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A Synthetic Model of the Mn_3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II

Kanady, Jacob S. and Tsui, Emily Y. and Day, Michael W. and Agapie, Theodor (2011) A Synthetic Model of the Mn_3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II. Science, 333 (6043). pp. 733-736. ISSN 0036-8075.

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Within photosynthetic organisms, the oxygen-evolving complex (OEC) of photosystem II generates dioxygen from water using a catalytic Mn_(4)CaOn cluster (n varies with the mechanism and nature of the intermediate). We report here the rational synthesis of a [Mn_(3)CaO_4]^(6+) cubane that structurally models the trimanganese-calcium–cubane subsite of the OEC. Structural and electrochemical comparison between Mn_(3)CaO_4 and a related Mn_(4)O_4 cubane alongside characterization of an intermediate calcium-manganese multinuclear complex reveals potential roles of calcium in facilitating high oxidation states at manganese and in the assembly of the biological cluster.

Item Type:Article
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Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2011 American Association for the Advancement of Science. Received for publication 24 March 2011; accepted for publication 5 July 2011. We thank California Institute of Technology, the Searle Scholars Program (T.A.), the Rose Hill Foundation (J.S.K.), and the NSF Graduate Research Fellowship Program (E.Y.T.) for funding. We also thank L. M. Henling for assistance with crystallography. The Bruker KAPPA APEXII x-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation and Facilities: Departmental Multi-User Instrumentation award to Caltech (CHE-0639094). Crystallographic data have been deposited at the Cambridge Crystallographic Database Centre, and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition numbers 817379 (3), 817683 (4), and 817924 (5).
Funding AgencyGrant Number
Searle Scholars ProgramUNSPECIFIED
Rose Hill FoundationUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Issue or Number:6043
Record Number:CaltechAUTHORS:20110822-132939719
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Official Citation:A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II Jacob S. Kanady, Emily Y. Tsui, Michael W. Day, and Theodor Agapie Science 5 August 2011: 333 (6043), 733-736. [DOI:10.1126/science.1206036]
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:24980
Deposited By: Jason Perez
Deposited On:22 Aug 2011 21:12
Last Modified:03 Oct 2019 03:01

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