Enzymatic Polymerization for Precision Polymer Synthesis

Abstract

Our recent advances in enzymatic polymerization, defined as chemical polymer syntheses in vitro (in test tubes) via non-biosynthetic pathways catalyzed by an isolated enzyme, have been mainly reviewed. The major target macromolecules formed via the enzymatic polymerizations described in this article are polysaccharides, polyesters, and polyaromatics. For synthesis of polysaccharides and polyesters, hydrolases are used as catalysts; hydrolases catalyzing a bond-cleavage reaction by water induce the reverse reaction of hydrolysis, leading to polymer production by a bond-forming reaction in vitro. Specific enzyme catalysis provides a novel synthetic route with precise structure control not only for natural biopolymers such as cellulose, xylan, and chitin, but also for unnatural polysaccharides and polyesters, many of which are difficult to be synthesized by conventional methodologies. Oxidoreductases act as catalysts for oxidative polymerization of phenol, aniline, and their derivatives. A new class of phenolic polymers are synthesized without use of toxic formaldehyde under mild reaction conditions. Enzyme-model complexes also catalyze polymerizations for the synthesis of new high-performance polymeric materials.

Enzymatic Synthesis of Polyesters in Ionic Liquids

“…[8][9][10][11][12][13][14][15] Various monomer combinations have been developed for enzymatic synthesis of polyesters. Lipase catalysis induced enantioand regioselective polymerizations to give functional polyesters, most of which are very difficult to syntheScheme 1.…”

Polymers in the Pharmaceutical Applications - Natural and Bioactive Initiators and Catalysts in the Synthesis of Biodegradable and Bioresorbable Polyesters and Polycarbonates

“…Lipases could also catalyze ROP of cyclic monomers, with different ring sizes as well as monomers containing substituents in the ring: -methyl--propiolactone (1), -butyrolactone (2), -caprolactone (3), -methyl-valerolactone (4), 1,4-dioxan-2-one (5), -caprolactone (6), -ethyl--caprolactone (7), -heptanolactone (8), -decalactone (9), -dodecalactone (10) Coŕdova et al, 1999;Divakar, 2004;Dong, 1998Dong, , 1999Gorke et al, 2007;Henderson et al, 1996;Kobayashi, 2001aKobayashi, , 2001bKobayashi, , 2009MacDonald et al, 1995;Marcilla et al, 2006;Matsumoto et al, 1999;Mei et al, 2003;Namekawa et al, 1999;Rokicki, 2000;Sivalingam & Madras, 2004;Van Der Mee et al, 2006). Lipases can accommodate a wide variety of synthetic substrates and still be able to show stereo-and regio-selectivity.…”

“…The yield of the obtained polymers varied from 10 to 100%. The preferred lipase system generally used is a physically immobilized form of Candida Antarctica, commercially available as Novozyme-435 (Barrera-Rivera et al, 2009;Coŕdova et al, 1999;Divakar, 2004;Dong, 1998Dong, , 1999Gorke et al, 2007;Henderson et al, 1996;Kobayashi, 2001aKobayashi, , 2001bKobayashi, , 2009MacDonald et al, 1995;Marcilla et al, 2006;Matsumoto et al, 1999;Mei et al, 2003;Namekawa et al, 1999;Sivalingam & Madras, 2004;Van Der Mee et al, 2006).…”

Green chemistry: the emergence of a transformative framework

“…The enzymatic process reduces waste, phases out dangerous reagents, uses less solvent, and eliminates purification steps known to interfere with product yield (42). Catalysis by enzymes also provides routes to both natural and non-natural polymers, in many cases with precise control of structure (43). An enzymatic polymerization process has been used to produce macromolecules with superior antioxidant properties, having potential applications in a variety of industries.…”