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Where Water is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster

  • Author(s): Yano, Junko
  • Kern, Jan
  • Sauer, Kenneth
  • Latimer, Matthew J.
  • Pushkar, Yulia
  • Biesiadka, Jacek
  • Loll, Bernhard
  • Saenger, Wolfram
  • Messinger, Johannes
  • Zouni, Athina
  • Yachandra, Vittal K.
  • et al.
Abstract

Oxidation of water to dioxygen is catalyzed within photosystem II (PSII) by a Mn4Ca cluster, the structure of which remains elusive. Polarized extended X-ray absorption fine structure (EXAFS) measurements on PSII single crystals constrain the Mn4Ca cluster geometry to a set of three similar high-resolution structures. Combining polarized EXAFS and X-ray diffraction data, the cluster was placed within PSII taking into account the overall trend of the electron density of the metal site and the putative ligands. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 Angstrom resolution X-ray structures, and other previously proposed models.

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