纳米反应器研究进展

纳米反应器研究进展第1页/共42页ContentsConceptofNanoReactorRecentDevelopmentsofNanoreactors

MolecularNanoreactorMacromolecularNanoreactorBio-macromolecularNanoreactorOutlook第2页/共42页NanoReactorreactantsproductsInspiredbyNatureNanoReactorCompartmentalization/Accumulation/ConfinementStabilizedspecifictransitionstates&products(CascadeReactioninTime&Space)(TunedActivity,Selectivity&Stability)Well-defined

ReactionEnvironments

ChemicalConversionsinNatureEnzyme------Cell

nmμmCouplingofReactionsinTime&Space第3页/共42页DimensionMolecularNanoreactorSupramolecularNanoreactorMacromolecularNanoreactorBiomacromolecularNaonoreactorBuilt-upviaCovalentbondH-bondComplexationElectrostaticsVanderWaalsNanoReactorApplications:Targetchemicalsynthesis,nanoparticlesynthesis,catalysis,sensor,detector…MolecularNanoreactorSupramolecular&MacromolecularNanoreactorBiomacromolecularNanoreactor第4页/共42页MolecularNanoreactor

SpecificBindingInteraction(directional,selective)StabilizedTransitionState&LoweredEa

Renstein,D.G.Chem.Rev.1987,87,1047.Kirby,A.J.Angew.Chem.,Int.Ed.Engl.1996,35,707.SelectivelyRecognize&BindaDesiredSubstrate.Examples:crownether,calixrene,cyclodextrin,etc.(Covalent-bondedorself-assembled)EnzymemimicEnzymeMimicP450BindingCavityBreslow,R.;Huang,Y.;Zhang,X.;Yang,J.Proc.Natl.Acad.Sci.U.S.A.1997,94,11156.第5页/共42页1234Breslow,R.;Huang,Y.;Zhang,X.;Yang,J.Proc.Natl.Acad.Sci.U.S.A.1997,94,11156.CovalentMolecularNanoreactor----CyclodextrinFixationEffectEnzymemimic234Androstane-3,17-diolBreslow,R.;Zhang,X.;Huang,Y.J.Am.Chem.Soc.1997,119,4535.NoreactionMixture56第6页/共42页NoncovalentMolecularNanoreactorsHof,F.;Craig,S.L.;Nuckolls,C.;Rebek,J.,Jr.Angew.Chem.,Int.Ed.2002,41,1488.Covalent

Non-covalent(reversible)Y.Aoyama,Y.Tanaka,H.Toi,H.Ogoshi,J.Am.Chem.Soc.1988,110,634.T.Heinz,D.M.Rudkevich,J.Rebek,Jr.,Nature

1998,394,764.O.D.Fox,J.F.Y.Leung,J.M.Hunter,N.K.Dalley,R.G.Harrison,Inorg.Chem.2000,39,783.directionalandspecificH-bondComplexationmorerobust第7页/共42页NoncovalentMolecularNanoreactorviaHbondReactionAccelerationWiththeCapsule2:

Rateacceleration:manyyears(>humanlifescale)toseveraldaysHighselectivity:only1,4-additionproductwasobserved.Chen,J.;Rebek,J.,Jr.Org.Lett.2002,4,327.Notfitting---Noreaction1第8页/共42页Non-covalentNanoreactorviaComplexationYield:88%.Yield:90%.Yield:92%.ConfinementEffect“cavity-directedsynthesis”bowl-shapetube-shapecage-shapeYoshizawa,M.;Kusukawa,T.;Fujita,M.;Sakamoto,S.;Yamaguchi,K.J.Am.Chem.Soc.2001,123,10454.Yoshizawa,M.;Kusukawa,T.;Fujita,M.;Yamaguchi,K.J.Am.Chem.Soc.2000,122,6311.第9页/共42页Epoxidationofstyrene1:lifetime<10min&TON<5001-2:stableformanyhours&10-foldincreaseinTONMerlau,M.;DelPilarMejia,M.;Nguyen,S.T.;Hupp,J.T.Angew.Chem.,Int.Ed.2001,40,4239.StabilizationEffectNon-covalentNanoreactorviaComplexationCytochromeP450Complex1-29x18Ahalf-cavityTheenhancedstabilityandenhancedTONsofthecatalystassemblies[1.2]and[3.2]comparedtothefreecatalyst1.第10页/共42页SupramolecularNanoreactorsCellmimicCellMembrane:LiposomeSupramolecularNanoreactorMicelleNanoreactor

