Supramolecular Polymer Chemistry

376 Pages·2011·7.82 MB·English

Edited by Akira Harada
Supramolecular Polymer
Chemistry
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Chemistry
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V
Contents
Preface XIII
List of Contributors XV
Part One Formation of Supramolecular Polymers 1
1 MultipleHydrogen-BondedSupramolecularPolymers 3
WilcoP.J.Appel,MarkoM.L.Nieuwenhuizen,andE.W.Meijer
1.1 Introduction 3
1.1.1 HistoricalBackground 3
1.1.2 SupramolecularChemistry 4
1.1.3 SupramolecularPolymerizationMechanisms 4
1.2 GeneralConceptsofHydrogen-BondingMotifs 6
1.2.1 ArraysofMultipleHydrogenBonds 6
1.2.2 PreorganizationthroughIntramolecularHydrogenBonding 8
1.2.3 TautomericEquilibria 9
1.3 Hydrogen-BondedMain-ChainSupramolecularPolymers 10
1.3.1 TheEstablishmentofSupramolecularPolymers 10
1.3.2 SupramolecularPolymerizations 13
1.3.3 HydrophobicCompartmentalization 14
1.4 FromSupramolecularPolymerstoSupramolecularMaterials 16
1.4.1 ThermoplasticElastomers 16
1.4.2 PhaseSeparationandAdditionalLateralInteractionsin
SupramolecularPolymersintheSolidState 18
1.4.3 SupramolecularThermoplasticElastomersBasedonAdditional
LateralInteractionsandPhaseSeparation 19
1.5 FuturePerspectives 23
References 25
2 Cyclodextrin-BasedSupramolecularPolymers 29
AkiraHaradaandYoshinoriTakashima
2.1 Introduction 29
2.2 SupramolecularPolymersintheSolidState 29
2.2.1 CrystalStructuresofCDAliphaticTethers 30
2.2.2 CrystalStructuresofb-CDsAromaticTethers 31
VI Contents
2.3 Formation of Homo-Intramolecular and Intermolecular Complexes by
CDs–GuestConjugates 33
2.3.1 SupramolecularStructuresFormedby6-Modifieda-CDs 33
2.3.2 SupramolecularStructuresFormedby6-Modifiedb-CDs 39
2.3.3 SupramolecularStructuresFormedby3-Modifieda-CDs 40
2.3.4 Hetero-SupramolecularStructuresFormedbyModifiedCDs 42
2.4 FormationofIntermolecularComplexesbyCDandGuestDimers 44
2.5 ArtificialMolecularMuscleBasedonc2-DaisyChain 45
2.6 ConclusionandOutlook 48
References 48
3 Supra-MacromolecularChemistry:TowardDesignofNewOrganic
MaterialsfromSupramolecularStandpoints 51
KazunoriSugiyasuandSeijiShinkai
3.1 Introduction 51
3.2 SmallMolecules,Macromolecules,andSupramolecules:
DesignoftheirCompositeMaterials 53
3.2.1 InteractionsbetweenSmallMoleculesandMacromolecules 53
3.2.2 InteractionsbetweenSmallMoleculesandMolecularAssemblies 56
3.2.3 InteractionsbetweenMolecularAssemblies 58
3.2.4 InteractionsbetweenMacromolecules 60
3.2.5 InteractionsbetweenMacromolecularAssemblies 63
3.2.6 InteractionsbetweenMacromoleculesandMolecularAssemblies 65
3.3 ConclusionandOutlook 67
References 68
4 PolymerizationwithDitopicCavitandMonomers 71
FrancescaTanciniandEnricoDalcanale
4.1 Introduction 71
4.2 Cavitands 72
4.3 Self-AssemblyofDitopicCavitandMonomers 75
4.3.1 StructuralMonomerClassificationofSupramolecular
Polymerization 75
4.3.2 HomoditopicCavitandsSelf-AssembledviaSolvophobicp-pStacking
Interactions 77
4.3.3 HeteroditopicCavitandsCombiningSolvophobicInteractions
andMetal–LigandCoordination 78
4.3.4 HeteroditopicCavitandsCombiningSolvophobicInteractions
andHydrogenBonding 82
4.3.5 HeteroditopicCavitandsSelf-assembledviaHost–Guest
