Shewanella oneidensisas a living electrode for controlled radical polymerization

Abstract

Metabolic engineering has facilitated the production of pharmaceuticals, fuels, and soft materials but is generally limited to optimizing well-defined metabolic pathways. We hypothesized that the reaction space available to metabolic engineering could be expanded by coupling extracellular electron transfer to the performance of an exogenous redox-active metal catalyst. Here we demonstrate that the electroactive bacterium can control the activity of a copper catalyst in atom-transfer radical polymerization (ATRP) via extracellular electron transfer. Using, we achieved precise control over the molecular weight and polydispersity of a bioorthogonal polymer while similar organisms, such as , showed no significant activity. We found that catalyst performance was a strong function of bacterial metabolism and specific electron transport proteins, both of which offer potential biological targets for future applications. Overall, our results suggest that manipulating extracellular electron transport pathways may be a general strategy for incorporating organometallic catalysis into the repertoire of metabolically controlled transformations.

Semi-biological approaches to solar-to-chemical conversion

“…231,236,279 Furthermore, the intracellular metabolism can be coupled with extracellular redox transformations to manufacture functional materials such as polymers and inorganic particles. [280][281][282] These materials may provide additional benefits to promote extracellular electron transfer or cytoprotection. 281 Advanced photochemistry provides another thrust in future development.…”

Creation of Conductive Graphene Materials by Bacterial Reduction Using Shewanella Oneidensis

“…S. oneidensis has evolved to use inorganic materials as an electron acceptor during anaerobic respiration. . S. oneidensis can deliver electrons to inorganic acceptor materials both by electron shuttles and via direct surface‐to‐surface contact mediated by its Mtr respiratory pathway, which consists of multiple different proteins which pass electrons from the bacterial cytoplasm, through the cell membranes, and up to the surface of the bacterium.…”

“…[14,22,23] One intriguing possibility to reduce graphene oxide in a more sustainable, easily up-scalable, and cost-efficient way is via the metal-oxide-reducing bacterium Shewanella oneidensis. [24][25][26] S. oneidensis has evolved to use inorganic materials as an electron acceptor during anaerobic respiration.. [27] S. oneidensis can deliver electrons to inorganic acceptor materials both by electron shuttles and via direct surface-to-surface contact mediated by its Mtr respiratory pathway, which consists of multiple different proteins which pass electrons from the bacterial cytoplasm, through the cell membranes, and up to the surface of the bacterium. [25,[26] When graphene oxide is provided, the electrons from S. oneidensis react with the oxygen groups of the graphene oxide, leading to a restoration of the sp 2 orbitals forming the characteristic hexagonal lattice of graphene.…”

Redox‐Active Polymers Connecting Living Microbial Cells to an Extracellular Electrical Circuit

“…Intriguingly, in the field of polymer chemistry, it has been recently reported that radical polymerization can be performed by utilizing microbial EET. [ 73–75 ] For example, Magennis et al. utilized Escherichia coli ( E. coli ) and Pseudomonas aeruginosa to regenerate Cu(I), a catalyst for the polymerization, to synthesize microbe‐templated polymers.…”