Sequential Oxidation and Reduction of Mono Methyl Ethers of Methyl 4,6-O-Benzylidene-α- and β-d-Glucopyranosides

(1) Both glutaminases A and B of Pseudomonas aeruginosa are inactivated by urea and guanidine hydrochloride, and the activities are partially restored by removal of the denaturants, while sodium lauryl sulfate denatured irreversibly the isozymes. (2) Glutaminase A consists of 4 identical subunits (mol. wt, 35,000) and B is composed of one polypeptide chain (mol. wt., 67,000). (3) Glutaminase A, which catalyzes the hydrolysis and also the hydroxylaminolysis of L and D isomers of glutamine and asparagine, does not act on γ-N-substituted glutamine e.g., γ-glutamylhydrazide. Some l- and d-γ-glutamyl derivatives, e.g., l- and d-γ-glutamyl-hydrazide, l- and d-γ-glutamylmethylester, and l-γ-glutamyl-l-alanine are substrates for glutaminase B, which does not catalyze the hydrolysis and hydroxylaminolysis of asparagine. α-Amino adipamic acid and α-amino substituted amino acids are inert for both the isozymes. (4) The acylation step is rate-limiting in the catalytic reactions by both the isozymes.     

Monomolar Etherification of Methyl 4, 6-O-Benzylidene-α- and β-d-Glucopyranosides

We have reported an inhibitory effect of Lactobacillus gasseri OLL2809 (OLL2809) on the growth of mouse endometrial tissue in the abdominal cavity. The present study aimed to investigate the efficacy of Lactobacillus gasseri OLL2809 (OLL2809) on pre-existing endometriosis implanted on the abdominal wall in diestrus Wistar-Imamichi female rats. One week after implantation, the volume of the endometrial tissue was measured after laparotomy. OLL2809 and dienogest were administered for 4 weeks. OLL2809 significantly enhanced the decrease in the volume (p<0.01) as compared with control. Complete healing was observed in two of nine rats, but in none of the control group. Dienogest did not show significant efficacy. These findings suggest that OLL2809 is useful not only in therapy of pre-existing endometriosis but also in the prevention of the growth of endometrial tissue.     

Enzymic Deacetylation of Methyl 2,3-Di-O-Acetyl-α- and β-D-Threofuranoside

Enzymic deacetylation of methyl 2,3-di-O-acaetyl-α- and β-D-threofuranoside using porcine liver esterase affords monoacetates only (in the case of the α-anomer, the 3-O-acetylderivative exclusively) without any further hydrolysis to the corresponding diols.     

The Modes of Binding Methyl—α (and β)-D-glucopyranosides and Some of their Derivatives to Concanavalin A—A Theoretical Approach

Abstract

The probable modes of binding of Methyl—α (and β)-D-glucopyranosides and some of their derivatives to concanavalin A have been proposed from theoretical studies. Theory predicts that βMeGlcP can bind to ConA in three different modes whereas α-MeGlcP can bind only in one mode. βMeGlcP in its most favourable mode of binding differs from α-MeGlcP in its alignment in the active-site of the lectin where it binds in a flipped or inverted orientation. Methyl substitution at the C-2 atom of the α-MeGlcP does not significantly affect the possible orientations of the sugar in the active-site of the lectin. Methyl substitution at C-3 or C-4, however, affects the allowed orientations drastically leading to the poor inhibiting power of Methyl-3-O-methyl-α-D-glucopyranoside and the inactivity of Methyl-4-O-methyl-α-D-glucopyranoside. These studies suggest that the increased activity of the α-MeGlcP over β-MeGlcP may be due to the possibility of formation of better hydrogen bonds and to hydrophobic interactions rather than to steric factors as suggested by earlier workers. These models explain the available NMR and other binding studies.     

