJIMOTO1986 Volume 34 Issue 8 Pages 3333-3340
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSDipeptidyl aminopeptidase III (DAP III) from a human placental post-microsomal supernatant was purified 760-fold by means of ammonium sulfate fractionation and successive chromatographies on diethylaminoethyl (DEAE)-cellulose, Sephadex G-200, Butyl-Toyopearl 650 and DEAE-Toyopearl columns. The enzyme showed a single band on sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis and its molecular weight was estimated to be 84000. The enzyme was strongly inhibited by metallochelators, and the activity lost was most effectively restored by the addition of Zn2+. The enzyme was also extremely inhibited by some sulfhydryl reagents such as p-chloromercuribenzoic acid (PCMB) and 5, 5'-dithiobis(2-nitrobenzoic acid) (DTNB), and the activity of the enzyme inhibited by DTNB was restored by the addition of thiol reagents. Among various β-naphthylamides examined, Arg-Arg-β-naphthylamide (Arg-Arg-βNA) was most rapidly hydrolyzed.View full abstractDownload PDF (799K) -
TAKAFUMI ISHIZAKA, MICHIYO MOTOJIMA, SHIGERU KOUNOSU, MASUMI KOISHI1986 Volume 34 Issue 8 Pages 3341-3347
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe in vitro release of poly(ethylene oxides) from bovine serum albumin microspheres was found to be biphasic. When the release of poly(ethylene oxides) was analyzed by using two theoretical equations, it was suggested that the poly(ethylene oxides) diffused in the albumin matrix of the microspheres without resistance, and the release rate was dependent only on the concentration gradient. This result can be ascribed to the large channels in the albumin matrix (larger than 55 Å). When the pH of the albumin solution used for microsphere preparation was changed from 5.0 to 7.4, the poly(ethylene oxide) release pattern was greatly modified.View full abstractDownload PDF (940K) -
MOTOHARU IWATSURU, KIYOSHI SHIMIZU1986 Volume 34 Issue 8 Pages 3348-3353
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSSolubilization of drugs with surfactants often causes changes of the absorbance and the maximum absorption wavelength. In this study, it was found that the shifts of the absorption maxima of alkylparabens depended on the concentration of the surfactant, sodium dodecyl sulfate, but not on the concentration of the drugs. The first derivative absorption spectrum was used to evaluate the wavelength shift.The distribution parameter is defined as the ratio of the amount of the drug in the micellar phase (calculated from the absorption shift-length) divided by the amount of surfactant in the micellar phase to the amount of the drug in the bulk phase divided by the amount of surfactant in the bluk phase. This distribution parameter differs from the partition coefficient. It was found that the longer the alkyl chain length of the alkylparabens, the greater the absorption shift-length and the distribution parameter. Alkylparabens are very difficult to differentiate from each other in terms of the absorption spectra, but can easily be distinguished by using the distribution parameter. This approach may be generally useful for distinguishing drug homologs.View full abstractDownload PDF (603K) -
YOSHIYUKI KOIDA, MASAO KOBAYASHI, MASAYOSHI SAMEJIMA1986 Volume 34 Issue 8 Pages 3354-3361
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe influence of drug properties such as solubility and core shape on microencapsulation with ethyl cellulose (EC) by the phase separation method was studied. Drugs having various solubilities from about 1% to 37% in the 1st fluid of the disintegration test in JP (vitamin C, vitamin B6, isoniazid, trimebutine maleate and theophylline) were pulverized, granulated into spherical or cylindrical shapes, and used as core materials to eliminate the influence of crystal shape. To obtain spherical microcapsules (MC) having a uniform wall, various preparation conditions were tested; wall thickness could be adjusted by changing the cooling time. It was found by use of spherical core materials of vitamin C and isoniazid that the permeability constants, Pm, linearly decreased as the wall thickness increased up to 12 μm, and then remained constant. Comparison of microcapsules containing the above five drugs revealed that the content of EC in MC decreased with increasing drug hydrophilicity. The dissolution rates from MC having a wall thickness of 12-15 μm were slower for less water-soluble drugs, though the plots of dissolution percent against the so-called reduced time showed similar dissolution patterns. Pm values were almost the same for all drugs except theophylline. As regards core shape, crystalline material showed the fastest dissolution, followed by cylinder and sphere in that order.View full abstractDownload PDF (910K) -
