pH响应性表面对蛋白质吸附的调控

820118ACTAPOLYMERICASINICANo．8Aug．2011812*802011-03-252011-04-252097408620920102035＊＊[e-mail]10．3724/SP．J．1105．2011．11075pH*1121211＊＊12151232430070PtBMAPMAA．X、．PMAApH．pHpH．pH．pH=9pH=439．pH．pH1．．2～4．5．．PMAA．pHpH6～9．PMAApH、10．PMAApH．SI-ATRPPMAA．pH．11.1n1000.56mm0.5cm×0.5cm．tBMAAldrichCuBrFluka3-APTESAldrich2-BIBBAldrichNNN'N″N″-PMDETAAldrichFibrinogenMW=341kDapI=5.5Calbiochem125INaI．．1.2PMAASI-ATRPPMAA1．11ATRP．3.3mgCuBr2、7.15mgCuBr、0.031mLPMDETA、4mLtBMA3mL8pH．30min．60℃10min．Schlenk60℃30min120min240min．．PtBMA20mL3mL37%80℃2h．．Fig．1ProcessforgraftingPMAAfromsiliconsurface1aminosilanizationofsurface2immobilizationofinitiator3SI-ATRPoftBMAfrominitiator-immobilizedsurfaceand4hydrolysisofPtBMAtoPMAA1.3ESCALABMKIIXXPSVGScientificM-88J．A．WoollamSL200C．pH．Si-PMAApH30min．6．1.412．125I125I．PBSpH479960.25mL1mg/mLPBS3h．0.25mLPBS310min/Wallac2480Wizard3″PerkinElmer．3．μg/cm2．22.1PMAAATRPATRPMAA13．PtBMA．PtBMAPMAA2．Fig．2RelationshipofthethicknessofPtBMAandPMAAgraftlayerwiththepolymerizationtime4h3182011．、1．、、1415．Si-PtBMASi-PMAAC/N3.541.953.502.00．Table1PropertiesofthesamplesurfacesaSurfaceC/NexperimentC/NtheoryThicknessnmContactangle°Si-PtBMA3.543.5030.4±1.294.0±1.3Si-PMAA1.952.0019.2±0.845.3±1.6aEachvaluewasaveragedfromsixparallelmeasurements．3．16．．3Si-PtBMA53.2%PtBMAPMAA．Si-PtBMASi-PMAA1718．Si-PMAA．pH=7.4PMAA19．Fig．3AdsorptionoffibrinogenunderPBSbufferpH=7.4onSiSi-PtBMAandSi-PMAAsurfacesDataaremean±standarderrorn=3．2.2PMAApHPMAA———．pHPMAAPMAA15．PMAA．4pHCOO－pH．Si-PMAApH．Fig．4ReversibleconformationchangesofPMAAchainsandwatercontactangleofSi-PMAAsurfaceatdifferentpHSi-PMAApH=9pH=4．5pH．Fig．5ReversiblechangeofthestaticwatercontactangleroomtemperaturefortheSi-PMAAsurfaceafterexposingtosolutionswithtwodifferentpHDataaremeans±thestandarderrorn=6．pHSi-PMAA4188pH．5.5pH=4pH=9．6pH=4pH=9．pH20．PMAApH=43.08μg/cm2pH=90.08μg/cm239．pH．Fig．6AdsorptionoffibrinogenunderPBSbufferwithdifferentpHonunmodifiedandPMAA-graftedsiliconsurfacesDataaremean±standarderrorn=3．521．Si-PMAApHpH．pH=4PMAApH=9PMAA．pH=422．3ATRPPtBMAPMAA．Si-PMAApHpHpH．．pH=4pH=9Si-PMAA39．pH．REFERENCES1ChenHYuanLSongWWuZLiD．ProgPolymSci200833111059～10872WangYijuanJiangHongliangHuYingqianZhuKangjie．ActaPolymericaSinica20054524～5283SunLipingDuYuminChenLingyunHuangRonghuaChenXiao．ActaPolymericaSinica20042191～1954GilESHudsonSA．ProgPolymSci200429121173～12225TsapikouniTSMissirlisYF．MaterSciEngB20081521-32～76YuQChenHZhangYYuanLZhaoTLiXWangH．Langmuir2010262317812～178157YangJunLiuXiaoyunYanJieLiLanZhaLiusheng．