2015
Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18O Kinetic Isotope Effects
Khan S, Yang K, Ertem M, Batista V, Brudvig G. Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18O Kinetic Isotope Effects. ACS Catalysis 2015, 5: 7104-7113. DOI: 10.1021/acscatal.5b01976.Peer-Reviewed Original ResearchBiomimetic oxomanganese complexesO2 evolutionOxomanganese complexesElusive reaction intermediatesKinetic oxygen isotope effectO2-evolving complexPhotosystem IIFirst bindsTurnover conditionsPrevious kinetic studiesComplexesOxygen evolutionComplete mechanismEvolutionMechanismSpeciesBindsStrong evidenceIntermediatesTurnoverHighest barrier stepKinetic isotope effectsTriplet Oxygen Evolution Catalyzed by a Biomimetic Oxomanganese Complex: Functional Role of the Carboxylate Buffer
Rivalta I, Yang K, Brudvig G, Batista V. Triplet Oxygen Evolution Catalyzed by a Biomimetic Oxomanganese Complex: Functional Role of the Carboxylate Buffer. ACS Catalysis 2015, 5: 2384-2390. DOI: 10.1021/acscatal.5b00048.Peer-Reviewed Original ResearchOxomanganese complexesTriplet oxygenOxygen evolutionWater splittingCatalytic oxygen evolutionO bond formationBiomimetic oxomanganese complexesNucleophilic water moleculeUnderlying reaction mechanismGreen plant chloroplastsPhotosynthetic oxygen evolutionWater ligandsCarboxylate ligandsInorganic coreMn complexesSuperoxo speciesNoninnocent roleCarboxylate groupsWater moleculesSubstrate waterBond formationSynthetic complexesCarboxylate buffersNucleophilic attackRedox potential
2014
Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis
Rivalta I, Brudvig G, Batista V. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis. 2014, 1-14. DOI: 10.1002/9781118698648.ch1.Peer-Reviewed Original ResearchOxygen-evolving complexBiomimetic oxomanganese complexesOxomanganese complexesDensity functional theoryQuantum mechanics/molecular mechanics (QM/MM) hybrid methodsHigh-resolution spectroscopyPhotosystem IIStructure of PSIIX-ray absorption fine structure spectraX-ray radiationExtended X-ray absorption fine structure (EXAFS) spectraProteinaceous side chainsWater oxidation catalysisArtificial photosynthetic devicesFine structure spectraO bond formationWater splitting mechanismX-ray crystallographyOxomanganese clusterResolution spectroscopyX-ray diffraction dataSemiconductor surfacesOxidation catalysisPhotosynthetic devicesX-ray model
2013
Electrostatic Effects on Proton Coupled Electron Transfer in Oxomanganese Complexes Inspired by the Oxygen-Evolving Complex of Photosystem II
Amin M, Vogt L, Vassiliev S, Rivalta I, Sultan MM, Bruce D, Brudvig GW, Batista VS, Gunner MR. Electrostatic Effects on Proton Coupled Electron Transfer in Oxomanganese Complexes Inspired by the Oxygen-Evolving Complex of Photosystem II. The Journal Of Physical Chemistry B 2013, 117: 6217-6226. PMID: 23570540, PMCID: PMC3753004, DOI: 10.1021/jp403321b.Peer-Reviewed Original ResearchConceptsOxomanganese complexesElectron transferOxygen-evolving complexComplexes 6Electrostatic effectsΜ-oxo bridgeDensity functional theory levelTerminal water ligandsBiomimetic oxomanganese complexesPhotosystem IIOxidation state transitionsContinuum electrostatic modelWater ligandsLigand substituentsOxidation midpoint potentialsOxo bridgeCalculated pKaProton transferElectrostatic interactionsTheory levelElectrostatic contributionMidpoint potentialMn oxidationElectrostatic modelFree energyComputational Studies of the Oxygen-Evolving Complex of Photosystem II and Biomimetic Oxomanganese Complexes for Renewable Energy Applications
Rivalta I, Brudvig G, Batista V. Computational Studies of the Oxygen-Evolving Complex of Photosystem II and Biomimetic Oxomanganese Complexes for Renewable Energy Applications. ACS Symposium Series 2013, 1133: 203-215. DOI: 10.1021/bk-2013-1133.ch011.Peer-Reviewed Original Research
2012
Oxomanganese complexes for natural and artificial photosynthesis
