A resonance raman marker band characterizes the slow and fast form of cytochrome c oxidase

Kruse F, Anh Duc Nguyen , Dragelj J, Heberle J, Hildebrandt P, Mroginski MA, Weidinger IM (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 143

Pages Range: 2769-2776

Journal Issue: 7

DOI: 10.1021/jacs.0c10767

Abstract

Cytochrome c oxidase (CcO) in its as-isolated form is known to exist in a slow and fast form, which differ drastically in their ability to bind oxygen and other ligands. While preparation methods have been established that yield either the fast or the slow form of the protein, the underlying structural differences have not been identified yet. Here, we have performed surface enhanced resonance Raman (SERR) spectroscopy of CcO immobilized on electrodes in both forms. SERR spectra obtained in resonance with the heme a3 metal-to-ligand charge transfer (MLCT) transition at 650 nm displayed a sharp vibrational band at 748 or 750 cm^-1 when the protein was in its slow or fast form, respectively. DFT calculations identified the band as a mode of the His-419 ligand that is sensitive to the oxygen ligand and the protonation state of Tyr-288 within the binuclear complex. Potential-dependent SERR spectroscopy showed a redox-induced change of this band around 525 mV versus Ag/ AgCl exclusively for the fast form, which coincides with the redox potential of the Tyr-O/Tyr-O^- transition. Our data points to a peroxide ligand in the resting state of CcO for both forms. The observed frequencies and redox sensitivities of the Raman marker band suggest that a radical Tyr-288 is present in the fast form and a protonated Tyr-288 in the slow form.

Involved external institutions

Technische Universität Dresden

Germany (DE) Technische Universität Berlin

Germany (DE) Freie Universität Berlin

Germany (DE)

How to cite

APA:

Kruse, F., Anh Duc Nguyen, ., Dragelj, J., Heberle, J., Hildebrandt, P., Mroginski, M.A., & Weidinger, I.M. (2021). A resonance raman marker band characterizes the slow and fast form of cytochrome c oxidase. Journal of the American Chemical Society, 143(7), 2769-2776. https://doi.org/10.1021/jacs.0c10767

MLA:

Kruse, Fabian, et al. "A resonance raman marker band characterizes the slow and fast form of cytochrome c oxidase." Journal of the American Chemical Society 143.7 (2021): 2769-2776.

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