上转换荧光纳米材料的水溶性修饰-王亚立

PＲOGＲESSINCHEMISTＲYDOI10.7536/PC151207http//．progchem．ac．cnProgressinChemistry2016285617～627*＊＊430072/、、。、、、、、。、、、。O631TB383A1005-281X201605-0617-11201512201612016515*No．21375098TheworkwassupportedbytheNationalNaturalScienceFoundationofChinaNo．21375098．＊＊[e-mail]UpconversionNanoparticles*WangYaliLiZhenLiuZhihong＊＊CollegeofChemistryandMolecularScienceWuhanUniversityWuhan430072ChinaAbstractUpconversionnanoparticlesUCNPshavebeenwidelyemployedinbiosensingbioimagingphotodynamictherapyanddrugdeliveryinthepasttenyears．Presentlyupconversionnanoparticlesareobtainedviathermaldecompositionco-precipitationandsolvothermalmethodswitholeylamineoroleicacidassurfactantsalwayshavelowsizedispersitystrongluminescenceanddispersewellinnonpolarsolventslikecyclohexane．Howeverthesekindsofnanoparticlesarenormallycoveredbyalayerofoleicacidoroleylaminemoleculesandhencearenotsuitablefordirectlyusinginbiologicalenvironments．Thesubsequentsurfacemodificationwhichcanturnhydrophobicnanoparticlesintohydrophiliconesisthereforerequired．Thesemethodsincludeligandexchangeligandoxidationamphiphilicpolymercoatingsilicacoatingandligandremovalandsoon．ThisaccountthrowsacriticallookatthemethodsforsurfacemodificationandfunctionalizationthatleadtoUCNPsforuseinaqueousmediaanddiscussestheadvantagesanddisadvantagesofthesestrategies．KeywordsupconversionnanoparticlehydrophobichydrophilicligandsurfacemodificationContents1Introduction2Surfacemodification2.1Ligandoxidation2.2Ligandexchange2.3Amphiphilicligandcoating2.4Ligandremoval2.5Layer-by-layerassemblyＲeview·618·ProgressinChemistry2016285617～6272.6Silicacoatingandsilanization3Bioconjugation3.1Covalentconjugation3.2Electrostaticattraction3.3VanderWaalsBonding3.4DirectattachmentofbiomoleculetoNPsurface4Conclusionandoutlook1、。Yb3+980nmEr3+、Tm3+、Ho3+。NaYF41～4。。、、、5～7。、、、、。8。、、Yan910LaCF3COO3、LaF3。Liu11、。//1213。。、、。、、、14～16。1pH、234、。261123456。114Fig．1Typicalsurfacemodificationstrategiesforupconversionnanoparticles142.1Lemieux-vonＲudloff1718、1920、。1718Lemieux-vonＲudloffMnO4－IO4－。、、2016285617～627·619·。MnO2MnO2。Liu21MnO280%。MnO2MnO2。1920。。。2.2、、。2223、24、25、26、2728302931、29、3233。2.2.1。Yin29240℃22。。Murray35、NOBF4BF－4BF－4DMF、DMSO。BF－4Han36Chen37NOBF4。、、、Fe2O3、、MnS2。2.2.22223、272830、24。—SH、—NH2、—COOH、—PO3H14。。Song26NaYF4∶Yb3+Er3+Ag+222。226Fig．2SilvercoatingontheUCNPsmodifiedbythioglycolicacid262.2.3PAA2931、PEI29、33、32PEG、34。Ｒeview·620·ProgressinChemistry2016285617～627pH。VanVeggel327502000。200075012nm。2.2.4Vinogradov3865%。18%。