An uncharacteristically low-potential flavin governs the energy landscape of electron bifurcation

Wise, Courtney E.; Ledinina, Anastasia E.; Mulder, David W.; Chou, Katherine J.; Peters, John W.; King, Paul W.; Lubner, Carolyn E.

doi:10.1073/pnas.2117882119

Title: An uncharacteristically low-potential flavin governs the energy landscape of electron bifurcation

Journal Article · 14 March 2022 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2117882119 · OSTI ID:1854951

^[1]; Ledinina, Anastasia E. ^[1];

^[1]; Chou, Katherine J. ^[1]; Peters, John W. ^[2];

^[1];

^[1]

Biosciences Center, National Renewable Energy Laboratory, Golden, CO 80401
Institute of Biological Chemistry, Washington State University, Pullman, WA 99163

Significance Nature has long been an inspiration for materials design, as it exemplifies exquisite control of both matter and energy. Electron bifurcation, a mechanism employed in biological systems to drive thermodynamically unfavorable and energetically challenging chemical reactions, is one such example. A key feature of bifurcating enzymes is the ability of a single redox cofactor to distribute a pair of electrons across two spatially separated electron transfer pathways. Here, we report on the empirical determination of both the one-electron potential and two-electron potential of the bifurcating flavin cofactor in the NADH-dependent ferredoxin-NADP ⁺ oxidoreductase I (NfnSL) enzyme. Insights arising from the defined energy landscape of this bifurcation site may underlie the design of synthetic catalysts capable of generating high-energy intermediates.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: US Department of Agriculture; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1854951

Report Number(s):: NREL/JA-2700-77008; e2117882119

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 12 Vol. 119; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Title: An uncharacteristically low-potential flavin governs the energy landscape of electron bifurcation

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