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Donor—Acceptor Electronic Coupling in Ruthenium-Modified Heme Proteins

Casimiro, Danilo R. and Beratan, David N. and Onuchic, José Nelson and Winkler, Jay R. and Gray, Harry B. (1996) Donor—Acceptor Electronic Coupling in Ruthenium-Modified Heme Proteins. In: Mechanistic Bioinorganic Chemistry. Advances in Chemistry. No.246. American Chemical Society , Washington, DC, pp. 471-485. ISBN 9780841230620. http://resolver.caltech.edu/CaltechAUTHORS:20180406-080326896

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Abstract

The rates of electron transfer (ET) in six Ru-modified cytochrome c derivatives were analyzed in terms of four theoretical models describing donor-acceptor electronic coupling. The simplest model, which treats the protein as a homogeneous medium, fails to describe the variations in ET rates with changes in donor-acceptor separation. The three other models explicitly account for the inhomogeneity of the polypeptide matrix and are more successful in describing the electronic couplings. Calculations of relative coupling strengths give results within an order of magnitude of experimentally determined values for cytochrome c. The homogeneousmedium model is more successful in describing ET in Ru-modified myoglobin, and two of the inhomogeneous-medium models suggest that multiple pathways are important in mediating the electronic coupling.


Item Type:Book Section
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ba-1995-0246.ch018DOIArticle
https://pubs.acs.org/doi/abs/10.1021/ba-1995-0246.ch018PublisherArticle
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 1995 American Chemical Society. Received for review July 19, 1993. Accepted revised manuscript December 10, 1993. Published in print 5 May 1996. We thank A. Kuki and R. A. Marcus for preprints of references 13 and 43, respectively. This research was supported by the National Science Foundation, the National Institutes of Health, the Department of Energy, and the Arnold and Mabel Beckman Foundation.
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Department of Energy (DOE)UNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Record Number:CaltechAUTHORS:20180406-080326896
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180406-080326896
Official Citation:Donor—Acceptor Electronic Coupling in Ruthenium-Modified Heme Proteins Danilo R. Casimiro, David N. Beratan, José Nelson Onuchic, Jay R. Winkler, and Harry B. Gray Mechanistic Bioinorganic Chemistry. May 5, 1996, 471-485 DOI:10.1021/ba-1995-0246.ch018
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85673
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2018 16:07
Last Modified:06 Apr 2018 16:07

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