Rapid Visible Light-Mediated Controlled Aqueous Polymerization with In Situ Monitoring

We report a simple procedure for rapid, visible light-mediated, controlled radical polymerization in aqueous solutions. Based on the photoelectron transfer reversible addition–fragmentation chain transfer (PET–RAFT) polymerization, fast chain propagation at room temperature in water was achieved in the presence of reductant and without prior deoxygenation. A systematic study correlating irradiation intensity and polymerization kinetics, enabled by in situ nuclear magnetic resonance spectroscopy, provided optimized reaction conditions. The versatility of this procedure was demonstrated through a rapid triblock copolymer synthesis, and incorporation of water-labile activated esters for direct conjugation of hydrophilic small molecules and proteins. In addition, this technique boasts excellent temporal control and provides a wide range of macromolecular materials with controlled molecular weights and narrow molecular weight distributions

Metal-Free Removal of Polymer Chain Ends Using Light

A light-mediated method for the facile removal of polymer end groups that are common to controlled radical polymerization techniques is presented. This metal-free strategy is general, being effective for chlorine, bromine, and thiocarbonylthio moieties as well as a number of different polymer families (styrenic, acrylic, and methacrylic). In addition to solution reactions, this process is readily translated to thin films, where light mediation allows the straightforward fabrication of hierarchically patterned polymer brushes