Aerobic Radical Polymerization Mediated by Microbial Metabolism

Performing radical polymerizations under ambient conditions is a significant challenge because molecular oxygen is an effective radical quencher. Here we show that the facultative electrogen Shewanella oneidensis can control metal-catalyzed living radical polymerizations under apparent aerobic conditions by first consuming dissolved oxygen via aerobic respiration, then directing extracellular electron flux to a metal catalyst. In both open and closed containers, S. oneidensis enabled living radical polymerizations without requiring the pre-removal of oxygen. Polymerization activity was closely tied to S. oneidensis anaerobic metabolism through specific extracellular electron transfer (EET) proteins and was effective for a variety of monomers using low (ppm) concentrations of metal catalysts. Finally, polymerizations survived repeated challenges of oxygen exposure and could be initiated using lyophilized or spent (recycled) cells. Overall, our results demonstrate how the unique ability of S. oneidensis to use both oxygen and metals as respiratory electron acceptors can be leveraged to address salient challenges in polymer synthesis.