Synthesis and Antiviral Evaluation of the β-L-Enantiomers of Some Thymine 3′-Deoxypentofuranonucleoside Derivatives

Abstract

3′-Deoxy-β-L-erythro- (3), 3′-deoxy-β-L-thero- (6), 2′-fluoro- (7) and 2′-azido-2′,3′-dideoxy-β-L-erythro- (10) pentofuranonucleoside derivatives of thymine have been synthesized and their antiviral properties examined. All these derivatives were stereospecifically prepared by glycosylation of thymine with a suitable peracylated 3-deoxy-L-erythro-pentofuranose sugar (1), followed by appropriate chemical modifications. The prepared compounds were tested for their activity against HIV, but they did not show an antiviral effect.     

Some Derivatives of 5α-Ketosteroid Hydrazones: Synthesis from Tigogenin and Antituberculosis Activity

Isonicotinoylhydrazones and thiosemicarbazones of some 5-ketosteroids were synthesized from tigogenin, and their structures were confirmed by NMR and IR spectroscopy and mass spectrometry. Their antimycobacterial activities were studied and it was shown that some of the synthesized isonicotinoylhydrazones exhibit a high antituberculosis activity.     

Microbial Oxidation of α-Methylstyrene and β-Methylstyrene

An unidentified bacterial strain S107B1, isolated from soil by use of isopropylbenzene as a carbon source, was shown to bring about oxidation of α-methylstyrene and β-methylstyrene,

One of the oxidation products produced from α-methylstyrene was identified as the new compound, (—)-cis-23-dihydroxy-1-isopropenyl-6-cyclohexene.

The same strain S107B1 also oxidized β-methylstyrene and produced 3-phenylpropionaldehyde and benzoic acid.

From these results, the existence of reductive step for the aerobic degradation of these aromatic hydrocarbons by this strain was made clear. The initial attack on these aromatic hydrocarbons and a cyclohexenediol compound formed from α-methylstyrene were discussed.     

Chemical Conversion of Some Ribonucleosides into the Corresponding β-D-Arabinofuranosyl Derivatives1

Abstract

Five 3′,5′-di-O-acylribonucleosides were converted into the corresponding β-D-arabinofuranosyl derivatives through DMSO-oxidation followed by NaBH₄-reduction and deacylation with NaOMe-MeOH.     

Preparation and Properties of the 5,6- and 4,6(5,7)-Dinitro Derivatives of Benzimidazole and their 1-β-D-Ribofuranosides

Abstract

Nitration of benzimidazole leads to the formation of the two isomeric 5,6- and 4,6(5,7)-dinitrobenzimidazoles, which may be isolated by fractional crystallization. The chloromercury salts of these were employed to synthesize the corresponding 1-β-D-ribofuranosides, unequivocally characterized by ¹H NMR spectroscopy. Reference is made to the biological significance of these results.     

Methyl 2,3-Di-O-(L-α-aminobutyryl)-α-D-glucopyranoside,a New Sweet Substance,and Tastes of Related Compounds of Neutral Amino Acids and D-Glucose Derivatives

Methyl 2,3-di-(O-(L-phenylalanyl)-±-D-glucopyranoside and other O-aminoacyl sugars composed of neutral amino acids were synthesized to discover their tastes. Among them, phenylalanine derivatives were strongly bitter [the bitterness of methyl 2,3-di-O-(L-phenylalanyl-L-phenylalanyl-L-phenylalanyl)-±-D-glucopyranoside are equal to that of strychnine], on the other hand, O-aminoacyl sugars composed of amino acids having short side chain were very sweet; The sweetness of methyl 2,3-di-O-(L-±-aminobutyryl)-±-D-glucopyranoside is more than 50 times as strong as that of sucrose.     

Some 3-Amino and 3-Substituted-amino Derivatives of α4-Norpyridoxol

Some analogs of α⁴-norpyridoxol in which 3-hydroxyl group is replaced by amino and substituted-amino groups have been prepared and evaluated for anticoccidal activity. 3-Aroylamino analogs of α⁴-norpyridoxol have some coccidiostatic effect towards Eimeria tenella.     

