超分子研究方向概述

超分主讲：潘梅化学的内1、化学的内------化学是一门理论和实验推动并驾齐驱的科学出理论之思维，…。在自然科学中，化 ---唐有棋1数学是研究“数”“形”和“系统”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、生命、地球各门学科可以按照研究从简单到复杂 数学物 化 生物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科信息科生材料科信息科生命什么是化 Chemistryisthestudyofthepropertiesofmaterialsandthechangesthatmaterialsundergo ，化学物质构成了物体（气，液，固等） 次，如电子、中子、质子和原子核总称亚原子微粒subatomic 分子，本质上就是一个核——电子体系相互联系，并且通过所谓“自组装”（self–assembling)或“自组织”（self-organizing）构筑成的某种高级结构体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19世纪：化学是原子的科学20世纪：化学是分子 55万2340万

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：泛分子的十个

21世纪化学研究的十个

21世纪化学研究的几个从合成、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 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 经过近20多年的快速发展，超分子化学已远远了原来有机化学主客装、超分子器件，超分子材料等，构成了化学大中一个颇具的新兴的分子信息化学。它包括在分子水平和结构特征上的信息，以:TheLock& proposedthatanenzymeinteractswithitssubstrateasakeydoeswithitslockin1894.Recognizedevenbeforemolecularstructurewaswellunderstoodthatshapematters.Specificinteractionbetweentwospeciesrequirescomplementaryshape&chemistrylikeakeyfittingintoalock.Thisconceptlaidthebasisformolecularrecognition,thediscriminationbyahostbetweenanumberofguests.（1902NobelNobel ---SupramolecularJean-MarieLehn(1939-,France)DonaldJ.Cram(1919-,USA)SharedtheNobelPrizeinChemistry1987“Fortheirdevelopmentanduseofmoleculeswithstructure-specificinteractionsofhigh家莱恩因开发和使用具高选择性、结构特异性相互反应的分子，而共获得1987

CharlesJ.Pedersen(1904-1989,CharlesCharlesJ.Pedersen:Crown冠醚O冠醚 ODibenzo-18-Crown-CharlesCharlesJ.Pedersen:CrownO Oxygenatomsdonateafractionoftheirelectron densitytoOO deficientspeciessuchasalkalications:Li,Na,KOOOQ:WhydidhegetOO fordifferentOO CharlesCharlesJ.DiscoveredessentiallybyThinkaboutstructure.3Dshape.ComputersimulationsandCPKPreparedanentireseriesofcrown-etherseachwiththeirownparticularselectivityforvariouscationsSelectivitybaseprimarilyonKIt’seasy:somefitsomeDonaldDonaldJ.Cram:Pre- “Spherand”-preorganized Q:WhatdidhemeanbyDonaldDonaldJ.Synthesizedahugeseriesofincreasinglycomplicatedhost-guestsystemsthatbindmoleculesinsteadofjustionsandeventuallytriestoemulateanenzymecatalyticsite.Introducestheideaofa“carcerand”-syntheticmolecular(jail)cells.PrimarycontributionistoshowhowpreorganizationistobindingShowstheapplicationofsomehostsforpracticalapplication:resolutionofracemicmixturesHowdo 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:InwhatwayarethesecomplexesfundamentallydifferentfromCram’s&Pedersen’s?Jean-MarieIntroduced“Cryptands”-bicyclichostsforbindingHostswithmultiplebindingPopularizedtheideaofself-assemblyandproducedsomeofthefirstgoodsyntheticexamplesBroadenedpeoples sonwhatsupramolecularchemistryisandtowhatitmayleadthewayTheflagbearerofsupramolecularchemistry-inmanywaysheearnedhisNobelPrizeafterthefactBeyondBeyondHost/GuestChemistry:Surface/Surfaceinteractions+ AssemblydoesAssemblydoesnotneedtoleadtodiscretestructuresQ:Towhatdoesthiskindofassemblyopenthe10-6

