Grafting-From Proteins Using Metal-Free PET-RAFT Polymerizations under Mild Visible-Light Irradiation

We report a new strategy toward polymer-protein conjugates using a grafting-from method that employs photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Initial screening of reaction conditions showed rapid polymerization of acrylamides under high dilution in water using eosin Y as a photocatalyst in the presence of a tertiary amine. A lysozyme-modified chain transfer agent allowed the same conditions to be utilized for grafting-from polymerizations, and we further demonstrated the broad scope of this technique by polymerizing acrylic and styrenic monomers. Finally, retention of the RAFT end group was suggested by successful chain extension with N-isopropylacrylamide from the polymer-protein conjugates to form block copolymer-protein conjugates. This strategy should expand the capabilities of grafting-from proteins with RAFT polymerization under mild conditions to afford diverse functional materials.