TOSHIKAZU YAMAGUCHI, CHISATO IKEDA, YUTAKA SEKINE1986 Volume 34 Issue 8 Pages 3362-3369
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSIntestinal absorption of nadolol, a new long-acting β-adrenergic blocking agent, was compared with those of six other β-blocking agents by the in situ ligated loop method in rats. It was found that nadolol was well absorbed from the duodenum, jejunum, ileum and colon, but not the stomach. The in situ intestinal absorption of β-blocking agents including nadolol was consistent with pH-partiton theory. The absorption of nadolol was, however, strongly inhibited by trihydroxy bile salts, sodium cholate and its taurine and glycine conjugates, but not by dihydroxy bile salts such as sodium chenodeoxycholate and sodium deoxycholate. An inhibitory effect on the absorption of nadolol was also found in vivo in rats with bile duct ligation. No inhibition of the absorption of other β-blocking agents by sodium cholate was observed. The results suggest a specific interaction between nadolol and trihydroxy bile salts, especially sodium cholate.View full abstractDownload PDF (793K) -
TERUTAKA TAKAHASHI, YUKO UEZONO, YUTAKA NAKANISHI1986 Volume 34 Issue 8 Pages 3370-3375
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe bioavailability of cinnarizine (CN) from three capsules was investigated in gastric-acidity-controlled rabbits (GAC-rabbits) with low and high acidities. Two commercial capsules (capsules A, B), which show poor dissolution in a low acidity medium, and one test capsule, whose dissolution in a low acidity medium was improved, were used. Rabbits with low acidity showed significantly lower Cmax and area under the plasma concentration-time curve (AUC) than rabbits with high acidity after administration of capsules A and B. Capsule A showed higher Cmax and AUC than capsule B in rabbits with low acidity. The difference of bioavailability between the two capsules appears to be due to difference of dissolution rate, depending on the gastric pH. The results obtained in this study corresponded very well with the results obtained in humans. Consequently, we conclude that the GAC-rabbit is a promising animal model for testing the bioavailability of a drug preparation showing gastric acidity-dependent bioavailability in humans. On the other hand, the bioavailability of CN from the test capsule was not affected by gastric acidity. Therefore, a small inter-subject variation of CN bioavailability can be expected on oral administration of the test capsule.View full abstractDownload PDF (641K) -
YOSHIAKI KAWASHIMA, TETUROU HANDA, HIROFUMI TAKEUCHI, MOTONARI OKUMURA ...1986 Volume 34 Issue 8 Pages 3376-3383
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPhenytoin crystals with improved mechanical strength, dissolution rate and bioavailability were obtained by using a novel crystallization process termed "spherical crystallization." An alkaline solution of phenytoin held at 40°C was poured into a well dispersed mixture of isopropyl acetate and hydrochloric acid containing a water-soluble polymer, e.g. polyethylene glycol (PEG), at 20°C. Fine crystals of phenytoin incorporating PEG in proportion to its concentration in the solvent were directly agglomerated. The agglomerates with PEG had a free-flowing property due to their spherical shape and smooth surface. The PEG incorporated in the agglomerate resulted in increased mechanical strength, dissolution rate and bioavailability of the resultant agglomerated crystals of phenytoin.View full abstractDownload PDF (920K) -
SHOZO MIYAZAKI, NORIO HASHIGUCHI, WEI-MIN HOU, CHIZUKO YOKOUCHI, MASAH ...1986 Volume 34 Issue 8 Pages 3384-3393
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSFibrinogen microspheres containing adriamycin were prepared and eveluated as a novel drug delivery system. The shape of the microspheres was invariably spherical. The average diameters were 2.4 and 1.7 μm, and the drug contents in the microspheres were 10.2 and 9.9%, for the microspheres prepared at 110 and 140°C, respectively. Release of the drug from fibrinogen microspheres was slow, and the drug release continued over. 7 d. These results indicated that drug-loaded fibrinogen microspheres could provide a sustained release property in vitro.The antitumor activity of fibrinogen microspheres containing adriamycin was evaluated against Ehrlich ascites carcinoma in mice on the basis of animal survival data. Tumor cell injections were performed on day 0 and microsphere injections on day 1, both intraperitoneally. A prolongation of the life span of tumor-bearing mice following injection of therapeutic microspheres was noted, and the microspheres containing adriamycin were therapeutically more active than adriamycin alone. The high chemotherapeutic efficiency of fibrinogen-adriamycin microspheres was striking at high doses, which would be toxic in the case of the drug alone.These results indicated that fibrinogen microspheres containing adriamycin may be effective in cancer chemotherapy. Microspheres composed of fibrinogen show good biocompatibility and could be useful as a novel drug carrier in injectable delivery systems for anticancer agents.View full abstractDownload PDF (1308K) -
