Abstract
This chapter reviews the synthesis of new polysaccharide materials by means of phosphorylase-catalyzed enzymatic α-glycosylations using polymeric glycosyl acceptors (or primers). Glycogen-based polysaccharide materials having the elongated amylose graft-chains were prepared by the phosphorylase-catalyzed successive α-glucosylations (polymerization) using glycogen as a multifunctional polymeric acceptor. Highly branched anionic polysaccharides were also synthesized by the phosphorylase-catalyzed α-glucuronylation of glycogen. The synthesis of amylose-grafted heteropolysaccharides composed of abundant polysaccharide main-chains, such as chitin/chitosan, (carboxymethyl)cellulose, alginate, and xanthan gum, was achieved by the phosphorylase-catalyzed enzymatic polymerization using the corresponding maltooligosaccharide-grafted polysaccharide acceptors.
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