Synthesis of glycosyl halides and glycosides via 1-O-sulfonyl derivatives

The reaction of an aldose derivative containing a free anomeric hydroxyl group with trifluoromethanesulfonic anhydride or methanesulfonic anhydride, in the presence of halide ion and s-collidine, furnishes a glycosyl halide; if an alcohol is then introduced, glycoside synthesis is effected in an overall, “one-pot” reaction. Several α-d-glucopyranosides, including disaccharides, have been prepared in high yield by using 2,3,4,6-tetra-O-benzyl-d-glucose as the aldose, and generating the corresponding glycosyl bromide(s) in situ. As a halide-exchange step is incorporated in the reaction sequence, orthoacetate formation was favored in reactions of 2,3,4,6-tetra-O-acetyl-d-glucose, such as occurs with per-O-acetylglycosyl halides. Methanesulfonic anhydride promotes glycosidation or orthoester formation in the absence of halide ion, as well as in its presence, whereas formation of an intermediate glycosyl halide appears to be necessary in order to moderate the more vigorous reactions of the trifluoro derivative. The analogous reaction of methanesulfonyl chloride with an aldose provides a ready route to glycosyl chlorides. Under the conditions employed for these various syntheses, acid-sensitive protecting groups may be used, including cyclic and acyclic acetals and O-trityl substituents.     

Paléobiogéographie de quelques Stephanocerataceae (Ammonitina) du Jurassique moyen et supérieur; une confrontation avec la théorie mobiliste

From Bajocian to lower Kimmeridgian, the subfamilyStephanocerataceae represents a large stock of the ammonite fauna. Though it is tributary of author's stratigraphical correlations and systematical interpretations, its geographical distribution with a drifting continents concept gives many teaching about the study of this superfamily, the continental drift and its consequences. Showing a world wide repartition at its apparition this stock then presents branches; the one (Stephanoceratidae) is not envisaged here; the second (Sphaeroceratidae and Cardioceratidae families) characterises rather the «boreal province; the third (Macrocephalitidae family) is chiefly specific of the «tethysian province. A «north-east pacific province with boreal affinities and a «south-east province with tethysian affinities are delimited. It is probably from its fauna that the tethysian macrocephalitid stock appears; first represented by ammonites specifically north american in middle and upper Bathonian stage, they extend during upper Bathonian and lower Callovian and reach South America and the Tethys. The presence of a narrow sea, on Patagonia, West Antarctica, East Africa, Madagascar and India, joining the Tethys and the south edge of Gondwania, is proved at various times, at Bajocian and Callovian stages.     

The threonine-sensitive homoserine dehydrogenase and aspartokinase activities of Escherichia coli K-12. Incubation of the enzyme in alkaline conditions: dissociation and disulfide-bridge formation.

Aspartokinase I - homoserine dehydrogenase I from Escherichia coli K-12, a homotetrameric enzyme, dissociates into dimers upon alkaline treatment. Both aspartokinase and homoserine dehydrogenase inactivation, as well as desensitazion towards L-threonine, occur in a multi-step process. Dithiothreitol stabilizes a dimeric form retaining full activity and sensitivity; L-homoserine stabilizing another dimeric form devoid of aspartokinase activity and retaining a substantial dehydrogenase activity insensitive toward L-threonine. A model is proposed showing that dissociation into dimers occurs in a first step, the resulting dimer losing both aspartokinase and homoserine dehydrogenase sensitivity in two subsequent steps involving the formation of intrachain disulfide bonds.     

LOLA ZRREGULARIS (CHLOROPHYTA-CLADOPHORACEAE): A NEW SPECIES FROM THE ROSS SEA,ANTARCTICA1

A small, loose lying, unbranched, filamentous alga from the Ross Sea, Antarctica, is described as a new species, Lola irregularis. The genus Lola is closely related to the genera Hormiscia, Rhizoclonium, and Chaetomorpha in the family Cladophoraceae. A key to all known species of Lola is included. This is the first record of a species of Lola south of the Antarctic convergence.     

Isolation and characterization of two asporogenous rifampicin resistant mutants of B. thuringiensis

Two rifampicin resistant mutants, Rif^r12 and Rif^r15, of B. thuringiensis Berliner have been isolated and characterized as true asporogenous mutants. Cells of Rif^r12 were blocked between stage I and stage II in the sporulation sequence; whereas cells of Rif^r15 mutant were blocked between stage II and stage III. It has been shown that two active forms of RNA-polymerase were present at t5 in Rif^r15 cells; as for wild type strain, the subunit composition of form I and form II were respectively ββ'_mα2 and β′βα2. In Rif^r12 cells, only one enzymatic form was found at t5 ; the subunit composition was determined as β′βσ_mα2 ; such a composition was characteristic for sporulation enzyme of wild type strain at t1,5. It is concluded that the sigma modification which occurs at about t1, is anterior to the β′ modification which is closely correlated with the forespore septum completion (t2). Thus, the timing of the modifications of B. thuringiensis RNA-polymerase previously suggested was clearly confirmed through the present study.In addition, both mutants present reduced levels of intracellular proteolytic activities, as compared with wild type strain, and the role of proteases is discussed.     

Reduction of oxidized inorganic nitrogen compounds by a new strain of Thiobacillus denitrificans

Denitrification by Thiobacillus denitrificans "RT" strain was investigated using manometry and gas chromatography. 1. From nitrate, resting cells produced only nitrogen anaerobically with thiosulfate as the electron donor. The data suggest that nitrate was assimilated and dissimilated by the same nitrate reductase, assayed with benzyl-viologen as the electron donor. 2. From nitrite, whole cells produced nitric oxide, nitrous oxide and nitrogen, using thiosulfate as the electron donor; nitrogen was the final product of the reduction. Crude extract reduced nitrite to nitrogen with p-phenylene-diamine and dimethyl-p-phenylene diamine as the electron donors, and produced nitric oxide, nitrous oxide and nitrogen with tetramethyl-p-phenylene-diamine as the electron donor. Nitrite was reduced to nitric oxide and nitrous oxide by crude extract using ascorbate-phenazine methosulfate as the electron donor. 3. From nitric oxide, whole cells produced nitrous oxide and nitrogen using thiosulfate as the electron donor, nitrogen was the final reduction product. Nitric oxide was reduced to nitrous oxide by crude extract with the ascorbate-phenazine methosulfate system. 4. Whole cells reduced nitrous oxide to nitrogen with thiosulfate as the electron donor. It was not possible to detect any nitrous oxide reductase activity in crude extract. 5. A scheme was of denitrification by Thiobacillus denitrificans "RT" strain.