Konoshin Onodera

Oxidation of carbohydrates with methyl sulfoxide containing phosphorus pentaoxide : I. Synthesis of some aldosuloses and aldosiduloses

Abstract Methyl sulfoxide containing phosphorus pentaoxide oxidizes secondary alcohol groups of carbohydrates to ketones. Oxidation proceeds most efficiently with N,N-dimethylformamide as solvent and with 3–4 molar equivalents of methyl sulfoxide and 1.5–2.0 molar equivalents of phosphorus pentaoxide. The following carbohydrates were oxidized to afford the corresponding aldosuloses and aldosiduloses in good or moderate yields: methyl4,6- O -benzylidene-2- O -( p -tolylsulfonyl)-α- D -gluco- and allo-pyranoside ( 1 and 18 ), methyl 2-acetamido-4,6- O -benzylidene-2-deoxy-α- D -gluco- and -allo-pyranoside ( 3 and 19 ), 1,2:5,6-di- O -isopropylidene-α- D -glucofuranose (6),1,2- O- isopropylidene-5- O -( p -tolylsulfonyl)-α- D -xylo- and -ribo-furanose ( 11 and 13 ), 1,2- O -isopropylidene-5- O -(di- O -phenylphosphono)-α- D -xylofuranose ( 14 ), and 1,2- O -isopropylidene-α- D -glucofuranurono-6,3-lactone ( 16 ).

Formation of nuclear polyhedral bodies and nuclear polyhedrosis virus of silkworm in mammalian cells infected with viral DNA

Abstract The infectious DNA of nuclear polyhedrosis virus of silkworm ( Bombyx mori Linne) caused production of characteristic nuclear polyhedral bodies in cultured FL cells of human amniotic origin, which did not support virus growth. The activity of the viral DNA in producing polyhedral bodies in FL cells was lost by pretreatment of the inoculum with DNase and by heating, but RNase was inactive. The polyhedral bodies formed in the cells were identical with those formed in cells of the silkworm with respect to their morphological and serological character. The polyhedral bodies isolated from FL cells and dissolved in alkali caused nuclear polyhedrosis when injected into silkworm pupae.

The nucleic acid of nuclear-polyhedrosis virus of the silkworm

Viral DNA was isolated from virus particles of nuclear-polyhedrosis of the silkworm, Bornbyx mori L., with 0·1 M -Na 2 CO 3 -NaHCO 3 buffer solution (pH 10·0), and then fractionated and purified on methylated albumin columns. Viral DNA showed a single peak on methylated albumin column fractionation as well as in analytical centrifugation, and the S 20,w of viral DNA was 13·1 s. The purified viral DNA was infectious. While DNase-treated DNA lost its infectivity, RNase-treated DNA was unaffected. The evidence that the ratio in viral DNA of adenine to thymine as well as of guanine to cytosine was equal to unity, that the DNA gave a sharp melting curve and that heat-denatured DNA was observed to react with formaldehyde showed that the DNA isolated was double-stranded DNA.

Conformational studies on some g̈a-glycopyranose derivatives

Abstract The conformations of eleven α-glycopyranosides and glycosylamine derivatives, and their acyl derivatives, were studied by n.m.r. spectral analysis in deuterium oxide and in methyl sulfoxide- d 6 . In deuterium oxide at room temperature, the α-glycosylamines examined were found to exist as a rapidly equilibrating mixture of the two chair conformations, but, in methyl sulfoxide- d 6 at room temperature, they were found to exist mainly in the 1C ( D ) [ C1 ( L )] conformation. However, the α-glycosides and their acyl derivatives examined were found to exist mainly in the C1 ( D ) [ 1C ( L )] conformation in various solvents.

