Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II
Abstract
Photosystem II (PSII) oxidizes water to produce oxygen through a four-step photocatalytic cycle. Understanding PSII structure–function relations is important for the development of biomimetic photocatalytic systems. The quantum mechanics/molecular mechanics (QM/MM) analysis of substrate water binding to the oxygen-evolving complex (OEC) has suggested a rearrangement of water ligands in a carousel mechanism around a key Mn center. Here, we find that the most recently reported X-ray free-electron laser (XFEL) crystallographic data obtained for the dark-stable S1 state and the doubly flashed S3 state at 2.25 Å resolution support the carousel mechanism. The features in the XFEL data and QM/MM model-simulated difference Fourier maps suggest that water displacement may occur from the so-called “narrow” channel, resulting in binding of a new water molecule to the OEC, and thus provide new insights into the nature of rearrangements of water ligands along the catalytic cycle before O=O bond formation.
- Authors:
-
[2];
[2]
- Department of Molecular Biophysics and Biochemistry, Yale University, New Haven, Connecticut 06520-8114, United States
- Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, United States
- Publication Date:
- Research Org.:
- Yale Univ., New Haven, CT (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States)
- OSTI Identifier:
- 1390663
- Alternate Identifier(s):
- OSTI ID: 1507570
- Grant/Contract Number:
- SC0001423, FG02- 05ER15646; FG02-05ER15646; SC0001423; P01 GM022778
- Resource Type:
- Published Article
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Name: ACS Energy Letters Journal Volume: 2 Journal Issue: 10; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wang, Jimin, Askerka, Mikhail, Brudvig, Gary W., and Batista, Victor S. Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II. United States: N. p., 2017.
Web. doi:10.1021/acsenergylett.7b00750.
Wang, Jimin, Askerka, Mikhail, Brudvig, Gary W., & Batista, Victor S. Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II. United States. https://doi.org/10.1021/acsenergylett.7b00750
Wang, Jimin, Askerka, Mikhail, Brudvig, Gary W., and Batista, Victor S. Tue .
"Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II". United States. https://doi.org/10.1021/acsenergylett.7b00750.
@article{osti_1390663,
title = {Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II},
author = {Wang, Jimin and Askerka, Mikhail and Brudvig, Gary W. and Batista, Victor S.},
abstractNote = {Photosystem II (PSII) oxidizes water to produce oxygen through a four-step photocatalytic cycle. Understanding PSII structure–function relations is important for the development of biomimetic photocatalytic systems. The quantum mechanics/molecular mechanics (QM/MM) analysis of substrate water binding to the oxygen-evolving complex (OEC) has suggested a rearrangement of water ligands in a carousel mechanism around a key Mn center. Here, we find that the most recently reported X-ray free-electron laser (XFEL) crystallographic data obtained for the dark-stable S1 state and the doubly flashed S3 state at 2.25 Å resolution support the carousel mechanism. The features in the XFEL data and QM/MM model-simulated difference Fourier maps suggest that water displacement may occur from the so-called “narrow” channel, resulting in binding of a new water molecule to the OEC, and thus provide new insights into the nature of rearrangements of water ligands along the catalytic cycle before O=O bond formation.},
doi = {10.1021/acsenergylett.7b00750},
journal = {ACS Energy Letters},
number = 10,
volume = 2,
place = {United States},
year = {2017},
month = {9}
}
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https://doi.org/10.1021/acsenergylett.7b00750
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Cited by: 9 works
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Figures / Tables:
Figure 1: Stereodiagram of superposition of the QM/MM S1 (yellow, magenta, silver, red, and blue) and S3 (salmon, green, dark magenta, pink, and blue) models, including six bidentate carboxylate ligands to highlight the moving parts to be expected in difference density features.
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