生物医用功能化磁性纳米粒子的制备与表征

烟台大学硕士学位论文生物医用功能化磁性纳米粒子的制备与表征姓名：孟强申请学位级别：硕士专业：材料学指导教师：徐仁根;丰伟悦20090601IPVAPEGFe3O4Fe3O4/PVAFe3O4/PEGPVAFe3O4PVA7.4%PVAPVAFe3O420-40nmFe3O4Fe3O4Fe3O4-OH11±3nm168nmICP-MS99.9313%Fe3O4Fe3O4IIFe3O4PEGPEGFe-O-SiFe3O463.4672.82%99.955%Fe3O4/PEGFe3O4PEGPEGFe3O4/PEGIIIAbstractTheresearchofmagneticnanoparticlesisoneofthefoucsinthefieldofbiomedicalnanomaterials.Magneticnanoparticlescoatedbydifferentpolymersormoleculescouldbeusedindifferentbiomedicalapplicationssuchascellseparation,magneticresonanceimagingcontrastenhancement,tissuerepair,immunoassay,hyperthermiaanddrugdelivery,etc.Inordertosynthesizethefunctionalmagneticnanoparticlesthatcouldarrivedtherequairsappliedinbiomedicalfields,werespectivelymodifiedthesurfaceofnanoparticlesbypolymers,PVAandPEG,whichwerenontoxicity,biodegradablity,andhadgoodwater-solubilityandbiocompatibility.Fe3O4/PVAandFe3O4/PEGmagneticpolymermicrospherepreparedwerecharacterizedbyFTIRTEMTGDLSICP-MSandVSM.Thespecificcontentinthispaperareasfollows:Fe3O4magneticnanoparticlesfirstlywerecoatedbyPVAviahydrogenbond.Afterrepresentation,WeconcludedthatthecontentsofPVAcoatingonthesurfaceofmagneticnanoparticlesinFe3O4/PVAcomplexwas7.4%;thewater-solubilityofcoatednanoparticleshadimproved;thedispersivityhadincreasedbecausethattheelectrostaticrepulsiveforcebetweenparticlesincreasedaftermodifyed.BecausethesizeoftheFe3O4magneticnanoparticlesusedasthemagneticcorewasbiggerandpoordistributed,themagneticpolymermicrospheregainedalsohadlargersizeandthedispersibityofitdidn’tarrivedtheprospectivestate.Tosynthesizegoodmagneticpolymermicrosphere,theremustbemagneticcorewhichhasfavorableproperties.SowedecidedtomaketheexperimentforpreparingFe3O4magneticnanoparticlesthathassmallsize,narrowdistribution,goodwater-solubilityandhighmagneticresponsive.WepreparedFe3O4magneticnanoparticlesbycoprecipitationmethodandtheoptimalconcitionwasobtainedthroughtheorthogonalexperiment.Theresultsofcharacterizationshewthatthesurfaceofsyntheticalmagneticnanoparticlesadsorbedplentyof–OHfunctionalgroupswhichofferedthenanoparticlesgoodhydrophilcityandmanysurfaceelectriccharges;theparticlesizewasuniformandtheaveragediameterwasonly11±3nm;thehydrodynamicIVdiameterswas168nmandthedistributionofsizewasnarrow;Fe3O4magneticnanoparticleshadhighsaturationmagnetizationandnearlysuperparamagneticfeature.Inaddition,thepurityofnanoparticleswas99.9313%obtainedbyICP-MS.Afercomparingthepropertiesofsyntheticalmagneticnanoparticleswithpurchased,weconcluedthatitwassuccessfullypreparedthatmagneticnanoparticleshadsmallsize,narrowdistribution,goodwater-solubilityandexcellentmagnetism.PEGwasusedasdressingagentformodifiedthesurfaceofFe3O4magneticnanoparticlesbythemethodofincubationinwaterbathandultrasonicationinturns.ThebetterconditionwasobtainedthroughdiscussingthefactorinfluencedthesizeofnanoparticlesbyDLS.ItwasfoundthatPEGwascombinedonthesurfaceofnanoparticlesviaFe-O-Sicovalentbond;coatednanoparticleshadlesssurfaceelectricchargesbutfavorabledispersivity,thereasonforthatwasdiscussedandanalyzedbythetheoryaboutcolloidaldispersionstability;theFecontentofcomplexwas63.4672.82%andthepurityofsamplewas99.955%;VSMresultsshewthehighsaturationmagnetizationandbetterparamagneticfeatureofFe3O4/PEGnanoparticles.Inshort,wesuccessfullypreparedtheFe3O4magneticnanoparticlesthathadbetterperformances.ThemodificationofPEGimprovedthebiocompatibility,dispersivityandwater-solubilityofnanoparticles.ThemagneticnanoparticlesprotectedbyPEGpolymercouldescapetheuptakeofmacrophagesoastoprolongthetimeofbloodcirculation.ItisclearthatFe3O4/PEGmagneticcomplexhasattainedtherequairsforthebiomedicalapplicationandcanpotentiallyusedinbiologyseparation,drugdeliveryandimmunoassay.Keywords:magneticnanoparticle,functionalization,PVA,PEG73111.1(nano-)[1][l-3][4]21.2Fe3O41.2.1Fe3O4VIIIAFeCoNiGdFeFe[5]FerriteFe3O4FeO·Fe2O3Fe3O424328Fe3O4Fe(III)Fe(III)Fe(II)Fe3O41.2.21.2.2.1109101510-9cm33SSuperparamagnetismFe3O416nm1.2.2.2PH=7.2~7.4-1.2.2.3-NH2-COOH-CHO-SH-OHDNARNA41.2.2.41.2.2.5201001/3DNA[6][7]1.3FeCoNi-Fe2O3Fe3O4CoFe2O4BaFe12O19CrO2Fe4NFe3O4Magnetiteγ5Fe3O41-100nm[8]d16nm[9,10]Fe3O4[11][12-15]Fe3O4(PCVD)-[16-22]1.3.1[Fe(CO)5][FeCP2][23]N2Fe(CO)5600Fe(CO)55~10nm150m2/g1.3.2Fe3O4Fe2++2Fe3++8OH-Fe3O4+4H2OFe2+Fe3+NH4OHNaOH6PHFe3O41-1[24]Fe3O4Fe2+/Fe3+PH1-1Fig.1-1ThesketchmapforsynthesisofmagneticnanoparticlesthroughcoprecipitationCheng[25]Fe2+Fe3+HClN(CH3)4OHPH6.21.4nmFe3O4[26]Fe3O410nmFe3O4Fe3O4[27]FeC13·6H2OFeCl2·6H2O1.8:1Fe3O430nm71emu·g-1Fe3O4-OHSi-OH-COOH71.3.3--Sol-GelSugimoto90-Sol-GelXu[28]40Fe(NO3)32h200400Fe3O4Dong[29]-Fe2O3ethyleneoxideEOEOHClFeCl3polyethyleneglycolPEGSol-GelSol-Gel100nm1.3.4(W/O)(O/W)5~70nm[30]O/WW/O3/()()()8Feltin[31]FeCl2sodiumdodecanesulphonateSDSFe(DS)2SDS3.711.6nmFe3O4Gupta[32]-2-(AOT)W/O1-2Fe2+Fe3+N2NaOH15nm1-2AOT/Fig.1-2StructureofAOT/n-hexanereversemicellesFe3O4Fe3O41.3.5organometallicprecursor9FeCoNi[33-35]Sun[36]Fe(acac)3Fe(CO)51,2-1,2-Fe3O44nmFePtFePt/Fe3O4Mfe2O4[37,38]1.3.6Fan[39]1.39gFeSO41.24gNa2S2O314ml10ml1.0mol/LNaOH14012h704h50nmFe3O490%3Fe2++2S2O32-+O2(aq)+4OHFe3O4(s)+