Efficient and reversible electron bifurcation with either normal or inverted potentials at the bifurcating cofactor

Journal Article (Journal Article)

A longstanding mystery surrounding electron bifurcation is the significance of inverted (or “crossed”) reduction potentials of the two-electron bifurcating cofactor. Using a many-electron open-system kinetic model, we show that reversible and efficient electron bifurcation is possible without inverted reduction potentials at the bifurcating site if the absolute value of the difference between first and second reduction potentials of the bifurcating species is sufficiently large (on the scale of the redox-potential span of the high- and low-potential branches). Surprisingly, the case with strong, normally ordered potentials at the bifurcating cofactor can produce electron bifurcation that is just as effective as the case with strongly inverted potentials. This finding amplifies the puzzle surrounding the recruitment of inverted potentials in the few well-characterized bifurcating systems of nature and suggests that electron bifurcating cofactors without strongly inverted potentials may yet be discovered.

Full Text

Duke Authors

Cited Authors

  • Yuly, JL; Zhang, P; Ru, X; Terai, K; Singh, N; Beratan, DN

Published Date

  • July 8, 2021

Published In

Volume / Issue

  • 7 / 7

Start / End Page

  • 1870 - 1886

Electronic International Standard Serial Number (EISSN)

  • 2451-9294

International Standard Serial Number (ISSN)

  • 2451-9308

Digital Object Identifier (DOI)

  • 10.1016/j.chempr.2021.03.016

Citation Source

  • Scopus