Bell-Shaped Electron Transfer Kinetics in Gold Nanoclusters - Zhang et al. - Unknown - Unknown

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SupportingInformationBell-ShapedElectronTransferKineticsinGoldNanoclustersHao-HuaDeng,a§Kai-YuanHuang,a§Chen-TingZhu,aJian-FengShen,aXiang-PingZhang,aHua-PingPeng,aXing-HuaXia,bWeiChena*aHigherEducationalKeyLaboratoryforNanoBiomedicalTechnologyofFujianProvince,DepartmentofPharmaceuticalAnalysis,FujianMedicalUniversity,Fuzhou350004,ChinabStateKeyLaboratoryofAnalyticalChemistryforLifeScienceandCollaborativeInnovationCenterofChemistryforLifeSciences,SchoolofChemistryandChemicalEngineering,NanjingUniversity,Nanjing210093,China*Tel/Fax:+8659122862016.Email:chenandhu@163.com(WeiChen)§Hao-HuaDengandKai-YuanHuangcontributedequallytothisworkS-1

1ExperimentalDetailsMaterialsandReagents.HAuCl4·3H2O,CC,DTT,4-(2-aminoethyl)pyridine(PyA),dopamine,2-(4-Nitrophenyl)ethanamine(EAN),methylviologen(MV2+),mitoxantrone(MXT),5-fluorouracil(5-FU),6-mercaptopurine(6-MP),vincristine(VCR),cyclophosphamide(CTX)andtamoxifen(TAM)werebroughtfromAladdinReagentCo.(Shanghai,China)(http://www.aladdin-e.com/).Banoxantrone(AQ4N)andcoenzymeQ10(CoQ10)werepurchasedfromSigma-AldrichReagentCo.(Shanghai,China)(https://www.sigmaaldrich.com/).Dopaquinone(DOPQ)waspreparedfromdopaminebypureoxygenoxidationandcalibratedwith3600M-1cm-1at475nm.1Allotherchemicalswerecommerciallyavailableandusedwithoutfurtherpurificationunlessotherwisestated.Allsolutionswerepreparedwithultrapurewater.Allglasswarewaspurgedwithaquaregia(HCl:HNO3=3:1,v/v)andrinsedcopiouslywithultrapurewaterbeforeuse.Instrumentation.UV-visible(UV-vis)absorptionspectrawereperformedusingaShimadzuUV-2450spectrophotometer(Japan)andthefluorescencespectrawererecordedusinganAgilentCaryEclipsespectrophotometer(USA).Transmissionelectronmicroscopy(TEM)imageswerecollectedusingaJEOLJEM-2100TEMinstrument(Japan).Ultrovioletphotoelectronspectrometer(UPS)wasmeasuredonaThermoESCALAB250XIelectronspectrometer(USA).FluorescencelifetimemeasurementswereconductedusinganEdinburghF900time-correlatedsingle-photon-countingfluorescencelifetimespectrometer(U.K.).Cyclicvoltammetricexperimentswereconductedonclassicthree-electrodesystem,inwhichbareglassycarbonelectrode(GCE)wasemployedastheworkingelectrode,aplatinumwirewasemployedastheauxiliaryelectrode,andanAg/AgClelectrodewasemployedasthereferenceelectrode.TheresultingsignalswererecordedwithaCHI660Celectrochemicalanalyzer(CHIInstrumentInc.,USA).Allexperimentswerepresentedatambienttemperature.SynthesisofCC/DTT-AuNCs.TheCC/DTT-AuNCsweresynthesizedaccordingtoourpreviousreportedmethodanddialyzedagainstultrapurewateratroomtemperatureindialysismembranewitha3.5kDacutofffor24hwithintermittentS-2

