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Tunneling matrix element in Ru-modified blue copper proteins: Pruning the protein in search of electron transfer pathways

Gehlen, John N. and Daizadeh, Iraj and Stuchebrukhov, A. A. and Marcus, R. A. (1996) Tunneling matrix element in Ru-modified blue copper proteins: Pruning the protein in search of electron transfer pathways. Inorganica Chimica Acta, 243 (1-2). pp. 271-282. ISSN 0020-1693. doi:10.1016/0020-1693(95)04917-7.

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We investigate with semi-empirical extended Hückel theory calculations the tunneling matrix element for electron transfer in three ruthenium-modified blue copper azurin molecules from the bacterium Pseudomonas aeruginosa which have been recently synthesized and studied experimentally by Gray and co-workers. All of the atoms in the protein can be included in the calculations with the method of transition amplitudes that has been developed recently. Our particular focus here, however, is to develop procedures that create a truncated protein much smaller than the initial 2000 atom one, the aim being to retain only those amino acids that are important to the electron tunneling mechanism. Such a procedure, which we refer to as ‘pruning’, is useful, first because it reduces the size of the problem, perhaps allowing for more accurate techniques to be used on the truncated protein, and second because it allows for the identification of the regions in the protein in which the tunneling electron is localized. The pruning procedures enable us to reduce the number of atoms required in an extended Hückel theory analysis of the tunneling mechanism by approximately a factor of 10 over that in the original protein.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1996 Elsevier Science S.A. It is a pleasure to dedicate this article to our colleague and friend, Harry Gray, whose work has provided so much inspiration and stimulation to us. We also thank him, Jay Winkler and Ralf Langen for many useful discussions. Part of the research conducted at UC Davis was supported by the grant of the Petroleum Research Fund and the start-up fund provided by the Department of Chemistry to AAS. One of us (RAM) was supported by grants from the National Science Foundation, the Of. rice of Naval Research, and NEDO. Calculations presented in this paper were performed on the CRAY supercomputer provided by Jet Propulsion Laboratory, Pasadena, CA.
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
New Energy and Industrial Technology Development Organization (NEDO) (Japan)UNSPECIFIED
Subject Keywords:Ru-modified; Blue copper protein; Electron transfer
Issue or Number:1-2
Record Number:CaltechAUTHORS:20150407-142735239
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Official Citation:John N. Gehlen, Iraj Daizadeh, A.A. Stuchebrukhov, R.A. Marcus, Tunneling matrix element in Ru-modified blue copper proteins: pruning the protein in search of electron transfer pathways, Inorganica Chimica Acta, Volume 243, Issues 1–2, 29 February 1996, Pages 271-282, ISSN 0020-1693, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56443
Deposited By: Tony Diaz
Deposited On:07 Apr 2015 21:34
Last Modified:10 Nov 2021 20:59

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