Photo-excited extracellular electron transfer of electroactive microorganism triggers RAFT polymerization.

Living cell-triggered reversible addition-fragmentation chain-transfer (RAFT) polymerization is of great value for construction of living materials with diverse applications. However, microorganisms-activated polymerization without end-group heterogeneity is not yet established. Here, we develop an electroactive microorganism-triggered polymerization system using Shewanella oneidensis-secreted flavins (as electron shuttles) to directly reduce chain transfer agents (CTAs) to continuously generate radicals, thus initiating RAFT polymerization. This S. oneidensis-triggered polymerization integrates microbial extracellular electron transfer pathway and photoinduced electron transfer to reduce CTAs for continuous radical generation. We then genetically engineer S. oneidensis to enhance flavins biosynthesis and transport, accomplishing increased conversion ratio ( > 90%) of poly(N, N-dimethylacrylamide) with low polydispersity (Ð < 1.20). In addition, the S. oneidensis-triggered RAFT polymerization is effective for various monomers and CTAs, being able to synthesize diverse block copolymers. Synergistic integration of synthetic biology and RAFT polymerization provides a sustainable and controllable polymerization platform.