Structure of the manganese complex in photosystem II: insights from X–ray spectroscopy
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- Vittal K. Yachandra
- Melvin Calvin Laboratory, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
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- J. Barber
- editor
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- J. M Anderson
- editor
抄録
<jats:p> We have used Mn K–edge absorption and Kβ emission spectroscopy to determine the oxidation states of the Mn complex in the various S states. We have started exploring the new technique of resonant inelastic X–ray scattering spectroscopy; this technique can be characterized as a Raman process that uses K–edge energies (1s to 4p, <jats:italic>ca</jats:italic> . 6550 eV) to obtain L–edge–like spectra (2p to 3d, <jats:italic>ca</jats:italic> . 650 eV). The relevance of these data to the oxidation states and structure of the Mn complex is presented. We have obtained extended X–ray absorption fine structure data from the S <jats:sub>0</jats:sub> and S <jats:sub>3</jats:sub> states and observed heterogeneity in the Mn–Mn distances leading us to conclude that there may be three rather than two di– <jats:italic>μ</jats:italic> –oxo–bridged units present per tetranuclear Mn cluster. In addition, we have obtained data using Ca and Sr X–ray spectroscopy that provide evidence for a heteronuclear Mn1Ca cluster. The possibility of three di– <jats:italic>μ</jats:italic> –oxo–bridged Mn–Mn moieties and the proximity of Ca is incorporated into developing structural models for the Mn cluster. The involvement of bridging and terminal O ligands of Mn in the mechanism of oxygen evolution is discussed in the context of our X–ray spectroscopy results. </jats:p>
収録刊行物
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- Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences
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Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences 357 (1426), 1347-1358, 2002-10-29
The Royal Society
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詳細情報 詳細情報について
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- CRID
- 1360011144489810944
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- NII論文ID
- 30018914323
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- ISSN
- 14712970
- 09628436
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