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 effects
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 measurements
2000
Kinetic analysis of the O2-forming reaction between [Mn(III)(dpa)2]− (dpa=dipicolinate) and potassium peroxomonosulfate
Limburg J, Crabtree* R, Brudvig* G. Kinetic analysis of the O2-forming reaction between [Mn(III)(dpa)2]− (dpa=dipicolinate) and potassium peroxomonosulfate. Inorganica Chimica Acta 2000, 297: 301-306. DOI: 10.1016/s0020-1693(99)00362-x.Peer-Reviewed Original ResearchO2-evolving complexPotassium peroxomonosulfateO2 evolutionComplexes of formulaO2-evolving reactionsFour-electron oxidationPhotosynthetic water oxidationPhotosystem IITerpy complexesWater oxidationManganese complexesKinetic analysisSide reactionsBond formationMolecular oxygenOxygen atomsReactionComplexesPeroxomonosulfateKey stepOxidationKobsManganeseTerpyridineTerpy
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
1986
Mechanism for photosynthetic O2 evolution.
Brudvig G, Crabtree R. Mechanism for photosynthetic O2 evolution. Proceedings Of The National Academy Of Sciences Of The United States Of America 1986, 83: 4586-4588. PMID: 3460059, PMCID: PMC323785, DOI: 10.1073/pnas.83.13.4586.Peer-Reviewed Original ResearchConceptsO2-evolving complexManganese complexesPhotosynthetic O2 evolutionS2 stateCubane-like complexCubane-like structureIntermediate oxidation statesEPR spectral dataO2 evolutionSpectral dataDisplacement of O2Coordination chemistryOxidation stateO bondS4 stateRecent EPRUV spectral dataManganese sitesStructural conversionComplexesMolecular mechanismsMn4O4ChemistryStructureEPR
1983
PROPERTIES OF THE S2 STATE ASSOCIATED WITH O2 EVOLUTION
Brudvig G, Casey J, Sauer K. PROPERTIES OF THE S2 STATE ASSOCIATED WITH O2 EVOLUTION. 1983, 159-164. DOI: 10.1016/b978-0-12-372360-4.50023-7.Peer-Reviewed Original ResearchS2 stateMultiline electron paramagnetic resonance (EPR) signalParamagnetic speciesO2 evolutionOxidation state changesPhotosynthetic water oxidationFinal oxidation productsElectron paramagnetic resonance signalS2 state EPR signalsCharge separation eventsS-state advancementMolecule of O2State EPR signalsParamagnetic resonance signalO2-evolving complexWater oxidationPhotosystem IIUnpaired electronOxidation productsEPR signalHyperfine structureResonance signalsSpinach chloroplastsSpeciesHyperfine lines