Complex saccharides

FIGURE 9.26 The carbohydrate tnoiedes of glycoproteins may be linked to the protein via (a) serine or threonine residues (in the O-linked saccharides) or (b) asparagine residues (in the N-linked saccharides), (c) N-Linked glycoproteins are of three types high mannose, complex, and hybrid, the latter of which combines structures found in the high mannose and complex saccharides. 

Constitutional studies have broadly followed the pattern of methyla-tion of the unsubstituted alcoholic groups in a carbohydrate, hydrolytic or oxidative disruption of the molecule and identification of the resulting methylated fragments. In this way methyl ethers have been invaluable in the determination of the ring structures of the monosaccharides and in the elucidation of the constitutions of the more complex saccharides. 

As a complement to the comprehensive Chapter on the biosynthesis of complex saccharides by Nikaido and Hassid in Vol. 26, where the products of biosynthesis were stressed, Kochetkov and Shibaev (Moscow) here emphasize the nucleotide sugar biosynthetic intermediates, themselves, in a detailed article on their chemistry and enzymology. 

Chapters 17 through 21 deal with carbohydrate-enzyme systems. Hehre presents some new ideas on the action of amylases. Kabat presents some new immunochemical studies on the carbohydrate moiety of certain water-soluble blood-group substances and their precursor antigens. Hassid reviews the role of sugar phosphates in the biosynthesis of complex saccharides. Pazur and co-workers present information obtained by isotopic techniques on the nature of enzyme-substrate complexes in the hydrolysis of polysaccharides. Gabriel presents a common mechanism for the production of 6-deoxyhexoses. An intermediate nucleoside-5 -(6-deoxyhexose-4-ulose pyrophosphate) is formed in each of the syntheses. 

The Role of Sugar Phosphate in the Biosynthesis of Complex Saccharides... 

Glycosyl—Enzyme Complex Intermediates in Biosynthesis of Complex Saccharides. The synthesis of nucleoside diphosphate sugars involves the transfer of a nucleotidyl group from a nucleoside triphosphate to a sugar 1-phosphate with the simultaneous release of pyrophosphate according to the following general reaction (11) ... 

Natural complex saccharides found to be formed from a particular substrate with an inversion of configuration seem to be more prevalent than those without inversion. 

In summary, the general equation for the synthesis of complex saccharides through transglycosylation may be expressed as follows. 

Analogues of complex saccharides, in which one or other of the acetal oxygens is replaced by a methylene residue or other heteroatoms, have received attention as biochemical probes and as potential therapeutic agents. The use of l-thio-1,2-isopropylidene acetals (TIA s) as annulating synthons for highly hydroxylated systems is illustrated by the synthesis of (3-C-, p-aza-C- and P-carba- galacto disaccharides. 

Fig. B.9.1. Molecules such as organic dyes, polycyclic aromatic compounds, organometallic complexes, saccharides, peptides, and polyamides bind to nucleic acids. Two major binding modes are possible — intercalation (left) and groove binding (right).

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