Aqueous photo-RAFT polymerization under ambient conditions: synthesis of protein–polymer hybrids in open air

Abstract

A photoinduced reversible addition-fragmentation chain-transfer (photo-RAFT) polymerization technique in the presence of sodium pyruvate (SP) and pyruvic acid derivatives was developed. Depending on the wavelength of light used, SP acted as a biocompatible photoinitiator or promoter for polymerization, allowing rapid open-to-air polymerization in aqueous media. Under UV irradiation (370 nm), SP decomposes to generate CO₂ and radicals, initiating polymerization. Under blue (450 nm) or green (525 nm) irradiation, SP enhances the polymerization rate <i>via</i> interaction with the excited state RAFT agent. This method enabled the polymerization of a range of hydrophilic monomers in reaction volumes up to 250 mL, eliminating the need to remove radical inhibitors from the monomers. In addition, photo-RAFT polymerization using SP allowed for the facile synthesis of protein-polymer hybrids in short reaction times (<1 h), low organic content (≤16%), and without rigorous deoxygenation and the use of transition metal photocatalysts. Enzymatic studies of a model protein (chymotrypsin) showed that despite a significant loss of protein activity after conjugation with RAFT chain transfer agents, the grafting polymers from proteins resulted in a 3-4-fold recovery of protein activity.