QM/MM models of the O2-evolving complex of photosystem II

Eduardo M. Sproviero, José A. Gascón, James P. McEvoy, Gary W Brudvig, Victor S. Batista

Research output: Contribution to journalArticle

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Abstract

This paper introduces structural models of the oxygen-evolving complex of photosystem II (PSII) in the dark-stable S1 state, as well as in the reduced S0 and oxidized S2 states, with complete ligation of the metal-oxo cluster by amino acid residues, water, hydroxide, and chloride. The models are developed according to state-of-the-art quantum mechanics/molecular mechanics (QM/MM) hybrid methods, applied in conjunction with the X-ray crystal structure of PSII from the cyanobacterium Thermosynechococcus elongatus, recently reported at 3.5 Å resolution. Manganese and calcium ions are ligated consistently with standard coordination chemistry assumptions, supported by biochemical and spectroscopic data. Furthermore, the calcium-bound chloride ligand is found to be bound in a position consistent with pulsed electron paramagnetic resonance data obtained from acetate-substituted PSII. The ligation of protein ligands includes monodentate coordination of D1-D342, CP43-E354, and D1-D170 to Mn(1), Mn(3), and Mn(4), respectively; η2 coordination of D1-E333 to both Mn(3) and Mn(2); and ligation of D1-E189 and D1-H332 to Mn(2). The resulting QM/MM structural models are consistent with available mechanistic data and also are compatible with X-ray diffraction models and extended X-ray absorption fine structure measurements of PSII. It is, therefore, conjectured that the proposed QM/MM models are particularly relevant to the development and validation of catalytic water-oxidation intermediates.

Original languageEnglish
Pages (from-to)1119-1134
Number of pages16
JournalJournal of Chemical Theory and Computation
Volume2
Issue number4
DOIs
Publication statusPublished - 2006

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Molecular mechanics
Photosystem II Protein Complex
Quantum theory
quantum mechanics
Chlorides
calcium
Calcium
chlorides
Ligands
manganese ions
ligands
x rays
Water
X ray absorption
metal clusters
Manganese
water
hydroxides
Paramagnetic resonance
amino acids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

QM/MM models of the O2-evolving complex of photosystem II. / Sproviero, Eduardo M.; Gascón, José A.; McEvoy, James P.; Brudvig, Gary W; Batista, Victor S.

In: Journal of Chemical Theory and Computation, Vol. 2, No. 4, 2006, p. 1119-1134.

Research output: Contribution to journalArticle

Sproviero, Eduardo M. ; Gascón, José A. ; McEvoy, James P. ; Brudvig, Gary W ; Batista, Victor S. / QM/MM models of the O2-evolving complex of photosystem II. In: Journal of Chemical Theory and Computation. 2006 ; Vol. 2, No. 4. pp. 1119-1134.
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