Analytical Methods in Supramolecular Chemistry (2-Volume Set)

815 Pages·2016·12.64 MB·English

by  Schalley C.A. (Ed.)

EditedbyChristophA.Schalley
AnalyticalMethods
inSupramolecularChemistry
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Edited by Christoph A. Schalley
Analytical Methods
in Supramolecular Chemistry
nd
2 , Completely Revised and Enlarged Edition
Volume 1
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V
ContentstoVolume1
Preface XIII
ListofContributors XV
1 Introduction 1
LenaKaufmannandChristophA.Schalley
1.1 SomeHistoricalRemarksonSupramolecularChemistry 1
1.2 TheNoncovalentBond:aBriefOverview 2
1.3 BasicConceptsinSupramolecularChemistry 4
1.3.1 MolecularRecognition:MolecularComplementarity 5
1.3.2 ChelateEffectsandPreorganization:EntropyFactors 5
1.3.3 CooperativityandMultivalency 7
1.3.4 TheThree‘‘Selfs’’:Self-Assembly,Self-Organization,Self-Sorting 8
1.3.5 TemplateEffects 12
1.3.6 Self-ReplicationandSupramolecularCatalysis 13
1.3.7 MolecularDevicesandMachines:ImplementingFunction 15
1.3.8 ExtendedAssemblies:LiquidCrystalsandSupramolecularGels 18
1.4 Conclusions:DiverseMethodsforaDiverseResearchArea 21
References 22
2 QuantitativeAnalysisofBindingProperties 27
KeijiHirose
2.1 TheoreticalPrinciples 27
2.1.1 TheBindingConstantsandBindingEnergies 27
2.1.2 AGeneralViewontheDeterminationofBindingConstants 28
2.1.3 GuidelineforExperiments 29
2.2 APracticalCourseofBindingConstantDeterminationbyUV/Vis
Spectroscopy 29
2.2.1 DeterminationofStoichiometry 29
2.2.2 EvaluationofComplexConcentration 33
2.2.3 PrecautionstoBeTakenWhenSettingConcentrationConditionsfor
theTitrationExperiment 34
2.2.3.1 Correlationbetween[H] ,[G] ,x,andK 34
0 0
2.2.3.2 HowtoSet[H] 36
0
VI Contents
2.2.3.3 HowtoSet[G] 36
0
2.2.4 DataTreatment 41
2.2.4.1 GeneralView 41
2.2.4.2 Rose–DragoMethodforUV/VisSpectroscopy 41
2.2.4.3 EstimationofError 43
2.2.5 ConclusionforUV/VisSpectroscopicMethod 43
2.3 PracticalCourseofActionforNMRSpectroscopicBindingConstant
Determination 44
2.3.1 DeterminationofStoichiometry 45
2.3.2 EvaluationofComplexConcentration 47
2.3.3 DataTreatmentforNMRMethod 47
2.3.3.1 Rose–DragoMethodforNMRSpectroscopy 47
2.3.3.2 EstimationofErrorforNMRMethod 49
2.3.3.3 NonlinearLeastSquareDataTreatmentofNMRTitration
Method 49
2.3.3.4 EstimationofErrorforNonlinearLeastSquareMethodofNMR
Spectroscopy 52
2.4 OtherImportantExampleswithPracticalActionsofData
Treatment 53
2.4.1 ExemplifiedDataTreatmentforaFluorescenceQuenchSystem 53
2.4.1.1 StaticQuenchingModelofa1:1ComplexationSystem 53
2.4.1.2 EstimationofErrorforApproximatedStraight-LineParametersby
LinearRegression 54
2.4.2 ExemplifiedDataTreatmentfora1:2ComplexationSystem 55
2.4.2.1 TypicalCaseStudyfora1:2ComplexationSystem 55
2.4.2.2 EstimationofErrorforGeneralFunctions 57
2.4.2.3 Modificationfor1:2ComplexationswithGuestProbeProton
Monitoring 57
2.4.3 Modificationfor2:1Complexations 57
