Hydrogel Micro and Nanoparticles

420 Pages·2012·11.84 MB·English

by  L. Andrew Lyon, Michael Joseph Serpe

Edited by
L. Andrew Lyon and Michael Joseph Serpe
Hydrogel Micro and Nanoparticles
Related Titles
Tadros,T.F. Tadros,T.F.
DispersionofPowdersinLiquids RheologyofDispersions
andStabilizationofSuspensions PrinciplesandApplications
2012 2010
ISBN:978-3-527-32941-0 ISBN:978-3-527-32003-5
Tadros,T.F. (ed.) Tadros,T.F. (ed.)
TopicsinColloidandInterface ColloidsandInterfaceScience
Science Series
2012 6VolumeSet
ISBN:978-3-527-31991-6 2008
ISBN:978-3-527-31461-4
Fernandez-Nieves, A., Wyss,
H., Mattsson,J.,Weitz,D. A.(eds.)
Platikanov,D., Exerowa, D.(eds.)
MicrogelSuspensions
HighlightsinColloidScience
FundamentalsandApplications
2009
2011
Hardcover
ISBN:978-3-527-32158-2
ISBN:978-3-527-32037-0
Tadros,T.F. (ed.)
Self-OrganizedSurfactant
Structures
2011
ISBN:978-3-527-31990-9
Edited by L. Andrew Lyon and Michael Joseph Serpe
Hydrogel Micro and Nanoparticles
TheEditors AllbookspublishedbyWiley-VCHarecarefully
produced.Nevertheless,authors,editors,and
Prof.L.AndrewLyon publisherdonotwarranttheinformationcontained
GeorgiaInst.ofTechnology inthesebooks,includingthisbook,tobefreeof
SchoolofChemistry&Biochem. errors.Readersareadvisedtokeepinmindthat
901AtlanticDr.NW statements,data,illustrations,proceduraldetailsor
AtlantaGA30332-0400 otheritemsmayinadvertentlybeinaccurate.
USA
LibraryofCongressCardNo.: appliedfor
Prof.MichaelJosephSerpe
BritishLibraryCataloguing-in-PublicationData
UniversityofAlberta Acataloguerecordforthisbookisavailablefromthe
DepartmentofChemistry BritishLibrary.
11227SaskatchewanDrive
Edmonton,AlbertaT6G2G2 Bibliographicinformationpublishedby
Canada theDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhispublica-
tionintheDeutscheNationalbibliografie;detailed
bibliographicdataareavailableontheInternetat
http://dnb.d-nb.de.
#2012Wiley-VCHVerlag&Co.KGaA,
Boschstr.12,69469Weinheim,Germany
Allrightsreserved(includingthoseoftranslation
intootherlanguages).Nopartofthisbookmaybe
reproducedinanyform–byphotoprinting,micro-
film,oranyothermeans–nortransmittedortrans-
latedintoamachinelanguagewithoutwritten
permissionfromthepublishers.Registerednames,
trademarks,etc.usedinthisbook,evenwhennot
specificallymarkedassuch,arenottobeconsidered
unprotectedbylaw.
