Abstract
The Mn4CaOX cluster catalyzes the light driven oxidation of water in Photosystem II. To understand the mechanistic details of this intriguing machine it is necessary to unravel not only the geometric but also the electronic structure of this complex. X-ray emission spectroscopy can be one important tool in this endeavour due to its unique sensitivity towards light atoms ligated to a metal center. In addition X-ray emission spectroscopy provides information of the charge density distribution over the metal centers in the complex and is sensitive to protonation changes of bridging oxygens, both important questions in the light of different proposed mechanisms for water oxidation in PSII. Here we show that X-ray emission spectra of PSII can be collected with sufficient S/N from PSII samples and can yield insights into the mechanism of water oxidation.
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References
Berthold D, et al. (1981) A Highly Resolved, Oxygen-Evolving Photosystem II Preparation from Spinach Thylakoid Membranes. Febs Letters 134:231–234
Ferreira KN, et al. (2004) Architecture of the Photosynthetic Oxygen-Evolving Center. Science 303: 1831–1838
Glatzel P, Bergmann U (2005) High Resolution 1s Core Hole X-Ray Spectroscopy in 3d Transition Metal Complexes—Electronic and Structural Information. Coord Chem Rev 249: 65–95
Guskov A, et al. (2009) Cyanobacterial Photosystem II at 2.9-Angstrom Resolution and the Role of Quinones, Lipids, Channels and Chloride. Nature Struct Mol Biol 16: 334–342
Kamiya N, Shen JR (2003) Crystal Structure of Oxygen-Evolving Photosystem II from Thermosynechococcus Vulcanus at 3.7-Å Resolution. Proc Natl Acad Sci USA 100: 98–103
Loll B, et al. (2005) Towards Complete Cofactor Arrangement in the 3.0 Å Resolution Structure of Photosystem II. Nature 438: 1040–1044
Messinger J, et al. (2001) Absence of Mn-Centered Oxidation in the S2-> S3 Transition: Implications for the Mechanism of Photosynthetic Water Oxidation. J Am Chem Soc 123: 7804–7820
Pushkar Y, et al. (2010) Direct Detection of Oxygen Ligation to the Mn4Ca Cluster of Photosystem II by X-Ray Emission Spectroscopy. Ang Chem Int Ed 49: 800–803
Smolentsev G, et al. (2009) X-Ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes. J Am Chem Soc 131: 13161–13167
Zouni A, et al. (2001) Crystal Structure of Photosystem II from Synechococcus Elongatus at 3.8 Å Resolution. Nature 409: 739–743
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© 2013 Zhejiang University Press, Hangzhou and Springer-Verlag Berlin Heidelberg
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Kern, J. et al. (2013). Direct Detection of Oxygen Ligands to the Mn4Ca Complex in Photosystem II by X-ray Emission Spectroscopy. In: Photosynthesis Research for Food, Fuel and the Future. Advanced Topics in Science and Technology in China. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-32034-7_48
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DOI: https://doi.org/10.1007/978-3-642-32034-7_48
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-32033-0
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