pH5～12。、。NaYF4∶YbEr。39。2.340。2.3.143、、4041。、、。Lu41341Fig．3Thestructureofthedesignedphospholipidandthecoatingprocess41DNA。pH。1μmol30000。42、43、44。。2.3.2-。-4546、-PMAO47～50、-PEG-b-PCL51、-PEG-b-PLA521-。Chow45∶=5∶865%35%2016285617～627·621·37。、、PBSpH=7.4Tris-borate-EDTApH=9.3。2.3.3。47～49。Liu47PEG-PMAO。Feng49。。pH=3～1350。2.4、pH5354。Capobianco53pH4。pHpH4。pHpH≤4pH≥7453。DLVO4pH53Fig．4ThesurfaceofUCNPsunderdifferentpH53。Liu5556Fluo-4。Ca2+5。1.2fM。5Ca2+55Fig．5SchematicillustrationoftheNIＲnanoprobefordetectionofcalcium552.5616。Li57。。。2.6、Ｒeview·622·ProgressinChemistry2016285617～627616Fig．6Thelayer-by-layerassemblyofUCNPs16、59。2.6.1Stber60～6667～70。2.6.1.1StberStber60～63。Veggel60Stber9nm。Zhang641～3nm。Stber。6566。Stber、。2.6.1.2。IgepalCO-52067。68～70。。2.6.2。Zhang717。Lin72～74Fe3O4@SiO2@mSiO2@NaYF4Yb/ErGd2O3Er@SiO2@mSiO2NaYF4Yb/Er@SiO2@mSiO2。Lin73CTABP123500℃。7NaYF4@silicaZnPc71Fig．7MesoporoussilicacoatingonthesurfaceofNaYF4@silicaandloadingofZnPc712.6.383236、58647576、69～71、77、7879、80。3--2016285617～627·623·58。、3--、3-3236、69～7180。33.1、、98182。868Fig．8Thesilanizationofsilica-coatedUCNPs6895Fig．9BioconjugationchemistryforhydrophilicNPsthroughcovalentbonding53.1.1、、、1-3--3-EDCN-NHS、。Liu8384ππ-π。3.1.2、、83。Chen86DMFO--NNN'N'-HBTU/NN-DIEAZrO2Ln3+CaF2Ln3+10。Liu87Sulfo-SMCCＲeview·624·ProgressinChemistry2016285617～62710HBTU/DIEA86Fig．10ThecovalentcouplingofbiotinwithNPswithHBTU/DIEAascrosslinker86MMP-2。CHO61SCN8990、。9192Li176-。Zako81Y2O3@SiO2-NH2NHSＲGD。3.1.3Wolfbei79dye-6Cu+。3.2Yan57Zetapotential=+14.25mVZetapotential=－28.95PBSpH=7.4。Liu93MA-PEG-NaYF4Yb/Tm@SiO2siＲNAsiＲNA。Liu9411。-23-。。Chen95LiYF4Yb/Erβ-96.3%。11FＲET94Fig．11TheFＲETmodelofUCNPsandsilvernanoclustersconnectedbyelectrostaticattraction943.3Li46P-PEG12。FsterMeHg+。3.4、。Lu96DNADNA13DNA2016285617～627·625·1246Fig．12DyesloadedinthehydrophobiclayerontheNPssurdface4613DNA96Fig．13ThedirectexchangebetweenDNAandoleate-coatedUCNPs96。DNADNA。4、、、、、。、、。、、、、、。。1234。、、。1HanSYDengＲＲXieXJLiuXG．Angew．Chem．Int．Ed．20145311702．2FrancüoisA．Chem．Ｒev．2004104139．3GaiSLLiCXYangPPLinJ．Chem．Ｒev．20141142343．4WangJWangFWangCLiuZLiuXG．Angew．Chem．Int．Ed．20115010369．5ZhouJLiuZLiFY．Chem．Soc．Ｒev20124131323．6GnachABednarkiewiczA．NanoToday．201276532．7ZhangFLiJShanJXuLZhaoD．Chem．EurJ．20091511010．8WangYHShenPLiCYWangYYLiuZH．Anal．Chem．2012841466．9ZhangYWSiＲYouLPYanCH．J．Am．Chem．Soc．20051273260．10MaiHXZhangYWSunLDYanCH．J．Phys．Chem．C200711113725．11WangFDengＲＲLiuXG．NatureProtocols200791634．12WenHLZhuHChenXHungTFWangBLZhuGYYuSFWangF．Angew．Chem．Int．Ed．2013