Publisher Summary This chapter provides an overview of the 13 Carbon-nuclear magnetic resonance ( 13 C-NMR) spectroscopy of monosaccharides. The 13 C-NMR spectroscopy has become increasingly important as a tool for the characterization and structural elucidation of sugars and their derivatives. Although 13 C-NMR is closely related to 1 H-NMR spectroscopy, especially when both types of spectra are recorded with Fourier-transform instruments, the two techniques are sufficiently different to be valuable complements to each other. In many cases, in particular when dealing with complex molecules such as polysaccharides, the amount of information obtainable from 1 H-NMR spectra is limited as compared to that revealed by 13 C- NMR spectra. This chapter provides an almost complete collection of 13 C- NMR chemical shifts of monosaccharides, their methyl glycosides, and acetates, along with the examples of shift data for as many different types of monosaccharide derivative as possible. It also provides details on sampling techniques and assignment techniques, and discusses the identity of monosaccharides, their structure determination, and conformational analysis .

Carbon-13 Nuclear Magnetic Resonance Spectroscopy of Monosaccharides

Publisher Summary This chapter discusses the chemistry, metabolism, and biological functions of sialic acids. Interest in the sialic acids has rapidly increased in recent years, especially because of the reorganization of their involvement in the regulation of a great variety of biological phenomena. The occurrence of sialic acids in plants has never unequivocally been established, although some positive reports exist. The acylneuraminic acids can be released from their glycosidic linkages either by dilute (aqueous or methanolic) acids or sialidases. The unequivocal determination of sialic acids occurring in low concentrations in many biological materials is rather difficult, and this explains the many errors that have been made in this field. The biosynthesis of N-acetylneuraminic acid (Neu5Ac) is briefly reported in this chapter and more attention is given to the enzyme reactions modifying this compound. Little information is available about the role of the modifications of sialic acid resulting in a species- and tissue-specific distribution of different N,O-acylated and O-methylated sialic acids.

Chemistry, Metabolism, and Biological Functions of Sialic Acids

ANTIGENIC SIMILARITIES BETWEEN BRAIN COMPONENTS AND BACTERIA CAUSING MENINGITIS: Implications for Vaccine Development and Pathogenesis

Bacterial polysaccharides are usually associated with the outer surface of the bacterium. They can form an amorphous layer of extracellular polysaccharide (EPS) surrounding the cell that may be further organized into a distinct structure termed a capsule. Additional polysaccharide molecules such as lipopolysaccharide (LPS) or lipooligosaccharide (LOS) may also decorate the cell surface. Polysaccharide capsules may mediate a number of biological processes, including invasive infections of human beings. Discussed here are the genetics and biochemistry of selected bacterial capsular polysaccharides and the basis of capsule diversity but not the genetics and biochemistry of LPS biosynthesis (for reviews see 100, 140).

The biochemistry and genetics of capsular polysaccharide production in bacteria

Considerations for formulating the second-generation pneumococcal capsular polysaccharide vaccine with emphasis on the cross-reactive types within groups.

http://www.jbc.org/content/250/5/1926.full.pdf

Structural determination of the sialic acid polysaccharide antigens of Neisseria meningitidis serogroups B and C with carbon 13 nuclear magnetic resonance.

The capsular polysaccharide antigen from Neisseria meningitidis serogroup 29-e contains equimolar quantities of 2-acetamido-2-deoxy-D-galactose and 3-deoxy-D-manno-octulosonic acid (KDO), the latter of which is rarely found in biopolymers other than lipopolysaccharides. Carbon-13 nuclear mangetic resonance in conjunction with other chemical data indicated that the polysaccharide is composed of an alternating sequence of these two residues, the linkages being at C-3 of galactosamine and C-7 of KDO in the alpha-D and beta-D configuration, respectively. The native 29-e polysaccharide is O-acetylated, the O-acetyl groups being located at C-4 and C-5 of the KDO residues. Assignments of signals in the 13C nuclear magnetic resonance spectrum of the 29-e polysaccharide were made by consideration of those in the spectra of the monomer models, which necessitated the first recorded syntheses of methyl-alpha- and beta-D-3-deoxy-manno-octulopyranosonic acid. Like the methyl alpha- and beta-D-ketosides of sialic acid (Na+ salts), the equivalent methyl alpha- and beta-D-ketosides of KDO exhibit large chemical shift differences in the exocyclic C-8 position dependent on anomeric configuration. This can again be attributed to hydrogen bonding between the axial carboxylate group of the methyl beta-D anomer of KDO (C1 conformation) and the primary hydroxyl group at C-8. This phenomenon is also exhibited by the beta-D-linked KDO units of the 29-e polysaccharide.

Structural elucidation of the 3-deoxy-D-manno-octulosonic acid containing meningococcal 29-e capsular polysaccharide antigen using carbon-13 nuclear magnetic resonance

The application of 13C-nuclear magnetic resonance spectroscopy to the structural determination of the capsular polysaccharide antigens of Neisseria meningitidis is described. Complete assignments of the spectra of the polysaccharides of serogroups A, B, C, W-135, X and Y were made and were based mainly on previous assignments made for the monomer units of the respective polysaccharides. This technique provides information on all structural aspects of the polysaccharides including composition, mode of linkage, location of O-acetyl substituents, sequence, and conformation. In addition, nuclear magnetic resonance is nondestructive, extremely rapid, and has enormous potential in bacteriological research.

A K Bhattacharjee

Papers

Structural determination of the sialic acid polysaccharide antigens of Neisseria meningitidis serogroups B and C with carbon 13 nuclear magnetic resonance.

Structural elucidation of the 3-deoxy-D-manno-octulosonic acid containing meningococcal 29-e capsular polysaccharide antigen using carbon-13 nuclear magnetic resonance

Strucutres of the capsular polysaccharides of Neisseria meningitidis as determined by 13C-nuclear magnetic resonance spectroscopy.