Monosaccharides polymeric chains

III. Biosynthesis of Monosaccharide Components, and Their Activation for Polymeric-Chain Formation... 

A modification of the monosaccharide units of polysaccharides may obviously be effected at different stages of the biosynthesis of a polymer (a) prior to formation of the activated form of a monosaccharide, (b) at the level of glycosyl nucleotides, (c) at the stage of formation of oligosaccharide intermediates, and (d) after the synthesis of a polymeric chain. 

The term monomeric mechanism will be used for the mechanism depicted in the left-hand part of Scheme 2 (sequence a). In this case, the monosaccharide residues are transferred consecutively from the corresponding glycosyl donors (Z-A or Z -B) onto a membrane-bound glycosyl acceptor. The acceptor is generally a monosaccharide residue, which may be a fragment of an oligosaccharide chain linked to a hydrophobic molecule embedded in a cell membrane. In many instances, the acceptor that is used for assembly of the polymeric chain (Y) is not identical to the final acceptor (X) of the chain, and further transfer of the chain from Y to X, or liberation of the polysaccharide molecule in the case of exocellular polysaccharides, is a necessary step in the biosynthesis. 

The final stages of the biosynthetic process may include transfer of a polysaccharide chain from an intermediate acceptor to a final acceptor, or liberation of the free polysaccharide. Monosaccharide residues included in a polymeric chain may be subjected to further enzymic modifications, such as incorporation of O-linked substituents (see Section III,6) or the epimeri-zation at C-5 of glycuronic acid residues mentioned in Section 111,1,c. 

It seemed of interest to check whether the type of biosynthetic mechanism involved may be related to the structure of the polymeric chain formed. In the block mechanism of chain assembly, formation of polyprenyl glycosyl diphosphates through transfer of glycosyl phosphate is a necessary step of the process. Thus far, only UDP-activated monosaccharides have been found to participate in this reaction (see Section 11,3). Consequently, the presence of a monosaccharide residue of this group in the main chain of a polymer may be regarded as a necessary condition for assembly of the chain through the block mechanism. 

Preparation of modified, bacterial polysaccharides having monosaccharide analogs inserted into the polymeric chain is of interest for study of the structure-properties relationship in these biopolymers. Incorporation of chemically prepared, modified, biosynthetic precursors of the polymers in enzymic reactions seems a promising approach for achieving this aim. Such an approach, which may be termed chemical-enzymic synthesis, has now been studied by our group,439-441 using O-specific polysaccharides (10-12) of Salmonella serogroups B and E as an example. 

Eliminations and other reactions do not necessarily take place only on the polymeric chain or only on the side groups. Combined reactions may take place, either with a cyclic transition state or with free radical formation. The free radicals formed during polymeric chain scission or during the side chain reactions can certainly interact with any other part of the molecule. Particularly in the case of natural organic polymers, the products of pyrolysis and the reactions that occur can be of extreme diversity. A common result in the pyrolysis of polymers is, for example, the carbonization. The carbonization is the result of a sequence of reactions of different types. This type of process occurs frequently, mainly for natural polymers. An example of combined reactions is shown below for an idealized structure of pectin. Only three units of monosaccharide are shown for idealized pectin, two of galacturonic acid and one of methylated galacturonic acid ... 

Polyprenyl glycosyl diphosphates operate mainly as membrane-linked glycosyl acceptors in the biosynthesis of carbohydrate chains of bacterial polymers. In reactions of polymerization of repeating units during polysaccharide synthesis, the polyprenyl diphosphate derivatives serve as donors of growing polysaccharide chain, but monosaccharide transfer from a polyprenyl glycosyl diphosphate has never been detected. 

In the case of branched polysaccharides, incorporation of side chains may take place through different mechanisms. In one of them, the assembly of the main chain is independent of the presence of side chains, and their incorporation into a polymeric molecule occurs as a modification of an initially formed, linear polysaccharide. Another situation is possible when incorporation of monosaccharide residues present in side chains is a necessary condition for elongation of the main chain, either through the monomeric or the block mechanism that is, intermediate formation of a linear, polysaccharide chain does not occur. Both mechanisms of incorporation of side chains were demonstrated to take place. 

Polysaccharides are naturally occurring polymers, which can be considered as derived from aldoses or ketoses by condensation polymerization. A polysaccharide derived from hexoses, for example, has the general formula (C6H]oOs)n. This formula, of course, tells us very little about the structure of the polysaccharide. We need to know what the monosaccharide units are and how many there are in each molecule how they are joined to each other and whether the huge molecules thus formed are straight-chained or branched, looped or coiled. 

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