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
2006
Water-Splitting Chemistry of Photosystem II
McEvoy JP, Brudvig GW. Water-Splitting Chemistry of Photosystem II. Chemical Reviews 2006, 106: 4455-4483. PMID: 17091926, DOI: 10.1021/cr0204294.Peer-Reviewed Original Research
2005
The mechanism of photosynthetic water splitting
McEvoy J, Gascon J, Batista V, Brudvig G. The mechanism of photosynthetic water splitting. Photochemical & Photobiological Sciences 2005, 4: 940-949. PMID: 16307106, DOI: 10.1039/b506755c.Peer-Reviewed Original ResearchConceptsProtein complex photosystem IIOxygen-evolving complexWater splittingPhotosynthetic water splittingGreen plant chloroplastsMolecular mechanics calculationsPhotosynthetic light reactionsRecent experimental resultsElectron transfer pathwayX-ray crystallographic modelSource of electronsProton concentration gradientPlant chloroplastsProduct protonsMechanics calculationsOxygenic photosynthesisDioxygen gasThylakoid lumenAerobic lifeElectronsThylakoid membranesCatalytic mechanismChemical energyPhotosystem IIManganese ionsNew Linear High-Valent Tetranuclear Manganese-Oxo Cluster Relevant to the Oxygen-Evolving Complex of Photosystem II with Oxo, Hydroxo, and Aqua Coordinated to a Single Mn(IV)
Chen, Collomb M, Duboc C, Blondin G, Rivière E, Faller J, Crabtree R, Brudvig G. New Linear High-Valent Tetranuclear Manganese-Oxo Cluster Relevant to the Oxygen-Evolving Complex of Photosystem II with Oxo, Hydroxo, and Aqua Coordinated to a Single Mn(IV). Inorganic Chemistry 2005, 44: 9567-9573. PMID: 16323946, DOI: 10.1021/ic051462m.Peer-Reviewed Original ResearchConceptsGround stateSpin statesFirst excited spin stateExcited spin statesSpin-triplet stateLarge energy gapOxygen-Evolving ComplexMn–Mn distanceDiamagnetic ground stateEnergy gapVariable-temperature magnetic susceptibility dataX-ray powder diffractionTriplet stateMagnetic susceptibility dataTetranuclear manganeseMnIV ionsGeneral Synthesis of Di-μ-oxo Dimanganese Complexes as Functional Models for the Oxygen Evolving Complex of Photosystem II
Chen H, Tagore R, Das S, Incarvito C, Faller J, Crabtree R, Brudvig G. General Synthesis of Di-μ-oxo Dimanganese Complexes as Functional Models for the Oxygen Evolving Complex of Photosystem II. Inorganic Chemistry 2005, 44: 7661-7670. PMID: 16212393, DOI: 10.1021/ic0509940.Peer-Reviewed Original ResearchConceptsDimanganese complexesCatalytic activitySeries of complexesGeneral preparative methodUV-visible spectroscopyElectrospray mass spectrometryOxygen-Evolving ComplexX-ray crystallographyPhotosystem IIParent complexEPR spectroscopyOxygen-evolving activityGeneral synthesisPreparative methodLigand librariesMass spectrometryHigh product purityComplexesMn dimersSpectroscopyProduct purityPrecursorsTerpyCrystallographyOxoConstruction and Characterization of Genetically Modified Synechocystis sp. PCC 6803 Photosystem II Core Complexes Containing Carotenoids with Shorter π-Conjugation than β-Carotene*
Bautista J, Tracewell C, Schlodder E, Cunningham F, Brudvig G, Diner B. Construction and Characterization of Genetically Modified Synechocystis sp. PCC 6803 Photosystem II Core Complexes Containing Carotenoids with Shorter π-Conjugation than β-Carotene*. Journal Of Biological Chemistry 2005, 280: 38839-38850. PMID: 16159754, DOI: 10.1074/jbc.m504953200.Peer-Reviewed Original ResearchMeSH KeywordsBeta CaroteneCarotenoidsCationsChlorophyllChromatographyChromatography, High Pressure LiquidElectronsGene DeletionLightManganeseModels, ChemicalModels, MolecularMutationOxidation-ReductionOxidoreductasesOxygenPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexPigmentationRhodobacter