Structure-based mechanism of photosynthetic water oxidation

James P. McEvoy, Gary W Brudvig

Research output: Contribution to journalArticle

176 Citations (Scopus)

Abstract

The recently-published 3.5 Å resolution X-ray crystal structure of a cyanobacterial photosystem II (PDB entry 1S5L) provides a detailed architecture of the oxygen-evolving complex (OEC) and the surrounding amino-acids [K. N. Ferreira, T. M. Iverson, K. Maghlaoui, J. Barber and S. Iwata, Science, 2004, 203, 1831-1838]. The revealed geometry of the OEC lends weight to certain hypothesized mechanisms for water-splitting, including the one propounded by this group, in which a calcium-bound water acts as a nucleophile to attack the oxygen of a MnV=O group in the crucial O-O bond-forming step [J. S. Vrettos, J. Limburg and G. W. Brudvig, Biochim. Biophys. Acta, 2001, 1503, 229-245]. Here we re-examine this mechanism in the light of the new crystallographic information and make detailed suggestions concerning the mechanistic functions (especially the redox and proton-transfer roles) of calcium, chloride and certain amino-acid residues in and around the OEC. In particular, we propose an important role for an arginine residue, CP43-Arg357, in abstracting protons from a substrate water molecule during the water-splitting reaction.

Original languageEnglish
Pages (from-to)4754-4763
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume6
Issue number20
DOIs
Publication statusPublished - Oct 21 2004

Fingerprint

Oxygen
Oxidation
oxidation
water splitting
Water
oxygen
water
amino acids
Amino Acids
calcium chlorides
Calcium Chloride
Nucleophiles
Proton transfer
Photosystem II Protein Complex
protons
nucleophiles
entry
attack
suggestion
Arginine

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Structure-based mechanism of photosynthetic water oxidation. / McEvoy, James P.; Brudvig, Gary W.

In: Physical Chemistry Chemical Physics, Vol. 6, No. 20, 21.10.2004, p. 4754-4763.

Research output: Contribution to journalArticle

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