2.4.4 DataTreatmentforaSystemHaving1:1and2:1
Complexations 58
2.5 Conclusion 59
References 66
3 IsothermalTitrationCalorimetryinSupramolecularChemistry 67
FranzP.Schmidtchen
3.1 Introduction 67
3.2 TheThermodynamicPlatform 69
3.3 AcquiringExperimentalCalorimetricData 72
3.3.1 DataEvaluation 81
3.4 ExtendingtheMeasurementRange 88
3.4.1 ExpandingtheScopeofITC 93
3.5 Perspectives 100
Acknowledgment 100
References 101
Contents VII
4 ExtractionMethods 105
HolgerStephan,ManjaKubeil,KerstinGloe,andKarstenGloe
4.1 Introduction 105
4.2 TheExtractionTechnique 106
4.3 TheTechnicalProcess 108
4.4 TheExtractionEquilibrium 109
4.5 PrinciplesofSupramolecularExtraction 112
4.6 ExamplesofSupramolecularExtraction 114
4.7 ConclusionsandFuturePerspectives 124
Acknowledgments 125
References 125
5 MassSpectrometryandGasPhaseChemistryofSupramolecules 129
DominikP.Weimann,MichaelKogej,andChristophA.Schalley
5.1 Introduction 129
5.2 Instrumentation 130
5.2.1 IonizationTechniquesSuitableforNoncovalentSpecies 131
5.2.1.1 Matrix-AssistedLaserDesorption/Ionization 131
5.2.1.2 ElectrosprayIonization 133
5.2.1.3 Resonance-EnhancedMultiphotonIonization(REMPI) 134
5.2.1.4 IonizationofNoncovalentSpecies 135
5.2.2 MassAnalyzers 135
5.2.2.1 QuadrupoleInstrumentsandQuadrupoleIonTraps 137
5.2.2.2 Time-of-Flight 138
5.2.2.3 IonCyclotronResonance 139
5.3 ParticularitiesandLimitationsofMassSpectrometry 141
5.4 BeyondAnalyticalCharacterization:TandemMSExperimentsforthe
ExaminationoftheGas-PhaseChemistryofSupramolecules 143
5.4.1 Collision-InducedDecay 144
5.4.2 Infrared-MultiphotonDissociation 145
5.4.3 BlackbodyInfraredRadiativeDissociation 146
5.4.4 Electron-CaptureDissociationandElectronTransfer
Dissociation 146
5.4.5 BimolecularReactions:H/D-ExchangeandGas-PhaseEquilibria 147
5.5 SelectedExamples 147
5.5.1 AnalyticalCharacterization:ExactMass,IsotopePatterns,Charge
State,Stoichiometry,Impurities 148
5.5.2 StructuralCharacterizationofSupramolecules 150
5.5.2.1 TheMechanicalBond:HowtoDistinguishMoleculeswithRespectto
TheirTopology 150
5.5.2.2 EncapsulationofGuestMoleculesinSelf-AssemblingCapsules 151
5.5.3 IonMobility:aZwitterionicSerineOctamer? 159
5.5.4 MassSpectrometryfortheDetectionofChirality 162
5.5.5 ReactivityStudiesofSupramoleculesinSolution 164
5.5.5.1 LigandExchangeinDimericHelicates 165
VIII Contents
5.5.5.2 TheDouble-SyringeTechniqueforMonitoringFast
Complex-FormationKineticsinSolution 169
5.5.6 ReactivityintheGasPhase:IsolatedSpeciesInsteadofDynamic
ExchangeProcesses 173
5.5.6.1 MetallosupramolecularSquaresandCages:aSupramolecular
EquivalenttoNeighborGroupAssistance 173
5.5.6.2 ASurprisingDendriticEffect:SwitchingFragmentation
Mechanisms 178
5.5.6.3 Gas-PhaseH/DExchangeforAnalyzingMolecularMobility 182
5.5.7 DeterminingThermochemicalData:theInfluenceofthe
Environment 188
5.5.7.1 CrownEther-AlkaliComplexes:QuestioningtheBest-FitModel 188
5.5.7.2 BIRD:ArrheniusKineticsofOligonucleotideStrandSeparationinthe
