Electroenzymatic Nitrogen Fixation Using an Organic Redox Polymer-Immobilized MoFe Protein System

Lee, Yoo Seok; Ruff, Adrian; Cai, Rong; Lim, Koun; Schuhmann, Wolfgang; Minteer, Shelley D

doi:10.1002/anie.202007198

Title: Electroenzymatic Nitrogen Fixation Using an Organic Redox Polymer-Immobilized MoFe Protein System

Journal Article · 03 June 2020 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202007198 · OSTI ID:1633080

Lee, Yoo Seok ^[1]; Ruff, Adrian ^[2]; Cai, Rong ^[3]; Lim, Koun ^[3]; Schuhmann, Wolfgang ^[2]; Minteer, Shelley D ^[3]

Univ. of Utah, Salt Lake City, UT (United States); University of Utah
Ruhr Univ., Bochum (Germany)
Univ. of Utah, Salt Lake City, UT (United States)

Nitrogenase is the single biological catalyst that is understood to convert dinitrogen (N₂) to ammonia (NH₃). Nitrogenase-catalyzed NH₃ formation in vivo is energetically intensive due to a series of events, including a Fe protein cycle coupled with ATP hydrolysis. Furthermore, the complexity of nitrogenase’s cofactors plagues related bioelectrodes by unstable and poor electric wiring between the cofactors and the electrode, thereby lowering the overall bioelectrocatalytic performance. We report an organic redox polymer-based electroenzymatic nitrogen fixation system using a metal-free redox polymer namely neutral red-modified poly(glycidyl methacrylate-co-methylmethacrylate- co-poly(ethyleneglycol)methacrylate) with a low redox potential of -0.58 V vs. SCE. The stable and efficient electric wiring of nitrogenase within the redox polymer matrix enables mediated bioelectrocatalysis of N₃ -, NO₂ - and N₂ to NH₃ catalyzed by the MoFe protein via the polymer-bound redox moieties distributed in the polymer matrix in the absence of the Fe protein. Bulk bioelectrosynthetic experiments produced 209 ± 30 nmol NH₃ nmol MoFe^-1 h^-1 from N₂ reduction. ¹⁵N₂ labeling experiments and NMR analysis were performed to confirm biosynthetic N₂ reduction to NH₃.

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Research Organization:: Fulcrum Bioscience, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office (EE-5A); German Research Foundation; European Research Council (ERC)

Grant/Contract Number:: SC0017845

OSTI ID:: 1633080

Alternate ID(s):: OSTI ID: 1641851; OSTI ID: 1641854; OSTI ID: 22947374

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 38 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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