Molecules at Work: Selfassembly, Nanomaterials, Molecular Machinery

402 Pages·5.86 MB·english

by  Pignataro B. (Ed.)

Editedby
BrunoPignataro
MoleculesatWork
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Molecules at Work
Selfassembly, Nanomaterials, Molecular Machinery
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V
Contents
Preface XIII
ListofContributors XXI
PartI SelfAssembly 1
1 Yoctoliter-SizedVesselsasPotentialBiologicalModels 3
SheshanathV.Bhosale,BradleyE.Wilman,andStevenJ.Langford
1.1 Introduction 3
1.2 CavitiesonGlassPlatesandGoldSurfaces 5
1.3 PreparationandConfirmationofRigidYoctowellCavity 6
1.3.1 ConfirmationofRigidGaps 7
1.4 MolecularSorting 7
1.5 Yoctowell-BasedMolecularRecognitionEvents 9
1.6 Conclusion 11
Acknowledgments 12
References 12
2 SwitchableHost–GuestInteractionsofSupramolecularRings
andCages 13
GuidoH.Clever
2.1 Introduction 13
2.2 Host–GuestChemistry 15
2.3 SwitchinginSupramolecularSystems 17
2.4 NaturalParagons 19
2.5 TypesofExternalInputandMethodsforAnalysis 20
2.5.1 SwitchableHostCompounds 21
2.5.2 SwitchableGuestCompounds 26
2.6 Conclusion 33
References 34
VI Contents
PartII NanoMaterials 39
3 TailoredGraphene-TypeMoleculesbyChemicalSynthesis 41
MilanKivalaandXinliangFeng
3.1 Introduction 41
3.2 SyntheticConceptstowardExpandedPAHs – Nanographenes 43
3.2.1 Hexabenzocoronenes(HBCs)andRelatedSystems 43
3.2.2 LargePAHs 48
3.2.3 GrapheneNanoribbons 55
3.2.4 Heteroatom-ContainingPAHs 60
3.3 ConclusionandOutlook 64
References 66
4 AnalyzingtheSurfaceAreaPropertiesofMicroporousMaterials 71
AbbieTrewin
4.1 Introduction 71
4.1.1 Energy 71
4.1.2 H Storage 71
2
4.1.3 CO CaptureandSequestration 72
2
4.1.4 GasSeparation 73
4.2 MicroporousMaterials 74
4.2.1 FrameworkMaterials 74
4.2.2 NetworkMaterials 74
4.2.3 MolecularMaterials 76
4.2.4 StructuralFlexibility 79
4.3 Porosity 81
4.3.1 WhatIsPorosity? 81
4.3.2 IntrinsicversusExtrinsicPorosity 81
4.3.3 MeasuringPorosity 82
4.3.4 CalculatedSurfaceAreasandSimulatedGasUptakes 83
4.3.5 Gas-DiffusionMechanisms 84
4.4 PorousMaterialsandCalculatingSurfaceAreas 85
4.4.1 FrameworkMaterials 85
4.4.2 NetworkMaterials 86
4.4.3 MolecularMaterials 88
4.4.4 MolecularSolidswithSomeExtrinsicPorosity 89
4.4.5 MolecularSolidswithIntrinsicPorosity 90
4.5 Summary 92
Acknowledgments 92
References 93
5 NanostructuredMaterialsBasedonCore-SubstitutedNaphthalene
Diimides 97
SheshanathV.Bhosale,BradleyE.Wilman,andStevenJ.Langford
5.1 Introduction 97
Contents VII
5.2 SynthesisofNovelcNDIDerivatives 99
5.3 ElectronTransfer 102
5.4 SupramolecularSelf-AssemblyofcNDI 105
5.5 Conclusion 110
Acknowledgments 110
References 110
6 MetalPhosphides:FromChemist’sOdditiestoDesignedFunctional
Materials 113
SophieCarenco,MatthieuDemange,Ce´dricBoissi`ere,Cle´mentSanchez,
andNicolasMe´zailles
6.1 Introduction 113
6.2 BulkMetalPhosphides:ALongHistory 113
6.2.1 ANewFamilyofSyntheticInorganicMaterials 113
6.2.2 FirstSetofApplications 114
