DOI: 10.1021/ja960056m. Mechanism of Proton-Coupled Electron Transfer for Quinone (QB) Reduction in Reaction Centers of Rb. Sphaeroides

Mechanism of Proton-Coupled Electron Transfer for Quinone (QB) Reduction in Reaction Centers of Rb. Sphaeroides

10.1021/ja960056m

Crossref journal-article

American Chemical Society (ACS)

Journal of the American Chemical Society (316)

Bibliography

Graige, M. S., Paddock, M. L., Bruce, J. M., Feher, G., & Okamura, M. Y. (1996). Mechanism of Proton-Coupled Electron Transfer for Quinone (QB) Reduction in Reaction Centers of Rb. Sphaeroides. Journal of the American Chemical Society, 118(38), 9005â9016.

Authors 5

M. S. Graige (first)
M. L. Paddock (additional)
J. M. Bruce (additional)
G. Feher (additional)
M. Y. Okamura (additional)

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Some factors that may cause discrepancies between experiment and theory have been discussed by R. A. Marcus (J.Phys.Chem.1968,72(3), 891−899). In our case, the major contributor to the uncertainty in the observed slope arises from possible changes to λ andTABwhich may accompany quinone substitution. Although the assumption of a constant λ andTABis reasonable, based on the nearly identical structures of the quinones used in this work, we have not verified experimentally that λ andTABremain constant throughout the series of quinones, and, therefore, cannot conclude unequivocally that the observed free energy dependence is different than expected for mechanisms 4 or 5. Discrepancies between experiment and the theoretical predictions of the Marcus theory can also arises if work terms (the work required to bring reactants together from an infinite separation to their separation distance in the reaction complex) are large or if there is a large asymmetry in the potential energy surfaces of reactants and products. These are, however, only minor contributors to the uncertainty in the reaction center system. The effect on the theoretical slope of even large asymmetries in the reactant and product potential energy surfaces is relatively small47dand work terms for electron transfer reactions in RCs are expected to be negligible since the redox centers are held at a constant separation by the protein matrix.
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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 1:45 a.m.)
Deposited	3 years, 11 months ago (Sept. 23, 2021, 9:23 a.m.)
Indexed	3 weeks, 5 days ago (Aug. 6, 2025, 8:51 a.m.)
Issued	29 years, 8 months ago (Jan. 1, 1996)
Published	29 years, 8 months ago (Jan. 1, 1996)
Published Online	28 years, 11 months ago (Sept. 25, 1996)
Published Print	29 years, 8 months ago (Jan. 1, 1996)

Funders 0

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BibTeX

@article{Graige_1996, title={Mechanism of Proton-Coupled Electron Transfer for Quinone (QB) Reduction in Reaction Centers of Rb. Sphaeroides}, volume={118}, ISSN={1520-5126}, url={http://dx.doi.org/10.1021/ja960056m}, DOI={10.1021/ja960056m}, number={38}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Graige, M. S. and Paddock, M. L. and Bruce, J. M. and Feher, G. and Okamura, M. Y.}, year={1996}, month=jan, pages={9005–9016} }

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