Polysaccharides controlled synthesis

STRUCTURE-CONTROLLED SYNTHESIS OF REGIOSPECIFICALLY MODIFIED POLYSACCHARIDES STARTING FROM A PYROLYSIS PRODUCT OF CELLULOSE... 

Recent progress of basic and application studies in chitin chemistry was reviewed by Kurita (2001) with emphasis on the controlled modification reactions for the preparation of chitin derivatives. The reactions discussed include hydrolysis of main chain, deacetylation, acylation, M-phthaloylation, tosylation, alkylation, Schiff base formation, reductive alkylation, 0-carboxymethylation, N-carboxyalkylation, silylation, and graft copolymerization. For conducting modification reactions in a facile and controlled manner, some soluble chitin derivatives are convenient. Among soluble precursors, N-phthaloyl chitosan is particularly useful and made possible a series of regioselective and quantitative substitutions that was otherwise difficult. One of the important achievements based on this organosoluble precursor is the synthesis of nonnatural branched polysaccharides that have sugar branches at a specific site of the linear chitin or chitosan backbone [89]. 

Polysaccharide synthesis is under enzymatic control, but does not occur from a template as in protein synthesis. For this reason, each molecule of a particular polysaccharide will have its own unique molecular weight. The molecular weight of a carbohydrate polymer is usually expressed as an average. Starch or cellulose chains, for example, may vary by several hundred thousand in their molecular weights between individual molecules. For an excellent review of carbohydrate chemistry, see Binkley (1988). 

Selective Production of Xylanases by Cellulolytic Microorganisms. Until recently there was little information on common or separate genetic control of cellulase and xylanase synthesis in microorganisms (60). Studies on this subject were complicated by the fact that numerous microbial ceUulases and xylanases are non-specific with respect to cellulose and xylan as substrates. As could be expected from a comparison of both polysaccharide structures, non-specificity is more frequently observed with cel-lulases, because their substrate binding sites can easily accommodate substrate using an unsubstituted p-(l 4)-linked chain of D-xylopyranosyl units. 

This section describes a detailed hypothesis for the control of polysaccharide synthesis and deposition in the wall during growth. 

Synthesis. The synthases are present at the endomembrane system of the cell and have been isolated on membrane fractions prepared from the cells (5,6). The nucleoside diphosphate sugars which are used by the synthases are formed in the cytoplasm, and usually the epimerases and the other enzymes (e.g., dehydrogenases and decarboxylases) which interconvert them are also soluble and probably occur in the cytoplasm (14). Nevertheless some epimerases are membrane bound and this may be important for the regulation of the synthases which use the different epimers in a heteropolysaccharide. This is especially significant because the availability of the donor compounds at the site of the transglycosylases (the synthases) is of obvious importance for control of the synthesis. The synthases are located at the lumen side of the membrane and the nucleoside diphosphate sugars must therefore cross the membrane in order to take part in the reaction. Modulation of this transport mechanism is an obvious point for the control not only for the rate of synthesis but for the type of synthesis which occurs in the particular lumen of the membrane system. Obviously the synthase cannot function unless the donor molecule is transported to its active site and the transporters may only be present at certain regions within the endomembrane system. It has been observed that when intact cells are fed radioactive monosaccharides which will form and label polysaccharides, these cannot always be found at all the membrane sites within the cell where the synthase activities are known to occur (15). A possible reason for this difference may be the selection of precursors by the transport mechanism. 

From the standpoint of synthesis of polysaccharides, the most significant aspect of a polymerization mechanism is whether or not it involves regio- and stereo-selective control. However, the structural and stereochemical problems with polysaccharide synthesis are generally simpler than those that obtain with a racemic, unsymmetrical monomer, such as (R, S)-propylene oxide. For example, a variable percentage of head-to-head and tail-to-tail sequences is found in... 

In addition to its role as an intermediate in cholesterol biosynthesis, isopentenyl pyrophosphate is the activated precursor of a huge array of biomolecules with diverse biological roles (Fig. 21-48). They include vitamins A, E, and K plant pigments such as carotene and the phytol chain of chlorophyll natural rubber many essential oils (such as the fragrant principles of lemon oil, eucalyptus, and musk) insect juvenile hormone, which controls metamorphosis dolichols, which serve as lipid-soluble carriers in complex polysaccharide synthesis and ubiquinone and plastoquinone, electron carriers in mitochondria and chloroplasts. Collectively, these molecules are called isoprenoids. More than... 

Sutherland, I. W. 1979. Microbied exopolysaccheirides Control of synthesis and acylation. In Microbial Polysaccharides and Polysaccharases. R. C. W. Berkeley, G. W. Gooday and D. C. Ellwood, (Editors). Academic Press, New York, pp. 1-34. Tacquet, A., Tison, F. and Devulder, B. 1961. Bactericidal action of yogurt on mycobacteria. Ann. Inst. Pasteur. 100, 581-587. (French)... 

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