Oxygenic Photoreactivity in Photosystem II Studied by Rotating Ring Disk Electrochemistry.
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Authors
Kornienko, Nikolay
Zhang, Jenny Z
Sokol, Katarzyna P
Lamaison, Sarah
Fantuzzi, Andrea
van Grondelle, Rienk
Rutherford, A William
Publication Date
2018-12-26Journal Title
J Am Chem Soc
ISSN
0002-7863
Publisher
American Chemical Society (ACS)
Volume
140
Issue
51
Pages
17923-17931
Language
eng
Type
Article
Physical Medium
Print-Electronic
Metadata
Show full item recordCitation
Kornienko, N., Zhang, J. Z., Sokol, K. P., Lamaison, S., Fantuzzi, A., van Grondelle, R., Rutherford, A. W., & et al. (2018). Oxygenic Photoreactivity in Photosystem II Studied by Rotating Ring Disk Electrochemistry.. J Am Chem Soc, 140 (51), 17923-17931. https://doi.org/10.1021/jacs.8b08784
Abstract
Protein film photoelectrochemistry has previously been used to monitor the activity of photosystem II, the water-plastoquinone photooxidoreductase, but the mechanistic information attainable from a three-electrode setup has remained limited. Here we introduce the four-electrode rotating ring disk electrode technique for quantifying light-driven reaction kinetics and mechanistic pathways in real time at the enzyme-electrode interface. This setup allows us to study photochemical H2O oxidation in photosystem II and to gain an in-depth understanding of pathways that generate reactive oxygen species. The results show that photosystem II reacts with O2 through two main pathways that both involve a superoxide intermediate to produce H2O2. The first pathway involves the established chlorophyll triplet-mediated formation of singlet oxygen, which is followed by its reduction to superoxide at the electrode surface. The second pathway is specific for the enzyme/electrode interface: an exposed antenna chlorophyll is sufficiently close to the electrode for rapid injection of an electron to form a highly reducing chlorophyll anion, which reacts with O2 in solution to produce O2•-. Incomplete H2O oxidation does not significantly contribute to reactive oxygen formation in our conditions. The rotating ring disk electrode technique allows the chemical reactivity of photosystem II to be studied electrochemically and opens several avenues for future investigation.
Keywords
0306 Physical Chemistry (incl. Structural)
Relationships
Is supplemented by: https://doi.org/10.17863/CAM.27714
Sponsorship
Royal Society Newton International Fellowship, ERC Consollidator Grant, BBSRC, EPSRC, French Corps of Bridges, Waters & Forests, VU University Amsterdam, ERC Advanced Investigator grant, EU FP7 project, Academy Professor grant from the Netherlands Royal Academy of Sciences
Funder references
European Research Council (682833)
Identifiers
External DOI: https://doi.org/10.1021/jacs.8b08784
This record's URL: https://www.repository.cam.ac.uk/handle/1810/285354
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