VesicleNanoreactorEmulsionNanoreactor

Enhancedreactionrateandselectivity(I)Increasedlocalconcentrationofthereactantsatthesurfaceorintheinteriorofthemicelle;(ii)Stabilizationofthetransitionstateofthereactionduetoafavorableinteractionwiththesurfactantmolecules;(iii)Combinedpolarity,microviscosity,andchargeeffectinsidethemicelle(amediumeffect).第11页/共42页Fuji,K.;Morimote,T.;Tsutsumi,K.;Kakiuchi,K.Angew.Chem.,Int.Ed.2003,42,2409.SupramolecularNanoreactorBiphaseReactiondpppwater-insolubleTPPTSwater-soluble第12页/共42页Polymermicelle,Polymervesicle,Lay-by-layer,Uni-macromoleculeZeolite,Sol-gel,MetalorganicframeworkOrganicmacromolecularnanoreactorInorganicmacromolecularnanoreactorMacromolecularNanoreactorsMacromolecularNanoreactors(Supra)molecularNanoreactors

Limitsinsize,stability,availability,surfacechargeCameron,N.S.;Corbierre,M.K.;Eisenberg,A.Can.J.Chem.1999,77,1311.Vastavailabilityofmonomerscompositions,molecularweights,dispersities,functionalities,shapesIncreasedstabilityandtherigidity,increasedlifetimetunablevesicle/micellesize,polarity,stability,toxicity,etc.IncreasedthicknessesReducedpermeability&lessfluidiccharacter

ComparedtomolecularmicelleMacromolecularmicellePS-PLAPS-PLAPEO-PEEPS-b-PALAJain,S.;Bates,F.S.Science2003,300,460.第13页/共42页

Polymer/NP:hybridnanocatalystMetal:Ag,Au,Co,Cu,Ni,Pb,Pd,Pt,Rh,andZn,etc.Oxide/sulfide:Fe2O3,TiO2,ZnO,CdS,CoS,CuS,FeS,PbS,andZnS,etc.InclusionofEnzymePolymerMicelleNanoreactor

SynthesisofNanoparticle第14页/共42页Combinedadvantagesofhomogeneous&heterogeneouscatalysisDissolvedinorganicsolvents,heterogeneousnature,recoveredbyultrafiltrationorprecipitationinpoorsolvents

Polymer/NP:HybridNanocatalystReactionscope:Hydrogenation,oxidation,Heck,Suzuki,carbonylation…PVP:poly(N-vinyl-2-pyrrolidone)Thecolloidmetalcatalystkeptincolloidalstateforrepeatedusefor6timeslasting56.5h,thetotalturn-over-numberreachesto19700cycles/atomRh.Wang,Q.;Liu,H.;Han,M.;Li,X.;Jiang,D.J.Mol.Catal.A:Chem.1997,118,145.Rh-PVP第15页/共42页PolymerVesicleforEnzymeInclusionResponsivegate-keepingNardin,C.;Thoeni,S.;Widmer,J.;Winterhalter,M.;Meier,W.Chem.Commun.2000,1433.Nardin,C.;Widmer,J.;Winterhalter,M.;Meier,W.Eur.Phys.J.E2001,4,403.Transmembranepotential-controlledgate-keeping

Closewith∆ϕ>100mVOmpF:gate-keeper第16页/共42页InorganicPorousNanoreactorZeoliteSol-gelderivedporoussolidMOF(Metalorganicframework)Rigidstructure,easytoprocess,vastavailabilityincomposition,porousstructureMesoporousMaterialsFacilesynthesisTunedsurface/frameworkpropertiesControllableporesize(100~102nm)andstructureLargeporevolumeandspecificsurfacearea

