Universal free-energy landscape produces efficient and reversible electron bifurcation.
Journal Article (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
- PMC7474648
Electronic International Standard Serial Number (EISSN)
- 1091-6490
International Standard Serial Number (ISSN)
- 0027-8424
Digital Object Identifier (DOI)
- 10.1073/pnas.2010815117
Language
- eng