Purification and Some Properties of Chaetomium trilaterale β-Xylosidase

A β-xyloside hydrolytic enzyme of the fungus Chaetomium trilaterale was further purified by a modification of Kawaminami’s procedure (DEAE-Sephadex A-25 and Sephadex G-75 column chromatography), followed by isoelectric focusing. The purified preparation was homogeneous by polyacrylamide disc gel electrophoreses at pH 4.3 and pH 8.3. The purified enzyme hydrolyzed β-d-glucopyranosides as well as β-d-xylopyranosides, and the ratio of β-glucosidase activity against β-xylosidase activity increased about 3 fold during the purification steps. The molecular weight of this preparation was estimated to be about 240,000 by Sephadex G-200 gel filtration and 118,000 by SDS-polyacrylamide slab gel electrophoresis. The isoelectric point was 4.86 and the amino acid composition was also determined.

The optimum pH was at 4.2 for phenyl β-d-glucoside and around 4.5 for phenyl β-d-xyloside. The β-xylosidase activity was relatively stable but β-glucosidase activity was rapidly inactivated, at the alkaline pH range above 11. The heating of the preparation at 60°C didn’t show a parallel inactivation of the two activities. N-Bromosuccinimide strongly inactivated both enzyme activities. Nojirimycin and glucono-l,5-lactone showed a stronger inhibition on β-xylosidase activity than on β-glucosidase activity. The maximal velocities decreased in the order; phenyl β-d-glucoside > cellobiose > phenyl β-d-xyloside > xylobiose; the value with phenyl β-d-glucoside was about 28-fold higher than that with phenyl β-d-xyloside.     

Purification and Some Properties of β-1, 3-Glucanase of Suspension-cultured Tobacco Cells

A laminaran-hydrolyzing enzyme was purified from the homogenate of suspension-cultured tobacco ceils by the treatment with ion-exchangers and gel filtration. The purified enzyme was homogemous in disc-electrophoresis and was a basic protein. The optimal pH of the enzyme was 5.0. The enzyme was stable at temperature below 40°C. The inhibitory effect of Hg²⁺ Cu²⁺ and Ag⁺ was observed. Investigation of the hydrolysis product revealed that the enzyme attacked laminaran endo-wise to form laminari-tetraose, -triose, -biose and glucose.     

Synthesis of 20α- and 20β-Amino-3,5-pregnadiene Derivatives and Antimicrobial Activity

Cellulose production by Acetobacter strains is enhanced by the addition of a small amount of cellulose to the production culture. The effect of an endo-β-1, 4-glucanase from Bacillus subtilis on the cellulose production by Acebohacter xylinum BPR2001 was examined by adding various amounts of the purified glucanase to the culture. The addition of a small amount of this glucanase enhanced cellulose production. Furthermore, it reduced the amount of a polysaccharide called acetan produced. However, an active-site mutant enzyme of the glucanase, which showed no enzyme activity but still had cellulose-binding ability, had no effect on cellulose production. It was concluded, therefore, that the endoglucanase activity itself, but not the cellulose-binding ability, was essential for the enhancement of cellulose production. The structural properties of the cellulose produced in the presence of the endoglucanase were found to be almost identical to those of native bacterial cellulose.     

Synthesis and Biological Evaluation of β-D-Pentofuranonucleoside Derivatives of 2-Azidoadenine and 6-Azidopurines

Abstract

β-D-pentofuranonucleoside derivatives of 2-azidoadenine and 6-azidopurines have been synthesized. The azido-tetrazolo tautomerism observed on such nucleoside analogues has been studied. The compounds were tested for their activity against HIV and HBV but they did not show significant antiviral effect.     

Acid-catalysed Reactions of Methyl β-(3,4-Dimethoxyphenyl) glycidate

Methyl trans-β-(3,4-dimethoxyphenyl)glycidate was found to rearrange to methyl 3,4-dimethoxyphenylpyruvate in high yield in DMSO, DMF or HMPT solution in the presence of boron trifluoride etherate or sulfuric acid at room temperature. It was also revealed that the glycidate, when treated with boron trifluoride in methanol at room temperature, opened at the β-position to give methyl β-(3,4-dimethoxyphenyl)-α-hydroxy-β-methoxy-propionate in 94% yield, which was a mixture of erythro and threo isomers in the ratio of 1 to 2.