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Structure-Function Relationships in the Mn4CaO5 Water-Splitting Cluster

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The Biophysics of Photosynthesis

Part of the book series: Biophysics for the Life Sciences ((BIOPHYS,volume 11))

Abstract

Mn4CaO5 cluster is the catalytic center for photosynthetic water-splitting harbored in photosystem II (PSII), a huge, multi-subunit membrane–protein complex located in the thylakoid membranes from cyanobacteria to higher plants. The structure of PSII has been analyzed at 1.9 Å resolution by X-ray crystallography, revealing a clear picture of the Mn4CaO5 cluster. In this chapter, principles of crystallization and crystal structure analysis are briefly introduced, followed by descriptions of the structure of the Mn4CaO5 cluster and its implications in the mechanism of water-splitting. Based on the geometric organization of the Mn4CaO5 cluster, the location of four terminal water ligands, the possible oxidation states of the four Mn ions reported so far, as well as the structural changes revealed by replacing the Ca ion with Sr, a mechanism for water-splitting was proposed and discussed.

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Abbreviations

DFT:

Density functional theory

EM:

Electron microscopy

EPR:

Electron paramagnetic resonance

EXAFS:

Extended X-ray absorption fine structure

FTIR:

Fourier transform infrared spectroscopy

NMR:

Nuclear magnetic resonance

OEC:

Oxygen-evolving complex

PSII:

Photosystem II

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Acknowledgements

Structural analysis of PSII at the atomic resolution described in this chapter was performed in collaboration with Drs. Nobuo Kamiya, Yasufumi Umena, and Keisuke Kawakami, and analysis of the Sr-PSII was performed in collaboration with Dr. Faisal H.M. Koua in addition to the above colleagues. I thank these colleagues for their continuous contributions. The work performed in the author’s laboratory is supported by a Grant-in-Aid for Specially Promoted Research from MEXT/JSPS of Japan.

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Authors and Affiliations

  1. Photosynthesis Research Center, Graduate School of Natural Science and Technology, Okayama University, Tsushima Naka 3-1-1, Kita-ku, Okayama, 700-8530, Japan

    Jian-Ren Shen Ph.D.

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Correspondence to Jian-Ren Shen Ph.D. .

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Editors and Affiliations

  1. Dept of Biochemistry & Molecular Biology, Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, USA

    John Golbeck

  2. Dept of Chemistry, Brock University, St. Catharines, Ontario, Canada

    Art van der Est

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Shen, JR. (2014). Structure-Function Relationships in the Mn4CaO5 Water-Splitting Cluster. In: Golbeck, J., van der Est, A. (eds) The Biophysics of Photosynthesis. Biophysics for the Life Sciences, vol 11. Springer, New York, NY. https://doi.org/10.1007/978-1-4939-1148-6_11

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