Étude du mycoside C2 de Mycobacterium avium

Mycoside C2 from Mycobacterium avium was extracted with ethanol—ether (1:1, v/v) and purified by column chromatography on silicic acid and silicagel G. The quantitative analysis of the hydrosoluble constituents leads to the following results: d-Phe, 1; d-allo-Thr, 2; d-Ala, 2; l-alaninol, 1; 3,4-di-O-methyl-l-rhamnose, 1; 6-deoxy l-talose, 0.5; 3-O-methyl-6-deoxy l-talose, 0.5. The l-configuration of the amino alcohol was determined by oxidation to the amino acid which was not oxidized by d-amino acid oxidase. Peptides and glycopeptides obtained by mild hydrolysis were identified by mass spectrometry or by Edman sequential analysis. The following sequence was found: d-Phe—d-allo-Thr—d-Ala—d-allo-Thr—d-Ala—l-alaninol. The structure of the alaninol-di-O-methyl l-rhamnoside was determined by mass spectrometry. Alaninol is linked to the 3,4-di-O-methyl l-rhamnose most likely by an α-glycosidic linkage. Either 6-deoxy l-talose or its 3-O-methyl derivative are linked to the second molecule of allo-threonine. This position was determined by alkaline β-elimination of this sugar followed by catalytic hydrogenation and mild hydrolysis of the mycoside. These treatments gave a peptide identified by Edman sequential analysis as: d-allo-Thr—d-Ala—Abu—d-Ala—l-alaninol. The lipid moiety is a complex mixture of fatty acids in which palmitic acid is present. These results lead to the structure given in Formula I for the mycoside C2.

[1]  W. Gray,et al.  Rapid sequence analysis of small peptides. , 1970, Analytical biochemistry.

[2]  E. Lederer,et al.  Dt́ermination de séquences d'Acides aminés dans des oligopeptides par la spectrométrie de Masse—VI : Structure du mycoside Cb, peptidoglycolipide de mycobacterium butyricum , 1966 .

[3]  V. P. Bhavanandan,et al.  STUDIES ON GLYCOPROTEINS. XI. THE O-GLYCOSIDIC LINKAGE OF N-ACETYLGALACTOSAMINE TO SERYL AND THREONYL RESIDUES IN OVINE SUBMAXILLARY GLAND GLYCOPROTEIN. , 1965, Biochimica et biophysica acta.

[4]  S. Harbon,et al.  The linkage between sugars and amino acids in ovine submaxillary gland mucoprotein “OSM” , 1964 .

[5]  E. Lederer,et al.  Structure du mycoside C2 de Mycobacterium avium , 1963 .

[6]  K. Biemann,et al.  Application of Mass Spectrometry to Structure Problems. XIV.1Acetates of Partially Methylated Pentoses and Hexoses , 1963 .

[7]  B. Witkop,et al.  Gramicidin A. I. Determination of Composition and Amino Acid Configuration by Enzymatic and Gas Chromatographic Methods , 1963 .

[8]  E. Lederer.  Sur la structure de quelques métabolites microbiens biologiquement actifs , 1963 .

[9]  O. S. Chizhov,et al.  Mass spectrometry of carbohydrate derivatives , 1963 .

[10]  E. Lederer,et al.  Structure du mycoside Cm, peptido-glycolipide de Mycobacterium marianum , 1962 .

[11]  K. Piez,et al.  A modified procedure for the automatic analysis of amino acids. , 1960, Analytical biochemistry.

[12]  D. Russell.  Ninhydrin as a reagent for N-methyl-amino acids , 1960 .

[13]  M. Rees.  Studies on the amide and C-terminal residues in proteins. 4. Separation and quantitative determination of beta-amino alcohols. , 1958, Biochemical Journal.

[14]  R. Lemieux,et al.  PREPARATIVE PARTITION CHROMATOGRAPHY OF CARBOHYDRATES ON CELITE COLUMNS , 1956 .

[15]  Z. Dische,et al.  A specific color reaction of methylpentoses and a spectrophotometric micromethod for their determination. , 1948, The Journal of biological chemistry.

[16]  W. Haworth,et al.  CCCXXVIII.—The development of a novel form of stereoisomerism in the sugar series. Part I. The third variety of triacetyl methylrhamnoside , 1929 .

[17]  T. Purdie,et al.  CXXI.—The alkylation of rhamnose , 1906 .