超分子研究方向概述

超分子与物主讲：潘梅化学的1、化学的化学是这样一门科学，它和其他学科的相互交叉与渗透日益深化，新的化------化学是一门理论和实验推动并驾齐驱的科化学是一门中心的、实用的、创造性学出理论之思维，…。在自然科学 ---唐有棋1数学是研究“数”“形”和“系统”的最根本的基础2物理学是研究自然界物质－能量系统的最普遍规律的科学）化学是一门承上启下的中心科学Central化学是与资源、环境、能源、材料、信息、生空间和核科学等朝阳科学（Sun-risesciences）都有紧密的联如果把科学比拟为各门学科可以按照研究从简单到复杂 领头学科中心学科前沿学化学要用数理、生物学要用数理化、医学要用数理化材料信息生命材料信息生命什么是化 Chemistryisthestudyofthepropertiesofmaterialsandthechangesthatmaterialsundergo 次，如电子、中子、质子和原子核总称亚原子微粒subatomic 核——电子体系–（self-organizing）构筑成的某种高级结SupramolecularChemistry:chemistrybeyondthemolecule,supramolecularchemistryaimsatdevelo highlycomplexchemicalsystemsfromcomponentsinteractingbynoncovalentintermolecularforces---Jean-MarieLehn 化学家StephenJ.Lippard1998在讨论化学的未来25年时有一段 21世纪化学的特19世纪：化学是原子的科学20世纪：化学是分子认识分子及化合 2340万

21世纪：Panmolecules—— pacificconference)度的态和组装态，直到分子材料、分子器件和分子机器的合成和反应，、剪裁和组-- --21世纪化学研究的对象：泛分子的十

21世纪化学研究的十个

21世纪化学研究的几个特从合成、自组装make合成化学的新方法：化、组合化、模板化、定性更加注重2、超分子化学的定义及其发展历学。超分子化学是基于分子间的非共价键相互作用而形成的分子 体的组装、结构与功能。 由分子到超分子和分子间相互作用的关系，正如由原子到分子和共价键超分子化学 世纪三十年代，当时是胶体化学的一个鼎盛时期，德国K.L.体系。但实际上，直到1978年，法国J.M.Lehn基于传统的植 的:TheLock& proposedthatanenzymeinteractswithitssubstrateasakeydoeswithitslockin1894.Recognizedevenbeforemolecularstructurewaswellunderstoodthatshapematters.Specificinteractionbetweentwospeciesrequirescomplementaryshape&chemistrylikeakeyfittingintoalock.Thisconceptlaidthebasisformolecularrecognition,thediscriminationbyahostbetweenanumberofguests.（1902NobelNobel ---SupramolecularJean-MarieLehn(1939-,France)DonaldJ.Cram(1919-,USA)SharedtheNobelPrizeinChemistry1987“Fortheirdevelopmentanduseofmoleculeswithstructure-specificinteractionsofhigh、佩家莱恩因开发和使用具高选择性、结构特性相互反应的而共获1987

CharlesJ.Pedersen(1904-1989,CharlesCharlesJ.Pedersen:Crown冠醚O冠醚 OCharlesCharlesJ.Pedersen:CrownO Oxygenatomsdonatefractionoftheir densitytoOO deficientspeciessuchasalkalications:Li,Na,KOOOQ:WhydidhegetOO fordifferentOO CharlesCharlesJ.DiscoveredessentiallybyThinkaboutstructure.3Dshape.ComputersimulationsandCPKPreparedanentireseriesofcrown-etherseachwiththeirownparticularselectivityforvariouscationsSelectivitybaseprimarilyon15-crown-KIt’seasy:somefitsomeDonaldDonaldJ.Cram:Pre- “Spherand”-preorganized Q:WhatdidhemeanbyDonaldDonaldJ.Synthesizedahugeseriesofincreasinglycomplicatedhost-guestsystemsthatbindmoleculesinsteadofjustionsandeventuallytriestoemulateanenzymecatalyticsite.Introducestheideaofa“carcerand”-syntheticmolecular(jail)cells.PrimarycontributionistoshowhowpreorganizationistobindingShowstheapplicationofsomehostsforapplication:resolutionofracemicHowdo lwhichisahost&whichisa