PrintISBN: 978-3-527-33033-1
ePDFISBN: 978-3-527-64645-6
ePubISBN: 978-3-527-64644-9
mobiISBN: 978-3-527-64643-2
oBookISBN: 978-3-527-64642-5
CoverDesign Grafik-DesignSchulz,Fußgönheim
Typesetting ThomsonDigital,Noida,India
PrintingandBinding MarkonoPrintMediaPteLtd,
Singapore
V
Contents
List of Contributors XIII
Foreword XIX
Preface XXIII
1 ThermallySensitiveMicrogels:FromBasicSciencetoApplications 1
HeChengandGuangzhaoZhang
1.1 Introduction 1
1.2 TheoreticalBackground 2
1.2.1 ThermodynamicsofVolumePhaseTransition 2
1.2.2 InternalMotion 3
1.2.3 DynamicsofMicrogel 4
1.2.4 KineticsCalculationofReversibleAggregation 6
1.3 BasicPhysicsofMicrogels 7
1.3.1 VolumePhaseTransition 7
1.3.2 InternalMotion 9
1.3.2.1 InternalMotionsinGoodSolvent 9
1.3.2.2 InternalMotionsinYandPoorSolvents 11
1.3.3 DynamicsofCation-InducedAggregationofThermallySensitive
Microgels 14
1.3.3.1 Salt-InducedComplexation 14
1.3.3.2 ComplexationBetweenMicrogelsandProtein 18
1.3.3.3 AggregationofSphericalMicrogels 18
1.3.4 Non-ErgodicandErgodicPhenomenaofPhysical
CrosslinkedGel 21
1.4 Applications 25
1.5 Conclusions 27
References 29
2 ThermosensitiveCore–ShellMicrogels:BasicConceptsand
Applications 33
YanLuandMatthiasBallauff
2.1 Introduction 33
2.2 VolumeTransitioninSingleParticles 35
VI Contents
2.3 ConcentratedSuspensions:3DCrystallization 40
2.4 ParticlesonSurfaces:2DCrystallization 41
2.5 ConcentratedSuspensions:Rheology 42
2.6 Core–ShellParticlesasCarriersforCatalysts 45
2.6.1 MetalNanoparticles 45
2.6.2 Enzymes 50
2.7 Conclusion 53
References 54
3 Core–ShellParticleswithaTemperature-SensitiveShell 63
HarumaKawaguchi
3.1 Introduction 63
3.2 PreparationofCore–ShellParticleswithaTemperature-
SensitiveShell 63
3.2.1 SpontaneousFormationoftheCore–ShellStructure
viaEmulsionPolymerizationandSoap-FreeEmulsion
Polymerization 63
3.2.2 FormationofaTemperature-SensitiveShellbySeeded
Polymerization 66
3.3 PreparationofHairyParticleswithTemperature-SensitiveHair 66
3.3.1 HairyParticleFormationfromBlockCopolymerMicelles 67
3.3.2 HairyParticleFormationThroughInSituFormationofSurface
ActiveMaterial 68
3.3.3 HairyParticleFormationThroughHairGrowthonCore
Particles 68
3.3.3.1 HairyParticleFormationThroughHairGrowthonRigidCore
Particles 69
3.3.3.2 HairyParticleFormationThroughHairGrowthonMicrogels 70
3.3.3.3 GraftPolymerizationofNIPAMfromaCMCMicrogelUsingthe
CericIonRedoxSystem 71
3.3.4 HairyParticleFormationThroughtheAttachmentofHydrophilic
PolymerChainstotheSurfaceofCoreParticles(Grafting-to
Method) 73
3.4 Properties,FunctionsandApplicationsofCore–ShellParticles
withaTemperature-SensitiveShell 75
3.4.1 VolumePhaseTransitionoftheTemperature-SensitiveShelland
AccompanyingChangesinPhysicalPropertiesoftheParticles 75
3.4.2 Two-DimensionalAssemblyofHairyParticlesandOptical
Properties 76
3.4.3 Other2DAssembly – Temperature-SensitivePickeringEmulsionby
PNIPAMHairyParticles 77
3.4.4 FluorescenceResonanceEnergyTransfer(FRET)ParticlesTunedby
Temperature 77
3.5 Conclusions 78
References 79
Contents VII
