Carbon capsular polysaccharides

The pyruvic acid may also be linked to vicinal positions. When linked to 0-3 and 0-4 of a D-galactopyranosyl residue (40), the dioxolane ring becomes cw-fused. In the limited number of known examples, the absolute configuration at the acetalic carbon atom is (S), as in 40. There are some examples of tra -fused dioxolane rings, and these are more sensitive to hydrolysis with acid than the others. Thus, pyruvic acid is acetalically linked to 0-3 and 0-4 of an a-L-rhamnopyranosyl residue in the Klebsiella type 72 capsular polysaccharide, to 0-2 and 0-3 of an a-D-galactopyranosyl residue in the Streptococcus pneumoniae type 4 capsular polysaccharide, and to 0-2 and 0-3 of a S-D-glucopyranosyluronic acid residue in the Klebsiella K1 capsular polysaccharide. " In the extracellular polysaccharide from... 

Two of the most frequent monosaccharide components of bacterial polymers belonging to this group have been the subjects of articles in this Series. They are 3-deoxy-D-manno-2-octulosonic acid,247 a normal constituent of the core region of bacterial lipopolysaccharides that is also present in some other polymers, and N-acetylneuraminic acid,248 found in several capsular polysaccharides. Enolpyruvate phosphate serves as the precursor of the C-l-C-3 fragment of the monosaccharides, with D-arabinose 5-phosphate or 2-acetamido-2-deoxy-D-mannose 6-phosphate being an acceptor for transfer of the three-carbon unit. Characteristic, activated forms of these monosaccharides are the CMP derivatives. 

The 3-deoxy-D-ma/ino-2-octulosonic acid 8-phosphate synthase (KDO synthase or KdoS EC 4.1.2.16) is an enzyme involved in the biosynthesis of the eight-carbon sugar KDO [63], a constituent of the capsular polysaccharides (K-antigens) and outer membrane lipopolysaccharides (LPS, endotoxin) of Gram-negative bacteria [156], as well as of the cell wall of algae and a variety of plants [157], In vivo, the enzyme catalyzes the irreversible addition of 26 to D-arabinose 5-phosphate (Ara5P, 32) to form KDO 8-phosphate 33 [158]. The... 

Figure 8. Carbon-13 NMR spectra of three capsular polysaccharides.

A synthesis of a dimeric ribitol fragment of a capsular polysaccharide is mentioned in Chapters 3 and 7, and a one-carbon chain elongation procedure converting hexoses to hept-l-ynitols is referred to in Chapter 13. 

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