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 oxidationWater 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 bindingCatalystIsomerizationOccupancy 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 residuesMolecules
2023
Redox leveling of the Kok cycle of photosystem II established by water ligand binding to the oxygen evolving complex
Liu J, Yang K, Brudvig G, Batista V. Redox leveling of the Kok cycle of photosystem II established by water ligand binding to the oxygen evolving complex. Biophysical Journal 2023, 122: 199a-200a. DOI: 10.1016/j.bpj.2022.11.1210.Peer-Reviewed Original Research
2022
Binding of the substrate analog methanol in the oxygen-evolving complex of photosystem II in the D1-N87A genetic variant of cyanobacteria
Kalendra V, Reiss KM, Banerjee G, Ghosh I, Baldansuren A, Batista VS, Brudvig GW, Lakshmi KV. Binding of the substrate analog methanol in the oxygen-evolving complex of photosystem II in the D1-N87A genetic variant of cyanobacteria. Faraday Discussions 2022, 234: 195-213. PMID: 35147155, DOI: 10.1039/d1fd00094b.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexDensity functional theorySolar water-splitting protein complexTwo-dimensional hyperfine sublevel correlation spectroscopyPhotosystem IIQuantum mechanics/molecular mechanicsHyperfine sublevel correlation spectroscopyWater oxidation reactionWater oxidationCatalytic clustersOxidation reactionSubstrate waterMolecular mechanicsCorrelation spectroscopyFunctional theorySubstrate analoguesLight energyMethanolComplexesReactionIntermediatesDetailed mechanismCatalystSpectroscopyWaterGlycerol binding at the narrow channel of photosystem II stabilizes the low-spin S2 state of the oxygen-evolving complex
Flesher DA, Liu J, Wiwczar JM, Reiss K, Yang KR, Wang J, Askerka M, Gisriel CJ, Batista VS, Brudvig GW. Glycerol binding at the narrow channel of photosystem II stabilizes the low-spin S2 state of the oxygen-evolving complex. Photosynthesis Research 2022, 152: 167-175. PMID: 35322325, PMCID: PMC9427693, DOI: 10.1007/s11120-022-00911-0.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexHydrogen bond networkS2 stateEPR signalPhotosystem II cyclesX-ray crystal structureRelative stabilityState EPR signalsD1-Asp61Water oxidationCatalytic intermediatesPhotochemical oxidationEPR spectraGlycerol moleculesCrystal structureCyanobacterial PSIIMultiline signalState SiPhotosystem IIOxidationRelative intensitiesComplexesEffect of glycerolExperimental conditionsStability
2021
High-resolution cryo-electron microscopy structure of photosystem II from the mesophilic cyanobacterium, Synechocystis sp. PCC 6803
Gisriel CJ, Wang J, Liu J, Flesher DA, Reiss KM, Huang HL, Yang KR, Armstrong WH, Gunner MR, Batista VS, Debus RJ, Brudvig GW. High-resolution cryo-electron microscopy structure of photosystem II from the mesophilic cyanobacterium, Synechocystis sp. PCC 6803. Proceedings Of The National Academy Of Sciences Of The United States Of America 2021, 119: e2116765118. PMID: 34937700, PMCID: PMC8740770, DOI: 10.1073/pnas.2116765118.Peer-Reviewed Original ResearchConceptsCryo-electron microscopy structurePCC 6803Photosystem IIWater oxidationMicroscopy structureMesophilic cyanobacteriumHigh-resolution cryo-electron microscopy structuresOxygen-evolving photosystem IILight-driven water oxidationCyanobacterial photosystem IIHigh-resolution structuresD1 subunitPSII structureSynechocystis spLarge water channelsGenetic manipulationC-terminusBiophysical dataActive siteCyanobacteriumSpStructural pictureSubunitsOxidationWater channelsHeterogeneous Composition of Oxygen-Evolving Complexes in Crystal Structures of Dark-Adapted Photosystem II
Wang J, Gisriel CJ, Reiss K, Huang HL, Armstrong WH, Brudvig GW, Batista VS. Heterogeneous Composition of Oxygen-Evolving Complexes in Crystal Structures of Dark-Adapted Photosystem II. Biochemistry 2021, 60: 3374-3384. PMID: 34714055, DOI: 10.1021/acs.biochem.1c00611.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexMetal ionsPhotosystem IIElectron density peakIndividual metal ionsElectron density distributionNumber of electronsPSII dimersMetal centerWater oxidationOxidation stateElectron numberHomodimeric protein complexElectronsCrystal structurePSII structureDensity distributionDensity peaksComplexesRedox stateIonsDimersMonomersPeakOxidationDo crystallographic XFEL data support binding of a water molecule to the oxygen-evolving complex of photosystem II exposed to two flashes of light?
