Wet-Chemical Synthesis of Pd-Au Core-Shell Nanoparticles (8 nm):From Nanostructure to Biological Properties(1).docx

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1、GhemistryJSFJ1M睛fDOI:10.1002s1ct.201800638z_Materia1sScienceinc.Nanomateria1s&Po1ymersWet-Chemica1SynthesisofPd-AuCore-She11Nanopartic1es(8_nm):FromNanostructuretoBio1ogica1Properties8 A1exanderRostekJa1MarinaBreischJb1Kateryna1ozaa1Pau1oR.A.F.GarciaJc19 Gnstiano1.P.OIiveiraz1c1OIegPrymak,MarCHeggen

2、z1d1ManfredKo11erb1ioCristinaSengstock,(b1andMatthiasEpp1e*1a1areofspecia1interest.Core-she11nanostructuresandnanoa11oysp1ayimportantro1esandopenupnewpossibi1itiesduetotheirtuneab1eproperties,e.g.inheterogeneouscata1ysis.PdAucore-she11nanopartic1eswithapa11adiumcore(diameter14about5.5nm)andago1dshe1

3、1(thicknessabout1.7nm)wereISwet-chemica11ysynthesizedinaneasywater-basedone-pot162*3+synthesisbysequentia1reductionofPdandAuwith17g1ucoseinthepresenceofpo1y(N-Viny1pyrro1idone)(PVP).The18meta1sarepresentinaboutequa1amounts(mo1arratioPd:Au19about2:1)withac1earseparationbetweencoreandshe11.The20reacti

4、onwasmonitoredin-situbysma11-ang1eX-rayscattering21(SAX;-ShOWg-in忧ia1gFQ4h0f-hepa11adUmseeds,22fo11owedbytheepitacticformationofthego1dshe11.Thecore-232425Intreduction26Inorganicandmeta11icnanopartic1esrepresentawe11-estab27Iishedfie1dofnanoscience,medicine,cata1ysis,andindustry.28Nob1emeta1s1ikerho

5、dium,pa11adium,p1atinum,si1ver;andgo1de1ectrocata1ysis,magnetism,andbiomedica1app1ications.Inparticu1ar,pa11adium-go1dnanopartic1es(PdAu)areofconsiderab1einterestinheterogeneouscata1ysis,e.g.forvariousredox35 reactions.Thisismain1yascribedtothemodu1ationofthe36 propertiesofpa11adiumbya11oyingitwithg

6、o1d,bothe1ectroni-(4)ca11yandstructura11y.Zhangeta1.havepub1ishedacompre-38hensivereviewaboutthesynthesisandthepropertiesof39PdAubimeta11icnanopartic1es,incore-she11form(PdAuand40AuPd)andina11oyedform,inc1udingnon-spherica1nano-41PartiC1es.424344(a A.Rostek,Dr.K.1oza,Dr.O.Prymak,Prof.Dr.M.Epp1e45Ino

7、rganicChemistryandCenterforNanointegrationDuisburg-(Essen4GCeNIDE),UniversityofDuisburg-Essen,Universitaetsstr.7,45141Essen,47GermanyE-mai1:matthias.epp1euni-due.de48(b M.Breisch,Prof.Dr.M.K11er,Prof.Dr.C.SengstockBergmannshei1UniversityHospita1/Surgica1Research,Ruhr-UniversityofBochum,Brk1e-de-1a-C

8、amp-P1atz1,44789Bochum,Germany(c P.R.A.F.Garcia,Prof.Dr.C.1.P.O1iveiraInstituteofPhysics,UniversityofSoPau1o,RuadoMato1371,S%oPau1o,SoPau1o,05314-970,Brazi1(d Dr.M.HeggenUhemiStryJS品M金匕2345ErnstRuskaCentreforMicroscopyandSpectroscopywithE1ectrons,ForschungszentrumJ1ichGmbH,52425J1ich,GermanySupporti

9、nginformationforthisartic1eisavai1ab1eontheWWWunderhttps:doi.org/10.1002/s1ct.201800638she11characterofthepartic1eswasconfirmedbyhighreso1utionscanningtransmissione1ectronmicroscopy(STEM)andenergy-dispersiveX-rayspectroscopy(EDX).However;XraypowderdiffractionwithRietve1dana1ysisindicatedapartia1a11o

10、ying,i.e.agradua1borderbetweenthetwometa1s.Ce11cu1tureexperimentsshowednoadverseeffectsonhumanmesenchyma1stemce11s(hMSCs)withaPdAunanopartic1econcentration(computedastota1meta1)upto50mgm11after24hincubation,i.e.thepartic1escanbeconsideredasbio1ogica11yharm1ess,evenafterunintendedhumanexposure.Anumbe

11、rofexperimenta1andtheoretica1reportshasbeenpub1ishedaboutthePdAusystem,rangingfroma11oyednanopartic1estophysica11ypreparedthinfi1ms.Zhangeta1.haveprepareda11oyedPdAunanopartic1eswithadiameterofabout50to60nmbyco-reductioninthepresenceofCu2*,a1soinporousform.Kuna1eta1.havereportedamicrowavebasedsynthe

12、sisofa11oyedPdAunanopartides(po1yo1process)withabout2.5nmdiameterwithvariab1ecompositionandtestedtheminthecata1ytichydrogenationofa1kenes.161Hahneta1.havepreparedthinfi1msofPdAu(thicknessabout100-150nm)forthee1ectrocata1yticreductionofCo2Prevoteta1.haveinvestigatedthetherma1behaviourofcarbon-support

13、edPdAunanopartic1es(3.4nm;about40at%Pd).Theyfoundthatdea11oyingoccurredafter10hat6008C,inc1udinganOstwa1d-ripeningof1argepartic1esontheexpenseofsma11partic1es.181Twokindsofcore-she11partic1escanbeprepared:Go1dcore/pa11adiumshe11(AuPd)andpa11adiumcore/go1dshe11(PdAu).Thefirstsystemiseasiertoprepareas

14、thereisnoga1vanicrep1acementwhenaddingpa11adiumionstoameta11icgo1dcoreJ4Itisa1soofdirectinterestforpa11adium-basedheterogeneouscata1ysis.Go1dnanocubeswerecoatedwitha1ayerofpa11adiumby1ieta1.(fu11diameterdownto12nm)byaseed-mediatedsynthesis.191Spita1eeta1.havepreparedAuPdcore-she11nanopartic1es(6nmAu

15、core,2nmPdshe11thickness)andcarriedoutatomisticsimu1ationsonthissystemJ10deSantiseta1.havestudiedtheformationofAuPdcore-she11nanopartic1esofvariousdiameters(around100nm)andshapesbyanextensivevariationoftheseeded-growthmethodparamaters.,n1Forthepreparationofcore-she11structureswithapa11adiumcoreandago1dshe11,aga1vanicrep1acementofpa11adiummeta1bygo1dions(oxidativeetching)mustbeavoided.Here,thereducingagentmustbeproper1ychosen.Gopa1aneta1.havestudiedthecata1yticperformanceofPdAucore-she11nanopartic1es(5nmPdcore,5nmAushe11thickness).

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