Studies on the synthesis of unsaturated nucleoside analogs

Abstract An unsaturated 6-deoxy- l -hexopyranosyltheophylline diacetate was synthesized, starting from l -rhamnopyranose tetraacetate ( 1 ), by the fusion procedure with the use of p -toluenesulfonic acid, and also through dehydration with phosphorus pentaoxide by way of 2,3,4-tri- O -acetyl- l -rhamnopyranose ( 2 ) in N,N -dimethyl-formamide. It was found that 2,3,4-tri- O -acetyl-1,5-anhydro-1,6-dideoxy- l - arabino -hex-1-enitol (2,3,4-tri- O -acetyl-2-hydroxy- l -rhamnal) ( 3 ) was involved as an intermediate. The following glycal derivatives were condensed with theophylline by the fusion procedure: 2-hydroxy- d -glucal tetraacetate, d -galactal triacetate, 2-hydroxy- d -glucal tetraacetate, d -galactal triacetate, 2-hydroxy- d -galactal tetraacetate ( 6 ), 2-hydroxy- d -xylal triacetate, l -rhamnal diacetate, and 1,2,4,6-treta- O -acetyl-3-deoxy- d - threo -hex-2-enopyranose ( 7 ). The unsaturated nucleoside analogs thus synthesized are described.

Infrared spectra of the sulfonic esters of monosaccharides

Abstract The orientation of sulfonyloxy groups at different carbon atoms of the pyranose ring of monosaccharides has been examined by analysis of infrared spectra in the 800–900 cm −1 region, with particular reference to axial and equatorial orientations of the sulfonyloxy groups. Axial sulfonyloxy groups show a strong absorption band at 880–890 cm −1 , whereas equatorial ones absorb at 840–850 cm −1 . The absorption frequency is not affected by variations in the kind of hexopyranose, by the kind and position of the sulfonyloxy groups on the pyranose ring, or by the kind of phase used for the measurement.

Properties of flacherie virus of the silkworm, Bombyx mori

Abstract The flacherie virus of the silkworm, Bombyx mori , was isolated from infected larvae reared under aseptic conditions. Two types of infectious particles, tentatively designated FVS I and FVS II, were separated by density gradient centrifugation. Some properties of the separated particles were investigated. Electron micrographs showed that FVS I and FVS II were spherical particles with diameters of 27 ± 2 nm and 22 ± 2 nm, respectively. The sedimentation coefficients of FVS I and FVS II were 180 S and 134 S, respectively. It was concluded from experiments of incorporation of 3 H-uracil inoculated into diseased larvae at late stage of flacherie disease that the nucleic acid of FVS II was RNA. The two types of particles were present in Sakaki and Wadayama strains of flacherie virus.

Studies on lipids in the hemolymph of the silkworm, Bombyx mori, during the course of nucleopolyhedrosis.

Abstract Total lipids were determined in the hemolymph of the silkworm, Bombyx mori, infected with nucleopolyhedrosis virus. In the phospholipid fraction lecithin, phosphatidylserine, and phosphatidylethanolamine were detected. Hydrolysis of phospholipid gave two substances which were not identified. One of them gave a positive reaction with the iodine vapor test and the other gave positive reactions both with the iodine vapor and the ninhydrin tests. Cholesterol was identified as the only component of the cholesterol fraction in the body fluid of diseased as well as of normal silkworms. Fatty acids increased when polyhedra were released into the body fluid. Palmitic and stearic acids were detected, together with an unidentified fatty acid, as the components of the fatty acid fraction.

Polysaccharide synthesis from mono- and oligo-saccharides by the action of phosphorus pentoxide in dimethyl sulphoxide

Abstract Phosphorus pentoxide-dimethyl sulphoxide (P 4 O 10 -DMSO) was found predominantly to catalyse the polymerization reaction of carbohydrates at below 35°C and the oxidation reaction at 60–65°C. A series of new synthetic polysaccharides were prepared from mono- and oligo-saccharides including 2-acetamido-2-deoxy- d -glucose and hexuronic acids in up to 48% yield by the action of P 4 O 10 -DMSO at 10–25°C. These synthetic polysaccharides showed s 20,w 0.68–1.34S, and the degree of polymerization fell in 15.3–4.7 monosaccharide units per polysaccharide chain on the basis of reducing end-group assay. A structural analysis by the methylation of the synthetic glucan (2) revealed α-1,4- and α-1,6-glucosidic linkages as main chains with various branchings. The synthetic polysaccharides contained 1.3–15.9% phosphorus, but the linkages are unknown.

RNA isolated from polyhedra of a nuclear polyhedrosis of the silkworm.

Abstract RNA was isolated from the nuclear polyhedra of a nuclear polyhedrosis of the silkworm. The properties of the RNA were studied. The value of s20, w is 7.25 and that of ϵ(P) is 8181. Bases other than adenine, guanine, cytosine, and uracil were not found.