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Natureisnotalways………sothereisaneedtodesignandsynthesizethatperformusefulfunctions……maybeusingnatureasaninspirationNature’sCatalysts-Enzymes:Enzymes:BiologicalCatalystswithremarkableefficiencyandselectivity.BiomimeticBiomimeticCatalysisofIntermodularAminoacylJ.J.AM.CHEM.SOC.2007,129,748-749NaturalSensors-TasteChemicalbindingandNaturalMaterials(polymers)SpiderSilkNaturalMaterials(helix)Meso-Su,C.-Y.etalJ.Chem.Soc.,DaltonTrans.2001,(16),WenbinLinetal.,CHEM.COMMUN.,2003,Howtodo

andutilizeExperimentsinsupramolecularchemistryMolecular

MolecularStructure:Diffraction

TheLinkbetweenStructureand

TheLinkbetweenStructureand反Searchforytical AFM,Chip-structuringwithion Biochip-SmartPolymerwithtunable Lowk-AntireflectiveSurfacesSwitchableMaterialsPropertiesSub-100nm BlockCopolymerSelfAimDevelopmentofNewApplicativeSubmitCollaborative„FWF-Pakete“,FFF-Projects,SFB-CrystalFirstcoinedbyG.M.J. idtinAddresstheproblemofcrystalpredictioninthecontextoforganicsolidstatephotochemicalreactionofcinnamicacidDevelopedbyG.R.Desirajuet.al.inTheunderstandingofintermolecularinteractionsinthecontextofcrystalpackingandintheutilizationofsuchunderstandinginthedesignofnewsolidswithdesiredphysicalandchemicalproperties.MolecularPeterJ.Formationofdiscretesupramolecularspecieswithwell-defined,predesignedshapesandgeometriesbasedonself-assemblystrategy.M.MolecularpanelingviaCrystalCoordinationhybridInorganicOrganicCrystal

HydrogenKitagawaetalAngew.Chem.Int.Ed.2004,43,MolecularM.Fujita,etal.,Chem.Commun.,2001,(6),509-Platonic

Truncated Snub Intermolecularbondisagenerictermthatincludesionpairing(electrostatic),hydrophobicandhydrophillicinteractions,hydrogen-bonding,host-guestinteractions,pi-stacking,andVanderWallsinteractions.Somewouldalsoincludethecoordinatebondinthislistiftheroleofthemetalistoactasanatta 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配位金属原子和配位体间形成的共价配键 超分子合成合成子：用已知的或合成操作所能形成Asupramolecularsynthonisastructuralunitformedbyintermolecularinteractions(e.gcarboxylicacidH-bondeddimerObservednative SupramolecularStructuralVirtualmutant

IncerebroMolecularrecognition—theprocessbywhichonemoleculebindsonlytoitsspecifictargetandtonoother.Itisthedegreeofelectronicandstericcomplementaritybetweenhostandguestthat,ingeneral,dictatesthemagnitudeofanymolecularrecognitionthatoccursforagivensupramolecularsystem.Thepresenceofchiralityinhostandguestwilllikewiseaffecttheinteractionbetweenthem.Chiralitycanperhapsbeseenasa‘secondorder’sourceofstoredstructuralinformationthatisavailableforexploitation,oftenwithdramaticeffect,forachievinganadditionaltypeofhost–guestrecognitionbasedon‘handedness’.Ofcentralimportanceinarangeofbiologicalandmedicalareasincluding,forexample,fieldsasdiverseasimmunology,pharmacologyandgenetics.Offundamentalimportancetoanumberofchemicalareas.Theserangefromsensorandother yticalapplications,throughseparationscience,toaspectsofcatalysis.Molecularrecognitionisalsocrucialtoorganictemplatingeffectswhich,themselves,representaspecializedformofself-assembly 生物大分子的相互作用，信号传导，生物调材料组超分催化剂设计冠 空腔直/

适合的离（直径四面体三环氮杂冠醚中N原子的四4布，对同样大小的K+和NH+44NH+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 结合过程中的构象中性分子Host-guestchemistry Abranchofchemistryinwhichresearchersstudytheinteractionsbetweentwomolecules(naturalorsynthetic)withthegoalofeithermimickingorblockingabiologicaleffectcausedbythemolecules'interaction.Preorganisationeffectimpliesthatthemorecloselythebindingsitesofahostmoleculearearrangedforbindingtoaguest,thelargerwillbetheassociationconstantforthecorrespondinghost–guestcomplex.Therewillbeminimalchangeinthedegreesofconformationalfreedomofthehostonbindingtotheguest,suchlower‘lossofdisorder’ofthehostfavoursentropiccontributiontotheoverallfreeenergyofhost–guestcomplexassembly:Classically,allthreewillplayasequentialroleincomplexation.Namely,appropriatepreorganisationofthebondingsitesinthehostforreceivingtheguestthuspredisposestheformerforguestrecognition.This,inturn,promotesspontaneousself-assemblyoftherequiredsupramolecularentity.Inpart,thestabilityoftheguestdependsuponthedegreeofpreorganisationofhostwithrespecttoguestsincetheforcesactingintherecognitionstepwillalso,inessence,continuetoactintheproductafterHost-GuestSystemandMolecularSupramoleculeisamolecularsysteminwhichthecomponentsareheldreversiblybyintermolecularforces,notbycovalentbondsX

