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Electron Flow through Metalloproteins

Winkler, Jay R. and Gray, Harry B. (2014) Electron Flow through Metalloproteins. Chemical Reviews, 114 (7). pp. 3369-3380. ISSN 0009-2665. PMCID PMC3981952. https://resolver.caltech.edu/CaltechAUTHORS:20131204-141845630

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Abstract

Electron flow through proteins and protein assemblies in the photosynthetic and respiratory machinery commonly occurs between metal centers or other redox cofactors that are separated by relatively large molecular distances, often in the 10−20 Å range. To inorganic chemists, such long-distance electron transfer was a mystery for many years, as we were accustomed to close-contact models for the transition states of simple self-exchange reactions between metal ions in aqueous solution. One of our favorite reactions was the ferrous/ferric self-exchange, which had been investigated thoroughly by Richard (Dick) Dodson at the Brookhaven National Laboratory in the 1940s (and published in Journal of the American Chemical Society in 1950). Dodson showed that the half-time for this reaction was on the order of seconds, which he noted was “fast” but in today’s femtosecond world is very “slow”. Indeed, this very simple electron transfer, where no bonds are formed or broken, was found to be orders of magnitude slower than long-distance electron flow through metalloprotein molecules. How could this be?


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/cr4004715DOIArticle
http://pubs.acs.org/doi/abs/10.1021/cr4004715PublisherArticle
http://dx.doi.org/10.1021/cr4007126ErrataCorrection
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3981952/PubMed CentralArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4963290/PubMed CentralCorrection
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 2013 American Chemical Society. Received: August 26, 2013. Published: November 27, 2013. Electron transfer research in our laboratories is supported by the National Institutes of Health (DK-019038), the National Science Foundation (CHE-1305124), and the Arnold and Mabel Beckman Foundation.
Errata:The following text was omitted from the manuscript: ACKNOWLEDGMENTS Electron transfer research in our laboratories is supported by the National Institutes of Health (DK-019038), the National Science Foundation (CHE-1305124), and the Arnold and Mabel Beckman Foundation.
Funders:
Funding AgencyGrant Number
NIHDK-019038
NSFCHE-1305124
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:7
PubMed Central ID:PMC3981952
Record Number:CaltechAUTHORS:20131204-141845630
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20131204-141845630
Official Citation:Electron Flow through Metalloproteins Jay R. Winkler and Harry B. Gray Chemical Reviews 2014 114 (7), 3369-3380
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42835
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Dec 2013 00:31
Last Modified:03 Oct 2019 06:02

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