2024
Water Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II
Liu J, Yang K, Long Z, Armstrong W, Brudvig G, Batista V. Water Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II. Journal Of The American Chemical Society 2024, 146: 15986-15999. PMID: 38833517, DOI: 10.1021/jacs.4c02926.Peer-Reviewed Original ResearchProton-coupled electron transferOxygen-evolving complexWater insertionWater ligandsCatalytic cycleMolecular dynamicsO-O bondQuantum mechanics/molecular mechanicsConformational changesFree energy changeLigand environmentElectron transferLigand exchangePhotosystem IIOxygen evolutionWater binding mechanismsEnergy changeLigandBinding mechanismAqueous environmentRedoxWater bindingLigand bindingCatalystIsomerization
2021
Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution
Hu G, Crabtree R, Brudvig G. Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution. Inorganica Chimica Acta 2021, 526: 120507. DOI: 10.1016/j.ica.2021.120507.Peer-Reviewed Original ResearchOrganometallic complexesCoordination complexesCatalyst precursorsOrganometallic ligandsOrganometallic precursorsOxygen evolution catalystsUseful catalyst precursorsBlue solutionPyalk ligandCoordination precursorsChelating ligandHomogeneous catalystsIrOx nanoparticlesActive speciesNanoparticle formationNanoparticle generationOxygen evolutionIsomeric mixtureOxidative activationCore unitLigandsCatalystComplexesActivation processPrecursors8.22 Oxygen Evolution of Photosystem II
Huang H, Brudvig G. 8.22 Oxygen Evolution of Photosystem II. 2021, 569-588. DOI: 10.1016/b978-0-12-409547-2.14871-1.Peer-Reviewed Original ResearchProtein complex photosystem IIWater oxidation reactionPhotosystem IIWater oxidation mechanismOxygen-evolving complexSolar energy storageNatural photosynthesisKey reactionOxygen evolutionEnergy storageReactionPhotosynthesisCurrent knowledgeDetailed mechanismEssential componentGlobal scaleComplexesMechanism
2019
N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox‐Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution
Lant H, Michaelos T, Sharninghausen L, Mercado B, Crabtree R, Brudvig G. N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox‐Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution. European Journal Of Inorganic Chemistry 2019, 2019: 2115-2123. DOI: 10.1002/ejic.201801343.Peer-Reviewed Original ResearchAlkoxide moietyOxidation stateOxygen evolutionHigher Mn oxidation statesCatalytic oxygen evolutionO-pincer ligandMn oxidation statePincer ligandRedox levelingElectrochemical dataLow overpotentialProtonation stateProton lossEPR experimentsMn IIIO intermediateRelated seriesMn–VMn IIMoietyLigandsOverpotentialDicationCatalystCatalysis
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
2005
Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex
Howard D, Tinoco A, Brudvig G, Vrettos J, Allen B. Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex. Journal Of Chemical Education 2005, 82: 791. DOI: 10.1021/ed082p791.Peer-Reviewed Original ResearchBioinorganic modelsWater oxidationMn4 clusterArtificial water oxidation catalystsBioinorganic model complexesCatalytic oxygen evolutionWater oxidation catalystsPhotosystem IIPhotosynthetic water oxidationUV-visible spectroscopyOxygen-Evolving ComplexDeuterium kinetic isotope effectsPhotosystem II Oxygen Evolving ComplexKinetic isotope effectsBioinorganic chemistryTerpy complexesInorganic synthesisPlace of H2OManganese complexesModel complexesPrimary oxidantManganese clusterOne-electronOxygen evolutionActive site
2004
Investigation of the Functional Role of Ca2+ in the Oxygen‐Evolving Complex of Photosystem II: A pH‐Dependence Study of the Substitution of Ca2+ by Sr2+