KAZUO MARUYAMA, SHOJI AWAZU, HIDEO NISHIGORI, MOTOHARU IWATSURU1986 Volume 34 Issue 8 Pages 3394-3402
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of various fatty acids on the ligand-binding sites of human serum albumin (HSA) were investigated. The present results provide evidence for the independence of the four classified binding sites and for the existence of distinct high-affinity sites for long-chain (C12-C18) and for medium-chain (C6-C10) fatty acids. The binding of long-chain fatty acids to HSA at low molar ratios (0.5-2.0) of fatty acid to HSA caused marked conformational changes. Site I and the bilirubin-site were sensitive to these conformational changes : Site I became asymmetrical and the bilirubin-site acquired a cooperative nature. On the other hand, the diazepam-site and Site II were little affected. The binding of medium-chain fatty acids to HSA at low molar ratios (vide supra) caused competitive ligand displacement. These acids did not change the comformation of HSA, but they perturbed Site II to a limited extent, making Site II more aymmetric. These effects enhanced the circular dichroism spectrum of flufenamic acid-HSA complex. These results confirmed that the diazepam-site and Site II are distinct sites.At a high molar excess (4.0-8.0) of fatty acid to HSA, the binding of ligands to HSA was inhibited in a complicated manner that appeared to reflect a combination of competitive effects and conformational changes.View full abstractDownload PDF (894K) -
YOSHIAKI KAWASHIMA, TETSUROU HANDA, HIROFUMI TAKEUCHI, MOTONARI OKUMUR ...1986 Volume 34 Issue 8 Pages 3403-3407
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe effects of polyethylene glycol (PEG) 4000 dissolved in the crystallization solvent on the size of agglomerated crystals of phenytoin prepared by the spherical crystallization technique with a bridging liquid (i.e. isopropyl acetate) were investigated. The average diameter of agglomerated crystals at equilibrium, where the rates of growth and destruction of the agglomerates were balanced, decreased linearly with PEG concentration, since the PEG reduced the cohesive force tending to agglomerate the crystals of the bridging liquid by decreasing the interfacial tension and the wettability of the bridging liquid. Changes in the compaction of the crystal agglomerates and in the kinematic viscosity of the dispersing medium with increasing PEG concentration caused the agglomeration rate to change non-linearly with respect to PEG concentration.View full abstractDownload PDF (823K) -
SHIGERU YAKOU, SACHIKO YAMAZAKI, TAKASHI SONOBE, TSUNEJI NAGAI, MASAYA ...1986 Volume 34 Issue 8 Pages 3408-3414
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSThe coprecipitates of Phenytoin (PHT) with combinations of carriers such as sodium deoxycholate and polyvinylpyrrolidone (DC-Na-PVP), sodium deoxycholate and polyethylene glycol (DC-Na-PEG), and sodium deoxycholate and hydroxypropylcellulose (DC-Na-HPC) were prepared. The dissolution characteristics of various coprecipitates were determined by the use of the JPX dissolution test apparatus in a pH 6.8 test medium. All of the coprecipitates prepared with combined carriers significantly enhanced the dissolution rate of PHT. Among them, the combination of PVP-DC-Na (1 : 1) as a carrier for the coprecipitate resulted in the fastest dissolution of PHT, but the dissolution rate of coprecipitate containing polyethylene glycol 4000 (PEG 4000), or hydroxypropylcellulose (HPC) was similar to that in the absence of the polymer. The dissolution rate of PHT coprecipitates with PEG 4000 and DC-Na, or HPC and DC-Na was silghtly enhanced in the medium containing 0.1% polysorbate 80. Unexpectedly, the PHT-DC-Na coprecipitate containing PVP showed a depressed dissolution rate in the same medium. A two-way cross-over study was carried out for a coprecipitate of PHT, DC-Na and PVP prepared in ratio of 1 : 1 : 1 (w/w) and the physical mixture of these ingredients in six rabbits. The area under the blood concentration-time curve of PHT following the administration of the coprecipitate was about 1.63 times that of the physical mixture in rabbits. It is suggested that PVP-DC-Na is a useful combination of carriers for PHT coprecipitates, considerably improving the dissolution and bioavailability of poorly water-soluble PHT.View full abstractDownload PDF (712K) -
HIDEO KOMATSU, KAZUTAKA HIGAKI, HIROKAZU OKAMOTO, KAZUKO MIYAGAWA, MIT ...1986 Volume 34 Issue 8 Pages 3415-3422
