Proteins as substrates for controlled radical polymerization

This review describes fundamental contributions in the area of proteins as macroinitiators and macro-chain transfer agents (CTA) for controlled radical polymerization (CRP). The review specifically highlights the concept of 'grafting-from' proteins, as new and efficient chemistry has been developed to polymerize directly from protein substrates in aqueous media. As the past ten years have shown, CRP has proven a powerful tool in the functionalization of proteins. This review considers the methods used to install protein based initiators and CTAs, the principle examples of ATRP and RAFT as polymerization methods, and finishes with more advanced methodologies such as the combination of genetic modifications and polymer chemistry, proteins as nanoparticles for drug delivery, and unnatural amino acid initiators.