超分子與物主講：潘梅化學的1、化學的化學是這樣一門科學，它和其他學科的相互交叉與滲透日益深化，新的化------化學是一門理論和實驗推動并駕齊驅的科化學是一門中心的、實用的、創(chuàng)造性學出理論之思維，…。在自然科學 ---唐有棋1數(shù)學是研究“數(shù)”“形”和“系統(tǒng)”的最根本的基礎2物理學是研究自然界物質－能量系統(tǒng)的最普遍規(guī)律的科學）化學是一門承上啟下的中心科學Central化學是與資源、環(huán)境、能源、材料、信息、生空間和核科學等朝陽科學（Sun-risesciences）都有緊密的聯(lián)如果把科學比擬為各門學科可以按照研究從簡單到復雜 領頭學科中心學科前沿學化學要用數(shù)理、生物學要用數(shù)理化、醫(yī)學要用數(shù)理化材料信息生命材料信息生命什么是化 Chemistryisthestudyofthepropertiesofmaterialsandthechangesthatmaterialsundergo 次，如電子、中子、質子和原子核總稱亞原子微粒subatomic 核——電子體系–（self-organizing）構筑成的某種高級結SupramolecularChemistry:chemistrybeyondthemolecule,supramolecularchemistryaimsatdevelo highlycomplexchemicalsystemsfromcomponentsinteractingbynoncovalentintermolecularforces---Jean-MarieLehn 化學家StephenJ.Lippard1998在討論化學的未來25年時有一段 21世紀化學的特19世紀：化學是原子的科學20世紀：化學是分子認識分子及化合 2340萬

21世紀：Panmolecules—— pacificconference)度的態(tài)和組裝態(tài)，直到分子材料、分子器件和分子機器的合成和反應，、剪裁和組-- --21世紀化學研究的對象：泛分子的十

21世紀化學研究的十個

21世紀化學研究的幾個特從合成、自組裝make合成化學的新方法：化、組合化、模板化、定性更加注重2、超分子化學的定義及其發(fā)展歷學。超分子化學是基于分子間的非共價鍵相互作用而形成的分子 體的組裝、結構與功能。 由分子到超分子和分子間相互作用的關系，正如由原子到分子和共價鍵超分子化學 世紀三十年代，當時是膠體化學的一個鼎盛時期，德國K.L.體系。但實際上，直到1978年，法國J.M.Lehn基于傳統(tǒng)的植 的:TheLock& proposedthatanenzymeinteractswithitssubstrateasakeydoeswithitslockin1894.Recognizedevenbeforemolecularstructurewaswellunderstoodthatshapematters.Specificinteractionbetweentwospeciesrequirescomplementaryshape&chemistrylikeakeyfittingintoalock.Thisconceptlaidthebasisformolecularrecognition,thediscriminationbyahostbetweenanumberofguests.（1902NobelNobel ---SupramolecularJean-MarieLehn(1939-,France)DonaldJ.Cram(1919-,USA)SharedtheNobelPrizeinChemistry1987“Fortheirdevelopmentanduseofmoleculeswithstructure-specificinteractionsofhigh、佩家萊恩因開發(fā)和使用具高選擇性、結構特性相互反應的而共獲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.分子間鍵（次級鍵 ——＋ ＋＋＋

—+——＋—+——＋（b）常規(guī)氫鍵X- X,Y=F,O,N,C,非常規(guī)氫 X- X- X- （c）M-L金屬原子和配位體間形成的共價配鍵 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分子識 生物大分子的相互作材料組超分催化劑設計 適合的離 （/ （b）四面體三環(huán)氮雜冠醚中N原子的布，對同樣大小的K+和NH+4NH+結合4生物分子相互作TwobiomoleculesthatinteractwithBig Small氧氣 ，鐮刀型貧=oxygenHeamoglobinProtein,transportsoxygenintheAntibodies,鎖 原是超分子體系識別功能和專一選擇功能鎖和間每一局部是弱的相互作用，但各個局部之間相 模型–分子形狀的互補 結合過程中的構中性分 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

Y

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超分子自組裝：分子之間依靠分子間相互作超分子自組裝的根據(jù)電子因素：各種分子間作用力幾何因素：分子的幾何形狀和大小互相NotalwaysItneedstobenotedthatsupramolecularsystemsmayalsoformkineticratherthanthermodynamicThissituationwilltendtobemorelikelyforlargersupramolecularassembliesincorporatingmanyintermolecularcontacts,especiallywhen yrigidcomponentsareinvolved.Itmayalsotendtooccurwhenmetalions,andespeciallykineticallyinertmetalions,areincorporatedintheframeworkoftheresultingsupramolecularentity.When,forexample,anintermediateproductintheassemblyprecipitatesoutofsolutionbecauseofitslow VerylittlecorrespondinginformationisavailableconcerningtheircontactsindirectingthecourseoftheassemblySupramolecularHost-guestCatenanesandHelicalSyntheticMesoscaleyin(萬古霉素）anaturalguestforD-Ala-D-（D-丙氨酰－D丙氨酸naturallyoccuring-(1,4)-linkedglucoseCatalyticactivityofcyclodextrinswithguestmoleculesModificationofthechemicalreactivityofguestmoleculesImprovementofsolubilityofStabilisationoflight-oroxygen-sensitivesubstancesProtectionagainstdegradationbyFixationofveryvolatileRebek’sTripoddimerencapsulatesResorcinol間苯二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