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSButylparaben (BP) was added to liposomes prepared by the hydration method from egg phosphatidylcholine (egg PC), cholesterol, and dicetylphosphate in a molar ratio of 4 : 2 : 1 for the purpose of antimicrobial preservation. Most of the BP was entrapped in liposomes near the polar surface of the lipid bilayers, and rapid equilibrium was observed in its distribution between liposomes and the outer aqueous phase.The antimicrobial activities of liposomes containing BP were studied qualitatively against eight kinds of microorganisms. Although the liposome suspension without BP (empty liposomes) had no effect on the microorganisms, liposome suspensions with BP showed antimicrobial activities. The preservative effect was roughly proportional to the free cencentration (not the total concentration) of BP.Percutaneous penetration of liposomes containing BP after topical application was studied in vivo in guinea pigs by autoradiography. 14C-BP in liposomes as observed to penetrate into the body, but no difference was found in its distribution pattern in comparison with that after administratoin as an ointment. On the other hand, 14C-dipalmitoylphosphatidylcholine, a marker of egg PC, remained on the skin surface and was scarcely detected in the body, suggesting that the percutaneous penetration of liposomes themselves did not occur.View full abstractDownload PDF (1374K) -
HIDEO KOMATSU, HIROKAZU OKAMOTO, KAZUKO MIYAGAWA, MITSURU HASHIDA, HIT ...1986 Volume 34 Issue 8 Pages 3423-3430
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSPercutaneous penetration of 14C-butylparaben (BP) from a liposome suspension was studied in vitro using a flow-through type diffusion chamber. The amount of 14C-BP that penetrated through the skin of guinea pigs from liposome suspension decreased as the lipid content increased. This suggested that BP in the outer aqueous phase mainly contributed to the percutaneous penetration. However, 14C-BP in liposomes was also demonstrated to participate in the penetration to a small extent. Mathematical analysis based on diffusion theory supported these findings.Substantial entrapment of BP in liposomes was maintained during the period of the in vitro experiment (30 h), indicating that the free concentration of BP would be maintained in the donor region after the application of the liposome formulation to it. Furthermore, liposomes induced neither alteration of the barrier function of the stratum corneum nor denaturation of skin proteins in vitro. These findings are consistent with a contribution of direct BP absorption from liposomes at the skin surface.View full abstractDownload PDF (768K) -
TAKASHI HIROTA, TETSUTO NAMBA, KENJI SASAKI1986 Volume 34 Issue 8 Pages 3431-3434
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSReactions of pyridine and quinoline N-oxides with N-methylformamide are described. N-Methylcarbamoylation occurred at the C-2 or C-4 position of pyridine and quinoline derivatives.View full abstractDownload PDF (498K) -
SUGURU TAKATSUTO, NOBUO IKEKAWA1986 Volume 34 Issue 8 Pages 3435-3439
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAnalysis of four pairs of 3α, 22, 23- and 3β, 22, 23-trihydroxybrassinosteroids with modified side chains as their methaneboronate-trimethylsilyl (TMS) derivatives by gas chromatography-mass spectrometry (GC-MS) was carried out using a 1% OV-17 packed glass column and an electron impact ion source. In every case, the 3α-isomer had a much shorter retention time than the corresponding 3β-isomer. Both isomers showed almost the same fragment ions in their mass spectra, but their relative intensities were greatly different, particularly for the ions corresponding to the molecular ion minus 90 (TMSOH). These differences should be diagnostic for distinguishing the 3α- and 3β-isomers of 2-deoxybrassinosteroids from natural sources.View full abstractDownload PDF (539K) -
HIROSHI SUEMUNE, YUKAKO MIZUHARA, HIROYUKI AKITA, KIYOSHI SAKAI1986 Volume 34 Issue 8 Pages 3440-3444
Published: August 25, 1986
Released on J-STAGE: March 31, 2008
JOURNAL FREE ACCESSAn enzymatic synthesis of 2, 3-O-isopropylidene-sn-glycerol (10), the synthetic key intermediate for platelet-activating factor, was achieved. Several 1, 3-di-O-acyl-2-benzylglycerols (5a-d) were synthesized from dihydroxyacetone dimer (2), and subjected to enzyme-catalyzed asymmetric hydrolysis. The optical purities of the mono-hydrolyzed products (6) were determined from the 400 MHz proton nuclear magnetic resonance spectra after conversion of 6 to the esters of (-)α-methoxy-α-trifluoromethylphenylacetic acid. Upon hydrogenolysis of the benzyl ether, followed by protection of diol and hydrolysis of the acetate, (-)-6a afforded 10.View full abstractDownload PDF (599K)