Universal Free-Energy Landscape Produces Efficient and Reversible Electron Bifurcation

J. Yuly, P. Zhang, Carolyn Lubner, J. Peters, D. Beratan

Research output: Contribution to journalArticlepeer-review

26 Scopus Citations

Abstract

For decades, it was unknown how electron-bifurcating systems in nature prevented energy-wasting short-circuiting reactions that have large driving forces, so synthetic electron-bifurcating molecular machines could not be designed and built. The underpinning free-energy landscapes for electron bifurcation were also enigmatic. We predict that a simple and universal free-energy landscape enables electron bifurcation, and we show that it enables high-efficiency bifurcation with limited short-circuiting (the EB scheme). The landscape relies on steep free-energy slopes in the two redox branches to insulate against short-circuiting using an electron occupancy blockade effect, without relying on nuanced changes in the microscopic rate constants for the short-circuiting reactions. The EB scheme thus unifies a body of observations on biological catalysis and energy conversion, and the scheme provides a blueprint to guide future campaigns to establish synthetic electron bifurcation machines.

Original languageAmerican English
Pages (from-to)21045-21051
Number of pages7
JournalProceedings of the National Academy of Sciences of the United States of America
Volume117
Issue number35
DOIs
StatePublished - 2020

Bibliographical note

Publisher Copyright:
© 2020 National Academy of Sciences. All rights reserved.

NREL Publication Number

  • NREL/JA-2700-76177

Keywords

  • Bioenergetics
  • Chemiosmotic hypothesis
  • Electron bifurcation
  • Electron transfer
  • Short-circuiting

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