bindingsitesfaceinward,orbindingsitesfaceoutward,orTwoormoremoleculesheldtogetherinauniquestructuralrelationshipbynon-covalent(weak)forces.OOOOOONJean-Marie穴醚穴醚ONOOJML’sfamous[2.2.2]Jean-MarieJean-MarieLehn:Self-NN2NN NN2NNNN3Q:InwhatwayarethesecomplexesdifferentfromCram’s&Jean-MarieIntroduced“Cryptands”-bicyclichostsforbindingHostswithmultiplebindingPopularizedtheideaofself-assemblyandproducedsomeofthefirstgoodsyntheticexamplesBroadenedpeoples sonwhatsupramolecularchemistryisandtowhatitmayleadthewayTheflagbearerofsupramolecularchemistry-inwaysheearnedhisNobelPrizeaftertheBeyondHost/G Surface/Surfaceinteractions+Divergentorexo-supramolecular AssemblydoesAssemblydoesnotneedtoleadtodiscretestructuresQ:Towhatdoesthiskindofassemblyopenthe10-6

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Natureisnotalways………sothereisaneedtodesignandsynthesizemoleculesthatperformusefulfunctions……maybeusingnatureasanNature’sCatalysts-Enzymes:Enzymes:BiologicalCatalystswithremarkableefficiencyandselectivity.BiomimeticBiomimeticCatalysisofIntermodularAminoacylJ.J.AM.CHEM.2007,129,748-NaturalSensors-TasteChemicalbindingandNaturalMaterials(polymers)SpiderSilkNaturalMaterials(helix)Meso-Su,C.-Y.etalJ.Chem.Soc.,DaltonTrans.2001,(16),WenbinLinetal.,CHEM.COMMUN.,2003,Howtodo

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TheLinkbetweenStructureand反Searchfor AFM,Chip-structuringwithionBiomedical SmartPolymerwithtunable Lowk-SwitchableMaterialsSub-100nm BlockCopolymerSelfAimDevelopmentofNewApplicativeSubmitCollaborative„FWF-Pakete“,FFF-Projects,SFB-CrystalFirstcoinedbyG.M.J. idtinAddresstheproblemofcrystalpredictioninthecontextoforganicstatephotochemicalreactionofcinnamicDevelopedbyG.R.Desirajuet.al.inTheunderstandingofintermolecularinteractionsinthecontextofcrystalpackingandintheutilizationofsuchunderstandinginthedesignofnewsolidswithdesiredphysicalandchemicalproperties.MolecularPeterJ.Formationofdiscretesupramolecularspecieswithwell-predesignedshapesandgeometriesbasedonself-assemblyM.MolecularpanelingviaCrystalCoordinationhybridInorganicOrganicCrystal

Self-KitagawaetalAngew.Chem.Int.Ed.2004,43,MolecularM.Fujita,etal.,Chem.Commun.,2001,(6),509-Archimedean

Intermolecularbondisagenerictermthatincludesionpairing(electrostatic),hydrophobicandhydrophillicinteractions,hydrogen-bonding,host-guestinteractions,pi-stacking,andVanderWallsinteractions.Somewouldalsoincludethecoordinatebondinthislistiftheroleofthemetalistoa anatta enttemplate.structuralunitswithinsupermoleculeswhichcanbeformedand/orassembledbyknownorconceivablesyntheticoperationsinvolvingintermolecularinteractions."(Desiraju)Therecognitionanduseofthesespacialarrangementsofintermolecularinteractionsfollowsthesamelinesasinconventionalorganicsynthesis.分子间键（次级键 ——＋ ＋＋＋

