Enzymatic Polymerization

Abstract

This article deals with recent advances in enzymatic polymerizations, defined as chemical polymer synthesis in 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.

Production of biodegradable polyesters via enzymatic polymerization and solid state finishing

“…Biocatalysts maintain their chemical and physical structure after the reaction, and therefore, they can be reused. 11 According to literature, most research teams of PEs focus on enzymatic polymerization using lipases in nonconventional media. In nature, lipases catalyze the hydrolysis of esters of fatty acids; nonetheless, in organic medium they show a reverse operation, leading to ester bonds formation.…”

Mechanistic limitations in the synthesis of polyesters by lipase‐catalyzed ring‐opening polymerization

“…Polymerization reactions catalyzed by enzymes produce polymers that are biodegradable and relatively pure due to the reaction specificity and absence of toxic metal catalysts during synthesis. Lipase-catalyzed polymerization of lactones is one example of these reactions and offers a promising approach to the synthesis of polyesters (Kobayashi et al, 2001;Matsumura, 2002). No byproducts such as alcohols are produced and no substrates need to be activated in comparison with condensation polymerization; reactions can be highly efficient, and functionalized oligomers and polymers can be prepared (Kobayashi et al, 2001).…”

Enzymatic Synthesis of Polyesters via Polycondensation

“…by lipase-catalyzed polymerization [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. By using lipase catalysis, functional aliphatic polyesters have been synthesized by various polymerization modes (Scheme 2).…”