Interactions 84
4.3.6 HomoditopicCavitandsSelf-assembledviaHost–Guest
Interactions 88
4.4 ConclusionsandOutlook 91
References 92
Contents VII
PartTwo SupramolecularPolymerswithUniqueStructures 95
5 PolymersContainingCovalentlyBondedandSupramolecularly
AttachedCyclodextrinsasSideGroups 97
HelmutRitter,MonirTabatabai,andBernd-KristofMüller
5.1 PolymerswithCovalentlyBondedCyclodextrinsasSideGroups 97
5.1.1 SynthesisandPolymerizationofMonofunctionalCyclodextrin
Monomers 98
5.1.2 Polymer-AnalogousReactionwithMonofunctional
Cyclodextrin 100
5.1.3 Structure–PropertyRelationshipofPolymersContaining
CyclodextrinsasSideGroup 102
5.2 SideChainPolyrotaxanesandPolypseudorotaxanes 105
5.2.1 SideChainPolyrotaxanes 106
5.2.2 SideChainPolypseudorotaxane(Polymer(Polyaxis)/
Cyclodextrin(Rotor)) 111
References 120
6 AntibodyDendrimersandDNACatenanes 127
HiroyasuYamaguchiandAkiraHarada
6.1 MolecularRecognitioninBiologicalSystems 127
6.1.1 SupramolecularComplexFormationofAntibodies 127
6.1.2 SupramolecularComplexesPreparedbyDNAs 129
6.1.3 ObservationofTopologicalStructuresofSupramolecularComplexes
byAtomicForceMicroscopy(AFM) 129
6.2 AntibodySupramolecules 130
6.2.1 StructuralPropertiesofIndividualAntibodyMolecules 130
6.2.2 SupramolecularFormationofAntibodieswithMultivalent
Antigens 130
6.2.2.1 SupramolecularFormationofAntibodieswithDivalentAntigens 131
6.2.2.2 DirectObservationofSupramolecularComplexesof
AntibodieswithPorphyrinDimers 133
6.2.2.3 ApplicationsfortheHighlySensitiveDetectionMethodofSmall
MoleculesbytheSupramolecularComplexesbetweenAntibodiesand
MultivalentAntigens 134
6.2.3 SupramolecularDendrimersConstructedbyIgMandChemically
ModifiedIgG 136
6.2.3.1 PreparationofAntibodyDendrimersandtheirTopological
Structures 136
6.2.3.2 BindingPropertiesofAntibodyDendrimersforAntigens 136
6.3 DNASupramolecules 139
6.3.1 ImagingofIndividualPlasmidDNAMolecules 139
6.3.2 PreparationofNickedDNAbytheAdditionofDNaseIto
PlasmidDNA 140
6.3.3 CatenationReactionwithTopoisomeraseI 141
VIII Contents
6.3.4 AFMImagesofDNACatenanes 143
6.3.5 DNA[n]CatenanesPreparedbyIrreversibleReactionwith
DNALigase 144
6.4 Conclusions 145
References 146
7 CrownEther-BasedPolymericRotaxanes 151
TerryL.PriceJr.andHarryW.Gibson
7.1 Introduction 151
7.2 DaisyChains 153
7.3 SupramolecularPolymers 156
7.4 DendriticRotaxanes 157
7.5 DendronizedPolymers 158
7.6 MainchainRotaxanesBasedonPolymericCrowns
(IncludingCrosslinkedSystems) 161
7.7 SideChainRotaxanesBasedonPendentCrowns 166
7.8 Poly[2]rotaxanes 170
7.9 Poly[3]rotaxanes 173
7.10 PolymericEndGroupPseudorotaxanes 176
7.11 ChainExtensionandBlockCopolymersfrom
EndGroups 176
7.12 StarPolymersfromCrownFunctionalizedPolymers 179
References 181
PartThree PropertiesandFunctions 183
8 ProcessiveRotaxaneCatalysts 185
JohannesA.A.W.Elemans,AlanE.Rowan,andRoelandJ.M.Nolte
8.1 Introduction 185
8.2 ResultsandDiscussion 185
8.2.1 Catalysis 185
8.2.2 Threading 187
8.3 Conclusion 192
References 192
9 EmergingBiomedicalFunctionsthrough‘Mobile’Polyrotaxanes 195
NobuhikoYui
9.1 Introduction 195
9.2 MultivalentInteractionusingLigand-Conjugated
Polyrotaxanes 196
