2024
Mutation-induced shift of the photosystem II active site reveals insight into conserved water channels
Flesher D, Liu J, Wang J, Gisriel C, Yang K, Batista V, Debus R, Brudvig G. Mutation-induced shift of the photosystem II active site reveals insight into conserved water channels. Journal Of Biological Chemistry 2024, 300: 107475. PMID: 38879008, PMCID: PMC11294709, DOI: 10.1016/j.jbc.2024.107475.Peer-Reviewed Original ResearchOxygen-evolving complexPhotosystem II active sitePhotosystem IIJahn-Teller distortionPhotosystem II complexD1-Asp170Jahn-TellerResolution cryo-EM structureMutation-induced structural changesCryo-EM structureMagnetic propertiesD1 subunitActive siteOxygenic photosynthesisMutagenesis studiesLight-driven water oxidationSpectroscopic propertiesStructural basisSpectroscopic dataAmino acidsWater oxidation mechanismPhotosystemMutationsMutation-induced shiftWater oxidationPhotochemical Oxidation of Substrate Water Analogs and Halides by Photosystem II
Shin J, Kanyo J, Debus R, Brudvig G. Photochemical Oxidation of Substrate Water Analogs and Halides by Photosystem II. Advanced Energy Materials 2024 DOI: 10.1002/aenm.202401292.Peer-Reviewed Original ResearchWater oxidation catalysisRedox-active cofactorsOxidation catalysisWater oxidationSubstrate photooxidationProtein-pigment complexesRedox chemistryPhotochemical reductionSubstrate waterNative PSIISmall moleculesO 2 evolutionHalidesO-2ChloridePhotooxidationPhotochemical oxidationPSII complexesBound chlorideKinetic profilesPhotosystem IISubstratePutative water channelsCatalystCatalysisOccupancy 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 residuesMoleculesSelecting between Ammonia and Water Oxidation: Electrochemical Oxidation of Ammonia in Water Using an Organometallic–Inorganic Hybrid Anode
Liu H, Jayworth J, Crabtree R, Brudvig G. Selecting between Ammonia and Water Oxidation: Electrochemical Oxidation of Ammonia in Water Using an Organometallic–Inorganic Hybrid Anode. ACS Catalysis 2024, 14: 2842-2846. DOI: 10.1021/acscatal.3c05899.Peer-Reviewed Original ResearchHybrid anodeWater oxidationBlue layerElectrochemical oxidation of ammoniaOxidation of ammoniaElectrochemical oxidationSurface poisoningAqueous solventAmmonia oxidationOptimal operating conditionsAqueous solutionAmbient conditionsE appOperating conditionsAnodeFormation of nitriteOxidationOptimum selectionAmmoniaSolventNitrateNanoclustersDinitrogenElectrodeEcofriendly products
2023
(Invited) Water Oxidation Catalysis with Atomically Defined Active Sites on Nanostructured Materials for Solar Energy Applications
Brudvig G. (Invited) Water Oxidation Catalysis with Atomically Defined Active Sites on Nanostructured Materials for Solar Energy Applications. ECS Meeting Abstracts 2023, MA2023-01: 2149-2149. DOI: 10.1149/ma2023-01372149mtgabs.Peer-Reviewed Original ResearchWater oxidation catalystsMolecular catalystsSolar fuel productionWater oxidationMolecular water oxidation catalystsPhoto-electrochemical water oxidationWater oxidation catalysisNatural photosynthetic systemsPhotoelectrochemical water oxidationMetal oxide surfacesMetal oxide photoanodesFuel productionOxidation catalysisCatalytic performanceOxide photoanodesOxide surfaceNanostructured materialsBioinspired materialsCatalystLimited stabilityActive siteOxide materialsHigh activityPhotosynthetic systemsSolar energy applicationsBodipy and Dipyrrin as Unexpected Robust Anchoring Groups on TiO2 Nanoparticles