capsulatusSpectrophotometrySpectrophotometry, InfraredSynechocystisTemperatureTime FactorsTyrosineConceptsPhytoene desaturase geneII core complexesDesaturase genePS II core complexesSynechocystis spCore complexPS II assemblyCarotene desaturase genePhotosystem II core complexPCC 6803Rhodobacter capsulatusWild typeMutant strainRedox functionPhotosystem IISecondary electron transfer pathwayGenesElectron transfer pathwayLight-induced formationCarotenoidsSpChlorophyllConjugated pi-electron systemPathwayComplexes
2004
Dimer-of-Dimers Model for the Oxygen-Evolving Complex of Photosystem II. Synthesis and Properties of [MnIV 4O5(terpy)4(H2O)2](ClO4)6
Chen H, Faller J, Crabtree R, Brudvig G. Dimer-of-Dimers Model for the Oxygen-Evolving Complex of Photosystem II. Synthesis and Properties of [MnIV 4O5(terpy)4(H2O)2](ClO4)6. Journal Of The American Chemical Society 2004, 126: 7345-7349. PMID: 15186173, DOI: 10.1021/ja037389l.Peer-Reviewed Original Research
2003
Raman spectra and normal coordinate analyses of low-frequency vibrations of oxo-bridged manganese complexes
Cua A, Vrettos J, de Paula J, Brudvig G, Bocian D. Raman spectra and normal coordinate analyses of low-frequency vibrations of oxo-bridged manganese complexes. JBIC Journal Of Biological Inorganic Chemistry 2003, 8: 439-451. PMID: 12761665, DOI: 10.1007/s00775-002-0433-4.Peer-Reviewed Original Research
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 measurementsEffects of tail‐like substituents on the binding of competitive inhibitors to the QB site of photosystem II
Reifler M, Szalai V, Peterson C, Brudvig G. Effects of tail‐like substituents on the binding of competitive inhibitors to the QB site of photosystem II. Journal Of Molecular Recognition 2001, 14: 157-165. PMID: 11391786, DOI: 10.1002/jmr.529.Peer-Reviewed Original ResearchConceptsQB siteAqueous phasePhotosystem IIBulk aqueous phaseCritical micelle concentrationTriazine-type herbicidesQuinone-binding sitePhenylurea moietyEffect of chargeAlkyl chainsHydrophobic tailSolvent conditionsMicelle concentrationPara positionPhenylurea compoundsS-triazineAlkylamino groupSubstituentsSmall libraryHydrophobic linkerMolecular rulerHydrophilic domainsNonspecific bindingChargeCompetitive inhibitorCarotenoid Photooxidation in Photosystem II
Tracewell C, Vrettos J, Bautista J, Frank H, Brudvig G. Carotenoid Photooxidation in Photosystem II. Archives Of Biochemistry And Biophysics 2001, 385: 61-69. PMID: 11361027, DOI: 10.1006/abbi.2000.2150.Peer-Reviewed Original ResearchConceptsPhotosystem IIElectron transfer reactionsPhotosynthetic reaction centersWater oxidationLight-harvesting pigmentsCarotenoid cationOxidizing intermediatesElectron transferRedox roleBacterial photosynthesisReaction centersPhysical methodsCationsPhotooxidationCarotenoid compositionRedoxOxidationIntermediatesAlternate pathwayCarotenoidsMinireviewReactionPhotoprotectionPossible rolePigmentsMechanism 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
2000
Characterization of the O2-Evolving Reaction Catalyzed by [(terpy)(H2O)MnIII(O)2MnIV(OH2)(terpy)](NO3)3 (terpy = 2,2‘:6,2‘ ‘-Terpyridine)
Limburg J, Vrettos J, Chen H, de Paula J, Crabtree R, Brudvig G. Characterization of the O2-Evolving Reaction Catalyzed by [(terpy)(H2O)MnIII(O)2MnIV(OH2)(terpy)](NO3)3 (terpy = 2,2‘:6,2‘ ‘-Terpyridine). Journal Of The American Chemical Society 2000, 123: 423-430. PMID: 11456544, DOI: 10.1021/ja001090a.Peer-Reviewed Original Research
1999
Orientation of the Tetranuclear Manganese Cluster and Tyrosine Z in the O2-Evolving Complex of Photosystem II: An EPR Study of the S2YZ • State in Oriented Acetate-Inhibited Photosystem II Membranes †