Lee C, Brudvig G. Investigation of the Functional Role of Ca2+ in the Oxygen‐Evolving Complex of Photosystem II: A pH‐Dependence Study of the Substitution of Ca2+ by Sr2+. Journal Of The Chinese Chemical Society 2004, 51: 1221-1228. DOI: 10.1002/jccs.200400178.Peer-Reviewed Original ResearchOxygen-evolving complexOxygen evolution activityPhotosystem IISr 2Water oxidation chemistryOxidation of waterPH dependenceMetal ions resultsTetranuclear manganese clusterElectron acceptor sidePH dependence studyOxidation chemistryWater oxidationManganese clusterLewis acidOxygen-evolving activityOxygen evolutionEssential acidic groupAcidic groupsSubstitution of Ca2Ions resultsOnly ionsCatalytic siteCa 2Chloride ions
2003
Two Redox-Active β-Carotene Molecules in Photosystem II †
Tracewell C, Brudvig G. Two Redox-Active β-Carotene Molecules in Photosystem II †. Biochemistry 2003, 42: 9127-9136. PMID: 12885246, DOI: 10.1021/bi0345844.Peer-Reviewed Original ResearchMeSH KeywordsAdaptation, PhysiologicalBeta CaroteneCyanobacteriaDarknessElectron Spin Resonance SpectroscopyFree RadicalsFreezingLight-Harvesting Protein ComplexesNormal DistributionOxidation-ReductionPhotochemistryPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexSpectroscopy, Near-InfraredSpinacia oleraceaTyrosineConceptsSecondary electron transfer pathwayElectron transfer pathwayElectron paramagnetic resonance spectroscopyElectron transfer reactionsElectron transfer pathParamagnetic resonance spectroscopyHole-hopping mechanismPS II core complexesΒ-carotene moleculesPS II membranesII core complexesPhotosystem IIIR spectroscopyPS IILow temperatureCharge separationElectrostatic interactionsOxygen evolutionResonance spectroscopyLow-temperature illuminationInhibited samplesSpectroscopyEquilibrated statePeak variesSynechocystis PCC 6803
2001
Photosynthetic Water Oxidation in Cytochromeb 559 Mutants Containing a Disrupted Heme-binding Pocket*
Morais F, Kühn K, Stewart D, Barber J, Brudvig G, Nixon P. Photosynthetic Water Oxidation in Cytochromeb 559 Mutants Containing a Disrupted Heme-binding Pocket*. Journal Of Biological Chemistry 2001, 276: 31986-31993. PMID: 11390403, DOI: 10.1074/jbc.m103935200.Peer-Reviewed Original ResearchMeSH KeywordsAnimalsBase SequenceCarrier ProteinsChlamydomonas reinhardtiiCytochrome b GroupDNA PrimersElectron Spin Resonance SpectroscopyHeme-Binding ProteinsHemeproteinsMutagenesis, Site-DirectedMutationOxidation-ReductionPhotosynthesisPhotosynthetic Reaction Center Complex ProteinsPhotosystem II Protein ComplexWaterConceptsPhotosynthetic oxygen evolutionMethionine mutantsWild typeAlpha subunitLight-saturated ratePhotosystem two complexWild-type levelsHeme of cytochromePhotosynthetic water oxidationHeme-binding pocketOxygen evolutionChloroplast mutantsPSII supercomplexesHistidine axial ligandsChlamydomonas reinhardtiiGlutamine mutantTyrosine mutantsMutantsType levelsRedox roleHemeSubunitsOxygen evolution activityTyrosineComplexes
1989
Bioinorganic Chemistry of Manganese Related to Photosynthetic Oxygen Evolution
Brudvig G, Crabtree R. Bioinorganic Chemistry of Manganese Related to Photosynthetic Oxygen Evolution. Progress In Inorganic Chemistry 1989, 37: 99-142. DOI: 10.1002/9780470166383.ch2.Peer-Reviewed Original Research
1983
The effect of temperature on the formation and decay of the multiline EPR signal species associated with photosynthetic oxygen evolution
Brudvig G, Casey J, Sauer K. The effect of temperature on the formation and decay of the multiline EPR signal species associated with photosynthetic oxygen evolution. Biochimica Et Biophysica Acta (BBA) - Bioenergetics 1983, 723: 366-371. DOI: 10.1016/0005-2728(83)90042-7.Peer-Reviewed Original Research