4 pH-ResponsiveNanogels:SynthesisandPhysicalProperties 81
BengHoonTan,JeremyPangKernTan,andKamChiuTam
4.1 Introduction 81
4.2 PreparationTechniquesforpH-ResponsiveNanogels 82
4.2.1 EmulsionPolymerization 82
4.2.2 PhysicalSelf-AssemblyofInteractivePolymers 84
4.3 StructuralPropertiesofpH-ResponsiveNanogels 85
4.3.1 DistributionofCrosslinkingMonomers 85
4.3.2 KineticModelingofFunctionalGroupDistributionsin
Nanogels 86
4.4 SwellingofpH-ResponsiveNanogels 87
4.4.1 MechanismofpH-ResponsiveSwelling 87
4.4.2 TheoryofSwellingandElasticityofpH-ResponsiveNanogels 91
4.4.3 EffectofIonicStrength 93
4.5 RheologicalBehaviorofpH-ResponsiveNanogels 96
4.6 ApproachtoModelpH-ResponsiveNanogelProperties 97
4.7 OsmoticCompressibilityofpH-ResponsiveNanogelsinColloidal
Suspensions 106
4.8 ConclusionsandFuturePerspectives 109
References 110
5 Poly(N-Vinylcaprolactam)Nano-andMicrogels 117
ChengChengandAndrijPich
5.1 Introduction 117
5.2 Poly(N-Vinylcaprolactam):Synthesis,StructureandPropertiesin
Solution 117
5.3 ThermalBehaviorofPoly(N-Vinylcaprolactam)inWater 120
5.4 PVCLNano-andMicrogels 123
5.4.1 HomopolymerPVCLMicrogels 125
5.4.2 CopolymerPVCLMicrogels 129
5.4.3 CompositeandHybridMicrogels 133
5.5 Conclusions 137
References 137
6 DoublyCrosslinkedMicrogels 141
BrianR.Saunders
6.1 Introduction 141
6.1.1 DefinitionsandClassificationsofSXandDXMicrogels 141
6.1.2 ABriefHistoryofDoublyCrosslinkedMicrogels 142
6.1.3 Stimulus-ResponsiveDXMicrogels 143
6.1.4 GeneralEquationsGoverningHydrogelSwelling 143
6.1.5 GeneralEquationsGoverningHydrogelMechanical
Properties 144
6.2 MethodsofPreparation 145
6.2.1 DXMicrogelAggregates 146
VIII Contents
6.2.2 MicrogelCrosslinkedHydrogels 146
6.2.3 Microgel-ReinforcedHydrogels 146
6.2.4 DXMicrogelCrystalsbySmallMoleculeAddition 147
6.2.5 Self-CrosslinkedDXMicrogelCrystals 147
6.2.6 InterpenetratingDXMicrogels 148
6.3 MethodsofCharacterization 148
6.3.1 1HNuclearMagneticResonance 148
6.3.2 ConfocalMicroscopy 149
6.3.3 ScanningElectronMicroscopy 150
6.3.4 SwellingExperiments 150
6.3.5 Optical 152
6.3.6 DynamicRheology 153
6.3.7 CompressionModulusMeasurements 154
6.3.8 TensileTesting 154
6.4 Morphology 155
6.4.1 MorphologyTypes 155
6.4.2 MorphologyControl 156
6.5 Properties 157
6.5.1 SwellingPropertiesofDXMicrogelsandControl 157
6.5.2 OpticalTuning 158
6.5.3 MechanicalPropertiesofDXMicrogelsandControl 158
6.5.4 ComparisonofPropertieswithMicrogels 161
6.5.5 ComparisonofPropertieswithConventional
Hydrogels 162
6.6 PotentialApplications 162
6.6.1 PhotonicApplications 162
6.6.2 BiomedicalApplications 163
6.7 Conclusion 165
References 166
7 ATRP:AVersatileToolTowardUniformlyCrosslinkedHydrogels
withControlledArchitectureandMultifunctionality 169
JeongAeYoon,JungKwonOh,WenwenLi,TomaszKowalewski,
andKrzysztofMatyjaszewski
7.1 IncorporatingCrosslinkingReactionsintoControlledRadical
Polymerization 169
7.2 EffectofNetworkHomogeneityonThermoresponsiveHydrogel
Performance 171
7.2.1 PerformanceofMacroscopicHydrogels 172
