Photosynthetic water oxidation: Binding and activation of substrate waters for O-O bond formation

David J. Vinyard, Sahr Khan, Gary W Brudvig

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Photosynthetic water oxidation occurs at the oxygen-evolving complex (OEC) of Photosystem II (PSII). The OEC, which contains a Mn4CaO5 inorganic cluster ligated by oxides, waters and amino-acid residues, cycles through five redox intermediates known as Si states (i = 0-4). The electronic and structural properties of the transient S4 intermediate that forms the O-O bond are not well understood. In order to gain insight into how water is activated for O-O bond formation in the S4 intermediate, we have performed a detailed analysis of S-state dependent substrate water binding kinetics taking into consideration data from Mn coordination complexes. This analysis supports a model in which the substrate waters are both bound as terminal ligands and react via a water-nucleophile attack mechanism.

Original languageEnglish
Pages (from-to)37-50
Number of pages14
JournalFaraday Discussions
Volume185
DOIs
Publication statusPublished - 2015

Fingerprint

Chemical activation
activation
Oxidation
oxidation
Water
Substrates
water
Oxygen
Nucleophiles
Photosystem II Protein Complex
nucleophiles
Coordination Complexes
oxygen
Electronic properties
Oxides
attack
amino acids
Structural properties
Ligands
Amino Acids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Photosynthetic water oxidation : Binding and activation of substrate waters for O-O bond formation. / Vinyard, David J.; Khan, Sahr; Brudvig, Gary W.

In: Faraday Discussions, Vol. 185, 2015, p. 37-50.

Research output: Contribution to journalArticle

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