2024
Occupancy Analysis of Water Molecules inside Channels within 25 Å Radius of the Oxygen-Evolving Center of Photosystem II in Molecular Dynamics Simulations
Kaur D, Reiss K, Wang J, Batista V, Brudvig G, Gunner M. Occupancy Analysis of Water Molecules inside Channels within 25 Å Radius of the Oxygen-Evolving Center of Photosystem II in Molecular Dynamics Simulations. The Journal Of Physical Chemistry B 2024, 128: 2236-2248. PMID: 38377592, DOI: 10.1021/acs.jpcb.3c05367.Peer-Reviewed Original ResearchOxygen-evolving centerWater moleculesPhotosystem IIPositions of water moleculesAnalysis of water moleculesCatalyze water oxidationHydrogen bond networkOccupancy of water moleculesMolecular dynamics simulationsD1-D61Electron density mapsMolecular dynamics analysisProton transferWater oxidationCrystallographic dataIce latticeMD simulationsMolecular dynamicsStructural transitionDynamics simulationsSubstrate waterOxygen-evolvingRoom temperatureProtein residuesMolecules
2015
Triplet 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
2013
Water oxidation chemistry of photosystem II
Brudvig G. Water oxidation chemistry of photosystem II. The FASEB Journal 2013, 27: 98.1-98.1. DOI: 10.1096/fasebj.27.1_supplement.98.1.Peer-Reviewed Original ResearchOxygen-evolving complexWater oxidation chemistryOxidation chemistryCrystal structurePhotosystem IISubstrate water moleculesRedox-active tyrosinesX-ray crystal structureFour-electron oxidationIntermediate oxidation statesSolar fuel productionSignificant side reactionsSpecific redox stateCyanobacterial photosystem IIDesign of materialsInorganic chemistryX-ray crystallographic informationRedox stateOxidation stateWater moleculesCatalytic cycleENDOR spectroscopySide reactionsChemical problemsSpectroscopic data
2008
Quantum Mechanics/Molecular Mechanics Study of the Catalytic Cycle of Water Splitting in Photosystem II
Sproviero EM, Gascón JA, McEvoy JP, Brudvig GW, Batista VS. Quantum Mechanics/Molecular Mechanics Study of the Catalytic Cycle of Water Splitting in Photosystem II. Journal Of The American Chemical Society 2008, 130: 3428-3442. PMID: 18290643, DOI: 10.1021/ja076130q.Peer-Reviewed Original ResearchConceptsSubstrate water moleculesWater moleculesMu-oxo bridgeOxygen-evolving complexWater splittingQuantum mechanics/molecular mechanics (QM/MM) hybrid methodsQuantum Mechanics/Molecular Mechanics StudySolar fuel production systemsPhotosystem IIX-ray diffraction structureMolecular mechanics studySecond coordination shellCyanobacterium Thermosynechococcus elongatusOxomanganese clusterDioxygen evolutionTerminal ligandsXRD structureCatalytic clustersCP43-R357Ligand exchangeCatalytic reactionCatalytic cycleReaction intermediatesS0 stateNucleophilic attack
2004
Structure-based mechanism of photosynthetic water oxidation
McEvoy J, Brudvig G. Structure-based mechanism of photosynthetic water oxidation. Physical Chemistry Chemical Physics 2004, 6: 4754-4763. DOI: 10.1039/b407500e.Peer-Reviewed Original ResearchOxygen-evolving complexO bond-forming stepSubstrate water moleculesX-ray crystal structureBond-forming stepPhotosynthetic water oxidationWater splitting reactionResolution X-ray crystal structureCyanobacterial photosystem IIÅ resolution X-ray crystal structureCP43-Arg357Water oxidationStructure-based mechanismWater moleculesCertain amino acid residuesAmino acid residuesCrystal structureMechanistic functionPhotosystem IIArginine residuesCrystallographic informationLends weightResiduesNucleophilesOxidation
2002
