Structural Changes in the Mn4Ca Cluster and the Mechanism of Photosynthetic Water Splitting

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Photosynthetic water oxidation, where water is oxidized to dioxygen, is a fundamental chemical reaction that sustains the biosphere. This reaction is catalyzed by a Mn4Ca complex in the photosystem II (PS II) oxygen-evolving complex (OEC): a multiproteinassembly embedded in the thylakoid membranes of green plants, cyanobacteria, and algae. The mechanism of photosynthetic water oxidation by the Mn4Ca cluster in photosystem II is the subject of much debate, although lacking structural characterization of the catalytic intermediates. Biosynthetically exchanged Ca/Sr-PS II preparations and x-ray spectroscopy, including extended x-ray absorption fine structure (EXAFS), allowed us to monitor Mn-Mn and Ca(Sr)-Mn distances in the ... continued below

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Pushkar, Y.; Yano, J.; Sauer, K.; Boussac, A. & Yachandra, V.K. October 25, 2007.

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Photosynthetic water oxidation, where water is oxidized to dioxygen, is a fundamental chemical reaction that sustains the biosphere. This reaction is catalyzed by a Mn4Ca complex in the photosystem II (PS II) oxygen-evolving complex (OEC): a multiproteinassembly embedded in the thylakoid membranes of green plants, cyanobacteria, and algae. The mechanism of photosynthetic water oxidation by the Mn4Ca cluster in photosystem II is the subject of much debate, although lacking structural characterization of the catalytic intermediates. Biosynthetically exchanged Ca/Sr-PS II preparations and x-ray spectroscopy, including extended x-ray absorption fine structure (EXAFS), allowed us to monitor Mn-Mn and Ca(Sr)-Mn distances in the four intermediate S states, S0 through S3, of the catalytic cycle that couples the one-electron photochemistry occurring at the PS II reaction center with the four-electron water-oxidation chemistry taking place at the Mn4Ca(Sr) cluster. We have detected significant changes in the structure of the complex, especially in the Mn-Mn and Ca(Sr)-Mn distances, on the S2-to-S3 and S3-to-S0 transitions. These results implicate the involvement of at least one common bridging oxygen atom between the Mn-Mn and Mn-Ca(Sr) atoms in the O-O bond formation. Because PS II cannot advance beyond the S2 state in preparations that lack Ca(Sr), these results show that Ca(Sr) is one of the critical components in the mechanism of the enzyme. The results also show that Ca is not just a spectator atom involved in providing a structural framework, but is actively involved in the mechanism of water oxidation and represents a rare example of a catalytically active Ca cofactor.

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  • Journal Name: Proceedings of the National Academy of Science; Journal Volume: 105; Journal Issue: 6; Related Information: Journal Publication Date: Feb. 12, 2008

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  • Report No.: LBNL-2303E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 971344
  • Archival Resource Key: ark:/67531/metadc928857

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  • October 25, 2007

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  • Nov. 13, 2016, 7:26 p.m.

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  • Nov. 18, 2016, 4:18 p.m.

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Pushkar, Y.; Yano, J.; Sauer, K.; Boussac, A. & Yachandra, V.K. Structural Changes in the Mn4Ca Cluster and the Mechanism of Photosynthetic Water Splitting, article, October 25, 2007; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc928857/: accessed August 20, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.