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Proton-Coupled Electron Flow in Protein Redox Machines

Dempsey, Jillian L. and Winkler, Jay R. and Gray, Harry B. (2010) Proton-Coupled Electron Flow in Protein Redox Machines. Chemical Reviews, 110 (12). pp. 7024-7039. ISSN 0009-2665. PMCID PMC3005815. https://resolver.caltech.edu/CaltechAUTHORS:20110124-105132769

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Abstract

Electron transfer (ET) reactions are fundamental steps in biological redox processes. Respiration is a case in point: at least 15 ET reactions are required to take reducing equivalents from NADH, deposit them in O_2, and generate the electrochemical proton gradient that drives ATP synthesis. Most of these reactions involve quantum tunneling between weakly coupled redox cofactors (ET distances > 10 Å) embedded in the interiors of folded proteins. Here we review experimental findings that have shed light on the factors controlling these distant ET events. We also review work on a sensitizer-modified copper protein photosystem in which multistep electron tunneling (hopping) through an intervening tryptophan is orders of magnitude faster than the corresponding single-step ET reaction.If proton transfers are coupled to ET events, we refer to the processes as proton coupled ET, or PCET, a term introduced by Huynh and Meyer in 1981. Here we focus on two protein redox machines, photosystem II and ribonucleotide reductase, where PCET processes involving tyrosines are believed to be critical for function. Relevant tyrosine model systems also will be discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/cr100182b DOIArticle
http://pubs.acs.org/doi/full/10.1021/cr100182bPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3005815PubMed CentralArticle
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2010 American Chemical Society. Received June 11, 2010. Publication Date (Web): November 17, 2010. This article is part of the 2010 Proton-Coupled Electron Transfer special issue. Our work is supported by the NIH (DK019038, GM068461), an NSF Center for Chemical Innovation Grant (CHE-0802907), GCEP (Stanford), CCSER (Gordon and Betty Moore Foundation), and the Arnold and Mabel Beckman Foundation.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NIHDK019038
NIHGM068461
NSFCHE-0802907
Stanford Global Climate and Energy Project (GCEP)UNSPECIFIED
Caltech Center for Sustainable Energy ResearchUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:12
PubMed Central ID:PMC3005815
Record Number:CaltechAUTHORS:20110124-105132769
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110124-105132769
Official Citation:Proton-Coupled Electron Flow in Protein Redox Machines Jillian L. Dempsey, Jay R. Winkler, Harry B. Gray Chemical Reviews 2010 110 (12), 7024-7039
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:21864
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:04 Feb 2011 19:48
Last Modified:22 Nov 2019 09:58

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