Anderson, Ian C.Gomez, Darwin C.Zhang, MeijingKoehler, Stephen J.Figg, C. Adrian2025-10-162025-10-162025-01-10https://hdl.handle.net/10919/138225Protein photocatalysts provide a modular platform to access new reaction pathways and affect product outcomes, but their use in polymer synthesis is limited because co-catalysts and/or co-reductants are required to complete catalytic cycles. Herein, we report using zinc myoglobin (ZnMb), an inherently photoactive protein, to mediate photoinduced electron/energy transfer (PET) reversible addition-fragmentation chain transfer (RAFT) polymerizations. Using ZnMb as the sole reagent for catalysis, photomediated polymerizations of N,N-dimethylacrylamide in PBS were achieved with predictable molecular weights, dispersity values approaching 1.1, and high chain-end fidelity. We found that initial apparent rate constants of polymerization increased from 4.6x10-5 s-1 for zinc mesoporpyhrin IX (ZnMIX) to 6.5x10-5 s-1 when ZnMIX was incorporated into myoglobin to yield ZnMb, indicating that the protein binding site enhanced catalytic activity. Chain extension reactions comparing ZnMb-mediated RAFT polymerizations to thermally-initiated RAFT polymerizations showed minimal differences in block copolymer molecular weights and dispersities. This work enables studies to elucidate how protein modifications (e.g., secondary structure folding, site-directed mutagenesis, directed evolution) can be used to modulate polymerization outcomes (e.g., selective monomer additions towards sequence control, tacticity control, molar mass distributions).application/pdfenCreative Commons Attribution 4.0 InternationalBiocatalysisPhotocatalysisPolymerizationPET-RAFTReversible-deactivation radical polymerizationArticle - Refereedhttps://doi.org/10.1002/anie.202414431642394688741521-3773