Enzyme-Initiated Reversible Addition鈥揊ragmentation Chain Transfer Polymerization

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• 作者：Baohua Zhang ; Xinjun Wang ; Anqi Zhu ; Kai Ma ; Yue Lv ; Xiao Wang ; Zesheng An
• 刊名：Macromolecules
• 出版年：2015
• 出版时间：November 10, 2015
• 年：2015
• 卷：48
• 期：21
• 页码：7792-7802
• 全文大小：690K
• ISSN：1520-5835

文摘

Biocatalysis is promising for sustainable production of polymers. Enzyme-initiated reversible addition鈥揻ragmentation chain transfer (RAFT) polymerization is reported. Horseradish peroxidase (HRP) catalyzes oxidation of acetylacetone (ACAC) by hydrogen peroxide to generate ACAC radicals, which in the presence of a suitable chain transfer agent initiate efficient and well-controlled RAFT polymerization in aqueous buffer solution at room temperature. The versatility of HRP-initiated RAFT polymerization was demonstrated by controlled polymerization of a wide range of monomers, including both more and less activated monomers, under a variety of conditions, including both homogeneous solution polymerization and heterogeneous dispersion polymerization conditions. In all cases, the polymerization afforded excellent pseudo-first-order kinetics, predictable molecular weights, and narrow molecular weight distributions. Operation via RAFT mechanism of this HRP-initiated polymerization was confirmed by a combination of MALDI-ToF, NMR, and UV鈥搗is as well as by chain extension to make well-defined block copolymers. The mildness, specificity, and biocompatibility of HRP-initiated RAFT polymerization were illustrated by controlled polymerization in undiluted fetal bovine serum (FBS) solution. RAFT polymerization initiated by glucose oxidase (GOx)鈥揌RP enzymatic cascade catalysis was developed, opening up a new avenue to potential green synthesis of precision polymers by controlled radical polymerization in air.