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Photosystem II: Structure and mechanism of the water:plastoquinone oxidoreductase

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Abstract

This mini-review briefly summarizes our current knowledge on the reaction pattern of light-driven water splitting and the structure of Photosystem II that acts as a water:plastoquinone oxidoreductase. The overall process comprises three types of reaction sequences: (a) light-induced charge separation leading to formation of the radical ion pair P680+•Q −•A ; (b) reduction of plastoquinone to plastoquinol at the QB site via a two-step reaction sequence with Q −•A as reductant and (c) oxidative water splitting into O2 and four protons at a manganese-containing catalytic site via a four-step sequence driven by P680+• as oxidant and a redox active tyrosine YZ acting as mediator. Based on recent progress in X-ray diffraction crystallographic structure analysis the array of the cofactors within the protein matrix is discussed in relation to the functional pattern. Special emphasis is paid on the structure of the catalytic sites of PQH2 formation (QB-site) and oxidative water splitting (Mn4O x Ca cluster). The energetics and kinetics of the reactions taking place at these sites are presented only in a very concise manner with reference to recent up-to-date reviews. It is illustrated that several questions on the mechanism of oxidative water splitting and the structure of the catalytic sites are far from being satisfactorily answered.

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Abbreviations

BChl:

Bacteriochlorophyl

BPheo:

Bacteriopheophytin

Chl:

Chlorophyll

EET:

Excited state energy transfer

ENDOR:

Electron nuclear double resonance

EPR:

Electron paramagnetic resonance

ESEEM:

Electron spin echo envelope modulation

ET:

Electron transfer

EXAFS:

Extended X-ray absorption fine structure

FTIR:

Fourier transform infra red

MGDG:

Monogalactosyldiacylglycerol

NHFe:

Nonheme iron

PBRC :

Purple bacterial reaction center

PG:

Phosphatidylglycerol

Pheo:

Pheophytin

PQ:

Plastoquinone

PS I:

Photosystem I

PS II:

Photosystem II

QENS:

Quasielastic neutron scattering

RC:

Reaction center

RP:

Radical pair

SQDG:

Sulfoquinovosyldiacylglycerol

TMH:

Transmembrane helix

UQ:

Ubiquinone

WOC:

Water-oxidizing complex

XANES:

X-ray absorption near edge spectroscopy

XRDC:

X-ray diffraction crystallography

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Acknowledgement

The authors would like to thank A. Zouni, B. Loll, J. Biesiadka and W. Saenger for helpful discussions regarding the PSII structure, S. Renger and P. Kühn for preparing the electronic versions of Fig. 2 and Figs. 4 and 7, respectively. The support by DFG-Sonderforschungsbereich 429, TP A1 (GR) and 498, TP C7 (JK) is gratefully acknowledged.

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  1. Institut für Chemie, Max-Volmer-Laboratorium für Biophysikalische Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany

    Jan Kern & Gernot Renger

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Kern, J., Renger, G. Photosystem II: Structure and mechanism of the water:plastoquinone oxidoreductase. Photosynth Res 94, 183–202 (2007). https://doi.org/10.1007/s11120-007-9201-1

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