6.2.3 BulkMetalPhosphidesandToday’sApplications 114
6.3 WhitePhosphorusfortheLow-TemperatureSynthesisofMetal
PhosphideNanoparticles 115
6.3.1 WhitePhosphorusasaLow-TemperatureReagent 115
6.3.2 Aryl-andAlkyl-Phosphinesas‘‘P’’AtomDonorinHarshConditions
fortheSynthesisofMetalPhosphideNanoparticles 115
6.3.3 NickelPhosphideNanoparticlesfromP inStoichiometricandMild
4
Conditions 116
6.3.4 GeneralizationoftheWhitePhosphorusNanoscaleRoute 118
References 119
7 ‘‘ArtificialSupermolecule’’:ProgressintheStudyofII–VColloidal
SemiconductorNanocrystals 121
ShidingMiao,AlexanderEychmu¨ller,andStephenG.Hickey
7.1 Introduction 121
7.2 OpticalPropertiesofII–VNanocrystals 124
7.2.1 Absorption 124
7.2.2 Photoluminescence 127
7.2.3 LifetimeMeasurement 131
7.3 SynthesisofII–VNanocrystals 133
7.3.1 SynthesisMethods 133
7.3.2 SynthesisofCd P Nanocrystals 134
3 2
7.3.2.1 ‘‘Hot-Injection’’Synthesis 134
7.3.2.2 High-Temperature,Gas-BubblingSynthesiswithExSitu-Produced
PH 139
3
7.3.3 SynthesisofZn P Nanocrystals 140
3 2
7.3.4 SynthesisofCd As Nanocrystals 142
3 2
7.3.5 SummaryoftheSynthesisofII–VNanocrystals 143
7.4 ConclusionsandOutlook 143
References 146
VIII Contents
8 LuminescentDendrimers 155
GiacomoBergamini
8.1 Introduction 155
8.2 IntrinsicPhotochemicalandPhotophysicalPropertiesofOrganic
Dendrimers 156
8.3 EnergyTransferandEnergyUpconversioninMultichromophoric
Dendrimers 161
8.4 DendrimersasLigandsforMetalIons 164
8.5 Self-Assembly 168
8.6 DendrimersasPhotoswitchableHosts 170
8.7 ConclusionandPerspectives 172
References 173
9 FabricationofUltramicroporousSilicaMembranesforPervaporation
andGasSeparation 177
VittorioBoffa
9.1 UltramicroporousSilicaMembranes 177
9.1.1 Context 177
9.1.2 GasSeparationandPervaporation 177
9.1.3 Fabrication 180
9.1.4 MicroporosityAssessmentinSilicaMembranes 182
9.1.5 HydrothermalStability–InstabilityofMicroporous
Silica 184
9.2 M O –SilicaMembrane 185
x y
9.2.1 Fabrication 185
9.2.2 Stability,Selectivity,andReactivity 187
9.2.3 MembraneOptimization 193
9.3 HybridOrganic-SilicaMembranes 193
9.3.1 Fabrication 193
9.3.2 ‘‘Hydrophobic’’SilicaMembranes 196
9.3.3 MembranesfromBridgedOrganosilanes 197
9.3.4 Organic-SilicaMembranesforCO Separation 199
2
9.4 PerspectivesintheFabricationandApplicationofSilica
Membranes 200
References 200
10 NewDirectionsintheFightagainstCancer:FromMetalComplexesto
NanostructuredMaterials 207
SantiagoGo´mez-Ruiz
10.1 Introduction 207
10.2 MetalComplexesinCancerTreatment 208
10.2.1 PlatinumComplexes 208
10.2.2 Non-PlatinumTransition-MetalComplexes 210
10.2.2.1 Group4MetalComplexes 211
10.2.2.2 Group8MetalComplexes 213
Contents IX
10.2.2.3 Group11MetalComplexes 216
10.2.3 MainGroup-MetalComplexes 219
10.2.3.1 GalliumComplexes 219
10.2.3.2 TinComplexes 220
10.3 NanostructuredMaterialsinCancerTreatments 221
10.3.1 MacromolecularSystems 222
10.3.1.1 Cucurbit[n]urilsandCyclodextrins 222
10.3.1.2 LiposomesandLipidNanocapsules 223
10.3.1.3 OtherMacromolecularSystems 224
