大分子自组装研究的进展_江明.ppt

大分子自组装研究的进展StudiesonMacromolecularSelf-assembly江明复旦大学高分子科学系,分子组装是最普遍的物理化学现象，是构建生命体系的基本途径,大分子自组装是超分子化学和高分子科学的交叉领域Macromolecularself-assembly-interdisciplinaryresearchfieldImportantPartofSupramolecularChemistryandpolymerscience大分子自组装是创造具有纳米或亚微米尺度的结构新物质的简单和清洁的途径Simpleandcleanwaystocreatenew,structuredpolymericmaterials(softmatters)innanoorsub-microsizes,美国科学杂志于2005年出版专刊，提出了21世纪亟待解决的25个重大科学问题，化学自组装是其中唯一的化学问题。,RobertF.ServiceScience2005,309,95.,MacromolecularSelf-assembly:大分子自组装的两重含义：以大分子为组装单元构建组装体Macromoleculesasbuildingblockstoformstructuredassemblies以小分子为组装单元构建超分子聚合物SmallmoleculesasbuildingblockstoformSupramolecularPolymers,ACiferri,MacromolecularRapidCommunications,2002,23,511,A,B,Buildingblocks:smallmoleculeswithproton-donatingandprotonacceptinggroups,A,B,SupramolecularPolymersALittleworkinChina,Macromoleculesasbuildingblockstoformstructuredassemblies,Micellizationofblockcopolymersinselectivesolvents,Covalentbondsconnectingthecoreandshell,selectivesolventforredblock,selectivesolventforblueblock,Characters:Size10-200nmAmphiphilicityApplications:EncapsulationDrug-delivery,Micro-reactor:Nano-metalparticles,Nano-semi-conductorparticlesCatalysis,至80年代末我国无系统性大分子自组装研究先驱性的研究Pioneerwork90年代初吉林大学沈家骢,张希等,气/液界面“浮萍”与“倒浮萍”膜组装,提出了类“浮萍”与“倒浮萍”聚合物超薄膜的模型，利用亲、疏水力进行组装，为解决聚合物膜的稳定性与有序度相矛盾的问题提供了新思路。,沈家骢、张希等Langmuir,1994,10,2727ThinSolidFilms,1992,210,625Macromolecules,1991,24,4986Macromolecules,1990,23,5158,系列学术研讨会1991年沈家骢H.Ringsdorf长春夏季化学研讨会：有序功能体系国际香山科学讨论会-1994年超分子体系1998年超分子体系:从分子构筑到功能组装2001年超分子体系：材料科学与生命科学间的桥梁2004年超分子体系：从微米/纳米结构研究材料科学和生物技术的方法,杨柏,吉林大学张希,清华大学高长有,浙江大学SupramolecularLayeredStructureMulti-layermembreneNano-patteringofsurfaceHollowmicro-encapsules,基于高分子胶束的层状组装：偶氮苯分子的包覆与光致异构化速率的提高,一般偶氮苯在固态膜中的光致异构化速率和效率常常比其在溶液中低。我们巧妙的利用高分子胶束结构所提供的微环境，使偶氮苯光致异构化的速率在固态膜中比其在溶液中还快一倍。,LbL薄膜,甲苯溶液,张希等etal.Langmuir,2006,22,3906,4.0710-3,9.0310-3,1.1410-2,复旦大学FudanUniversityMingJiang（江明）DaoyongChen（陈道勇）PingYao（姚萍）,90年代初，研究兴趣在高分子氢键相互作用和相容性问题,PS(OH)-XX8mol%PMMA,大分子络合物驱动力：氢键自发过程分子组装？,EachAchaininteractswithmanyBchainsandviceversa,无规则的聚集体,separatedcoils,+,我们反复思考的问题是：能否通过高分子间的络合作用实现规则组装？,我们提出并成功地实现了“高分子胶束化的非嵌段共聚物路线”“Block-copolymer-freeroutesforpolymericmicellizationviainterpolymercomplexation”,Interactiongroups,将质子给体基限于链的端基上Restrictingthereactiongroupswithincertainpositionsalongthechain,OneofApproaches,hydrogenbondingleadstograftcopolymersandthen非共价键合胶束(NCCM),Protondonorends,Protonacceptor,NCCM,In,obverseandreverseNCCMofCPB/PVPy,PVPy,CPB,nitromethane,Inchloroform,ObverseNCCM,ReverseNCCM,hexane,polybutadienewithcarboxylgroupsatends,PVPy-(CPB),(PVPy)-CPB,HydrodynamicDiameter(Dh)Distribution,多种途径实现“非嵌段共聚物胶束化”均聚物，离聚物，齐聚物，接枝