Nanocatalysis(compartmentalization)DrugdeliveryAdsorption/separation/sensorNano-structuredmaterialssynthesis

In-situorpostinclusionZeolite第17页/共42页“Fish-in-net”forEnzymeYang,X.;Li,Z.;Liu,B.;Klein-Hofmann,A.;Tian,G.;Feng,Y.;Ding,Y.;Su,D.;Xiao,F.Adv.Mater.2006,18,410.第18页/共42页BiomacromolecularNanoreactorTobaccoMosaicVirus.2130identicalproteinbuildingblockshelicalmotifaroundtheviralRNAahollowtubeof300x18nminsizeacentralchannelthathasadiameterof4nm.Bychemicallycontrollingthesurfacechargeofthevirus,metallizationwasselectivelyperformedontheoutercylindricalsurfaceorintheinnercavity.Shenton,W.;Douglas,T.;Young,M.;Stubbs,G.;Mann,S.Adv.Mater.1999,11,253.Dujardin,E.;Peet,C.;Stubbs,G.;Culver,J.N.;Mann,S.NanoLett.2003,3,413.Outside:lysine,argininepKa11~12.5Inside:asparticandglutamicacidpKa1~3and6~8第19页/共42页OutlookHierarchical-structuredNanoreactorsSingle-molecularnanoreactorwithdefinedbindingcavityMicelleandvesicleassembliesaspotentialcellmembraneandenzymemimicsNumerousnewavenuesprovidedbysupramolecularchemistryPredefinedbindingsites(selective,reversible)TunablecavitydimensionSmartenvironment-response(gate-keeping)Rigidity,processibility,compatibility.ChemistryMolecularBiologyConstructionofaSynthetic

Cell!

ThankYouforYourAttention!第20页/共42页References(1)Gorenstein,D.G.Chem.Rev.1987,87,1047.(2)Kirby,A.J.Angew.Chem.,Int.Ed.Engl.1996,35,707(3)Breslow,R.;Huang,Y.;Zhang,X.;Yang,J.Proc.Natl.Acad.Sci.U.S.A.1997,94,11156.(4)Yoshizawa,M.;Kusukawa,T.;Fujita,M.;Sakamoto,S.;Yamaguchi,K.J.Am.Chem.Soc.2001,123,10454.(5)Merlau,M.;DelPilarMejia,M.;Nguyen,S.T.;Hupp,J.T.Angew.Chem.,Int.Ed.2001,40,4239.(6)Fuji,K.;Morimote,T.;Tsutsumi,K.;Kakiuchi,K.Angew.Chem.,Int.Ed.2003,42,2409.(7)Wang,Q.;Liu,H.;Han,M.;Li,X.;Jiang,D.J.Mol.Catal.A:Chem.1997,118,145.(8)Nardin,C.;Thoeni,S.;Widmer,J.;Winterhalter,M.;Meier,W.Chem.Commun.2000,1433.(9)Nardin,C.;Widmer,J.;Winterhalter,M.;Meier,W.Eur.Phys.J.E2001,4,403.(10)Peyratout,C.S.;Mohwald,H.;Dahne,L.Adv.Mater.2003,15,1722.(11)Yang,X.;Li,Z.;Liu,B.;Klein-Hofmann,A.;Tian,G.;Feng,Y.;Ding,Y.;Su,D.;Xiao,F.Adv.Mater.2006,18,410.(12)Shenton,W.;Douglas,T.;Young,M.;Stubbs,G.;Mann,S.Adv.Mater.1999,11,253.(13)Dujardin,E.;Peet,C.;Stubbs,G.;Culver,J.N.;Mann,S.NanoLett.2003,3,413第21页/共42页(14).Walter,C.J.;Anderson,H.L.;Sanders,J.K.M.J.Chem.Soc.,Chem.Commun.1993,458.(15).Yoshizawa,M.;Kusukawa,T.;Fujita,M.;Yamaguchi,K.J.Am.Chem.Soc.2000,122,6311.

(16).