Water oxidation chemistry of photosystem II
Vrettos J, Brudvig G. Water oxidation chemistry of photosystem II. Philosophical Transactions Of The Royal Society B Biological Sciences 2002, 357: 1395-1405. PMID: 12437878, PMCID: PMC1693042, DOI: 10.1098/rstb.2002.1136.Peer-Reviewed Original ResearchConceptsManganese clusterProton-coupled electron transfer stepsO bond-forming stepPhotosystem IIWater oxidation chemistryBond-forming stepElectron transfer stepFour-electron oxidationTetranuclear manganese clusterOxidation chemistryWater moleculesModel chemistryO bondNucleophilic attackIon selectivityBiophysical studiesChemistryCalcium sitesOxidationSpecific roleModel systemComplexesHis190Recent studiesWater
2001
Quantifying the Ion Selectivity of the Ca2+ Site in Photosystem II: Evidence for Direct Involvement of Ca2+ in O2 Formation †
Vrettos J, Stone D, Brudvig G. Quantifying the Ion Selectivity of the Ca2+ Site in Photosystem II: Evidence for Direct Involvement of Ca2+ in O2 Formation †. Biochemistry 2001, 40: 7937-7945. PMID: 11425322, DOI: 10.1021/bi010679z.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexTrivalent metal ionsMetal ionsPSII samplesPhotosystem IISubstrate water moleculesSmall metal ionsO2 evolutionSteady-state enzyme kineticsWater oxidationAqua ionsWater moleculesLewis acidO2 formationIonic radiusIon selectivityKcal/Monovalent ionsIonsExtrinsic polypeptidesFree energyEnzyme kineticsStructural cofactorSr2Activity measurementsMechanism of photosynthetic water oxidation: combining biophysical studies of photosystem II with inorganic model chemistry
Vrettos J, Limburg J, Brudvig G. Mechanism of photosynthetic water oxidation: combining biophysical studies of photosystem II with inorganic model chemistry. Biochimica Et Biophysica Acta 2001, 1503: 229-245. PMID: 11115636, DOI: 10.1016/s0005-2728(00)00214-0.Peer-Reviewed Original ResearchMeSH KeywordsCrystallographyElectron TransportHemerythrinHydrogen-Ion ConcentrationKineticsManganeseModels, ChemicalModels, MolecularOrganometallic CompoundsOxidation-ReductionOxygenPhotosynthesisPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexProtonsThylakoidsTyrosineWaterConceptsPhotosynthetic water oxidationWater oxidationOxygen-evolving complexProton-coupled electron transferTetranuclear manganese clusterMu-oxo bridgePhotosystem IIReduction of manganeseOOH speciesWater moleculesElectron transferModel chemistryManganese clusterNucleophilic attackDiferric siteFerric hydroperoxideOxidationD1 polypeptideBiophysical studiesOxyhemerythrinBiophysical resultsStructural modelDioxygenChemistryProtonation
1999
A mechanistic and structural model for the formation and reactivity of a MnV[double bond, length half m-dash]O species in photosynthetic water oxidation
Limburg J, Szalai V, Brudvig G. A mechanistic and structural model for the formation and reactivity of a MnV[double bond, length half m-dash]O species in photosynthetic water oxidation. Dalton Transactions 1999, 0: 1353-1362. DOI: 10.1039/a807583b.Peer-Reviewed Original ResearchProtein complex photosystem IIPhotosynthetic water oxidationWater oxidationMn4 clusterModel complexesO bond-forming stepO bond-forming reactionsRedox-active tyrosine residueSubstrate water moleculesBond-forming reactionsO bond formationBond-forming stepHydrogen bond networkTetranuclear Mn clusterElectrophilic oxygen atomHydroxide ligandMnO speciesOrganic oxidationLength halfWater moleculesObserved reactivityBond formationNucleophilic attackOxygen atomsKey intermediate