酶催化可控自由基聚合是一类环境友好、可持续性发展的合成精密高分子的新兴方法。本申请书提出研究氧化酶（包括黄素类葡萄糖氧化酶和含铜的漆酶）催化引发的可逆加成-断裂链转移（RAFT）聚合。在黄素类氧化酶催化体系中，拟研究葡萄糖还原黄素后与氧化性底物构成氧化还原引发对，产生自由基引发RAFT聚合。在漆酶催化体系中，漆酶直接利用空气中的氧气氧化还原性底物产生自由基，从而引发RAFT聚合。拟研究的内容包括酶催化动力学、自由基产生机理、RAFT均相与异相聚合。

Enzyme-catalyzed controlled radical polymerization is emerging as an environmentally benign and sustainable approach for precision polymer synthesis. This proposal aims to study reversible addition-fragmentation chain transfer (RAFT) polymerization initiated by oxidases including flavin-containing glucose oxidase and copper-containing laccase. For the glucose oxidase initiating system, the flavin reduced by glucose will interact with an oxidizing substrate to form a redox pair to produce radicals that will then initiate RAFT polymerization. For the laccase initiating system, laccase will use oxygen in air to oxidize reducing substrates to generate radicals and RAFT polymerization will then be initiated. The proposed research will focus on enzyme catalysis dynamics, radical generation mechanisms, and RAFT homogeneous and heterogeneous polymerizations.