10.3.2 CeramicMaterials 224
10.3.2.1 NanostructuredCalcium-Phosphate-BasedMaterialsFunctionalized
withMetalComplexes 226
10.3.2.2 MesoporousSilicasFunctionalizedwithMetalComplexes 227
10.3.2.3 CarbonNanotubesFunctionalizedwithMetalComplexes 228
10.3.3 Nanoparticles 230
References 230
PartIII MolecularMachinery 243
11 MolecularRotors:ImagingIntracellularViscosity 245
MarinaK.Kuimova
11.1 Introduction 245
11.2 TheoreticalBackground 246
11.3 BiologicalApplicationsofMolecularRotors 247
11.3.1 Fluorescence-Lifetime-BasedMolecularRotors 249
11.3.2 Time-ResolvedFluorescenceAnisotropyMeasurementsofMolecular
Rotors 252
11.3.3 RatiometricFluorescentMolecularRotors 255
11.3.4 RatiometricMolecularRotorMeasurementsofViscosityduring
PDT 257
11.4 ConclusionsandOutlook 258
Acknowledgments 259
References 259
12 Surface-FunctionalizedInorganicColloidalNanocrystalsinFunctional
NanocompositeMaterialsforMicrofabrication 263
ChiaraIngrosso,MarinellaStriccoli,AngelaAgostiano,andMariaLucia
Curri
12.1 Introduction 263
12.2 ColloidalNanocrystals:Properties,Synthesis,andSurface
Functionalization 264
12.2.1 PropertiesofNanocrystals 264
12.2.2 ColloidalSynthesisofNanocrystals 265
12.2.3 SurfaceFunctionalizationofNanocrystals 266
12.3 NC-BasedNanocompositesforMicrofabrication 269
X Contents
12.4 ConclusionsandFuturePerspectives 279
References 280
13 FluorescenceSensingofTemperatureandOxygenwithFullerenes 285
Ma´rioN.Berberan-SantosandCarlosBaleiza˜o
13.1 Introduction 285
13.2 ThermallyActivatedDelayedFluorescence:FundamentalAspects 287
13.3 SensingApplications 292
13.3.1 OxygenSensing 293
13.3.1.1 Sub-ppmOxygenSensorBasedonC 294
70
13.3.1.2 C inaDualSensorSystem 297
70
13.3.2 TemperatureSensing 300
13.3.2.1 C DispersedinPolymerFilms 302
70
13.3.2.2 C EncapsulatedinPolymerNanoparticles 304
70
13.4 ConclusionsandFuturePerspectives 307
Acknowledgments 308
References 308
14 GoingbeyondGlucoseSensingwithBoronicAcidReceptors 315
AlexanderSchiller
14.1 Introduction 315
14.2 IndicatorDisplacementAssaysfortheDetectionofSugars 316
14.3 GlucoseSensingwithBoronicAcidReceptors 317
14.3.1 AllostericIndicatorDisplacementAssayfortheDetectionof
Carbohydrates 318
14.3.2 AIDASaccharideSensingSystem – Boronic-Acid–AppendedBenzyl
BipyridinumSaltsandaFluorescentReporterDye 319
14.3.3 AIDAGlucoseSensorforContinuousMonitoring 320
14.4 Solution-PhaseSensorArrayswithBoronic-Acid-Appended
BipyridiniumSalts 321
14.4.1 RecognitionofNeutralSaccharides 322
14.4.2 RecognitionofPhosphosugarsandNucleotides 324
14.5 Carbohydrate-ActiveEnzymeAssays 327
14.6 Boronic-Acid-AppendedBipyridiniumSaltsat
Work – NOVOSIDES 330
14.7 ConclusionsandPerspectives 333
Acknowledgments 334
References 334
15 DesignofNovelIridiumComplexestoObtainStableandEfficient
Light-EmittingElectrochemicalCells 339
Rub`enD.Costa
15.1 BriefHistoryofElectroluminescenceandOptoelectronicDevices 339
15.2 Light-EmittingElectrochemicalCells:MotivationandDefinition 340