Synthesis of daunosamine-containing disaccharides

Treatment of 2,3,6-trideoxy-1,4-di-O-(p-nitrobenzoyl)-3-(trifluoroacetamido)-l-lyxo-hexopyranose (1) with benzyl 2,3-dideoxy-d-glycero-pentopyranoside and p-toluenesulfonic acid gave a mixture of benzyl 2,3,6-trideoxy-4-O-p-nitrobenzoyl-3- (trifluoroacetamido)-l-lyxo-hexopyranoside (49%) and benzyl 2,3-dideoxy-4-O-[2,3,6-trideoxy-4-O-(p-nitrobenzoyl)-3-(trifluoroacetamido)-α-l-lyxo-hexopyranosyl]-d-glycero-pentopyranoside (4, 20 %). The structure of the disaccharide 4 was confirmed by a detailed, mass-spectrometric analysis in three modes, namely, negative- and positive-ion, chemical ionization, and electron impact. Similar treatment of the bis(p-nitrobenzoate) 1 with ethyl 2,3-dideoxy-d-glycero-pentopyranoside gave the ethyl glycoside and the desired disaccharide, showing that the transglycosylation is not restricted to benzyl glycosides. Removal of the p-nitrobenzoyl and the benzyl groups from 4 gave the disaccharide 2,3-dideoxy-4-O-(2,3,6-trideoxy-3-trifluoroacetamido-α-l-lyxo-hexopyranosyl)-d-glycero-pentopyranose.     

Synthesis of 7-(tetrahydropyran-2-yl)- and 7-(4-acetoxytetrahydropyran-2-yl)-ε-rhodomycinone and 7-(tetrahydropyran-2-yl)-ε-pyrromycinone

The ¹³C.n.m.r spectra of water-soluble and -insoluble glucans synthesized by enzymes isolated from six strains of Streptococcus mutans are interpreted. The glucans are shown to be composed primarily of α(1→3)- and α-(1→6)-linked glucosyl residues, and the relative abundance of each linkage is estimated from peak areas. Treatment of water-insoluble glucans with dextranase is found to result in water-soluble and -insoluble products, the former enriched in α-(1→6)-linkages and the latter in α-(1→3)-linkages. The structural conclusions arrived at by ¹³C-n.m.r. spectroscopy are consistent with data from methylation analysis and ¹H-n.m.r. spectroscopy.     

Analysis of tadpole growth following gamma-ray irradiation

This investigation reports observations on the growth of Rana cyanophlyctis tadpoles following a whole body gamma-ray exposure. The effect on the body and hind limb size is perhaps the most significant of the period of latency. A dose of 2,000 R serves as a stressor and activates ACTH secretion in the tadpoles. The resultant somatotrophic hormone (STH) inhibition and subsequent recovery during the following days seem an integral part of the radiation syndrome.     

The reduction of aldehydes by broad bean and maize alcohol dehydrogenases and a study of the substrate binding to the enzyme protein

Alcohol dehydrogenase was prepared from 2-day germinating maize and 3-day germinating broad-bean seeds by ammonium sulphate fractionation of sodium phosphate extracts, chromatography onDEAE cellulose and Sephadex G-200. The activity of the broad beanADH amounted to182 800 units per mg protein, that of maizeADH 79 000 units per mg protein. Besides oxidation of a series of alcohols at pH optimum in the alkaline region and with KM equalling 10-2M, alcohol dehydrogenases isolated from both plants catalyze the reduction of acetaldehyde, n-propanal, n-butanal, isobutanal and crotonal at pH optimum in the neutral region with KM equalling 10-3M. The inhibition studies using fatty acids and chloride ions revealed that the oxidation of alcohols is inhibited competitively by both types of inhibitors, with inhibition constants of 10-2M and 10-1M, respectively. The inhibition in the presence of acetaldehyde is non-competitive since the inhibitors do not compete with acetaldehyde and do not form an enzyme-NADH-inhibitor complex, yet they obviously react with the enzyme-NAD product only, thus giving rise to an enzyme-NAD-inhibitor complex. These differences in the behaviour of inhibitors may be interpreted in the sense that the binding sites of ethanol and acetaldehyde as substrates for broad bean and maize alcohol dehydrogenases are non equivalent. The nonequivalency discussed in the text.     

Reactions of 3-(1-arylhydrazono-L-threo-2,3,4-trihydroxybutyl)-1-methyl-2-Quinoxalinones

The 1-methyl derivatives (3 and 4) of 3-(1-phenyl- (1) and 3-(1-p-bromophenylhydrazono-L-threo-2,3,4-trihydroxybutyl)-2-quinoxalinone (2) were prepared by methylation. Periodate oxidation of 3 gave 1-methyl-3-[1-(phenylhydrazono)glyoxal-1-yl]-2-quinoxalinone (5), which, on reduction with sodium borohydride, gave the corresponding 3-[2-hydroxy-1-(phenylhydrazono)ethyl] derivative (8). Reaction of 5 with hydroxylamine or benzoylhydrazine gave the corresponding 2-oxime (6) and 2-(benzoylhydrazone) (7), respectively. Acetic anhydride causes one molecule of 3 or 4 to undergo elimination of two molecules of water, with simultaneous acetylation and ring closure to afford pyrazoles 9 and 10, respectively. Pyrolysis of the triacetate of 3 led to the elimination of acetic acid from the sugar and the hydrazone residue, to give the 3-[5-(acetoxymethyl)-1-phenylpyrazol-3-yl] derivatives (9). Acetic acid was found to effect the same rearrangement, but without acetylation, of 1, 2, and 3 to give the 3-[5-(hydroxymethyl)] derivatives 11, 12, and 13, respectively. The structure of these pyrazoles was confirmed by a series of reactions, including methylation and acetylation. The n.m.r. and i.r. spectra of the compounds were investigated.     

The effect of amitrole (3-amino-1H-1,2,4-triazole) on cytokinin activity and sexual reproduction in the yeast Schizosaccharomyces octosporus

Cytokinin activity in extracts from actively growing cultures ofSchizosaccharomyces octosporus was greatly reduced by exposure to amitrole (5 × 10^–3M). Amitrole treatment, at the same concentration, stimulated cell enlargment and ascus production in this organism. These data suggest that a relationship may exist between low levels of endogenous cytokinins, cell expansion in preference to cell division, and ascus formation.     

The use of Opalina sudafricana in a biological test for diagnosing disordered metabolism of tryptophan in human subjects

Injections of urine of patients with bladder cancer linked with bilharziasis, simple urinary bilharziasis, ascariasis or ancylostomiasis, induced cyst formation found in Opalina sudafricana when injected into its host Bufo regularis. It is suggested that the carcinogenic tryptophan metabolites present in the injected urine reach the parasites in the recta of the experimental toads and stimulate them to divide mitotically to form small forms which eventually encyst. This test may be of a diagnostic help in detecting any abnormality in tryptophan metabolism in some human patients.