CaltechAUTHORS
Published May 13, 2021 | Version Supplemental Material + Published
Journal Article Open

Temperature Dependence of Charge and Spin Transfer in Azurin

Creators

  • 1. ROR icon Weizmann Institute of Science
  • 2. ROR icon Duke University
  • 3. ROR icon University of Padua
  • 4. ROR icon California Institute of Technology
  • 5. ROR icon Uppsala University
  • 6. ROR icon University of Pittsburgh

Abstract

The steady-state charge and spin transfer yields were measured for three different Ru-modified azurin derivatives in protein films on silver electrodes. While the charge-transfer yields exhibit weak temperature dependences, consistent with operation of a near activation-less mechanism, the spin selectivity of the electron transfer improves as temperature increases. This enhancement of spin selectivity with temperature is explained by a vibrationally induced spin exchange interaction between the Cu(II) and its chiral ligands. These results indicate that distinct mechanisms control charge and spin transfer within proteins. As with electron charge transfer, proteins deliver polarized electron spins with a yield that depends on the protein's structure. This finding suggests a new role for protein structure in biochemical redox processes.

Additional Information

© 2021 The Authors. Published by American Chemical Society. Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). Received: February 9, 2021; Revised: April 23, 2021; Published: April 29, 2021. R.D.T., A.M., and D.N.B. acknowledge the support from the National Institutes of Health Grant GM-48043. R.N. acknowledges the partial support from the Minerva Foundation and the Israel Science Foundation. D.H.W. acknowledges support from the NSF (CHE-1900078). Research at Caltech was supported by the National Institute of Diabetes and Digestive and Kidney Diseases of the National Institutes of Health under award number R01DK019038. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank Dr. Jeffrey J. Warren for providing Ru-modified azurins. The authors declare no competing financial interest.

Attached Files

Published - acs.jpcc.1c01218.pdf

Supplemental Material - jp1c01218_si_001.pdf

Files

acs.jpcc.1c01218.pdf

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Additional details

Identifiers

PMCID
PMC8154855
Eprint ID
108928
Resolver ID
CaltechAUTHORS:20210503-115703615

Funding

NIH
GM-48043
MINERVA (Israel)
Israel Science Foundation
NSF
CHE-1900078
NIH
R01DK019038

Dates

Created
2021-05-07
Created from EPrint's datestamp field
Updated
2023-07-18
Created from EPrint's last_modified field