Enzymatic Polymerization

Abstract

This article deals with recent advances in enzymatic polymerizations, defined as chemical polymer synthesisin vitro(in test tubes) via nonbiosynthetic pathways catalyzed by an isolated enzyme. The principal target macromolecules via the enzymatic polymerization are polysaccharides, poly(amino acid)s, polyesters, polycarbonates, polyaromatics, and vinyl polymers. For synthesis of polysaccharides, poly(amino acid)s, polyesters, and polycarbonates, hydrolases are used as catalyst; hydrolases, enzymes catalyzing a bond‐cleavage reaction by water, induce the reverse reaction of hydrolysis, leading to polymer production by a bond‐forming reaction. Specific enzyme catalysis provides a novel synthetic route for not only natural biopolymers such as cellulose, xylan, and chitin, but also unnatural polysaccharides, polyesters, poly(amino acid)s, and polycarbonates, many of which are difficult to be synthesized by conventional methodologies. Oxidoreductases act as catalyst for oxidative polymerization of phenol, aniline, and their derivatives, for polymer modification via oxidative coupling, and for production of vinyl polymers. A new class of phenolic polymers are synthesized without use of toxic formaldehyde under mild reaction conditions. Enzyme‐model complexes also catalyze the synthesis of new phenolic polymer materials.