O-antigen polysaccharide

A structural study on lipid A and the O-specific polysaccharide of the lipopoly-saccharide from a clinical isolate of Bacteroides vulgatus from a patient with Crohn s disease was conducted by Hashimoto and coworkers [39]. They separated two potent virulence factors, capsular polysaccharide (CPS) and lipopolysaccharide (LPS), from a clinical isolate of B. vulgatus and characterized the structure of CPS. Next, they elucidated the strucmres of O-antigen polysaccharide (OPS) and lipid A in the LPS. LPS was subjected to weak acid hydrolysis to produce the lipid A fraction and polysaccharide fraction. Lipid A was isolated by PLC, and its structure was determined by MS and NMR. 

The O-antigen polysaccharides of Klebsiella serotype 05 and Escherichia coli 08 were prepared by mild hydrolysis of the lipopolysaccharides. A bacteriophage enzyme hydrolyzed both polymers,3150 giving the trisaccharide /3-D-Man-(l - 2)-a-D-Man-(l -> 2)-D-Man. 

L.V. (1981). Synthesis of the O-antigenic polysaccharide of Salmonella newington and of its analogue differing in configuration at the only glycosidic centre. Tetrahedron 37 Suppl. 1 19-156 Lehmann, V. (1977). Isolation, purification, and properties of an... 

Table Y Physical Properties of Pseudomonas aeruginosa Immunotype 2 O-Antigenic Polysaccharide...

The architectonics of O-antigenic polysaccharides unambiguously indicates that the most appropriate approach to their synthesis is to assemble the biopolymer out of prefabricated repeating units. The practical solution of this problem can be. achieved by several pathways (cf. 7) the following three most obvious ones will be discussed. 

The synthesis of the j>. newington O-antigenic polysaccharide by the chemical polymerization pathway will be discussed as an example (J 6 J 7) The first and the most difficult task consists in the preparation of the monomer itself, i. e. , the properly functionalized, oligosaccharide repeating unit. The most usual approach is to introduce the required functions into the already-existing oligosaccharide molecule. 

All three approaches can be expected to find application in the preparation of various O-antigenic polysaccharides and their analogues to solve different problems of molecular immunology. 

Figure 3. Structures of the O-antigenic polysaccharide chain in Salmonella bacteria of serogroups C2 and C3 and a synthetic disaccharide glycoconjugate (O-antigen 8-specific). Results of immunofluorescence studies (IFL) of these structures.

The structure of the O-antigenic polysaccharide chain in Salmonella serogroup Cl (0 antigens 6, 7) has not been established in detail (22). Hence, it has not been possible to identify the structural elements representing the determinant of serogroup 0-antigen 07. 

Figure 4. Structures of the O-antigenic polysaccharide chains in Salmonella bacteria ofserogroup E and a synthetic trisaccharide gly coconjugate (O-antigen 3-specific). Results of ELISA and immunofluorescence (IFL) studies. Key m, S. anatum (03, 10) , S. senftenburg (01, 3, 19) , BSA a, S. typhimurium (04, 5,...

The substrate, i,e. the O-antigenic polysaccharide chain, can carry several substituents on the basic tetrasaccharide repeating unit in form of D-glucose residues or O-acetyl groups (Figure 7). 

TABLE I. Salmonella typhimurium Infection in Calves Delayed Skin Reactivity with Specificity for O-Antigenic Polysaccharide Chain... 

N. K. Kochetkov, in L. Anderson and F. M. Unger (Eds.), Synthesis of O-antigenic polysaccharides. Pathways for the polymerization of oligosaccharide repeating units, Bacterial Lipopolysaccharides Structure, Synthesis and Biological Activities, ACS Symp. Ser., Vol. 231, Amer. Chem. Soc., New York, 1983, pp. 65-81. 

N. K. Kochetkov, Unusual monosaccharides Components of O-antigenic polysaccharides of microorganisms, Russian Chem. Rev., 65 (1996) 735-768. 