GasPhase 190
5.6 Conclusions 191
References 192
6 DiffusionNMRinSupramolecularChemistryandComplexed
Systems 197
YoramCohen,LiatAvram,TamarEvan-Salem,SaritSlovak,
NoamShemesh,andLimorFrish
6.1 Introduction 197
6.2 ConceptsofMolecularDiffusion 198
6.3 MeasuringDiffusionwithNMR 198
6.3.1 TheBasicPulseSequence 198
6.3.2 TheStimulatedEcho(STE)DiffusionSequence 201
6.3.3 TechnicalIssuesinDiffusionNMR 203
6.3.4 TheLEDandBPLEDSequences 205
6.3.5 DOSY – DiffusionOrderedSpectroscopy 206
6.4 ApplicationsofDiffusionNMRinSupramolecularChemistry:
SelectedExamples 209
6.4.1 BindingandAssociationConstants 209
6.4.2 EncapsulationandMolecularCapsules 216
6.4.3 MolecularSize,Shape,andSelf-Aggregation 225
6.4.4 DiffusionasaFilter:VirtualSeparationandLigandScreening 245
6.4.5 Organometallics,ReactiveIntermediates,andSupercharged
SupramolecularSystems 250
6.4.6 SupramolecularPolymers 254
6.5 AdvantagesandLimitationsofHighResolutionDiffusionNMR 259
6.6 DiffusionNMRandChemicalExchange 260
6.7 DiffusionModesandSignalDecayinDiffusionMR
Experiments 265
6.8 ApplicationsofDiffusionNMRinComplexSystems 269
6.8.1 ZeolitesandCarbonNanotubes 269
6.8.2 MicellesandEmulsions 272
Contents IX
6.8.3 Liposomes 274
6.8.4 OrganicConductors 274
6.8.5 BiologicalSystems:CellsandTissues 275
6.9 SummaryandOutlook 276
References 279
7 PhotophysicsandPhotochemistryofSupramolecularSystems 287
BernardValeur,Ma´rioNunoBerberan-Santos,MoniqueM.Martin,
andPascalPlaza
7.1 Introduction 287
7.2 SpectrophotometryandSpectrofluorometry 288
7.2.1 DeterminationoftheStoichiometryandAssociationConstantsof
SupramolecularComplexesfromSpectrophotometricor
SpectrofluorometricTitrations 288
7.2.2 CooperativityandAnticooperativity 290
7.2.3 PossibleDifferencesinBindingConstantsintheGroundStateandin
theExcitedState 293
7.2.4 InformationonPhotoinducedProcessesfromFluorescence
Spectra 293
7.2.4.1 PhotoinducedElectronTransferinaCalixarene-BasedSupermolecule
DesignedforMercuryIonSensing 293
7.2.4.2 ExcitationEnergyTransferinanInclusionComplexofa
MultichromophoricCyclodextrinwithaFluorophore 295
7.3 Time-ResolvedFluorescenceTechniques 296
7.3.1 GeneralPrinciples 297
7.3.2 PulseFluorometry 300
7.3.3 Phase-ModulationFluorometry 302
7.3.3.1 PhaseFluorometersUsingaContinuousLightSourceandan
Electro-OpticModulator 302
7.3.3.2 PhaseFluorometersUsingtheHarmonicContentofaPulsed
Laser 304
7.3.4 DataAnalysis 304
7.3.5 LifetimeStandards 306
7.3.6 ExamplesofApplication 306
7.3.6.1 PhotoinducedElectronTransferinaSelf-AssembledZinc
Naphthalocyanine–FullereneDiad 306
7.3.6.2 ExcitationEnergyTransferinaSelf-AssembledZincPorphyrin–Free
BasePorphyrinDiad 307
7.3.6.3 ExcimerFormationofCyanobiphenylsinaCalix[4]resorecinarene
Derivative 309
7.3.6.4 RecoveryoftheDistributionsofDecayTimesfromtheFluorescence
DecaysinSupramolecularMultichromophoricSystems 309
7.4 FluorescenceAnisotropy 311
7.4.1 GeneralPrinciples 312
7.4.2 ExamplesofApplication 316