Protein-polymer bioconjugates via a versatile oxygen tolerant photoinduced controlled radical polymerization approach

The immense application potential of amphiphilic protein-polymer conjugates remains largely unexplored, as established grafting from synthetic protocols involve time-consuming, harsh and disruptive deoxygenation methods, while grafting to approaches result in low yields. Here we report an oxygen tolerant, photoinduced CRP approach which readily affords quantitative yields of protein-polymer conjugates within 2h, avoiding damage to the secondary structure of the protein and providing easily accessible means to produce biomacromolecular assemblies. Importantly, our methodology is compatible with multiple proteins (e.g. BSA, HSA, GOx, beta-galactosidase) and monomer classes including acrylates, methacrylates, styrenics and acrylamides. The polymerizations are conveniently conducted in plastic syringes and in the absence of any additives or external deoxygenation procedures using low-organic content media and ppm levels of copper. The robustness of the protocol is further exemplified by its implementation under UV, blue light or even sunlight irradiation as well as in buffer, nanopure, tap or even sea water. Amphiphilic protein-polymer conjugates remain largely unexplored due to synthetic protocols being complex. Here the authors explore an oxygen tolerant, photoinduced reversible-deactivated radical polymerization approach, which readily affords quantitative yields within 2h and thus avoids damage to the secondary structure of the proteins.