NonYDifferentDifferentHost/GuestInclusion NestingPerching CapsularTypesTypesofChelate Self-Self-Assembly:Theidealsupramolecularsystemrequiresonlymixingofthecomponentcompoundsinordertoproducethedesiredaggregate.Theideaofspontaneousself-assemblycomesintoplaybecausethemolecularcomponentsare'preorganized'andthuscontaininformationintheformofmolecularrecognitionfeaturesthataremutuallycomplementary."Thearchitecturalandfunctionalfeaturesoforganizedsupramolecularstructuresresultfromthemolecularinformationstoredinthecomponentsandfromtheactivegroupswhichtheybear.““Molecularsynthesisisatechnologythatchemistsusetomakemoleculesbyformingcovalentbondsbetweenatoms.Molecularself-assemblyisaprocessinwhichmolecules(orpartsofmolecules)spontaneouslyformorderedaggregatesandinvolvesnohumanintervention;theinteractionsinvolvedusuallyarenoncovalent.”(GeorgeM.Whitesides)Self-Self-Assembly:maybedefinedastheprocessbywhichasupramolecularspeciesformsspontaneouslyfromitscomponents.Forthemajorityofsyntheticsystemsitappearstobeabeautifullysimpleconvergentprocess,givingrisetotheassembledtargetinastraightforwardmanner.(Stoddart)Self-assemblyisveryfarfromauniquefeatureofsupramolecularsystems–itisubiquitousthroughoutlifechemistry.Biologicalsystemsaside,self-assemblyisalsocommonplacethroughoutchemistry.Thegrowthofcrystals,theformationofliquidcrystals,thespontaneousgenerationofsyntheticlipidbilayers,thesynthesisofmetalco-ordinationcomplexes,andthealignmentofmoleculesonexistingsurfacesarebutafewofthemanymanifestationsofself-assemblyinchemicalsystems.Adistinctivefeatureofusingweak,non-covalentforces,orforthatmattermetal–donorbonds,inmolecularassembliesisthatsuchinteractionsarenormallyreadilyreversiblesothatthefinalproductisinthermodynamicequilibriumwithitscomponents(usuallyviaitscorrespondingpartiallyassembledintermediates).Thisleadstoanadditionalpropertyofmostsupramolecularsystems:theyhaveanin-builtcapacityforerrorcorrectionnotnormallyavailabletofullycovalentsystems.自组超分子自组装：分子之间依靠分子间相互作电子因素：各种分子间作用力得到几何因素：分子的几何形状和大小互相Itneedstobenotedthatsupramolecularsystemsmayalsoformunderkineticratherthanthermodynamiccontrol.Thissituationwilltendtobemorelikelyforlargersupramolecularassembliesincorporatingmanyintermolecularcontacts,especiallywhen yrigidcomponentsareinvolved.Itmayalsotendtooccurwhenmetalions,andespeciallykineticallyinertmetalions,areincorporatedintheframeworkoftheresultingsupramolecularentity.When,forexample,anintermediateproductintheassemblyprocessprecipitatesoutofsolutionbecauseofitslowsolubility. mechanismsofformationanddissociation.Littleinsightexistsintotheco-operativenatureofindividualhost–guestcontactsindirectingthecourseoftheassemblyprocesses.SupramolecularHost-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’sadoublehelixisSyntheticself-assembledcyclicpeptide CyclicPeptideNanotubesasScaffoldsforConductingDevicesHydrogen-bondinginteractionspromotestackingofcyclicpeptidesPi-systemsstackface-to-facetoallowconductionalongthelengthofthetubeCooperandMcGimpseyCYCLICBIOSYSTEMSCarbonOrganic-M.R.WhatisaItisanespeciallystable,hexameric,diskshapedThedisksspontaneouslystackinsolutiontoproducecylindricalThesubunitsweredesignedandsynthesizedtopossessaWatson-Crickdonor-donor-acceptorH-bondarrayofguanineandacceptor-acceptor-donorofcytosine.Eachsubunit(sixforeach“rosette”)alsopossessesasidechain;theidentityofwhichdictatesthefunctionalityoftheresultingThearrowsindicatetheDDA-AAD