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Closing Kok’s cycle of nature’s water oxidation catalysis

Author

Listed:
  • Yu Guo

    (Westlake University
    Westlake Institute for Advanced Study)

  • Lanlan He

    (Westlake University
    Westlake Institute for Advanced Study)

  • Yunxuan Ding

    (Westlake University
    Westlake Institute for Advanced Study)

  • Lars Kloo

    (KTH Royal Institute of Technology)

  • Dimitrios A. Pantazis

    (Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1)

  • Johannes Messinger

    (Umeå University, Linnaeus väg 6 (KBC huset)
    Uppsala University)

  • Licheng Sun

    (Westlake University
    Westlake Institute for Advanced Study
    Zhejiang Baima Lake Laboratory Co., Ltd.)

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.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50210-6
    DOI: 10.1038/s41467-024-50210-6
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    References listed on IDEAS

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