超分子研究方向概述

超分主講：潘梅化學(xué)的內(nèi)1、化學(xué)的內(nèi)------化學(xué)是一門理論和實驗推動并駕齊驅(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)上就是一個核——電子體系相互聯(lián)系，并且通過所謂“自組裝”（self–assembling)或“自組織”（self-organizing）構(gòu)筑成的某種高級結(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25年時有一段 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 55萬2340萬

21世紀(jì)：Panmolecules—— pacificconference)度的態(tài)和組裝態(tài)，直到分子材料、分子器件和分子機器的合成和反應(yīng)，、剪裁和組-- --21世紀(jì)化學(xué)研究的對象：泛分子的十個

21世紀(jì)化學(xué)研究的十個

21世紀(jì)化學(xué)研究的幾個從合成、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鍵超分子化 世紀(jì)三十年代，當(dāng)時是膠體化學(xué)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 經(jīng)過近20多年的快速發(fā)展，超分子化學(xué)已遠(yuǎn)遠(yuǎn)了原來有機化學(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

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配位金屬原子和配位體間形成的共價配鍵 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，信號傳導(dǎo)，生物調(diào)材料組超分催化劑設(shè)計冠 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(jié)合過程中的構(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