ABSTRACT
The conformational rigidity of polysaccharides is revealed by inspecting the conformational probability map of the polymer where a potential energy contour map is drawn as a function of the two rotational angles of the glycosidic linkage. The allowed area for a polysaccharide where no steric overlaps occur between residues is generally much smaller than that for a polypeptide. The polyfunctional nature of polysaccharides as polyalcohols explains their ability to form a multitude of intermolecular hydrogen bonds in the solid state. Coupled with the conformational rigidity of the chains, which results in a self-ordering tendency, almost all polysaccharides readily form microcrystalline phases in the solid state, where the crystal structures are marked by extensive hydrogen-bonding network.
