Metalloenzymatic radical polymerization using alkyl halides as initiators

A novel initiation strategy for enzyme-induced radical polymerization that makes use of alkyl halides is reported here. The approach is remarkably versatile and can be applied to emulsion polymerization as well as surface-initiated polymerization. The molecular weights of the polymers can be effectively regulated with either irreversible (i.e., l-cysteine) or reversible (i.e., 2-cyano-2-propyl dithiobenzoate) chain transfer agents, the latter resulting in a well-controlled, RAFT-type polymerization process.