2waterchange.2ThepreparedCC/DTT-AuNCsolutionwasstoredina4oCrefrigeratorforfurtheruse.Quenchingrateconstant(kq)measurements.Typically,0.1mLofCC/DTT-AuNCsolutionwasaddedto1.9mLofphosphatebuffer(20mM,pH=7.0)containingdifferentconcentrationsoftestedsubstances.Thefluorescenceemissionspectrumofthemixturewasrecordedimmediatelywithanexcitationwavelengthof285nm.MXTdetermination.Briefly,0.1mLofCC/DTT-AuNCsolutionwasaddedto1.9mLofphosphatebuffer(20mM,pH=7.0)containingdifferentconcentrationsofMXT.Thefluorescenceemissionspectrumofthemixturewasrecordedimmediatelywithanexcitationwavelengthof285nm.TAmeasurements.Thetransientabsorption(TA)spectraweremeasuredbyopticalpump-probespectroscopy.Theoutputofamode-lockedTi-sapphirelaseramplifier(Spectra-Physics)wasusedasasourceoffemtosecondradiation(800nm,35-40fs,1kHz,averagepower4W).Home-builtpump-probesetupwasusedforobtainingtransientabsorptionspectraandkinetics.TherequiredpumppulsewasgeneratedbyuseofanOpticalParametricAmplifier(TOPAS,Lightconversion).Whitelightcontinuum(350-850nm)generatedin3mmthicknessCaF2platewasusedasprobebeam.Theexperimentaldatawerefittedtoamultiexponentialdecayfunctionconvolutedwiththeinstrumentresponsefunction.Overalltimeresolutionwasabout20-30fs.Pump-probemeasurementswereperformedin1mmpathlengthquartzcuvettesundercontinuousmovementforhomogeneousirradiationduringexposure.Thepowerwascontrolled0.4mWat320nmexcitation.S-3

3FigureS1.ZetapotentialofCC/DTT-AuNCsinphosphatebuffer(pH7.0,20mM).FigureS2.FluorescenceemissionspectraofCC/DTT-AuNCsinthepresenceofdifferentconcentrationsof(A)NMP(a-f:0,10,50,100,250,and500μM),(B)EAN(a-f:0,1,5,10,15,and20μM),(C)AQ4N(a-f:0,0.01,0.05,0.10,0.15and0.20μM),and(D)DOPQ(a-g:0,0.5,1,2,3,4,and5μM).S-4

4FigureS3.FluorescencedecayprofilesofCC/DTT-AuNCsinthepresenceofNMP(1mM),EAN(50μM),AQ4N(1μM),MV2+(1μM)andDOPQ(5μM).FigureS4.FluorescenceemissionspectrumofCC/DTT-AuNCsandUV-visspectraofCC/DTT-AuNCsinthepresenceofNMP(1mM),EAN(25μM),AQ4N(1μM),MV2+(1μM)andDOPQ(5μM).S-5

5FigureS5.F0/Fasafunctionof(A)NMP,(B)EAN,(C)AQ4N,and(D)DOPQconcentrations.Notably,theplotofDOPQwascorrectedbyinnerfiltereffectsincethereisobviousabsorptionattheexcitationwavelengthofCC/DTT-AuNCs(FigureS4).FigureS6.CyclicvoltammogramcurveofAQ4Nin0.1MKClsolution(scanrate:50mV/s).S-6

6FigureS7.CyclicvoltammogramcurveofCC/DTT-AuNCsin0.1MKClsolution(scanrate:50mV/s).FigureS8.UPSspectrumofCC/DTT-AuNCs.FigureS9.OpticalenergygapofCC/DTT-AuNCs.S-7

7FigureS10.UPSspectrumofMXT.FigureS11.OpticalenergygapofMXT.FigureS12.UV-visabsorptionspectraofCCandDTT.S-8

8FigureS13.DynamictraceofexcitedstateabsorptionofCC/DTT-AuNCsat485nm.FigureS14.TimeresolutionprofileofexcitedstateabsorptionofCC/DTT-AuNCsat507nm.FigureS15.KinetictraceofexcitedstateabsorptionofCC/DTT-AuNCsat600nm.S-9

9FigureS16.KinetictraceofexcitedstateabsorptionofCC/DTT-AuNCsinthepresenceofMXT(2μM)at485nm.FigureS17.DynamicstraceofexcitedstateabsorptionofCC/DTT-AuNCsinthepresenceofMXT(2μM)at507nm.FigureS18.FluorescencedecayprofileofCC/DTT-AuNCsinthepresenceofMXT(1μM).S-10

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