On the mechanism of ubiquinone mediated photocurrent generation by a reaction center based photocathode

Friebe, Vincent M., Swainsbury, David J.K., Fyfe, Paul K., van der Heijden, Wessel, Jones, Michael R. and Frese, Raoul N. (2016) On the mechanism of ubiquinone mediated photocurrent generation by a reaction center based photocathode. Biochimica et Biophysica Acta - Bioenergetics, 1857 (12). pp. 1925-1934. ISSN 0005-2728

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Upon photoexcitation, the reaction center (RC) pigment-proteins that facilitate natural photosynthesis achieve a metastable separation of electrical charge among the embedded cofactors. Because of the high quantum efficiency of this process, there is a growing interest in their incorporation into biohybrid materials for solar energy conversion, bioelectronics and biosensing. Multiple bioelectrochemical studies have shown that reaction centers from various photosynthetic organisms can be interfaced with diverse electrode materials for the generation of photocurrents, but many mechanistic aspects of native protein functionality in a non-native environment is unknown. In vivo, RC's catalyse ubiquinone-10 reduction, protonation and exchange with other lipid phase ubiquinone-10s via protein-controlled spatial orientation and protein rearrangement. In contrast, the mechanism of ubiquinone-0 reduction, used to facilitate fast RC turnover in an aqueous photoelectrochemical cell (PEC), may not proceed via the same pathway as the native cofactor. In this report we show truncation of the native isoprene tail results in larger RC turnover rates in a PEC despite the removal of the tail's purported role of ubiquinone headgroup orientation and binding. Through the use of reaction centers with single or double mutations, we also show the extent to which two-electron/two-proton ubiquinone chemistry that operates in vivo also underpins the ubiquinone-0 reduction by surface-adsorbed RCs in a PEC. This reveals that only the ubiquinone headgroup is critical to the fast turnover of the RC in a PEC and provides insight into design principles for the development of new biophotovoltaic cells and biosensors.

Item Type: Article
Additional Information: Funding Information: M.R.J., P.K.F and D.J.K.S. acknowledge support from the Biotechnology and Biological Sciences Research Council of the UK (projects B13439 and BB/I022570/1 ). R.N.F. acknowledges support from the Dutch science foundation NWO for a vidi grant, D.M. for a veni grant (no. 722.011.003 ). M.R.J., R.N.F., D.J.K.S., V.M.F. and J.D.D. acknowledge support via EU COST Action TD1102 — Photosynthetic proteins for technological applications: biosensors and biochips (PHOTOTECH). Publisher Copyright: © 2016 Elsevier B.V.
Uncontrolled Keywords: bio-photovoltaics,bioelectronics,biosensors,biosolar cells,photoelectrochemistry,photosynthesis,biophysics,biochemistry,cell biology ,/dk/atira/pure/subjectarea/asjc/1300/1304
Faculty \ School: Faculty of Science > School of Biological Sciences
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Depositing User: LivePure Connector
Date Deposited: 17 Aug 2022 12:32
Last Modified: 22 Oct 2022 07:55
URI: https://ueaeprints.uea.ac.uk/id/eprint/87371
DOI: 10.1016/j.bbabio.2016.09.011

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