超分主講：潘梅化學(xué)的內(nèi)1、化學(xué)的內(nèi)------化學(xué)是一門理論和實(shí)驗(yàn)推動(dòng)并駕齊驅(qū)的科學(xué)出理論之思維，…。在自然科學(xué)中，化 ---唐有棋1數(shù)學(xué)是研究“數(shù)”“形”和“系統(tǒng)”2物理學(xué)是研究自然界物質(zhì)－能量系統(tǒng)的最普遍規(guī)律的科學(xué)）化學(xué)是一門承上啟下的中心科學(xué)Central化學(xué)是與資源、環(huán)境、能源、材料、信息、生命、地球各門學(xué)科可以按照研究從簡(jiǎn)單到復(fù)雜 數(shù)學(xué)物 化 生物領(lǐng)頭學(xué)科中心學(xué)科前沿學(xué)化學(xué)要用數(shù)理、生物學(xué)要用數(shù)理化、醫(yī)學(xué)要用數(shù)理化材料科信息科生材料科信息科生命什么是化 Chemistryisthestudyofthepropertiesofmaterialsandthechangesthatmaterialsundergo ，化學(xué)物質(zhì)構(gòu)成了物體（氣，液，固等） 次，如電子、中子、質(zhì)子和原子核總稱亞原子微粒subatomic 分子，本質(zhì)上就是一個(gè)核——電子體系相互聯(lián)系，并且通過(guò)所謂“自組裝”（self–assembling)或“自組織”（self-organizing）構(gòu)筑成的某種高級(jí)結(jié)構(gòu)體SupramolecularChemistry:chemistrybeyondthemolecule,supramolecularchemistryaimsatdevelo highlycomplexchemicalsystemsfromcomponentsinteractingbynoncovalentintermolecularforces---Jean-MarieLehn 化學(xué)家StephenJ.Lippard1998在討論化學(xué)的未來(lái)25年時(shí)有一段 21世紀(jì)化學(xué)的19世紀(jì)：化學(xué)是原子的科學(xué)20世紀(jì)：化學(xué)是分子 55萬(wàn)2340萬(wàn)

21世紀(jì)：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(jī)器的合成和反應(yīng)，、剪裁和組-- --21世紀(jì)化學(xué)研究的對(duì)象：泛分子的十個(gè)

21世紀(jì)化學(xué)研究的十個(gè)

21世紀(jì)化學(xué)研究的幾個(gè)從合成、自組裝make合成化學(xué)的新方法：化、組合化、模板化、定性更加注重2、超分子化學(xué)的定義及其發(fā)展歷學(xué)。超分子化學(xué)是基于分子間的非共價(jià)鍵相互作用而形成的分子 體的組裝、結(jié)構(gòu)與功能。 由分子到超分子和分子間相互作用的關(guān)系，正如由原子到分子和共價(jià)鍵超分子化 世紀(jì)三十年代，當(dāng)時(shí)是膠體化學(xué)的一個(gè)鼎盛時(shí)期，德國(guó)K.L.體系。但實(shí)際上，直到1978年，法國(guó)J.M.Lehn基于傳統(tǒng)的植 經(jīng)過(guò)近20多年的快速發(fā)展，超分子化學(xué)已遠(yuǎn)遠(yuǎn)了原來(lái)有機(jī)化學(xué)主客裝、超分子器件，超分子材料等，構(gòu)成了化學(xué)大中一個(gè)頗具的新興的分子信息化學(xué)。它包括在分子水平和結(jié)構(gòu)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家萊恩因開(kāi)發(fā)和使用具高選擇性、結(jié)構(gòu)特異性相互反應(yīng)的分子，而共獲得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

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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.分子間鍵（次級(jí)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配位金屬原子和配位體間形成的共價(jià)配鍵 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，信號(hào)傳導(dǎo)，生物調(diào)材料組超分催化劑設(shè)計(jì)冠 空腔直/

適合的離（直徑四面體三環(huán)氮雜冠醚中N原子的四4布，對(duì)同樣大小的K+和NH+44NH+結(jié)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(shí)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(gè)局部之間相 模型–分子形狀的互補(bǔ) 結(jié)合過(guò)程中的構(gòu)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.自組超分子自組裝：分子之間依靠分子間相互作電子因素：各種分子間作用力得到幾何因素：分子的幾何形狀和大小互相Itneedstobenotedthatsupramolecularsystemsmayalsoformunderkineticratherthanthermodynamiccontrol.Thissituationwilltendtobemorelikelyforlargersupramolecularassembliesincorporatingmanyintermolecularcontacts,especiallywhen yrigidcomponentsareinvolved.Itmayalsotendtooccurwhenmetalions,andespeciallykineticallyinertmetalions,areincorporatedintheframeworkoftheresultingsupramolecularentity.When,forexample,anintermediateproductintheassemblyprocessprecipitatesoutofsolutionbecauseofitslowsolubility. mechanismsofformationanddissociation.Littleinsightexistsintotheco-operativenatureofindividualhost–guestcontactsindirectingthecourseoftheassemblyprocesses.SupramolecularHost-guestCatenanesandHelicalSyntheticMesoscaleyin(萬(wàn)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’sadoublehelixisSyntheticself-assembledcyclicpeptide CyclicPeptideNanotubesasScaffoldsforConductingDevicesHydrogen-bondinginteractionspromotestackingofcyclicpeptidesPi-systemsstackface-to-facetoallowconductionalongthelengthofthetubeCooperandMcGimpseyCYCLICBIOSYSTEMSCarbonOrganic-M.R.WhatisaItisanespeciallystable,hexameric,diskshapedThedisksspontaneouslystackinsolutiontoproducecylindricalThesubunitsweredesignedandsynthesizedtopossessaWatson-Crickdonor-donor-acceptorH-bondarrayofguanineandacceptor-acceptor-donorofcytosine.Eachsubunit(sixforeach“rosette”)alsopossessesasidechain;theidentityofwhichdictatesthefunctionalityoftheresultingThearrowsindicatetheDDA-AAD