Lakshmi K, Eaton S, Eaton G, Brudvig G. Orientation of the Tetranuclear Manganese Cluster and Tyrosine Z in the O2-Evolving Complex of Photosystem II: An EPR Study of the S2YZ • State in Oriented Acetate-Inhibited Photosystem II Membranes †. Biochemistry 1999, 38: 12758-12767. PMID: 10504246, DOI: 10.1021/bi990780s.Peer-Reviewed Original ResearchCompetitive Binding of Acetate and Chloride in Photosystem II †
Kühne H, Szalai V, Brudvig G. Competitive Binding of Acetate and Chloride in Photosystem II †. Biochemistry 1999, 38: 6604-6613. PMID: 10350479, DOI: 10.1021/bi990341t.Peer-Reviewed Original ResearchA Functional Model for O-O Bond Formation by the O2-Evolving Complex in Photosystem II
Limburg J, Vrettos J, Liable-Sands L, Rheingold A, Crabtree R, Brudvig G. A Functional Model for O-O Bond Formation by the O2-Evolving Complex in Photosystem II. Science 1999, 283: 1524-1527. PMID: 10066173, DOI: 10.1126/science.283.5407.1524.Peer-Reviewed Original ResearchConceptsMolecular oxygenPhotosystem IIO bond formationPhotosynthetic water oxidationWater oxidationManganese dimerBond formationOxygen atomsActive siteIsotope labelingManganese ionsOxygenPhotosynthesisWaterSodium hypochloriteOxidationIonsFormationAtomsDimersComplexesO2Functional modelConversionHypochlorite
1998
Catalase-Free Photosystem II: The O2-Evolving Complex Does Not Dismutate Hydrogen Peroxide †
Sheptovitsky Y, Brudvig G. Catalase-Free Photosystem II: The O2-Evolving Complex Does Not Dismutate Hydrogen Peroxide †. Biochemistry 1998, 37: 5052-5059. PMID: 9548736, DOI: 10.1021/bi972872s.Peer-Reviewed Original Research
1997
Fluorescence Quenching by Chlorophyll Cations in Photosystem II †
Schweitzer R, Brudvig G. Fluorescence Quenching by Chlorophyll Cations in Photosystem II †. Biochemistry 1997, 36: 11351-11359. PMID: 9298954, DOI: 10.1021/bi9709203.Peer-Reviewed Original ResearchConceptsFluorescence quenchingPhotosystem IIElectron donorDonor sideElectron paramagnetic resonance spectroscopyRedox-active tyrosinesRedox-active centersCharge-separated stateSteady-state fluorescence quenchingParamagnetic resonance spectroscopyRedox-active componentsElectron donor sideElectron transfer pathwayCytochrome b559Redox stateFluorescence intensityO2-evolving complexPrimary electron donorReversible oxidationChlorophyll cationElectron donationFurther oxidationChlZRapid photooxidationDifferent sample preparation
1996
Isolation and Characterization of Spinach Photosystem II Membrane-Associated Catalase and Polyphenol Oxidase †
Sheptovitsky Y, Brudvig G. Isolation and Characterization of Spinach Photosystem II Membrane-Associated Catalase and Polyphenol Oxidase †. Biochemistry 1996, 35: 16255-16263. PMID: 8973199, DOI: 10.1021/bi9613842.Peer-Reviewed Original ResearchMeSH KeywordsAmino AcidsCatalaseCatechol OxidaseChloroplastsChromatography, High Pressure LiquidChromatography, Ion ExchangeCopperElectrophoresis, Polyacrylamide GelHot TemperatureIntracellular MembranesKineticsMolecular WeightOxygenOxygen ConsumptionPeptide MappingPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexSpectrophotometrySpinacia oleraceaSubstrate SpecificityConceptsPSII membranesCentre of PSIIUV-visible absorptionO2 evolution activityThylakoid membranesSpinach thylakoid membranesAnion-exchange chromatographyMembrane-associated catalaseHeme enzymesBatch adsorptionHeme catalasesMild heat treatmentHeat treatmentMolecular weightAnion-exchange beadsNative molecular weightPPOIrreversible aggregationGel filtrationFurther manipulationAdsorptionAmino acid compositionTriazoleMembraneChromatography