Enzyme-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization: Precision polymer synthesis...

Enzyme-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization provides a sustainable strategy for efficient production of well-defined polymers under mild conditions. Horseradish peroxidase (HRP), a heme-containing metalloenzyme, catalyzes oxidation of acetylacetone (ACAC) by hydrogen peroxide (H₂O₂) to generate ACAC radicals, initiating polymerization of vinyl monomers. This HRP/H₂O₂/ACAC ternary initiating system is applied to RAFT polymerization of different types of vinyl monomers. Furthermore, to overcome the inherent limitation of necessity for oxygen-free conditions, another enzyme, glucose oxidase (GOx) or pyranose 2-oxidase (P2Ox), with excellent deoxygenation capability, is introduced to consume oxygen by catalyzing oxidation of glucose to generate H₂O₂. The generated H₂O₂ is directly supplied to HRP catalysis for radical generation. Both GOx-HRP and P2Ox-HRP cascade catalysis afford RAFT polymerization with oxygen tolerance. In this chapter, we mainly focus on detailed synthetic protocols of RAFT polymerizations initiated by HRP/H₂O₂/ACAC ternary initiating system and P2Ox-HRP cascade catalysis. The general characterization and analytical methods used in these enzyme-initiated RAFT polymerizations are also included.