Imperial College London

Professor Bill Rutherford FRS

Faculty of Natural SciencesDepartment of Life Sciences

Chair in Biochemistry of Solar Energy
 
 
 
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Contact

 

+44 (0)20 7594 5329a.rutherford Website

 
 
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Location

 

702Sir Ernst Chain BuildingSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Kornienko:2018:10.1021/jacs.8b08784,
author = {Kornienko, N and Zhang, JZ and Sokol, K and Lamaison, S and Fantuzzi, A and van, Grondelle R and Rutherford, AW and Reisner, E},
doi = {10.1021/jacs.8b08784},
journal = {Journal of the American Chemical Society},
title = {Oxygenic photoreactivity in photosystem II studied by rotating ring disk electrochemistry},
url = {http://dx.doi.org/10.1021/jacs.8b08784},
year = {2018}
}

RIS format (EndNote, RefMan)

TY  - JOUR
AB - 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 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.
AU - Kornienko,N
AU - Zhang,JZ
AU - Sokol,K
AU - Lamaison,S
AU - Fantuzzi,A
AU - van,Grondelle R
AU - Rutherford,AW
AU - Reisner,E
DO - 10.1021/jacs.8b08784
PY - 2018///
SN - 1520-5126
TI - Oxygenic photoreactivity in photosystem II studied by rotating ring disk electrochemistry
T2 - Journal of the American Chemical Society
UR - http://dx.doi.org/10.1021/jacs.8b08784
UR - https://www.ncbi.nlm.nih.gov/pubmed/30188698
UR - http://hdl.handle.net/10044/1/64477
ER -