共聚物等均可用为组装单元,这是具有普遍意义的路线：Polyimide/PVPy-containingpolymersJACS,123,12097,2001;JPhysChemB,108,550,2004;108,5225,2004Carboxyl-endpolybutadiene(CPB)/Poly(vinylalcohol)(PVA)-Macromolecules,37,1537,2004Poly(carprolactone)(PCL)/Poly(acrylicAcid)(PAA),Langmuir21,1531,2005Poly(styrene-co-MAA)/Poly(vinlpyrollidone)Langmuir,17,6122,2001PCL/PMAA-g-PCLAngewChemIntlEdi,41,2950,2002,利用核-壳“非共价”连接，通过壳交联和核溶解获得空心球,Greatinterestinobtainingpolymerichollowspheres:LiuG,WooleyK,degradable,crosslinkable,blockcopolymer,selectivesolvent,crosslinking,photo-degradation,chemical-degradation,FromNCCMtoHollowSpheres,TEMImageofHollowSphereobtainedbycoredissolutionfromNCCMof(PCL)-PAA,环境响应胶束：pH,温度，光，离子强度等,HydroethylCellulose(HEC)gPoly(AcrylicAcid)HEC-g-PAA,Self-assemblyofDoubleHydrophilicGraftCopolymer,DouHJ,JiangMetal.AngewChemIntlEd42,1516,2003,Ce()/H+,HEC-g-PAA,Preparationofgraftcoplymer,接枝共聚物分子量的表征,CharacteristicdataofHEC-g-PAAcopolymers,Cellulase,+,PAAgrafts,AGU,Table2-2LLSCharacteristicdataofCAA-1andCAA-2,/=1.50Meansrandomcoil,RadiusofGyrationRgHydrodynamicRadiusRh,ThesolutionatpHrangeof2-3wasunstable:theapparentincreasedwithtime.Thevaluesmeasured20minafterthesolutionpreparationwereused.,Figure3-2ofHEC-g-PAAcopolymersasafunctionofpH.Theconcentrationwas1mg/ml.,pH3,molecularlydissolvedpH3),-COOHofPAAatpH3cancomplexwithHECandformthe“core”ofmicellesUncomplexedHECsegmentsformthe“shell”ofmicelles,(pH3,molecularlydissolvedAtlowpH,PAAprotonated,formingcomplexwithHECmainchaincore;HECwithoutPAAbranchesformedshellpH-controlledcomplexation-inducedmicellization(lowgraftingdensityisnecessary!),COOHCOO-+H+,pH,pH,AtlowpH,CrosslinkingofPAAgrafts-tolockthestructure,Dialysisagainstwater,pH37:DLS:size350nm650nmTEM:micelleshollowspheres,AtpH7,HollowSpheresForm!,pH3-7:pH-dependentmicelle-hollow-spheretransition,pH1.3交联PAA,pHincrease,Core-crosslinkedmiclle,Lowcrosslinkingdensityisnecessary!,pH=1.3Stablemicelle,交联剂：2,2-(ethylenedioxy)bis(ethylamine),Dialysis,pH=7PAA+HECdecomplexation,Reversible?,pH3,protonation,complexation,pH7,deprotonation,de-complexation,disintergaration,Reversibilityofthetransition,pH3-7:pH-dependentmicelle-hollow-spheretransition,TEMobservations（CAA2）,pH=1.3pHinducedmicelles,pH=7Hollowspheres,pH=1.3pH-inducedmicellesafteronepHcycle,PNIPAM(Polyisopropylacrylamide)-basedreversiblethermo-sensitivityAdvFunctMat15,695(2005),PAA-basedpH4.58.5,volumeincreasesby130timesLangmuir21,1531(2005),Buildingblock:linearpolymersArchitecturaleffect?DendrimerandDendronasbuildingblocks,PreparationofDendronG3,H-BondingDendronizedPolymers,FormationofnanoparticlesfromG3/PVPincommonsolvent,ultrasonictreatment,Hollowspheres?,Collapsedthin-layerhollowspheres?,Crosslinkedhollowspheres-muchhighstrength,G3/PVP23Thickwallhollowspheres,Self-assemblydrivenbyH-BondingOtherdrivingforces?Inclusioncomplexation?,环糊精cyclodextrin,7,hydrophilicity,hydrophobicity,StructuresandpropertiesofAdamantane(ADA),d77V18032623,Adamantane,Complexstableconstant105,The-CDcavityapparentlyhastheoptimumdimensionsforinteractionwithadamantanederivate.,7,Adamantane,CD,环糊精是研究的最多的作用主体在高分子方面主要是用于多聚轮烷-CD/PEO,如何将环糊精的包结络合用于构建高分子胶束？,通过inclusioncomplexation构建高分子胶束基本思路：合成分别带CD和ADA的亲水和疏水高分子，在水中形成通过inclusioninteraction连接的核壳胶束（NCCM）,ATRP,Mn=1.67x104,Mw/Mn=1.21,Mn=1.87x104,Mw/Mn=1.28,CD-containingmonomerGMA-CD,PGMA-CDMW10,400,Characters:Double-scalehydrophobicregions:100nmand0.7nmCavitiesavailableforsurfacemodification,NH2,-COOH,negativelycharged,positivelycharged,Micellesurfacemodification,HollowsphereofcrosslinkedPGMA-CD,DoubleScaleCavities,环糊精的包结络合在大分子组装研究中有很大的发展空间:表面活性剂;纳米金属粒子;光响应有机分子;催化,陈道勇等：聚合反应/组装同步法合成纳米结构Macromolecules2005,38,3550,Most-AccessedArticles:20051.NanoporousPolystyreneContainingHydrophilicPoresfromanABCTriblockCopolymerPrecursorRzayev,J.;Hillmyer,M.A.Macromolecules2005,38(1),pp3-5.2.AOne-PotApproachtothePreparationofOrganicCore-ShellNanoobjectswithDifferentMorphologiesPeng,H.;Chen,D.;Jiang,M.Macromolecules2005,38(9),pp3550-3553.3.SynthesisandDirectVisualizationofBlockCopolymersComposedofDifferentMacromolecularArchitecturesPyun,J.;Tang,C.;Kowalewski,T.;Frechet,J.M.J.;Hawker,C.J.Macromolecules2005,38(7),pp2674-2685.4.Deep-RedElectroluminescentPolymers:4.SynthesisandCharacterizationofNewLow-Band-GapConjugatedCopolymersforLight-EmittingDiodesandPhotovoltaicDevicesYang,R.;Tian,R.;Yan,J.;Zhang,Y.;Yang,J.;Hou,Q.;Yang,W.;Zhang,C.;Cao,Y.Macromolecules2005,38(2),pp244-253.,2005据,2005全年第二,陈道勇，江明AccountofChemicalResearch,38,494,2005StrategiesforConstructingPolymericMicellesandHollowSpheresinSolutionviaSpecificIntermolecularInteractions,新挑战：从合成高分子到天然大分子TargetMaterials:MicellesorNanocore-shellhydrogelmadeofproteinsandpolysacchridsbiocompatible,biodegradable,non-toxicandeveneatable（可食用性）PingYao(姚萍），FudanUniversity,Ovalbumin(白蛋白）andLysozyme（溶菌酶）,Ovalbumin:385aa,Mw47000DaIsoelectricPoint4.7,7nm4.5nm5nm,Lysozyme:129aa,Mw14351DaIsoelectricPoint10.7,3.8nm2.4nm2.2nm,5.3,4.7,10.7,已寻求到合适途径获得核壳纳米微凝胶MixingatpH5.3,weakinteractionAdjustpH10.3,Lysaggregates,OvalProtectionHeatdenatured,具有普遍意义的途径,Globular+Globular:OvalbuminandLysozymeBovineSerumAlbuminandLysozymeOvalbuminandOvertransferrinLinear+Globular:as-Casein+Overtransferrin(as,beta,kappa-)Casein+LysozymeGlobularproteins+PolysaccharideOvalbumin+ChitosanYaoetal:Langmuir22,2754,2006Biopolymers81,29,2006JColloisInterfaceSci.,inpressBiopolymersinpres