Metabolic engineering produces fuels, pharmaceuticals, and materials using microbial catalysts. We sought to expand the power of these catalysts by redirecting respiratory electron flux from Shewanella oneidensis to a metal polymerization catalyst.

Our microbial polymerization features characteristics of controlled radical polymerization such as first-order kinetics, narrow molecular weight distributions and block-copolymer synthesis. Catalyst performance and polymer microstructure were a strong function of bacterial metabolism, specific electron transport proteins, and catalyst design.

Overall, our results suggest that manipulating biological electron transport pathways may be a general strategy for allowing bacteria to produce or communicate with synthetic materials.

Scheme 1. (a) Electron equivalents generated from S. oneidensis MR-1 reduce a metal catalyst from an inactive state (MOX) to an active state (MRED) to enable ATRP, (b) molecular weight and polydispersity of poly(OEOMA500) as a function of monomer conversion, (c) rescue of normal polymerization activity via knockout complementation with a plasmid encoding MtrC.
Scheme 1. (a) Electron equivalents generated from S. oneidensis MR-1 reduce a metal catalyst from an inactive state (MOX) to an active state (MRED) to enable ATRP, (b) molecular weight and polydispersity of poly(OEOMA500) as a function of monomer conversion, (c) rescue of normal polymerization activity via knockout complementation with a plasmid encoding MtrC.