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Effect of exothermicity on electron transfer rates in photosynthetic molecular models

Joran, A. D. and Leland, B. A. and Felker, P. M. and Zewail, A. H. and Hopfield, J. J. and Dervan, P. B. (1987) Effect of exothermicity on electron transfer rates in photosynthetic molecular models. Nature, 327 (6122). pp. 508-511. ISSN 0028-0836. https://resolver.caltech.edu/CaltechAUTHORS:20160511-144721087

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Abstract

To appreciate fully the significance of the high-resolution crystal structure of the reaction-centre complex from the purple bacterium Rhodopseudomonas viridis, there is increasing impetus to construct models to ascertain how the specific variables such as distance, exothermicity and solvent control the rates of electron transfer through the integral membrane protein complex. Recently, we have determined the effect of a 4 Å change in distance (at fixed exothermicity, solvent and temperature) on the rates of photon-induced electron transfer for two porphyrin-quinone assemblies separated by rigid spacers3,4. From picosecond fluorescence lifetime measurements on zinc meso-phenyloctamethylporphyrin coupled to a benzoquinone moiety via one and two bicyclo[2.2.2]octyl spacers (10 and 14 Å, edge-to-edge), we deteremined that the rates of electron transfer are 1010 s−1 and ≤107s−1, respectively (the exothermicity, −ΔG = 1.0eV in acetonitrile at 25 °C). This result revealed that the porphyrin-quinone separated by a 10-Å spacer would be ideally suited, with regard to picosecond fluorescence techniques for a study of exothermicity effects at fixed distance and solvent. Here we report the fluorescence lifetimes of a homologous series of seven porphyrin-quinone molecules, each with differently substituted ben-zoquinones separated by an identical rigid phenylbicyclo[2.2.2]octane spacer (10 Å, edge-to-edge) which vary with respect to driving force for electron transfer from the first excited singlet state of the porphyrin. The key features of this series of molecules lie in the fact that the edge-to-edge distance is fixed and ΔG is tunable. Thus, the effect of exothermicity on electron transfer can be measured while avoiding major perturbations of the electronic structure.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1038/327508a0DOIArticle
http://www.nature.com/nature/journal/v327/n6122/abs/327508a0.htmlPublisherArticle
ORCID:
AuthorORCID
Dervan, P. B.0000-0001-8852-7306
Additional Information:© 1987 Nature Publishing Group. Received 6 October 1986; accepted 9 March 1987. A.H.Z. J.J.H. and P.B.D. thank the NSF for support. We thank Professor R. Marcus for helpful discussions, Professor F. Anson's group for assistance with the electrochemistry, and J.M. Warman for critical reading of the manuscript.
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Issue or Number:6122
Record Number:CaltechAUTHORS:20160511-144721087
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160511-144721087
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67011
Collection:CaltechAUTHORS
Deposited By: Victoria Brennan
Deposited On:19 May 2016 23:56
Last Modified:26 Nov 2019 11:15

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