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.
| Original language | English |
|---|---|
| Pages (from-to) | 2299-2306 |
| Number of pages | 8 |
| Journal | ACS Energy Letters |
| Volume | 2 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - Oct 13 2017 |
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ASJC Scopus subject areas
- Chemistry (miscellaneous)
- Renewable Energy, Sustainability and the Environment
- Fuel Technology
- Energy Engineering and Power Technology
- Materials Chemistry
Cite this
Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II. / Wang, Jimin; Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S.
In: ACS Energy Letters, Vol. 2, No. 10, 13.10.2017, p. 2299-2306.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II
AU - Wang, Jimin
AU - Askerka, Mikhail
AU - Brudvig, Gary W
AU - Batista, Victor S.
PY - 2017/10/13
Y1 - 2017/10/13
N2 - 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.
AB - 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.
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U2 - 10.1021/acsenergylett.7b00750
DO - 10.1021/acsenergylett.7b00750
M3 - Article
AN - SCOPUS:85031286233
VL - 2
SP - 2299
EP - 2306
JO - ACS Energy Letters
JF - ACS Energy Letters
SN - 2380-8195
IS - 10
ER -