B. A. Dmitriev, A. V. Nikolaev, A. S. Shashkov, and N. K. Kochetkov, Block-synthesis of higher oligosaccharides Synthesis of hexa- and nona-saccharide fragments of the O-antigenic polysaccharide of Salmonella newington, Carbohydr. Res., 100 (1982) 195-206. 

V Shibaev Biosynthesis of salmonella O-antigenic polysaccharide specificity of glycosyl transferases... 

FIGURE 14.3 Structure of LPS with the core structure from Escherichia coli and the Salmonella species. Gal, galactose Glc, glucose Hep, L-glycero-D-manno-heptose O-PS, O-antigen polysaccharide. 

Abeyrathne, P.D., Daniels, C., Poon, K.K., Matewish, M.J., Lam, J.S. Functional characterization of WaaL, a ligase associated with linking O-antigen polysaccharide to the core of Pseudomonas aeruginosa lipopolysaccharide. J Bacteriol 187 (2005) 3002-3012. 

Amano K. An Interesting Property of O-Antigen Polysaccharide in lipopolysaccharide Cross-talk between Lipopolysaccharides of Helicobacter pylori and host cells through lewis blood group antigens. Trends Glycosci Glycotechnol 14 (2002) 105-114. 

Sebastian, S., Dillon, S.T., Lynch, J.G., Blalock, L.T., Balon, E., Lee, K.T., Comstock, L.E., Conlan, J.W., Rubin, E.J., Tzianabos, A.O., Kasper, D.L. A defined O-antigen polysaccharide mutant of Francisella tularensis live vaccine strain has attenuated virulence while retaining its protective capacity. Infect Immun 75 (2007) 2591-2602. 

Kocharova, N.A., Knirel, Y.A., Widmalm, G., Jansson, P.-E., Moran, A.P. Structure of an atypical O-antigen polysaccharide of Helicobacter pylori containing a novel monosaccharide 3-C-methyl-D-mannose. Biochemistry 39 (2000) 4755-4760. 

Table 16.2 O-Antigen polysaccharides found in the lipopolysaccharides from members of the Rhizobiales... 

Forsberg, L.S., Bhat, U.R., Carlson, R.W. Structural characterization of the O-antigenic polysaccharide of the lipopolysaccharide from Rhizobium etli strain CE3. A unique O-acetylated gly-can of discrete size, containing 3-0-methyl-6-deoxy-L-talose and 2,3,4-tri-O-methyl-L-fucose. J Biol Chem 275 (2000) 18851-18863. 

Forsberg, L.S., Noel, K.D., Box, J., Carlson, R.W. Genetic locus and structural characterization of the biochemical defect in the O-antigenic polysaccharide of the symbiotically deficient Rhizobium etli mutant, CE166 Replacement of N-acetylquinovosamine with its hexosyl-4-ulose precursor. J Biol Chem 278 (2003) 51347-51359. 

Bock K, Meldal M, Bundle DR, Iversen T, Garegg PJ, Norbeig T, Lindberg AA, Svenson SB (1984) The conformation of Salmonella O-antigenic polysaccharide chains of serogroup A, B and D1 predicted by semi-empirical hard-sphere (HSEA) calculations. Carbohydr Res 130 23-34... 

J. J. Zhang, Y. Zhu, and F. Kong, Synthesis of an L-rhamnose tetrasaccharide, the common and major structure of the repeating unit of the O-antigenic polysaccharide of a strain of Klebsiella pneumoniae and Pseudomonas hold, Carbohydr. Res., 336 (2001) 229-235. 

Heptoses are typical constituents of lipopolysaccharides (LPS), in most cases occurring in the core region in the L-gtycero-D-manno or n-glycero-n-manno configuration.239 However, a few other heptoses have been identified in the O-antigen polysaccharide of LPS, and these examples are discussed next. 

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