Jayworth J, Capobianco M, Liu H, Decavoli C, Crabtree R, Brudvig G. Bodipy and Dipyrrin as Unexpected Robust Anchoring Groups on TiO2 Nanoparticles. ECS Meeting Abstracts 2023, MA2023-01: 1410-1410. DOI: 10.1149/ma2023-01151410mtgabs.Peer-Reviewed Original ResearchTiO2 surfacePhoto-electrochemical water oxidationDye-sensitized solar cellsNatural photosynthetic systemsMetal oxide surfacesMetal oxide photoanodesCarboxylic acid groupsSolar fuel productionDipyrrin derivativesMolecular catalystsWater oxidationSynthetic stepsBF2 groupBODIPY chromophoreOxide photoanodesNitrogen atomsOxide surfaceSurface anchorAcid groupsMolecular complexesBioinspired materialsCovalent attachmentTiO2 nanoparticlesSurface bondsParent moleculeElectrocatalytic, Homogeneous Ammonia Oxidation in Water to Nitrate and Nitrite with a Copper Complex
Liu H, Lant H, Troiano J, Hu G, Mercado B, Crabtree R, Brudvig G. Electrocatalytic, Homogeneous Ammonia Oxidation in Water to Nitrate and Nitrite with a Copper Complex. ECS Meeting Abstracts 2023, MA2023-01: 2691-2691. DOI: 10.1149/ma2023-01552691mtgabs.Peer-Reviewed Original ResearchWater oxidationAmmonia oxidationO bond formationInitial mechanistic studiesMolecular catalystsCopper complexesMetal electrocatalystsFaradaic efficiencyAqueous mediaBond formationHigh selectivityOxidation processN2 productTitle reactionOxidationMechanistic studiesCatalysisComplexesRoom temperatureFriendly productionWaterElectrocatalystsElectrocatalyticNitrateCatalystAtomically dispersed Ir catalysts exhibit support-dependent water oxidation kinetics during photocatalysis
Zhang H, Liu T, Dulock N, Williams B, Wang Y, Chen B, Wikar H, Wang D, Brudvig G, Wang D, Waegele M. Atomically dispersed Ir catalysts exhibit support-dependent water oxidation kinetics during photocatalysis. Chemical Science 2023, 14: 6601-6607. PMID: 37350819, PMCID: PMC10283500, DOI: 10.1039/d3sc00603d.Peer-Reviewed Original ResearchWater oxidation activityIndium tin oxideActive siteOxidation activityHeterogeneous water oxidation catalysisHigh water oxidation activityWater oxidation catalysisWater oxidation kineticsOxidation catalysisWater oxidationIr catalystHeterogeneous catalystsDistinct active sitesLight sensitizerPrototypical reactionReaction mechanismDifferent supportsElectron scavengerCatalystTin oxideOxidation kineticsHigh temperatureLow temperatureStudied rangeCatalysisLigand Tuning in Cu(pyalk)2 Water Oxidation Electrocatalysis
Cody C, Caes Z, Capobianco M, Mercado B, Crabtree R, Brudvig G. Ligand Tuning in Cu(pyalk)2 Water Oxidation Electrocatalysis. Inorganics 2023, 11: 229. DOI: 10.3390/inorganics11060229.Peer-Reviewed Original ResearchWater oxidationWater oxidation electrocatalysisAnalogous copper complexesWater oxidation electrocatalystsArtificial photosynthetic systemsElectron-donating groupsSolar energy conversionPyalk ligandCatalyst tuningLigand tuningOxidation electrocatalystsCopper complexesFaradaic efficiencyLigand modificationCatalytic propertiesLigand formsAttractive scaffoldFirst-principles predictionPara positionGood activityMolecular systemsPhotosynthetic systemsEnergy conversionComplexesOxidation
2022
Structure of a dimeric photosystem II complex from a cyanobacterium acclimated to far-red light
Gisriel C, Shen G, Flesher D, Kurashov V, Golbeck J, Brudvig G, Amin M, Bryant D. Structure of a dimeric photosystem II complex from a cyanobacterium acclimated to far-red light. Journal Of Biological Chemistry 2022, 299: 102815. PMID: 36549647, PMCID: PMC9843442, DOI: 10.1016/j.jbc.2022.102815.Peer-Reviewed Original ResearchConceptsFar-red light photoacclimationChl dFar-red lightPhotosystem IIChl fWater-splitting enzymeEnergy transferDimeric photosystem II complexesCryo-EM structurePhotosystem II complexElectron transfer chainWater oxidationChl f moleculesDimeric complexStructure-function relationshipsPhotosynthetic machineryPsbH subunitProtein environmentMonomeric structureOxygenic photosynthesisVisible lightFormyl moietyF moleculesAccessory pigmentsTransfer chain
2020
Cryo-EM Structure of Monomeric Photosystem II from Synechocystis sp. PCC 6803 Lacking the Water-Oxidation Complex
