水杨酸酯与环糊精超分子体系光谱分析-spectral analysis of salicylate and cyclodextrin supramolecular system.docxVIP

beusedforfluorescenceprobetodetectthehydrogenbondingeffectandpolarityofmicroenvironment.InPart2,theinfluencesofCDsanditsderivativesonthedualfluorescenceofEHSandMSwerestudied.DualfluorescenceofEHSwasexaminedinaqueoussolutioncontainingα-CD,β-CDandγ-CD.Adetailedcomparisonofmolecularstructuresandsizesprovidesthegeometryofinclusioncomplexes.EHSwasfoundtoformthe1:1inclusioncomplexeswithα-CD,β-CDinaqueoussolutionatitslowerconcentration.HigherconcentrationofEHSisneededfortheformationofthe1:2cage-typeinclusioncomplexes.Theformationof1:1γ-CD-EHSwasexamined.Thecavitysizeisprimaryfactorininclusionprocesses.DualfluorescenceofEHSwasexaminedinaqueoussolutioncontainingnaturalandmethylatedβ-CDs.Thegeometryofinclusioncomplexes,thehydrogenbondingeffectinsupramolecularinclusionandtherecognitionofEHSwerediscussed.TheresultsshowthatEHSformshost-guestinclusioncomplexesinβ-CD,DM-β-CD,HDM-β-CDandHTM-β-CDsolutionandallcomplexesexhibitdualfluorescence.Ontheonehand,themethylsubstitutionwouldresultinthesterichindrance.Ontheotherhand,themethylsubstitutionwouldreducethepolarityofCDcavity.Effectofnumberandpositionofmethylsubstituentsonthesterichindrancewasimportant.AsanovelESIPTfluorescenceprobe,EHSdependsonthenumberandthepositionofthemethylsubstituent.DualfluorescenceofMSwasexaminedinaqueoussolutioncontainingβ-CD,methylated-β-cyclodextrin(M-β-CD)and2-hydroxypropyl-β-cyclodextrin(HP-β-CD)andcomparedwiththatofEHS.ItwasfoundthatdualfluorescenceofMScloselycorrelatewiththehydrogenbondingpropertyofitssurroundingmicroenvironment.Thesizesofsubstituentsattherimofβ-CDresultindifferentpolarityandsterichindranceatthecavityopening.TheintermolecularhydrogenbondinginteractionofMSchangesinthepresenceofdifferentβ-CDsaccordingly.WhenMSandEHSareboundtoβ-CDs,theirgroundstateequilibriashiftbutdifferentgeometryofinclusioncomplexesleadstodifferentdualfluorescence.Theformationconstantsindicatethatthebindingstrengthofβ-CDanditsderivativestoMSisintheorderM-β-CDHP-β-CDβ-CD.Keywords:Excitedstateintramolecularprotontransfer(