ActaPolymericaSinica20097638～6448KonradiRRuheJ．Macromolecules2005384345～43549ParnellAJMartinSJDangCCGeogheganMJonesRALCrookCJHowseJRRyanAJ．Polymer2009501005～101410ColeMAVoelckerNHThissenHGriesserHJ．Biomaterials20093091827～185011YuQZhangYChenHWuZHuangHChengC．ColloidsSurfB2010762468～47412YuQZhangYChenHZhouFWuZHuangHBrashJL．Langmuir201026118582～858813SankheAYHussonSMKilbeySM．Macromolecules20063941376～138314BoyesSGAkgunBBrittainWJFosterMD．Macromolecules200336259539～954815TreatNDAyresNBoyesSGBrittainWJ．Macromolecules200639126～2916KwakDWuYGHorbettTA．JBiomedMaterRes200574A169～83518201117OstuniEChapmanRGHolmlinRETakayamaSWhitesidesGM．Langmuir200117185605～562018PrimeKLWhitesidesGM．JAmChemSoc19931152310714～1072119deVosWMBiesheuvelPMdeKeizerAKleijnJMCohenStuartMA．Langmuir200824136575～658420ChenLLiuMBaiHChenPXiaFHanDJiangL．JAmChemSoc20091313010467～1047221NathNHyunJMaHChilkotiA．SurfSci20045701-298～11022HuoDLiYQianQKobayashiT．ColloidsSurfB200650136～42REGULATIONOFPROTEINADSORPTIONONpH-RESPONSIVESURFACESLIXin1YUQian12ZHANGYanxia12WUZhaoqiang1CHENHong11CollegeofChemistryChemicalEngineeringandMaterialsScienceSoochowUniversitySuzhou2151232SchoolofMaterialsScienceandEngineeringWuhanUniversityofTechnologyWuhan430070AbstractPolymethacrylicacidPMAAmodifiedsiliconsurfaceSi-PMAAwaspreparedviasurface-initiatedatomtransferradicalpolymerizationATRPoftert-butylmethacrylatetBMAoninitiator-immobilizedsiliconfollowedbythehydrolysisofPtBMAtoPMAAThesuccessfulgraftprocesswasconfirmedbyX-rayphotoelectronspectroscopyXPSellipsometryandwatercontactanglecharacterizationThePMAAmodifiedsurfaceexhibitedpHresponsibilityofbothsurfacewettabilityandproteinadsorptionAtlowerpHpH=4theSi-PMAAsurfacewasrelativehydrophobicwithawatercontactangleWCAvalueca．48.9°WithanincreasingpHthesurfaceturnedmorehydrophilicandatpH=9theWCAvaluewasca．12.1°ThispH-responsivesurfacewettabilitycanbeexplainedbytheconformationaltransitionofpolymerchainsTheadditionofbasewilldeprotonatethependantcarboxylicacidicgroupsresultinginswollenpolymerchainswithmanyionizedCOO－whicharefavorablefortheentranceofwatermoleculesandmakethesurfacemorehydrophilicThispH-sensitivewettabilityoftheSi-PMAAsurfacewasreversibleforrepeatedcyclesofalternatingtreatmentbysolutionwithdifferentpHFibrinogenadsorptionontheSi-PMAAandunmodifiedsiliconsurfacewasevaluatedbyradio-labelingmethodTheresultsindicatedthatfibrinogenadsorptiononunmodifiedsiliconsurfaceatpH9wasslightlylowerthanthatatpH4whileaftermodificationwithPMAAtheeffectofpHwasgreaterTheadsorptionatpH4wasca．39timeshigherthan