DOI: 10.1073/pnas.0405032101. Electron transfer between hemes in mammalian cytochrome <i>c</i> oxidase

Electron transfer between hemes in mammalian cytochrome c oxidase

10.1073/pnas.0405032101

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Fast intraprotein electron transfer reactions associated with enzymatic catalysis are often difficult to synchronize and therefore to monitor directly in non-light-driven systems. However, in the mitochondrial respiratory enzyme cytochrome oxidase aa 3 , the kinetics of the final electron transfer step into the active site can be determined: reverse electron flow between the close-lying and chemically identical hemes a 3 and a can be initiated by flash photolysis of CO from reduced heme a 3 under conditions where heme a is initially oxidized. To follow this reaction, we used transient absorption spectroscopy, with femtosecond time resolution and a time window extending to 4 ns. Comparison of the picosecond heme a 3 -CO photodissociation spectra under different redox states of heme a shows significant spectral interaction between both hemes, a phenomenon complicating the interpretation of spectral studies with low time resolution. Most importantly, we show that the intrinsic electron equilibration, corresponding to a ΔG 0 of 45-55 meV, occurs in 1.2 ± 0.1 ns. This is 3 orders of magnitude faster than the previously established equilibration phase of ≈3 μs, which we suggest to reflect a change in redox equilibrium closely following CO migration out of the active site. Our results allow testing a number of conflicting predictions regarding this reaction between both experimental and theoretical studies. We discuss the potential physiological relevance of fast equilibration associated with this low-driving-force redox reaction.

Bibliography

Pilet, E., Jasaitis, A., Liebl, U., & Vos, M. H. (2004). Electron transfer between hemes in mammalian cytochrome c oxidase. Proceedings of the National Academy of Sciences, 101(46), 16198â16203.

Authors 4

Eric Pilet (first)
Audrius Jasaitis (additional)
Ursula Liebl (additional)
Marten H. Vos (additional)

References 45 Referenced 67

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Dates

Type	When
Created	20 years, 9 months ago (Nov. 8, 2004, 8:25 p.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 8:32 a.m.)
Indexed	1 year, 1 month ago (July 7, 2024, 12:33 a.m.)
Issued	20 years, 9 months ago (Nov. 8, 2004)
Published	20 years, 9 months ago (Nov. 8, 2004)
Published Online	20 years, 9 months ago (Nov. 8, 2004)
Published Print	20 years, 9 months ago (Nov. 16, 2004)

Funders 0

None

BibTeX

@article{Pilet_2004, title={Electron transfer between hemes in mammalian cytochrome c oxidase}, volume={101}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0405032101}, DOI={10.1073/pnas.0405032101}, number={46}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Pilet, Eric and Jasaitis, Audrius and Liebl, Ursula and Vos, Marten H.}, year={2004}, month=nov, pages={16198–16203} }

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