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 ResearchMolecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst
Das S, Incarvito CD, Crabtree RH, Brudvig GW. Molecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst. Science 2006, 312: 1941-1943. PMID: 16809537, DOI: 10.1126/science.1127899.Peer-Reviewed Original ResearchConceptsHydrogen bondingMolecular recognitionH bondsCarboxylic acid groupsMolecular recognition elementsSynthetic catalystsSaturated CKemp's triacidSelective oxygenationCOOH groupRegioselective functionalizationH activationHigh selectivityAcid groupsRecognition groupReactive centerRecognition elementCatalystTriacidOrient substratesSelectivityBondingBondsControl experimentsSubstrate
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 ResearchMeSH KeywordsComputer SimulationManganeseModels, MolecularOxidation-ReductionOxygenPhotosynthesisWaterConceptsProtein 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 ionsConstruction 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 systemPathwayComplexesHigh‐Spin Chloro Mononuclear MnIII Complexes: A Multifrequency High‐Field EPR Study
Mantel C, Chen H, Crabtree R, Brudvig G, Pécaut J, Collomb M, Duboc C. High‐Spin Chloro Mononuclear MnIII Complexes: A Multifrequency High‐Field EPR Study. ChemPhysChem 2005, 6: 541-546. PMID: 15799481, DOI: 10.1002/cphc.200400484.Peer-Reviewed Original ResearchConceptsElectronic propertiesLigand field strengthHigh-Field EPR StudyPorphyrinic systemsTridentate ligandMnIII complexesDistorted octahedronLigands decreasesSolid stateJahn-Teller distortionPrevious complexesStructural characterizationCrystallographic dataEPR studiesMultifrequency EPRManganese ionsComplexesOctahedraTetragonal distortionE termDifferent temperaturesAnionsEPRLigandsProperties
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 studiesWaterTwo New Terpyridine Dimanganese Complexes: A Manganese(III,III) Complex with a Single Unsupported Oxo Bridge and a Manganese(III,IV) Complex with a Dioxo Bridge. Synthesis, Structure, and Redox Properties
Baffert C, Collomb M, Deronzier A, Pécaut J, Limburg J, Crabtree R, Brudvig G. Two New Terpyridine Dimanganese Complexes: A Manganese(III,III) Complex with a Single Unsupported Oxo Bridge and a Manganese(III,IV) Complex with a Dioxo Bridge. Synthesis, Structure, and Redox Properties. Inorganic Chemistry 2002, 41: 1404-1411. PMID: 11896708, DOI: 10.1021/ic0107375.Peer-Reviewed Original ResearchConceptsOxo bridgeElectrochemical behaviorX-ray structureMononuclear complexesComplexes 4Oxo complexesRedox propertiesAqua complexesDimanganese complexesOrganic mediaTrans complexesCis geometrySolid stateDioxo bridgeTrans geometryCis complexesDisproportionation processTrans configurationCrystallographic formsComplexesMn atomsCisMonooxoLigandsSynthesis
2001
Mechanism 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
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 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
Characterization of the Interaction between Manganese and Tyrosine Z in Acetate-Inhibited Photosystem II †
Szalai V, Kühne H, Lakshmi K, Brudvig G. Characterization of the Interaction between Manganese and Tyrosine Z in Acetate-Inhibited Photosystem II †. Biochemistry 1998, 37: 13594-13603. PMID: 9753446, DOI: 10.1021/bi9813025.Peer-Reviewed Original ResearchCalcium Binding Studies of Photosystem II Using a Calcium-Selective Electrode †
Grove G, Brudvig G. Calcium Binding Studies of Photosystem II Using a Calcium-Selective Electrode †. Biochemistry 1998, 37: 1532-1539. PMID: 9484223, DOI: 10.1021/bi971356z.Peer-Reviewed Original Research
1997
The Tetranuclear Manganese Cluster in Photosystem II: Location and Magnetic Properties of the S2 State As Determined by Saturation−Recovery EPR Spectroscopy †
Koulougliotis D, Schweitzer R, Brudvig G. The Tetranuclear Manganese Cluster in Photosystem II: Location and Magnetic Properties of the S2 State As Determined by Saturation−Recovery EPR Spectroscopy †. Biochemistry 1997, 36: 9735-9746. PMID: 9245405, DOI: 10.1021/bi970326t.Peer-Reviewed Original ResearchConceptsFirst excited spin stateSpin-lattice relaxationSpin statesMagnetic propertiesExcited spin statesS2-state multiline EPRNuclear spin-lattice relaxationSpin-lattice relaxation propertiesEffective magnetic momentLine shapeUntreated photosystem IIMagnetic momentDifferent spin statesDipolar modelNear resonanceGround spin stateSaturation-recovery EPR spectroscopyNuclear relaxation processesLarmor frequencyOrbach mechanismGreater relaxation enhancementTemperature-dependent enhancementDipole-dipole interactionTetranuclear manganese clusterS2-state multiline EPR signal
1994
Location of chlorophyllZ in photosystem II.
