An oxyl/oxo mechanism for oxygen-oxygen coupling in PSII revealed by an x-ray free-electron laser

Author:

Suga Michihiro12ORCID,Akita Fusamichi12ORCID,Yamashita Keitaro3ORCID,Nakajima Yoshiki1ORCID,Ueno Go3ORCID,Li Hongjie14ORCID,Yamane Takahiro1ORCID,Hirata Kunio3ORCID,Umena Yasufumi1,Yonekura Shinichiro1ORCID,Yu Long-Jiang1ORCID,Murakami Hironori5,Nomura Takashi34ORCID,Kimura Tetsunari6ORCID,Kubo Minoru34ORCID,Baba Seiki5ORCID,Kumasaka Takashi5ORCID,Tono Kensuke35ORCID,Yabashi Makina35ORCID,Isobe Hiroshi1ORCID,Yamaguchi Kizashi78,Yamamoto Masaki3ORCID,Ago Hideo3ORCID,Shen Jian-Ren1ORCID

Affiliation:

1. Research Institute for Interdisciplinary Science and Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima Naka, Okayama 700-8530, Japan.

2. Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.

3. RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan.

4. Department of Picobiology, Graduate School of Life Science, University of Hyogo, 3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.

5. Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan.

6. Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe 657-8501, Japan.

7. The Institute for Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan.

8. Institute for Nanoscience Design, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.

Abstract

Inspecting S states in photosynthesis Oxygenic photosynthesis uses a Mn 4 CaO 5 cluster in the oxygen-evolving complex to extract electrons from water and produce dioxygen. Visualizing each of the chemical states in this process, S 0 to S 4 , and assigning chemical identities and mechanisms on the basis of structures has been a challenge addressed recently by work at x-ray free-electron lasers. Suga et al. used serial crystallography at cryogenic temperatures to trap and determine the structures of several stable states during photosystem II water oxidation (see the Perspective by Britt and Marchiori). Changes around the water cluster already happen in the S 2 state and set the stage for water insertion that occurs during transition to the S 3 state. A short 1.9-angstrom distance between the two oxygen atoms in the S 3 state is consistent with theoretical studies supporting an oxyl/oxo mechanism for oxygen-oxygen coupling. Science , this issue p. 334 ; see also p. 305

Funder

RIKEN

JSPS

JST, PREST

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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