Light-induced structural changes and the site of O=O bond formation in PSII caught by XFEL

被引：505

作者：

Suga, Michihiro ^{[1
,2
]}

Akita, Fusamichi ^{[1
,2
,3
]}

Sugahara, Michihiro ^{[4
]}

Kubo, Minoru ^{[3
,4
]}

Nakajima, Yoshiki ^{[1
,2
]}

Nakane, Takanori ^{[5
]}

Yamashita, Keitaro ^{[4
]}

Umena, Yasufumi ^{[1
,2
]}

Nakabayashi, Makoto ^{[1
,2
]}

Yamane, Takahiro ^{[1
,2
]}

Nakano, Takamitsu ^{[1
,2
]}

Suzuki, Mamoru ^{[4
,6
]}

Masuda, Tetsuya ^{[4
,7
]}

Inoue, Shigeyuki ^{[4
,8
]}

Kimura, Tetsunari ^{[4
,9
]}

Nomura, Takashi ^{[4
]}

Yonekura, Shinichiro ^{[1
,2
]}

Yu, Long-Jiang ^{[1
,2
]}

Sakamoto, Tomohiro ^{[1
,2
]}

Motomura, Taiki ^{[1
,2
,10
]}

Chen, Jing-Hua ^{[1
,2
,11
]}

Kato, Yuki ^{[12
]}

Noguchi, Takumi ^{[12
]}

Tono, Kensuke ^{[13
]}

Joti, Yasumasa ^{[13
]}

Kameshima, Takashi

Hatsui, Takaki ^{[4
]}

Nango, Eriko ^{[4
,14
]}

Tanaka, Rie ^{[4
]}

Naitow, Hisashi ^{[4
]}

Matsuura, Yoshinori ^{[4
]}

Yamashita, Ayumi ^{[4
]}

Yamamoto, Masaki ^{[4
]}

Nureki, Osamu ^{[5
]}

Yabashi, Makina ^{[4
]}

Ishikawa, Tetsuya ^{[4
]}

Iwata, So ^{[2
,4
]}

Shen, Jian-Ren ^{[1
,2
,10
,11
]}

机构：

[1] Okayama Univ, Res Inst Interdisciplinary Sci, 3-1-1 Tsushima Naka, Okayama 7008530, Japan

[2] Okayama Univ, Grad Sch Nat Sci & Technol, 3-1-1 Tsushima Naka, Okayama 7008530, Japan

[3] Japan Sci & Technol Agcy, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 3320012, Japan

[4] RIKEN, SPring Ctr 8, 1-1-1 Kouto,Sayo Cho, Mikazuki, Hyogo 6795148, Japan

[5] Univ Tokyo, Grad Sch Sci, Dept Biol Sci, Bunkyo Ku, 2-11-16 Yayoi, Tokyo 1130032, Japan

[6] Osaka Univ, Inst Prot Res, Suita, Osaka 5650871, Japan

[7] Kyoto Univ, Grad Sch Agr, Div Food Sci & Biotechnol, Uji, Kyoto 6110011, Japan

[8] Univ Tokyo, Grad Sch Med, Dept Cell Biol & Anat, Bunkyo Ku, Hongo, Tokyo 1130033, Japan

[9] Kobe Univ, Grad Sch Sci, Dept Chem, Nada Ku, 1-1 Rokkodai, Kobe, Hyogo 6578501, Japan

[10] Univ Hyogo, Grad Sch Life Sci, Dept Picobiol, 3-2-1 Kouto,Kamigori Cho, Kobe, Hyogo 6781297, Japan

[11] Chinese Acad Sci, Inst Bot, Key Lab Photobiol, 20 Nanxincun, Beijing 100093, Peoples R China

[12] Nagoya Univ, Grad Sch Sci, Div Mat Sci, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648602, Japan

[13] Japan Synchrotron Radiat Res Inst, 1-1-1 Kouto, Sayo, Hyogo 6795198, Japan

[14] Kyoto Univ, Grad Sch Med, Dept Cell Biol, Sakyo Ku, Yoshidakonoe Cho, Kyoto 6068501, Japan

来源：

NATURE | 2017年 / 543卷 / 7643期

基金：

日本科学技术振兴机构;

关键词：

OXYGEN-EVOLVING COMPLEX; X-RAY-DIFFRACTION; PHOTOSYNTHETIC WATER OXIDATION; PHOTOSYSTEM-II; INFRARED DETECTION; OXIDIZING COMPLEX; PROTON RELEASE; MECHANISM; STATE; BINDING;

D O I：

10.1038/nature21400

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Photosystem II (PSII) is a huge membrane-protein complex consisting of 20 different subunits with a total molecular mass of 350 kDa for a monomer. It catalyses light-driven water oxidation at its catalytic centre, the oxygen-evolving complex (OEC)(1-3). The structure of PSII has been analysed at 1.9 angstrom resolution by synchrotron radiation X-rays, which revealed that the OEC is a Mn4CaO5 cluster organized in an asymmetric, `distorted-chair' form(4). This structure was further analysed with femtosecond X-ray free electron lasers (XFEL), providing the `radiation damage-free'(5) structure. The mechanism of O=O bond formation, however, remains obscure owing to the lack of intermediate-state structures. Here we describe the structural changes in PSII induced by two-flash illumination at room temperature at a resolution of 2.35 angstrom using time-resolved serial femtosecond crystallography with an XFEL provided by the SPring-8 angstrom compact free-electron laser. An isomorphous difference Fourier map between the two-flash and dark-adapted states revealed two areas of apparent changes: around the QB/non-haem iron and the Mn4CaO5 cluster. The changes around the QB/non-haem iron region reflected the electron and proton transfers induced by the two-flash illumination. In the region around the OEC, a water molecule located 3.5 angstrom from the Mn4CaO5 cluster disappeared from the map upon two-flash illumination. This reduced the distance between another water molecule and the oxygen atom O4, suggesting that proton transfer also occurred. Importantly, the two-flash-minus-dark isomorphous difference Fourier map showed an apparent positive peak around O5, a unique mu 4-oxo-bridge located in the quasi-centre of Mn1 and Mn4 (refs 4,5). This suggests the insertion of a new oxygen atom (O6) close to O5, providing an O=O distance of 1.5 angstrom between these two oxygen atoms. This provides a mechanism for the O=O bond formation consistent with that proposed previously(6,7.)

引用

页码：131 / +

页数：16

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