Author
Listed:
- Asmit Bhowmick
(Lawrence Berkeley National Laboratory)
- Rana Hussein
(Humboldt Universität zu Berlin)
- Isabel Bogacz
(Lawrence Berkeley National Laboratory)
- Philipp S. Simon
(Lawrence Berkeley National Laboratory)
- Mohamed Ibrahim
(Humboldt Universität zu Berlin
University of Lübeck)
- Ruchira Chatterjee
(Lawrence Berkeley National Laboratory)
- Margaret D. Doyle
(Lawrence Berkeley National Laboratory)
- Mun Hon Cheah
(Uppsala University)
- Thomas Fransson
(KTH Royal Institute of Technology)
- Petko Chernev
(Uppsala University)
- In-Sik Kim
(Lawrence Berkeley National Laboratory)
- Hiroki Makita
(Lawrence Berkeley National Laboratory)
- Medhanjali Dasgupta
(Lawrence Berkeley National Laboratory)
- Corey J. Kaminsky
(Lawrence Berkeley National Laboratory)
- Miao Zhang
(Lawrence Berkeley National Laboratory)
- Julia Gätcke
(Humboldt Universität zu Berlin)
- Stephanie Haupt
(Humboldt Universität zu Berlin)
- Isabela I. Nangca
(Lawrence Berkeley National Laboratory)
- Stephen M. Keable
(Lawrence Berkeley National Laboratory)
- A. Orkun Aydin
(Uppsala University)
- Kensuke Tono
(Japan Synchrotron Radiation Research Institute
RIKEN SPring-8 Center)
- Shigeki Owada
(Japan Synchrotron Radiation Research Institute
RIKEN SPring-8 Center)
- Leland B. Gee
(SLAC National Accelerator Laboratory)
- Franklin D. Fuller
(SLAC National Accelerator Laboratory)
- Alexander Batyuk
(SLAC National Accelerator Laboratory)
- Roberto Alonso-Mori
(SLAC National Accelerator Laboratory)
- James M. Holton
(Lawrence Berkeley National Laboratory
University of California
SLAC National Accelerator Laboratory)
- Daniel W. Paley
(Lawrence Berkeley National Laboratory)
- Nigel W. Moriarty
(Lawrence Berkeley National Laboratory)
- Fikret Mamedov
(Uppsala University)
- Paul D. Adams
(Lawrence Berkeley National Laboratory
University of California)
- Aaron S. Brewster
(Lawrence Berkeley National Laboratory)
- Holger Dobbek
(Humboldt Universität zu Berlin)
- Nicholas K. Sauter
(Lawrence Berkeley National Laboratory)
- Uwe Bergmann
(University of Wisconsin–Madison)
- Athina Zouni
(Humboldt Universität zu Berlin)
- Johannes Messinger
(Uppsala University
Umeå University)
- Jan Kern
(Lawrence Berkeley National Laboratory)
- Junko Yano
(Lawrence Berkeley National Laboratory)
- Vittal K. Yachandra
(Lawrence Berkeley National Laboratory)
Abstract
In natural photosynthesis, the light-driven splitting of water into electrons, protons and molecular oxygen forms the first step of the solar-to-chemical energy conversion process. The reaction takes place in photosystem II, where the Mn4CaO5 cluster first stores four oxidizing equivalents, the S0 to S4 intermediate states in the Kok cycle, sequentially generated by photochemical charge separations in the reaction center and then catalyzes the O–O bond formation chemistry1–3. Here, we report room temperature snapshots by serial femtosecond X-ray crystallography to provide structural insights into the final reaction step of Kok’s photosynthetic water oxidation cycle, the S3→[S4]→S0 transition where O2 is formed and Kok’s water oxidation clock is reset. Our data reveal a complex sequence of events, which occur over micro- to milliseconds, comprising changes at the Mn4CaO5 cluster, its ligands and water pathways as well as controlled proton release through the hydrogen-bonding network of the Cl1 channel. Importantly, the extra O atom Ox, which was introduced as a bridging ligand between Ca and Mn1 during the S2→S3 transition4–6, disappears or relocates in parallel with Yz reduction starting at approximately 700 μs after the third flash. The onset of O2 evolution, as indicated by the shortening of the Mn1–Mn4 distance, occurs at around 1,200 μs, signifying the presence of a reduced intermediate, possibly a bound peroxide.
Suggested Citation
Asmit Bhowmick & Rana Hussein & Isabel Bogacz & Philipp S. Simon & Mohamed Ibrahim & Ruchira Chatterjee & Margaret D. Doyle & Mun Hon Cheah & Thomas Fransson & Petko Chernev & In-Sik Kim & Hiroki Maki, 2023.
"Structural evidence for intermediates during O2 formation in photosystem II,"
Nature, Nature, vol. 617(7961), pages 629-636, May.
Handle:
RePEc:nat:nature:v:617:y:2023:i:7961:d:10.1038_s41586-023-06038-z
DOI: 10.1038/s41586-023-06038-z
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Cited by:
- Adel Beghiah & Patricia Saura & Sofia Badolato & Hyunho Kim & Johanna Zipf & Dirk Auman & Ana P. Gamiz-Hernandez & Johan Berg & Grant Kemp & Ville R. I. Kaila, 2024.
"Dissected antiporter modules establish minimal proton-conduction elements of the respiratory complex I,"
Nature Communications, Nature, vol. 15(1), pages 1-14, December.
- Yu Guo & Lanlan He & Yunxuan Ding & Lars Kloo & Dimitrios A. Pantazis & Johannes Messinger & Licheng Sun, 2024.
"Closing Kok’s cycle of nature’s water oxidation catalysis,"
Nature Communications, Nature, vol. 15(1), pages 1-11, December.
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