Wang J, Armstrong WH, Batista VS. Do crystallographic XFEL data support binding of a water molecule to the oxygen-evolving complex of photosystem II exposed to two flashes of light? Proceedings Of The National Academy Of Sciences Of The United States Of America 2021, 118: e2023982118. PMID: 34117119, PMCID: PMC8214663, DOI: 10.1073/pnas.2023982118.Peer-Reviewed Original ResearchIs Deprotonation of the Oxygen-Evolving Complex of Photosystem II during the S1 → S2 Transition Suppressed by Proton Quantum Delocalization?
Yang KR, Lakshmi KV, Brudvig GW, Batista VS. Is Deprotonation of the Oxygen-Evolving Complex of Photosystem II during the S1 → S2 Transition Suppressed by Proton Quantum Delocalization? Journal Of The American Chemical Society 2021, 143: 8324-8332. PMID: 34029102, DOI: 10.1021/jacs.1c00633.Peer-Reviewed Original ResearchLow-barrier hydrogen bondExtended X-ray absorption fine structureWater-derived ligandsQuantum delocalizationOxygen-evolving complexTetranuclear manganese-calcium-oxo clusterTwo-dimensional hyperfine sublevel correlation spectroscopyHydrogen bondsQuantum mechanics/molecular mechanics calculationsHyperfine sublevel correlation spectroscopyX-ray absorption fine structurePhotosystem IIModel catalytic systemsIsotropic proton hyperfine coupling constantsProton hyperfine coupling constantsZero-point energyMolecular mechanics calculationsAbsorption fine structureD1-D61Hyperfine coupling constantsKok cycleCatalytic systemLow overpotentialMechanics calculationsS2 transitionProton exit pathways surrounding the oxygen evolving complex of photosystem II
Kaur D, Zhang Y, Reiss KM, Mandal M, Brudvig GW, Batista VS, Gunner MR. Proton exit pathways surrounding the oxygen evolving complex of photosystem II. Biochimica Et Biophysica Acta (BBA) - Bioenergetics 2021, 1862: 148446. PMID: 33964279, DOI: 10.1016/j.bbabio.2021.148446.Peer-Reviewed Original ResearchConceptsOxygen-Evolving ComplexMulti-Conformation Continuum ElectrostaticsWater-filled channelsMolecular dynamicsSubstrate water moleculesHydrogen bond network analysisProton exit pathwayPhotosynthetic electron transfer chainProton transfer pathPhotosystem IISimilar free energiesInorganic coreWater chainWater moleculesAqueous surfaceElectron transfer chainContinuum electrostaticsProduct oxygenFree energyTransfer chainLarge channelsLikely exitTransfer pathLumenal sideComplexes
2020
Identification of a Na+‑Binding Site near the Oxygen-Evolving Complex of Spinach Photosystem II
Wang J, Perez-Cruet JM, Huang HL, Reiss K, Gisriel CJ, Banerjee G, Kaur D, Ghosh I, Dziarski A, Gunner MR, Batista VS, Brudvig GW. Identification of a Na+‑Binding Site near the Oxygen-Evolving Complex of Spinach Photosystem II. Biochemistry 2020, 59: 2823-2831. PMID: 32650633, DOI: 10.1021/acs.biochem.0c00303.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexSpinach photosystem IIRedox-active Mn ionPhotosystem IIOxygen evolution activityQuantum mechanical calculationsOxomanganese clusterHydroxide anionCommon counterionCryo-electron microscopy mapMechanical calculationsAmino acid residuesMn ionsIonsElectrostatic simulationsMicroscopy mapsAcid residuesComplexesDeprotonationAnionsCounterionsNaChlorideSitesClThe Mechanism of Substrate Delivery and Activation in the Solar Water Oxidation Reaction of Photosystem II
Lakshmi K, Kalendra V, Banerjee G, Ghosh I, Yang K, Batista V, Brudvig G. The Mechanism of Substrate Delivery and Activation in the Solar Water Oxidation Reaction of Photosystem II. Biophysical Journal 2020, 118: 610a. DOI: 10.1016/j.bpj.2019.11.3292.Peer-Reviewed Original Research
2019
Water Network Dynamics Next to the Oxygen-Evolving Complex of Photosystem II
Reiss K, Morzan U, Grigas A, Batista V. Water Network Dynamics Next to the Oxygen-Evolving Complex of Photosystem II. Inorganics 2019, 7: 39. DOI: 10.3390/inorganics7030039.Peer-Reviewed Original ResearchOxygen-evolving complexWater network dynamicsMolecular dynamics simulationsPhotosystem IICatalytic performanceHydrogen bondingProtein environmentLarge ionsS2 stateDynamics simulationsLarge channelsProton translocationWater diffusionComplexesPSII assemblyEigenvector centrality analysisWater networkGreat interestWater channelsDynamical natureBondingIonsWater transportMajor channelChloride
