Closing Kok’s cycle of nature’s water oxidation catalysis. Guo, Y., He, L., Ding, Y., Kloo, L., Pantazis, D. A., Messinger, J., & Sun, L. Nature Communications, 15(1):5982, July, 2024. Publisher: Nature Publishing Group![Closing Kok’s cycle of nature’s water oxidation catalysis [link]](https://bibbase.org/img/filetypes/link.svg "link")
Paper doi abstract bibtex The Mn4CaO5(6) cluster in photosystem II catalyzes water splitting through the Si state cycle (i = 0–4). Molecular O2 is formed and the natural catalyst is reset during the final S3 → (S4) → S0 transition. Only recently experimental breakthroughs have emerged for this transition but without explicit information on the S0-state reconstitution, thus the progression after O2 release remains elusive. In this report, our molecular dynamics simulations combined with density functional calculations suggest a likely missing link for closing the cycle, i.e., restoring the first catalytic state. Specifically, the formation of closed-cubane intermediates with all hexa-coordinate Mn is observed, which would undergo proton release, water dissociation, and ligand transfer to produce the open-cubane structure of the S0 state. Thereby, we theoretically identify the previously unknown structural isomerism in the S0 state that acts as the origin of the proposed structural flexibility prevailing in the cycle, which may be functionally important for nature’s water oxidation catalysis.
@article{guo_closing_2024,
title = {Closing {Kok}’s cycle of nature’s water oxidation catalysis},
volume = {15},
copyright = {2024 The Author(s)},
issn = {2041-1723},
url = {https://www.nature.com/articles/s41467-024-50210-6},
doi = {10.1038/s41467-024-50210-6},
abstract = {The Mn4CaO5(6) cluster in photosystem II catalyzes water splitting through the Si state cycle (i = 0–4). Molecular O2 is formed and the natural catalyst is reset during the final S3 → (S4) → S0 transition. Only recently experimental breakthroughs have emerged for this transition but without explicit information on the S0-state reconstitution, thus the progression after O2 release remains elusive. In this report, our molecular dynamics simulations combined with density functional calculations suggest a likely missing link for closing the cycle, i.e., restoring the first catalytic state. Specifically, the formation of closed-cubane intermediates with all hexa-coordinate Mn is observed, which would undergo proton release, water dissociation, and ligand transfer to produce the open-cubane structure of the S0 state. Thereby, we theoretically identify the previously unknown structural isomerism in the S0 state that acts as the origin of the proposed structural flexibility prevailing in the cycle, which may be functionally important for nature’s water oxidation catalysis.},
language = {en},
number = {1},
urldate = {2024-07-19},
journal = {Nature Communications},
author = {Guo, Yu and He, Lanlan and Ding, Yunxuan and Kloo, Lars and Pantazis, Dimitrios A. and Messinger, Johannes and Sun, Licheng},
month = jul,
year = {2024},
note = {Publisher: Nature Publishing Group},
keywords = {Bioinorganic chemistry, Catalytic mechanisms, Reaction mechanisms},
pages = {5982},
}
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In this report, our molecular dynamics simulations combined with density functional calculations suggest a likely missing link for closing the cycle, i.e., restoring the first catalytic state. Specifically, the formation of closed-cubane intermediates with all hexa-coordinate Mn is observed, which would undergo proton release, water dissociation, and ligand transfer to produce the open-cubane structure of the S0 state. 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