9.3 TheFormationofPolyrotaxaneLoopsasaDynamicInterface 197
9.4 CytocleavablePolyrotaxanesforGeneDelivery 199
9.5 Conclusion 201
9.6 Appendix 203
References 204
Contents IX
10 Slide-RingMaterialsUsingPolyrotaxane 205
KazuakiKatoandKohzoIto
10.1 Introduction 205
10.2 PulleyEffectofSlide-RingMaterials 208
10.3 SynthesisofSlide-RingMaterials 209
10.4 ScatteringStudiesofSlide-RingGels 211
10.5 MechanicalPropertiesofSlide-RingGels 213
10.6 SlidingGraftCopolymers 215
10.7 RecentTrendsofSlide-RingMaterials 216
10.7.1 Introduction:DiversificationoftheMainChainPolymer 216
10.7.2 Organic–InorganicHybridSlide-RingMaterials 219
10.7.3 DesignofMaterialsfromIntramolecularDynamicsof
Polyrotaxanes 224
10.8 ConcludingRemarks 226
References 227
11 Stimuli-ResponsiveSystems 231
AkihitoHashidzumeandAkiraHarada
11.1 Introduction 231
11.2 StimuliandResponses 231
11.2.1 Stimuli 231
11.2.1.1 Temperature 231
11.2.1.2 Pressure,Force,Stress,andUltrasound 232
11.2.1.3 pH 233
11.2.1.4 Chemicals 233
11.2.1.5 ElectromagneticWavesorLight 233
11.2.1.6 Redox 234
11.2.2 Responses 234
11.2.2.1 Movement 235
11.2.2.2 CaptureandReleaseofChemicals 235
11.2.2.3 ChemicalReactions 235
11.2.2.4 ChangeinViscoelasticProperties,orGel-to-SolandSol-to-Gel
Transitions 236
11.2.2.5 ChangeinColor 236
11.3 ExamplesofStimuli-ResponsiveSupramolecularPolymer
Systems 236
11.3.1 Temperature-ResponsiveSystems 236
11.3.2 Pressure-,Force-,andSonication-ResponsiveSystems 239
11.3.3 pH-ResponsiveSystems 241
11.3.4 Chemical-ResponsiveSystems 246
11.3.5 Photo-ResponsiveSystems 249
11.3.6 Redox-ResponsiveSystems 255
11.3.7 Multi-Stimuli-ResponsiveSystems 259
11.4 ConcludingRemarks 261
References 261
X Contents
12 PhysicalOrganicChemistryofSupramolecularPolymers 269
StephenL.CraigandDonghuaXu
12.1 IntroductionandBackground 269
12.2 LinearSupramolecularPolymers 270
12.2.1 N,C,N-PincerMetalComplexes 270
12.2.2 LinearSPs 272
12.2.3 TheoryRelatedtothePropertiesofLinearSPs 274
12.2.4 LinearSPsintheSolidState 275
12.3 Cross-LinkedSPsNetworks 276
12.3.1 ReversibilityinSemidiluteUnentangledSPs
Networks 276
12.3.2 PropertiesofSemidiluteEntangledSPsNetworks 283
12.3.3 TheStickyReptationModel 285
12.4 HybridPolymerGels 286
12.5 Conclusion 288
References 288
13 TopologicalPolymerChemistry:AQuestforStrange
PolymerRings 293
YasuyukiTezuka
13.1 Introduction 293
13.2 SystematicClassificationofNonlinearPolymer
Topologies 293
13.3 TopologicalIsomerism 296
13.4 DesigningUnusualPolymerRingsbyElectrostatic
Self-AssemblyandCovalentFixation 298
13.5 ConclusionandFuturePerspectives 302
References 303
14 StructureandDynamicBehaviorofOrganometallic
Rotaxanes 305
YujiSuzaki,TomokoAbe,ErikoChihara,ShintaroMurata,MasakiHorie,
andKohtaroOsakada
14.1 Introduction 305
14.1.1 CrystalsofPseudorotaxanes 307
14.1.2 SynthesisofFerrocene-Containing[2]Rotaxanesbythe
Threading-Followed-by-End-CappingStrategy 312
14.1.3 DethreactingReactionofRotaxane-LikeComplex 316
14.1.4 PhotochemicalPropertiesofFerrocene-Containing
Rotaxanes 318
14.1.5 Ferrocene-Containing[3]RotaxaneandSide-Chain
Polyrotaxane 320
14.1.5.1 StrategiesandSynthesisof [3]Rotaxanes 320
14.1.5.2 StrategiesandSynthesisofSide-Chain
TypePolyrotaxane 321