Gisriel C, Zhou K, Huang H, Debus R, Xiong Y, Brudvig G. Cryo-EM Structure of Monomeric Photosystem II from Synechocystis sp. PCC 6803 Lacking the Water-Oxidation Complex. Joule 2020, 4: 2131-2148. DOI: 10.1016/j.joule.2020.07.016.Peer-Reviewed Original ResearchOxygen-evolving complexPhotosystem II enzymeWater oxidation complexWater oxidationMetal clustersMechanism of photoactivationActive siteMonomeric photosystem IIPhotosystem IICryo-EM structureStructural rearrangementsComplexesPhotoactivationSynechocystis spPeripheral subunitsCationsComputational techniquesOxidationOverall biogenesisStructureMesophilic cyanobacteriumOxygenPCC 6803II enzymesPSII
2018
Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst
Rudshteyn B, Fisher K, Lant H, Yang K, Mercado B, Brudvig G, Crabtree R, Batista V. Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. ACS Catalysis 2018, 8: 7952-7960. DOI: 10.1021/acscatal.8b02466.Peer-Reviewed Original ResearchKinetic isotope effectsWater nucleophilic attack mechanismWater oxidation catalystsWater nucleophilic attackD Kinetic Isotope EffectO bond formationUV-visible spectraDensity functional theoryElectrochemical stepWater oxidationElectrochemical analysisTurnover frequencyDerivative complexesBond formationRadical speciesRational designCis formFunctional theoryIsotope effectRate-limiting stepCatalystComplexesAttack mechanismMechanistic findingsDeprotonationCatalysing water oxidation using nature’s metal
Brudvig G. Catalysing water oxidation using nature’s metal. Nature Catalysis 2018, 1: 10-11. DOI: 10.1038/s41929-017-0013-1.Peer-Reviewed Original Research
2017
Alternative Electron Acceptors for Photosystem II
Wiwczar J, Brudvig G. Alternative Electron Acceptors for Photosystem II. 2017, 51-66. DOI: 10.1007/978-3-319-48873-8_4.Peer-Reviewed Original ResearchElectron acceptorPhotosystem IIPhotochemical water oxidationElectron acceptor moleculesCobalt coordination complexesElectron acceptor sideElectron transfer pathwayRedox midpoint potentialAlternative electron transfer pathwaysCoordination complexesWater oxidationElectron transferMolecular oxygenMidpoint potentialCation exchangeExogenous electron acceptorsOxygenic photosynthetic organismsAcceptor sidePhotosynthetic electron transport chainAcceptorEnergy applicationsAlternative electron acceptorsThylakoid membranesCytochrome c.Photosynthetic organismsElectrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand
Fisher K, Materna K, Mercado B, Crabtree R, Brudvig G. Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand. ACS Catalysis 2017, 7: 3384-3387. DOI: 10.1021/acscatal.7b00494.Peer-Reviewed Original ResearchWater oxidationElectrocatalytic water oxidationPotential electrolysis experimentsWater oxidation electrocatalystsStrong donor characterCatalyst degradationTurnover frequencyElectrolysis experimentsDonor characterCatalytic turnoverBasic conditionsOxidationHarsh conditionsOxidation resistanceElectrocatalystsCatalystLigandsCopperComplexesO2NHEFormationDegradation
2016
Rutile TiO2 as an Anode Material for Water-Splitting Dye-Sensitized Photoelectrochemical Cells
Swierk J, Regan K, Jiang J, Brudvig G, Schmuttenmaer C. Rutile TiO2 as an Anode Material for Water-Splitting Dye-Sensitized Photoelectrochemical Cells. ACS Energy Letters 2016, 1: 603-606. DOI: 10.1021/acsenergylett.6b00279.Peer-Reviewed Original ResearchWater-splitting dye-sensitized photoelectrochemical cellsPhotoelectrochemical cellsDye-sensitized photoelectrochemical cellsR-TiO2Sensitized Photoelectrochemical CellsWater-Splitting DyeWater oxidation catalystsLight-absorbing dyeWide bandgap metal oxide semiconductorsWater oxidationWS-DSPECsRedox mediatorAnode materialsInjection yieldLight harvesterPhotocurrent generationMetal oxide semiconductorDye stabilityAnatase TiO2Rutile polymorphTiO2Injected electronsRutile TiO2Oxide semiconductorsDyeHeterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor
