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Title: 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:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [2]
  1. Department of Molecular Biophysics and Biochemistry, Yale University, New Haven, Connecticut 06520-8114, United States
  2. 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. https://doi.org/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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsenergylett.7b00750

Citation Metrics:
Cited by: 9 works
Citation information provided by
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Figures / Tables:

Figure 1 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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