Kusukawa,T.;Yoshizawa,M.;Fujita,M.Angew.Chem.,Int.Ed.2001,40,1879.(17)Aoyagi,M.;Biradha,K.;Fujita,M.J.Am.Chem.Soc.1999,121,7457.(18)Fujita,M.;Yu,S.-Y.;Kusukawa,T.;Funaki,H.;Ogura,K.;Yamaguchi,K.Angew.Chem.,Int.Ed.1998,37,2082.(19)Yu,S.-Y.;Kusukawa,T.;Biradha,K.;Fujita,M.J.Am.Chem.Soc.2000,122,2665.(20)Fujita,M.;Oguro,D.;Miyazawa,M.;Yamaguchi,K.;Ogura,K.Nature1995,378,469.(21)Kusukawa,T.;Fujita,M.Angew.Chem.,Int.Ed.1998,37,3142.(22)Ibukuro,F.;Kusukawa,T.;Fujita,M.J.Am.Chem.Soc.1998,120,8561.(22)Kusukawa,T.;Fujita,M.J.Am.Chem.Soc.1999,121,1397.(23)Kusukawa,T.;Yoshizawa,M.;Fujita,M.Angew.Chem.,Int.Ed.2001,40,1879.References(continued)第22页/共42页CovalentMolecularNanoreactor----Cyclodextrin120-foldrateenhancement>99%selectivity,R=tButylBreslow,R.;Schmuck,C.J.Am.Chem.Soc.1996,118,6601Breslow,R.;Anslyn,E.J.Am.Chem.Soc.1989,111,8931.RibonucleasemimicFixationEffect第23页/共42页Angew.Chem.Int.Ed.2006,ASAPEmulsion第24页/共42页Peyratout,C.S.;Mohwald,H.;Dahne,L.Adv.Mater.2003,15,1722.PolymerCapsulebyLbLShip-in-bottlePSS:polystyrenesulfonatePAH:poly(allylaminehydrochloride)PIC:diethylcyanine

Lay-by-layerControlledstabilityandpermeabilitybyshellthickness,ionstrength,pH,viscosity…第25页/共42页Macromolecules第26页/共42页Uni-macromoleculeDendrimer,hyperbranchedpolymer,star-polymer.possessaninnercompartmentcapableofaccommodatingguestmolecules,themaindifferencebeingthattheyarenotdynamicassemblies第27页/共42页BiomacroProtein,virusOMpfPorinsareintegralouter-membraneproteinsofGram-negativebacteriathatfunctionasmolecularsieves(withexclusionlimitsofaround600Da)andareresponsiblefortheuptakeofsmallmolecularnutrientsandtheremovalofwasteproducts.

Sinceporinexistsonlyin(gramnegative)bacteria,itistheidealtargetofantibacterialagents.第28页/共42页Apo-ferritinDouglas,T.;Dickson,D.P.E.;Betteridge,S.;Charnock,J.;Garner,C.D.;Mann,S.Science1995,269,54.第29页/共42页Pd-apo-ferritinUeno,T.;Suzuki,M.;Goto,T.;Matsumoto,T.;Nagayama,K.;Watanabe,Y.Angew.Chem.,Int.Ed.2004,43,2527第30页/共42页M13Bacteriophage.

Inanotherstudy,M13viruseshavebeenappliedastemplatesforthesynthesisofmonodisperse,crystallinenanowiresofdifferentcompositions.First,thegeneticallymodifiedM13virusscaffoldwasusedtoassemblecrystallinenanoparticlesintoa1Darray.Thiswasfollowedbyamineralizationprocess,andfinallythemineralizedviruswasannealed,allowingthepolycrystallineassemblytoformasingle-crystalnanowirethroughtheremovaloftheorganictemplate第31页/共42页

Cpmv----CowpeaMosaicVirus60copiesofanasymmetricunitwhichcontainstwoproteinsubunits:asmallsubunit,theAdomain,andalargesubunit,theB+Cdomain第32页/共42页MoleculeNanoreactorNature1998,394,764.J.Chem.Soc.,Chem.Commun.1993,458.Nature1995,378,469.ascatalystsinbimolecularr