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Electron flow through metalloproteins

Gray, Harry B. and Winkler, Jay R. (2010) Electron flow through metalloproteins. Biochimica et Biophysica Acta, 1797 (9). pp. 1563-1572. ISSN 0005-2728. doi:10.1016/j.bbabio.2010.05.001.

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Electron transfers in photosynthesis and respiration commonly occur between metal-containing cofactors that are separated by large molecular distances. Understanding the underlying physics and chemistry of these biological electron transfer processes is the goal of much of the work in our laboratories. Employing laser flash-quench triggering methods, we have shown that 20 Å, coupling-limited Fe(II) to Ru(III) and Cu(I) to Ru(III) electron tunneling in Ru-modified cytochromes and blue copper proteins can occur on the microsecond timescale both in solutions and crystals; and, further, that analysis of these rates suggests that distant donor–acceptor electronic couplings are mediated by a combination of sigma and hydrogen bonds in folded polypeptide structures. Redox equivalents can be transferred even longer distances by multistep tunneling, often called hopping, through intervening amino acid side chains. In recent work, we have found that 20 Å hole hopping through an intervening tryptophan is several hundred-fold faster than single-step electron tunneling in a Re-modified blue copper protein.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Gray, Harry B.0000-0002-7937-7876
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 2010 Published by Elsevier B.V. Received 10 February 2010; revised 21 April 2010; accepted 3 May 2010. Available online 10 May 2010. Our work is supported by NIH, NSF, and the Arnold and Mabel Beckman Foundation.
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Electron transfer; Cytochrome c; Azurin; Cytochrome b(562); Electron tunneling; Electron hopping
Issue or Number:9
Record Number:CaltechAUTHORS:20100831-100225099
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:19735
Deposited By: Tony Diaz
Deposited On:01 Sep 2010 19:24
Last Modified:08 Nov 2021 23:54

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