Abstract
No single method is available for establishing structure of polysaccharides because of their compositional and structural complexity. The most generally applicable chemical method for polysaccharide structure determination is methylation analysis. This technique, when used in combination with specific chemical cleavage methods such as partial acid hydrolysis, Smith degradation, nitrous acid deamination of 2-amino-2-deoxyaldoses, acetolysis, chromium trioxide oxidation, β-elimination at uronic acid residues, and oxidation and β-elimination, provides structural information relative to sequence, linkage positions, ring forms, the location of noncarbohydrate substituents, and anomeric configuration. The reductive cleavage method overcomes the disadvantages of standard methylation analysis. By appropriate choice of the catalyst, it is possible to achieve total reductive cleavage or partial, selective reductive cleavage. This chapter discusses experimental protocols for carrying out the reaction and the results obtained with some model permethylated polysaccharides.
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