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 effectsAnalysis of the Radiation-Damage-Free X‑ray Structure of Photosystem II in Light of EXAFS and QM/MM Data
Askerka M, Vinyard DJ, Wang J, Brudvig GW, Batista VS. Analysis of the Radiation-Damage-Free X‑ray Structure of Photosystem II in Light of EXAFS and QM/MM Data. Biochemistry 2015, 54: 1713-1716. PMID: 25710258, DOI: 10.1021/acs.biochem.5b00089.Peer-Reviewed Original ResearchConceptsPhotosystem II crystalsX-ray absorption fine structureExtended X-ray absorption fine structureAbsorption fine structurePhotosystem IIHigh-resolution structural modelS1 stateS0 stateOxygen-evolving complexRadiation damageX-ray diffraction studiesExtensive dark adaptationFine structureDiffraction studiesOxygen atomsManganese centersX-ray structureAtomsMM dataCrystalsStateEXAFSLightStructureResolutionComputational Insights on Crystal Structures of the Oxygen-Evolving Complex of Photosystem II with Either Ca2+ or Ca2+ Substituted by Sr2+
Vogt L, Ertem MZ, Pal R, Brudvig GW, Batista VS. Computational Insights on Crystal Structures of the Oxygen-Evolving Complex of Photosystem II with Either Ca2+ or Ca2+ Substituted by Sr2+. Biochemistry 2015, 54: 820-825. PMID: 25555204, DOI: 10.1021/bi5011706.Peer-Reviewed Original ResearchConceptsX-ray crystal structureCrystal structureQuantum mechanics/molecular mechanics calculationsQM/MM modelOxygen-Evolving ComplexMolecular mechanics calculationsPhotosystem IIWater oxidationMechanics calculationsComputational insightsReduced statesHeterocationsMM modelSubstitution resultsComplexesS statesStructureCationsBondsOxidationSr2Experimental dataW5WaterCalculations
2014
Structural Changes in the Oxygen-Evolving Complex of Photosystem II Induced by the S1 to S2 Transition: A Combined XRD and QM/MM Study
Askerka M, Wang J, Brudvig GW, Batista VS. Structural Changes in the Oxygen-Evolving Complex of Photosystem II Induced by the S1 to S2 Transition: A Combined XRD and QM/MM Study. Biochemistry 2014, 53: 6860-6862. PMID: 25347729, PMCID: PMC4230327, DOI: 10.1021/bi5011915.Peer-Reviewed Original ResearchStructural Studies of Oxomanganese Complexes for Water Oxidation Catalysis
Rivalta I, Brudvig G, Batista V. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis. 2014, 1-14. DOI: 10.1002/9781118698648.ch1.Peer-Reviewed Original ResearchOxygen-evolving complexBiomimetic oxomanganese complexesOxomanganese complexesDensity functional theoryQuantum mechanics/molecular mechanics (QM/MM) hybrid methodsHigh-resolution spectroscopyPhotosystem IIStructure of PSIIX-ray absorption fine structure spectraX-ray radiationExtended X-ray absorption fine structure (EXAFS) spectraProteinaceous side chainsWater oxidation catalysisArtificial photosynthetic devicesFine structure spectraO bond formationWater splitting mechanismX-ray crystallographyOxomanganese clusterResolution spectroscopyX-ray diffraction dataSemiconductor surfacesOxidation catalysisPhotosynthetic devicesX-ray model
2013
S0‑State Model of the Oxygen-Evolving Complex of Photosystem II
Pal R, Negre CF, Vogt L, Pokhrel R, Ertem MZ, Brudvig GW, Batista VS. S0‑State Model of the Oxygen-Evolving Complex of Photosystem II. Biochemistry 2013, 52: 7703-7706. PMID: 24125018, DOI: 10.1021/bi401214v.Peer-Reviewed Original ResearchConceptsOxygen-evolving complexS1 transitionQuantum mechanics/molecular mechanics modelsX-ray absorption fine structure spectroscopyExtended X-ray absorption fine structure (EXAFS) spectroscopyQM/MM modelAbsorption fine structure spectroscopyElectron transfer processHydrogen bonding networkFine structure spectroscopyPhotosystem IIX-ray diffraction dataMolecular mechanics modelPCET mechanismKok cycleWater moleculesWater splittingBonding networkS1 stateMn centersStructure spectroscopyS0 stateDiffraction dataMM modelSignificant rearrangement