Polysaccharides bacterial, biosynthesis

Some sugar residues in bacterial polysaccharides are etherified with lactic acid. The biosynthesis of these involves C)-alkylation, by reaction with enol-pyruvate phosphate, to an enol ether (34) of pyruvic acid, followed by reduction to the (R) or (5) form of the lactic acid ether (35). The enol ether may also react in a different manner, giving a cyclic acetal (36) of pyruvic acid. 

Polyisoprenol compounds exist in both bacteria and eukaryotic cells. They participate in the synthesis of bacterial polysaccharides and in the biosynthesis of N-... 

BIOSYNTHESIS OF BACTERIAL POLYSACCHARIDE CHAINS COMPOSED OF REPEATING UNITS... 

Branched-chain monosaccharides have now been detected as components of bacterial polysaccharides. The known examples include yersiniose [3,6-dideoxy-4-C-(hydroxyethyl)-D-xy/o-hexose228] from Y. pseudotuberculosis, a 3-C-(hydroxymethyl)pentofuranose from Coxiella bumetti,229 and 6-deoxy-3-C-methylhexoses from the same organism and from Nitrobacter hamburgiensis.229 Several branched-chain monosaccharides were identified as components of antibiotics, and the pathways of their biosynthesis in bacteria were studied. These investigations were discussed in detail by Grisebach in this Series.230 The usual precursors for the formation of the monosaccharides of this group are the nucleoside 6-deoxyhexosyl-4-ulose diphosphates 7a and 7b. 

Other monosaccharide components (of bacterial polysaccharides) that are structurally related to D-ribose include D-riburonic acid,232 identified in the exocellular polysaccharide produced by a strain of Rhizobium meliloti, and D-arabinose, frequently present as the furanose, in polysaccharides of mycobacterial cell-wall.233,234 L-Xylose235,236 should probably be included in the group, as it may be derived from D-arabinose through epimerization at C-4. Biosynthesis of these monosaccharides was not investigated. 

The most complete list of modified monosaccharide units of bacterial polysaccharides may be found in a review by Kenne and Lindberg.98 The present discussion is limited only to examples where some data on biosynthesis are available. 

This concept, known as273"275 the one enzyme-one linkage concept, has been widely used in discussions of the biosynthesis of carbohydrate chains in animal glycoproteins and proteoglycans. It implies that the structure of a carbohydrate chain is dictated by the specificity of the enzymes that participate in glycosidic-bond formation. Application of the same concept for discussion of the biosynthesis of bacterial polysaccharides seems worth while. 

The structures of polyprenyl diphosphate-linked intermediates of Salmonella O-specific-polysaccharide biosynthesis were confirmed by chemical synthesis of their analogs derived from the plant polyprenols ficaprenol and moraprenol (structurally related to bacterial polyprenol57) with the following study of their behavior as substrates of enzymic reactions. Synthetic polyprenyl a-D-galactopyranosyl diphosphate291,292 was found to serve as an effective acceptor for the transfer of L-rhamnosyl groups.293"295 Two synthetic, isomeric disaccharide derivatives,292 13 and296 14, were tested as acceptors for enzymic D-mannosyl transfer from GDP-Man, but only the former was found to be an efficient substrate.294... 

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