Rivalta I, Brudvig GW, Batista VS. Oxomanganese complexes for natural and artificial photosynthesis. Current Opinion In Chemical Biology 2012, 16: 11-18. PMID: 22481113, PMCID: PMC3335890, DOI: 10.1016/j.cbpa.2012.03.003.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexOxomanganese complexesArtificial photosynthesisQuantum mechanics/molecular mechanics (QM/MM) hybrid methodsArtificial photosynthetic devicesVisible-light photoexcitationInterfacial electron transferRecent X-ray dataX-ray crystallographyPhotosystem IIPhotosynthetic devicesMn catalystStructure/function relationsX-ray dataCarboxylate moietyElectron transferProton abstractionMn centersChromophoric linkersElectrostatic interactionsOEC structureCovalent attachmentS1 stateOxygen evolutionInexpensive materials
2010
Study of Proton Coupled Electron Transfer in a Biomimetic Dimanganese Water Oxidation Catalyst with Terminal Water Ligands
Wang T, Brudvig GW, Batista VS. Study of Proton Coupled Electron Transfer in a Biomimetic Dimanganese Water Oxidation Catalyst with Terminal Water Ligands. Journal Of Chemical Theory And Computation 2010, 6: 2395-2401. PMID: 20827389, PMCID: PMC2935188, DOI: 10.1021/ct1002658.Peer-Reviewed Original ResearchTerminal water ligandsWater ligandsOxomanganese complexesElectron transferRedox potentialProton Coupled Electron TransferWater oxidation catalystsCyclic voltammogram measurementsLewis base moietyOxidation of waterFree energy calculationsInorganic coreOxidation potentialOxidation statePrimary oxidantOxidation catalystMn centersBase moietyEnergy calculationsBiomimetic modelLigandsAnalogous conversionOxidationFree energyPhotosystem IICharacterization of Proton Coupled Electron Transfer in a Biomimetic Oxomanganese Complex: Evaluation of the DFT B3LYP Level of Theory
Wang T, Brudvig G, Batista VS. Characterization of Proton Coupled Electron Transfer in a Biomimetic Oxomanganese Complex: Evaluation of the DFT B3LYP Level of Theory. Journal Of Chemical Theory And Computation 2010, 6: 755-760. PMID: 20607115, PMCID: PMC2896228, DOI: 10.1021/ct900615b.Peer-Reviewed Original ResearchOxygen-evolving complexDensity functional theoryRedox processesElectron transferOEC of PSIIRedox potentialProton Coupled Electron TransferSolution magnetic susceptibilityCyclic voltammogram measurementsBiomimetic oxomanganese complexesPhotosystem IIOxidation state transitionsDFT-B3LYP levelBecke-3-LeeFree energy calculationsContinuum solvation modelOxomanganese complexesWater ligandsWater oxidationIR spectroscopyOxo bridgeOxidation stateB3LYP levelDi-muSolvation model
2008
Computational studies of the O2-evolving complex of photosystem II and biomimetic oxomanganese complexes
Sproviero EM, Gascón JA, McEvoy JP, Brudvig GW, Batista VS. Computational studies of the O2-evolving complex of photosystem II and biomimetic oxomanganese complexes. Coordination Chemistry Reviews 2008, 252: 395-415. PMID: 19190716, PMCID: PMC2350217, DOI: 10.1016/j.ccr.2007.09.006.Peer-Reviewed Original ResearchBiomimetic oxomanganese complexesOxygen-evolving complexOxomanganese complexesWater oxidationPhotosystem IIQuantum mechanics/molecular mechanics (QM/MM) hybrid methodsCatalytic centerQM/MM modelCatalytic metal clustersPhotosynthetic water oxidationX-ray crystallographyX-ray absorption fine structure measurementsAbsorption fine structure measurementsQuantum mechanical studyO2-evolving complexX-ray diffraction dataAmino acid residuesExtended X-ray absorption fine structure (EXAFS) measurementsDetailed molecular levelComputational chemistsWater splittingCatalytic cycleComparative quantum mechanical studyMetal clustersFine structure measurements
2006
Characterization of synthetic oxomanganese complexes and the inorganic core of the O2-evolving complex in photosystem II: Evaluation of the DFT/B3LYP level of theory
Sproviero EM, Gascon JA, McEvoy JP, Brudvig GW, Batista VS. Characterization of synthetic oxomanganese complexes and the inorganic core of the O2-evolving complex in photosystem II: Evaluation of the DFT/B3LYP level of theory. Journal Of Inorganic Biochemistry 2006, 100: 786-800. PMID: 16510187, DOI: 10.1016/j.jinorgbio.2006.01.017.Peer-Reviewed Original ResearchConceptsDFT/B3LYP levelOxomanganese complexesDFT/B3LYPB3LYP levelDensity functional theory (DFT) B3LYP levelBecke-3-LeeOxygen-evolving complexPhotosystem IISpin electronic statesInorganic coreImidazole ligandsMn complexesMu-oxoMagnetic experimental dataElectronic propertiesModest basis setsBasis setHybrid densityMechanistic studiesMn trimersComplexesMagnetic propertiesB3LYPTetramerBenchmark calculations