Materna K, Rudshteyn B, Brennan B, Kane M, Bloomfield A, Huang D, Shopov D, Batista V, Crabtree R, Brudvig G. Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor. ACS Catalysis 2016, 6: 5371-5377. DOI: 10.1021/acscatal.6b01101.Peer-Reviewed Original ResearchIridium Water Oxidation CatalystsMetal oxide semiconductor surfacesWater oxidation catalystsExperimental IR spectraOxide semiconductor surfaceWater oxidationHeterogenized catalystTurnover frequencyIR spectraSilatrane precursorCovalent attachmentFunctional groupsTurnover numberM KNO3CatalystSemiconductor surfacesPrecatalystOverpotentialCatalysisComputational modelingOxidationPrecursorsKNO3SpectraSurfaceA new method for the synthesis of β-cyano substituted porphyrins and their use as sensitizers in photoelectrochemical devices
Antoniuk-Pablant A, Terazono Y, Brennan B, Sherman B, Megiatto J, Brudvig G, Moore A, Moore T, Gust D. A new method for the synthesis of β-cyano substituted porphyrins and their use as sensitizers in photoelectrochemical devices. Journal Of Materials Chemistry A 2016, 4: 2976-2985. DOI: 10.1039/c5ta07226c.Peer-Reviewed Original ResearchPhotoelectrosynthetic cellsWater oxidationNew synthetic methodSolar cellsSensitive functional groupsHigh positive potentialsElectrochemical propertiesRedox mediatorSynthetic methodZinc porphyrinMost porphyrinsPhotoelectrochemical devicesFunctional groupsMild conditionsPresence of TrisPorphyrinsPotential candidateNanoparticulate TiOSensitizersOxidationPositive potentialsDyeMoleculesImproved yieldPhotocurrentComparison of heterogenized molecular and heterogeneous oxide catalysts for photoelectrochemical water oxidation
Li W, He D, Sheehan S, He Y, Thorne J, Yao X, Brudvig G, Wang D. Comparison of heterogenized molecular and heterogeneous oxide catalysts for photoelectrochemical water oxidation. Energy & Environmental Science 2016, 9: 1794-1802. DOI: 10.1039/c5ee03871e.Peer-Reviewed Original ResearchWater oxidation catalystsHeterogeneous oxide catalystsSurface recombination rateOxide catalystsPerformance of hematiteBulk metal oxide catalystsHeterogeneous water oxidation catalystsPerformance of photoelectrodesO interfacePhotoelectrochemical water oxidationChemical energy conversionRecombination rateMetal oxide catalystsImproved charge transferAdditional charge-transfer pathwaysCharge transfer pathwayCombination of catalystsPEC performancePEC systemHematite photoanodesWater splittingWater oxidationIr catalystOxidation catalystPhotoelectrochemical reactions
2015
Interfacial electron transfer in photoanodes based on phosphorus( v ) porphyrin sensitizers co-deposited on SnO 2 with the Ir(III)Cp* water oxidation precatalyst
Poddutoori P, Thomsen J, Milot R, Sheehan S, Negre C, Garapati V, Schmuttenmaer C, Batista V, Brudvig G, van der Est A. Interfacial electron transfer in photoanodes based on phosphorus( v ) porphyrin sensitizers co-deposited on SnO 2 with the Ir(III)Cp* water oxidation precatalyst. Journal Of Materials Chemistry A 2015, 3: 3868-3879. DOI: 10.1039/c4ta07018f.Peer-Reviewed Original ResearchInterfacial electron transferElectron paramagnetic resonanceQuantum dynamics simulationsElectron transferPhotoanode componentCatalytic water oxidationEfficient interfacial electron transferDynamics simulationsMetal oxide surfacesSolar cellsTime-resolved terahertz spectroscopy measurementsSteady-state fluorescenceTypes of porphyrinsTerahertz spectroscopy measurementsOxidation precatalystWater oxidationAxial coordinationChloride ligandsPorphyrin sensitizersOxidation stateCharge recombinationParamagnetic resonanceSnO 2Phosphorus porphyrinsSpectroscopy measurements