Universal free-energy landscape produces efficient and reversible electron bifurcation.

Published

Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Yuly, JL; Zhang, P; Lubner, CE; Peters, JW; Beratan, DN

Published Date

  • September 2020

Published In

Volume / Issue

  • 117 / 35

Start / End Page

  • 21045 - 21051

PubMed ID

  • 32801212

Pubmed Central ID

  • 32801212

Electronic International Standard Serial Number (EISSN)

  • 1091-6490

International Standard Serial Number (ISSN)

  • 1091-6490

Digital Object Identifier (DOI)

  • 10.1073/pnas.2010815117

Language

  • eng