Oxomanganese complexes for natural and artificial photosynthesis

Ivan Rivalta, Gary W Brudvig, Victor S. Batista

Research output: Contribution to journalArticle

56 Citations (Scopus)

Abstract

The oxygen-evolving complex (OEC) of Photosystem II (PSII) is an oxomanganese complex that catalyzes water-splitting into O 2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9Å resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S 1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn 3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H 2O(terpy)Mn III(μ-O) 2Mn IV(terpy)OH 2] 3+ (1, terpy=2,2':6',2'-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO 2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO 2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.

Original languageEnglish
Pages (from-to)11-18
Number of pages8
JournalCurrent Opinion in Chemical Biology
Volume16
Issue number1-2
DOIs
Publication statusPublished - Apr 2012

Fingerprint

Photosynthesis
Oxygen
Mechanics
Protons
Electrons
Molecular mechanics
Photosystem II Protein Complex
Photoexcitation
Quantum theory
X ray crystallography
X Ray Crystallography
Molecular Dynamics Simulation
Coulomb interactions
Static Electricity
Ligation
Molecular dynamics
Chlorides
X-Rays
Light
X rays

ASJC Scopus subject areas

  • Biochemistry
  • Analytical Chemistry

Cite this

Oxomanganese complexes for natural and artificial photosynthesis. / Rivalta, Ivan; Brudvig, Gary W; Batista, Victor S.

In: Current Opinion in Chemical Biology, Vol. 16, No. 1-2, 04.2012, p. 11-18.

Research output: Contribution to journalArticle

Rivalta, Ivan ; Brudvig, Gary W ; Batista, Victor S. / Oxomanganese complexes for natural and artificial photosynthesis. In: Current Opinion in Chemical Biology. 2012 ; Vol. 16, No. 1-2. pp. 11-18.
@article{6fb28e22fb2e45b49b34d4926b8aad6b,
title = "Oxomanganese complexes for natural and artificial photosynthesis",
abstract = "The oxygen-evolving complex (OEC) of Photosystem II (PSII) is an oxomanganese complex that catalyzes water-splitting into O 2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9{\AA} resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S 1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn 3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H 2O(terpy)Mn III(μ-O) 2Mn IV(terpy)OH 2] 3+ (1, terpy=2,2':6',2'-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO 2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO 2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.",
author = "Ivan Rivalta and Brudvig, {Gary W} and Batista, {Victor S.}",
year = "2012",
month = "4",
doi = "10.1016/j.cbpa.2012.03.003",
language = "English",
volume = "16",
pages = "11--18",
journal = "Current Opinion in Chemical Biology",
issn = "1367-5931",
publisher = "Elsevier Limited",
number = "1-2",

}

TY - JOUR

T1 - Oxomanganese complexes for natural and artificial photosynthesis

AU - Rivalta, Ivan

AU - Brudvig, Gary W

AU - Batista, Victor S.

PY - 2012/4

Y1 - 2012/4

N2 - The oxygen-evolving complex (OEC) of Photosystem II (PSII) is an oxomanganese complex that catalyzes water-splitting into O 2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9Å resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S 1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn 3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H 2O(terpy)Mn III(μ-O) 2Mn IV(terpy)OH 2] 3+ (1, terpy=2,2':6',2'-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO 2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO 2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.

AB - The oxygen-evolving complex (OEC) of Photosystem II (PSII) is an oxomanganese complex that catalyzes water-splitting into O 2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9Å resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S 1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn 3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H 2O(terpy)Mn III(μ-O) 2Mn IV(terpy)OH 2] 3+ (1, terpy=2,2':6',2'-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO 2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO 2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.

UR - http://www.scopus.com/inward/record.url?scp=84859640184&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84859640184&partnerID=8YFLogxK

U2 - 10.1016/j.cbpa.2012.03.003

DO - 10.1016/j.cbpa.2012.03.003

M3 - Article

VL - 16

SP - 11

EP - 18

JO - Current Opinion in Chemical Biology

JF - Current Opinion in Chemical Biology

SN - 1367-5931

IS - 1-2

ER -