Computational insights into the O2-evolving complex of photosystem II

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

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the exact configuration of the catalytic metal cluster and its ligation scheme. Computational modeling studies, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly including the influence of the surrounding protein, have proposed chemically satisfactory models of the fully ligated OEC within PSII that are maximally consistent with experimental results. The inorganic core of these models is similar to the crystallographic model upon which they were based, but comprises important modifications due to structural refinement, hydration, and proteinaceous ligation which improve agreement with a wide range of experimental data. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting in PSII as described by the intermediate oxidation states of the OEC. This review summarizes these recent advances in QM/MM modeling of PSII within the context of recent experimental studies.

Original languageEnglish
Pages (from-to)91-114
Number of pages24
JournalPhotosynthesis Research
Volume97
Issue number1
DOIs
Publication statusPublished - Jul 2008

Fingerprint

Photosystem II Protein Complex
Mechanics
photosystem II
oxygen evolving complex
Oxygen
Molecular mechanics
Quantum theory
Ligation
Spectrum Analysis
Extended X ray absorption fine structure spectroscopy
mechanics
Mutagenesis
Water
Electron Spin Resonance Spectroscopy
Fourier Transform Infrared Spectroscopy
X-Ray Diffraction
Hydration
Density functional theory
Mass spectrometry
Paramagnetic resonance

Keywords

  • Density functional theory (DFT)
  • Oxomanganese complexes
  • Oxygen evolution
  • Oxygen evolving center
  • Photosynthesis
  • Photosystem II
  • Quantum mechanics/molecular mechanics (QM/MM)
  • Water oxidation

ASJC Scopus subject areas

  • Plant Science
  • Cell Biology
  • Biochemistry

Cite this

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

In: Photosynthesis Research, Vol. 97, No. 1, 07.2008, p. 91-114.

Research output: Contribution to journalArticle

Sproviero, Eduardo M. ; McEvoy, James P. ; Gascón, José A. ; Brudvig, Gary W ; Batista, Victor S. / Computational insights into the O2-evolving complex of photosystem II. In: Photosynthesis Research. 2008 ; Vol. 97, No. 1. pp. 91-114.
@article{78e99078b96e47a1a66cff457352bf54,
title = "Computational insights into the O2-evolving complex of photosystem II",
abstract = "Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the exact configuration of the catalytic metal cluster and its ligation scheme. Computational modeling studies, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly including the influence of the surrounding protein, have proposed chemically satisfactory models of the fully ligated OEC within PSII that are maximally consistent with experimental results. The inorganic core of these models is similar to the crystallographic model upon which they were based, but comprises important modifications due to structural refinement, hydration, and proteinaceous ligation which improve agreement with a wide range of experimental data. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting in PSII as described by the intermediate oxidation states of the OEC. This review summarizes these recent advances in QM/MM modeling of PSII within the context of recent experimental studies.",
keywords = "Density functional theory (DFT), Oxomanganese complexes, Oxygen evolution, Oxygen evolving center, Photosynthesis, Photosystem II, Quantum mechanics/molecular mechanics (QM/MM), Water oxidation",
author = "Sproviero, {Eduardo M.} and McEvoy, {James P.} and Gasc{\'o}n, {Jos{\'e} A.} and Brudvig, {Gary W} and Batista, {Victor S.}",
year = "2008",
month = "7",
doi = "10.1007/s11120-008-9307-0",
language = "English",
volume = "97",
pages = "91--114",
journal = "Photosynthesis Research",
issn = "0166-8595",
publisher = "Springer Netherlands",
number = "1",

}

TY - JOUR

T1 - Computational insights into the O2-evolving complex of photosystem II

AU - Sproviero, Eduardo M.

AU - McEvoy, James P.

AU - Gascón, José A.

AU - Brudvig, Gary W

AU - Batista, Victor S.

PY - 2008/7

Y1 - 2008/7

N2 - Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the exact configuration of the catalytic metal cluster and its ligation scheme. Computational modeling studies, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly including the influence of the surrounding protein, have proposed chemically satisfactory models of the fully ligated OEC within PSII that are maximally consistent with experimental results. The inorganic core of these models is similar to the crystallographic model upon which they were based, but comprises important modifications due to structural refinement, hydration, and proteinaceous ligation which improve agreement with a wide range of experimental data. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting in PSII as described by the intermediate oxidation states of the OEC. This review summarizes these recent advances in QM/MM modeling of PSII within the context of recent experimental studies.

AB - Mechanistic investigations of the water-splitting reaction of the oxygen-evolving complex (OEC) of photosystem II (PSII) are fundamentally informed by structural studies. Many physical techniques have provided important insights into the OEC structure and function, including X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy as well as mass spectrometry (MS), electron paramagnetic resonance (EPR) spectroscopy, and Fourier transform infrared spectroscopy applied in conjunction with mutagenesis studies. However, experimental studies have yet to yield consensus as to the exact configuration of the catalytic metal cluster and its ligation scheme. Computational modeling studies, including density functional (DFT) theory combined with quantum mechanics/molecular mechanics (QM/MM) hybrid methods for explicitly including the influence of the surrounding protein, have proposed chemically satisfactory models of the fully ligated OEC within PSII that are maximally consistent with experimental results. The inorganic core of these models is similar to the crystallographic model upon which they were based, but comprises important modifications due to structural refinement, hydration, and proteinaceous ligation which improve agreement with a wide range of experimental data. The computational models are useful for rationalizing spectroscopic and crystallographic results and for building a complete structure-based mechanism of water-splitting in PSII as described by the intermediate oxidation states of the OEC. This review summarizes these recent advances in QM/MM modeling of PSII within the context of recent experimental studies.

KW - Density functional theory (DFT)

KW - Oxomanganese complexes

KW - Oxygen evolution

KW - Oxygen evolving center

KW - Photosynthesis

KW - Photosystem II

KW - Quantum mechanics/molecular mechanics (QM/MM)

KW - Water oxidation

UR - http://www.scopus.com/inward/record.url?scp=48549102241&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=48549102241&partnerID=8YFLogxK

U2 - 10.1007/s11120-008-9307-0

DO - 10.1007/s11120-008-9307-0

M3 - Article

VL - 97

SP - 91

EP - 114

JO - Photosynthesis Research

JF - Photosynthesis Research

SN - 0166-8595

IS - 1

ER -