Well-Defined Macromolecules Using Horseradish Peroxidase as a RAFT Initiase

Enzymatic catalysis and control over macromolecular architectures from reversible addition‐fragmentation chain transfer polymerization (RAFT) are combined to give a new method of making polymers. Horseradish peroxidase (HRP) is used to catalytically generate radicals using hydrogen peroxide and acetylacetone as a mediator. RAFT is used to control the polymer structure. HRP catalyzed RAFT polymerization gives acrylate and acrylamide polymers with relatively narrow molecular weight distributions. The polymerization is rapid, typically exceeding 90% monomer conversion in 30 min. Complex macromolecular architectures including a block copolymer and a protein‐polymer conjugate are synthesized using HRP to catalytically initiate RAFT polymerization. RAFT polymerization is performed using horseradish peroxidase to catalytically generate radicals. Well‐defined homo, block polymers are synthesized as well as a protein‐polymer conjugate