—+——＋—+——＋（b）常规氢键X- X,Y=F,O,N,C,非常规氢 X- X- X- （c）M-L金属原子和配位体间形成的共价配键 合成子：用已知的或合成操作所能形成Asupramolecularsynthonisastructuralunitformedbyintermolecularinteractions(e.gcarboxylicacidH-bondeddimerObservednative SupramolecularStructuralVirtualmutant

IncerebroMolecularrecognition—theprocessbywhichonemoleculebindsonlytoitsspecificandtonoItisthedegreeofelectronicandstericcomplementaritybetweenhostandguestthat,ingeneral,dictatesthemagnitudeofanymolecularrecognitionthatoccursforagivensupramolecularsystem.Thepresenceofchiralityinhostandguestwilllikewiseaffecttheinteractionbetweenthem.Chiralitycanperhapsbeseenasa‘secondorder’sourceofstoredstructuralinformationthatisavailableforexploitation,oftenwithdramaticeffect,forachievinganadditionaltypeofhost–guestrecognitionbasedon‘handedness’.Ofcentralimportanceinarangeofbiologicalandmedicalareasincluding,example,fieldsasdiverseasimmunology,pharmacologyandOffundamentalimportancetoanumberofchemicalareas.Theserangefromsensorandother yticalapplications,throughseparationscience,toaspectsofcatalysis.Molecularrecognitionisalsocrucialtoorganictemplatingeffectswhich,themselves,representaspecializedformofself-assembly分子识 生物大分子的相互作材料组超分催化剂设计 适合的离 （/ （b）四面体三环氮杂冠醚中N原子的布，对同样大小的K+和NH+4NH+结合4生物分子相互作TwobiomoleculesthatinteractwithBig Small氧气 ，镰刀型贫=oxygenHeamoglobinProtein,transportsoxygenintheAntibodies,锁 原是超分子体系识别功能和专一选择功能锁和间每一局部是弱的相互作用，但各个局部之间相 模型–分子形状的互补 结合过程中的构中性分 Abranchofchemistryinwhichresearchersstudytheinteractionsbetweentwomolecules(naturalorsynthetic)withthegoalofeithermimickingorblockingabiologicaleffectcausedbythemolecules'interaction.Preorganisationeffectimpliesthatthemorecloselythebindingsitesofahostmoleculearearrangedforbindingtoaguest,thelargerwillbetheassociationconstantforthecorrespondinghost–gomplex.Therewillbeminimalchangeinthedegreesofconformationalfreedomofthehostonbindingtotheguest,suchlower‘lossofdisorder’ofthehostfavoursentropiccontributiontotheoverallfreeenergyofhost–g Relationshipbetweenmolecularpreorganisation,recognitionandself-assembly:Classically,allthreewillplayasequentialroleincomplexation.Namely,appropriatepreorganisationofthebondingsitesinthehostforreceivingtheguestthuspredisposestheformerforguestrecognition.This,inturn,promotesspontaneousself-assemblyoftherequiredsupramolecularentity.Inpart,thestabilityoftheguestdependsuponthedegreeofpreorganisationofhostwithrespecttoguestsincetheforcesactingintherecognitionstepwillalso,inessence,continuetoactintheproductafterHost-GuestSystemandMolecularSupramoleculeisamolecularsysteminwhichthecomponentsareheldreversiblybyintermolecularforces,notbycovalentbonds

