Water effects on electron transfer in azurin dimers

Published

Journal Article

Recent experimental and theoretical analyses indicate that water molecules between or near redox partners can significantly affect their electron-transfer (ET) properties. Here, we study the effects of intervening water molecules on the electron self-exchange reaction of azurin (Az) by using a newly developed ab-initio method to calculate transfer integrals between molecular sites. We show that the insertion of water molecules in the gap between the copper active sites of Az dimers slows down the exponential decay of the ET rates with the copper-to-copper distance. Depending on the distance between the redox sites, water can enhance or suppress the electron-transfer kinetics. We show that this behavior can be ascribed to the simultaneous action of two competing effects: the electrostatic interaction of water with the protein subsystem and its ability to mediate ET coupling pathways. © 2006 American Chemical Society.

Full Text

Duke Authors

Cited Authors

  • Migliore, A; Corni, S; Di Felice, R; Molinari, E

Published Date

  • November 30, 2006

Published In

Volume / Issue

  • 110 / 47

Start / End Page

  • 23796 - 23800

International Standard Serial Number (ISSN)

  • 1520-6106

Digital Object Identifier (DOI)

  • 10.1021/jp064690q

Citation Source

  • Scopus