TY - JOUR
T1 - Oxomanganese complexes for natural and artificial photosynthesis
AU - Rivalta, Ivan
AU - Brudvig, Gary W.
AU - Batista, Victor S.
N1 - Funding Information:
V.S.B. acknowledges financial support from the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy ( DE-SC000-1423 ), and supercomputer time from National Energy Research Scientific Computing. NIH grants GM84267 and GM043278 supported the development of methods implemented in the studies. Studies of oxomanganese complexes for artificial photosynthesis were supported by the Office of Basic Energy Sciences of the U.S. Department of Energy ( DE-FG02-07ER15909 ). G.W.B. acknowledges support from NIH Grant GM32715 and U.S. Department of Energy grant DE-FG02-05ERI5646 for work on PSII.
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.
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U2 - 10.1016/j.cbpa.2012.03.003
DO - 10.1016/j.cbpa.2012.03.003
M3 - Review article
C2 - 22481113
AN - SCOPUS:84859640184
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 -