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NonDifferentDifferentHost/GuestInclusion Nesting CapsularTypesTypesofChelate Self-Self-Assembly:Theidealsupramolecularsystemrequiresonlymixingofthecomponentcompoundsinordertoproducethedesiredaggregate.Theideaofspontaneousself-assemblycomesintoplaybecausethemolecularcomponentsare'preorganized'andthuscontaininformationintheformofmolecularrecognitionfeaturesthataremutuallycomplementary."Thearchitecturalandfunctionalfeaturesoforganizedsupramolecularstructuresresultfromthemolecularinformationstoredinthecomponentsandfromtheactivegroupswhichtheybear.““Molecularsynthesisisatechnologythatchemistsusetomakemoleculesbyformingcovalentbondsbetweenatoms.Molecularself-assemblyisaprocessinwhi olecules(orpartsofmolecules)spontaneouslyformorderedaggregatesandinvolvesnohumanintervention;theinteractionsinvolvedusuallyarenoncovalent.”(GeorgeM.Whitesides)Self-Self-Assembly:maybedefinedastheprocessbywhichasupramolecularspeciesformsspontaneouslyfromitscomponents.Forthemajorityofsyntheticsystemsitappearstobeabeautifullysimpleconvergentprocess,givingrisetotheassembledinastraightforwardmanner.Self-assemblyisveryfarfromauniquefeatureofsupramolecularsystems–itisubiquitousthroughoutlifechemistry.Biologicalsystemsaside,self-assemblyisalsocommonplacethroughoutchemistry.Thegrowthofcrystals,theformationofliquidcrystals,thespontaneousgenerationofsyntheticlipidbilayers,thesynthesisofmetalco-ordinationcomplexes,andthealignmentofmoleculesonexistingsurfacesarebutafewofthemanymanifestationsofself-assemblyinchemicalsystems.Adistinctivefeatureofusingweak,non-covalentforces,orforthatmattermetal–donorbonds,inmolecularassembliesisthatsuchinteractionsarenormallyreadilyreversiblesothatthefinalproductisinthermodynamicequilibriumwithitscomponents(usuallyviaitscorrespondingpartiallyassembledintermediates).Thisleadstoanadditionalpropertyofmostsupramolecularsystems:theyhavein-builtcapacityforerrorcorrectionnotnormallyavailabletofullycovalent超分子自组装：分子之间依靠分子间相互作超分子自组装的根据电子因素：各种分子间作用力几何因素：分子的几何形状和大小互相NotalwaysItneedstobenotedthatsupramolecularsystemsmayalsoformkineticratherthanthermodynamicThissituationwilltendtobemorelikelyforlargersupramolecularassembliesincorporatingmanyintermolecularcontacts,especiallywhen yrigidcomponentsareinvolved.Itmayalsotendtooccurwhenmetalions,andespeciallykineticallyinertmetalions,areincorporatedintheframeworkoftheresultingsupramolecularentity.When,forexample,anintermediateproductintheassemblyprecipitatesoutofsolutionbecauseofitslow VerylittlecorrespondinginformationisavailableconcerningtheircontactsindirectingthecourseoftheassemblySupramolecularHost-guestCatenanesandHelicalSyntheticMesoscaleyin(万古霉素）anaturalguestforD-Ala-D-（D-丙氨酰－D丙氨酸naturallyoccuring-(1,4)-linkedglucoseCatalyticactivityofcyclodextrinswithguestmoleculesModificationofthechemicalreactivityofguestmoleculesImprovementofsolubilityofStabilisationoflight-oroxygen-sensitivesubstancesProtectionagainstdegradationbyFixationofveryvolatileRebek’sTripoddimerencapsulatesResorcinol间苯二CatenanesandTheInterlockingofTwoMolecularTwo-stationHelicalderivativesofnaturalhelicala-helicalDNA,RNA,and artificialhelicalb-andg-poly-amideshelicesmetalcomplexesLehn’sadoublehelixisself-assembledcyclicpeptide CyclicPeptideNanotubesasScaffoldsforConductingDevicesHydrogen-bondinginteractionspromotestackingofcyclicpeptidesPi-systemsstackface-to-facetoallowconductionalongthelengthoftheCooperandMcGimpseyCYCLICCarbonOrganic-M.R.WhatisaItisanespeciallystable,hexameric,diskshapedThedisksspontaneouslystackinsolutiontoproducecylindricalThesubunitsweredesignedandsynthesizedtopossessaWatson-Crickdonor-donor-acceptorH-bondarrayofguanineandacceptor-acceptor-donorofcytosine.Eachsubunit(sixforeach“rosette”)alsopossessesasidechain;theidentityofwhichdictatesthefunctionalityoftheresultingThea