Koulougliotis D, Innes J, Brudvig G. Location of chlorophyllZ in photosystem II. Biochemistry 1994, 33: 11814-22. PMID: 7918399, DOI: 10.1021/bi00205a018.Peer-Reviewed Original ResearchBacteriochlorophyllsChlorophyllCold TemperatureCyanidesDarknessDysprosiumEdetic AcidElectron Spin Resonance SpectroscopyIronLightLight-Harvesting Protein ComplexesManganeseMicrowavesModels, ChemicalOxidation-ReductionPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexSpinacia oleracea
1992
Using saturation-recovery EPR to measure distances in proteins: applications to photosystem II.
Hirsh D, Beck W, Innes J, Brudvig G. Using saturation-recovery EPR to measure distances in proteins: applications to photosystem II. Biochemistry 1992, 31: 532-41. PMID: 1310040, DOI: 10.1021/bi00117a033.Peer-Reviewed Original Research
1991
Mechanism of irreversible inhibition of O2 evolution in photosystem II by Tris(hydroxymethyl)aminomethane.
Rickert K, Sears J, Beck W, Brudvig G. Mechanism of irreversible inhibition of O2 evolution in photosystem II by Tris(hydroxymethyl)aminomethane. Biochemistry 1991, 30: 7888-94. PMID: 1651110, DOI: 10.1021/bi00246a003.Peer-Reviewed Original ResearchConceptsMn complexesPSII membranesRate of reactionO2 evolutionLow-temperature electron paramagnetic resonance (EPR) spectroscopyElectron paramagnetic resonance spectroscopyElectron donation reactionsPhotosystem IIElectron donation abilityParamagnetic resonance spectroscopyOxidation stateTris treatmentResonance spectroscopyS1 stateDark reactionTriIrreversible inhibitionReactionComplexesAminesIonsO2Effect of TrisMn2Spectroscopy
1990
Electron-transfer events leading to reconstitution of oxygen-evolution activity in manganese-depleted photosystem II membranes.
Miller A, Brudvig G. Electron-transfer events leading to reconstitution of oxygen-evolution activity in manganese-depleted photosystem II membranes. Biochemistry 1990, 29: 1385-92. PMID: 2159337, DOI: 10.1021/bi00458a007.Peer-Reviewed Original ResearchConceptsPhotooxidation of Mn2Photosystem II membranesO2 evolution activityMn complexesElectron donationMn-depleted photosystem IIPhotosystem IIElectron paramagnetic resonance spectroscopyFirst photochemical stepElectron donation reactionsCharge-separated stateElectron transfer eventsCytochrome bParamagnetic resonance spectroscopyMn-depleted photosystem II membranesOxygen evolution activityUntreated photosystem IILow quantum yieldSlower electron donationPhotochemical stepPrevious kinetic studiesTurnover reactionsElementary stepsElectron donorPhotooxidation
1989
Characterization of the multiple forms of cytochrome b559 in photosystem II.
Thompson L, Miller A, Buser C, de Paula J, Brudvig G. Characterization of the multiple forms of cytochrome b559 in photosystem II. Biochemistry 1989, 28: 8048-56. PMID: 2557895, DOI: 10.1021/bi00446a012.Peer-Reviewed Original ResearchConceptsCytochrome b559PSII membranesPhotosystem II protein complexUntreated PSII membranesExtrinsic polypeptidesLow-temperature photooxidationMn complexesPSII samplesEPR spectroscopyLigand fieldRedox titrationRedox formsEPR signalPhotosystem IIB559ComplexesThylakoid membranesPhotooxidationSpectroscopyProtein complexesUnique abilityMembraneTitrationConformationRemoval