High-Resolution Mn EXAFS of the Oxygen-Evolving Complex inPhotosystem II: Structural Implications for the Mn4Ca Cluster

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The biological generation of oxygen by the oxygen-evolving complex in photosystem II (PS II) is one of natures most important reactions. The recent X-ray crystal structures, while limited by resolutions of 3.2 to 3.5 A, have located the electron density associated with the Mn4Ca complex within the multi-protein PS II complex. Detailed structures critically depend on input from spectroscopic techniques such as EXAFS and EPR/ENDOR, as the XRD resolution does not allow for accurate determination of the position of Mn/Ca or the bridging and terminal ligand atoms. The number and distances of Mn-Mn/Ca/ligand interactions determined from EXAFS provide important constraints ... continued below

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Yano, Junko; Pushkar, Yulia; Glatzel, Pieter; Lewis, Azul; Sauer,Kenneth; Messinger, Johannes et al. September 6, 2005.

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The biological generation of oxygen by the oxygen-evolving complex in photosystem II (PS II) is one of natures most important reactions. The recent X-ray crystal structures, while limited by resolutions of 3.2 to 3.5 A, have located the electron density associated with the Mn4Ca complex within the multi-protein PS II complex. Detailed structures critically depend on input from spectroscopic techniques such as EXAFS and EPR/ENDOR, as the XRD resolution does not allow for accurate determination of the position of Mn/Ca or the bridging and terminal ligand atoms. The number and distances of Mn-Mn/Ca/ligand interactions determined from EXAFS provide important constraints for the structure of the Mn cluster. Here we present data from a high-resolution EXAFS method using a novel multi-crystal monochromator that show three short Mn-Mn distances between 2.7 and 2.8 A and hence the presence of three di-mu-oxobridged units in the Mn4Ca cluster. This result imposes clear limitations on the proposed structures based on spectroscopic and diffraction data and provides input for refining such structures.

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  • Journal Name: Journal of the American Chemical Society; Journal Volume: 127; Journal Issue: 43; Related Information: Journal Publication Date: 2005

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  • Report No.: LBNL--58781
  • Grant Number: DE-AC02-05CH11231
  • Grant Number: NIHGM 55302
  • DOI: 10.1021/ja054873a | External Link
  • Office of Scientific & Technical Information Report Number: 877682
  • Archival Resource Key: ark:/67531/metadc879079

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  • September 6, 2005

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  • Sept. 21, 2016, 2:29 a.m.

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  • Sept. 29, 2016, 8:36 p.m.

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Yano, Junko; Pushkar, Yulia; Glatzel, Pieter; Lewis, Azul; Sauer,Kenneth; Messinger, Johannes et al. High-Resolution Mn EXAFS of the Oxygen-Evolving Complex inPhotosystem II: Structural Implications for the Mn4Ca Cluster, article, September 6, 2005; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc879079/: accessed October 17, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.