7.2.2 MolecularLevelDehydrationKinetics 175
7.3 GelNetworksContainingFunctionalizedNanopores 176
7.3.1 EnhancedSwellingRatios 178
7.3.2 AcceleratedDeswellingKinetics 178
7.4 TowardMicro-andNano-SizedHydrogelsbyATRP 180
References 184
Contents IX
8 NanogelEngineeringbyAssociatingPolymersforBiomedical
Applications 187
YoshihiroSasakiandKazunariAkiyoshi
8.1 Introduction 187
8.2 PreparationofAssociatingPolymer-BasedNanogels 188
8.2.1 HydrophobicallyModifiedPolysaccharide 188
8.2.2 PhotoresponsiveMolecule-ModifiedPolysaccharides 190
8.2.3 ThermoresponsivePolymer-GraftedPolysaccharide 191
8.2.4 Metal–LigandModifiedPolysaccharides 192
8.2.5 Siloxane-ModifiedPolysaccharides 193
8.2.6 Protein-CrosslinkedNanogels 193
8.3 FunctionsofSelf-AssembledNanogels 194
8.3.1 Nano-EncapsulationofProteinsbytheNanogel:Nanogelsas
MacromolecularHosts 194
8.3.2 ArtificialMolecularChaperones 195
8.3.3 NanogelChaperonesinCell-FreeProteinSynthesis 196
8.4 ApplicationofPolysaccharideNanogelstoDDS 197
8.4.1 ProteinDelivery 198
8.4.2 NucleicAcidDelivery 199
8.5 IntegrationofNanogels 199
8.6 ConclusionandPerspectives 202
References 202
9 MicrogelsandBiologicalInteractions 209
MichaelH.Smith,AntoinetteB.South,andL.AndrewLyon
9.1 AnIntroductiontoPolymerBiomaterials 209
9.1.1 Hydrogels 210
9.1.2 HydrogelsasParticles 211
9.1.3 HydrogelParticleSynthesis 212
9.2 DrugDelivery 213
9.2.1 NanoparticlesandtheMononuclearPhagocyticSystem 214
9.2.2 NanoparticleSizeandSurfaceModificationforEnhanced
Delivery 214
9.2.3 NanogelCellularTargeting 216
9.2.3.1 PassiveTargeting:TheEnhancedPermeabilityandRetention
Effect 216
9.2.3.2 ActiveTargeting:NanoparticleBioconjugation 217
9.2.4 DegradationandReleaseofEncapsulatedCargo 220
9.2.4.1 ReleasebyReduction 220
9.2.4.2 ReleasebypHChanges 220
9.3 BiomaterialFilms 221
9.3.1 TheForeignBodyResponse 222
9.3.2 HydrogelsasaBiomaterialInterface 223
9.3.3 AntifoulingSurfaces 224
9.3.4 CellularAdhesion 225
X Contents
9.3.5 DrugRelease 227
9.4 Conclusion 228
References 229
10 OscillatingMicrogelsDrivenbyChemicalReactions 237
DaisukeSuzuki
10.1 Introduction 237
10.2 TypesofOscillatingMicrogels 238
10.3 SynthesisandFabricationofOscillatingMicrogels 240
10.4 ControlofOscillatoryBehavior 241
10.4.1 EffectonInductionPeriod 242
10.4.2 EffectonOscillationAmplitude 244
10.4.3 EffectonOscillationPeriodandWaveforms 247
10.5 Flocculating/DispersingOscillation 251
10.6 ConcludingRemarks 254
References 254
11 SmartMicrogel/NanoparticleHybridswithTunableOptical
Properties 257
MatthiasKargandThomasHellweg
11.1 Introduction 257
11.2 SynthesisofHybridGels 258
11.3 CharacterizationofHybridGels 260
11.4 HybridMicrogelswithPlasmonProperties 261
11.5 PhotoluminescentHybridMicrogels 269
11.6 Summary 272
References 274
12 MacroscopicMicrogelNetworks 281
ToddHoare
12.1 IntroductionandMotivation 281
12.2 PreparationofMicrogelNetworks 284
12.2.1 NetworkingStrategies 284
12.2.2 DirectMicrogelCrosslinking 285
12.2.2.1 HydrophobicAssembly 285
12.2.2.2 IonicAssembly 287
12.2.2.3 CovalentAssembly 289
12.2.3 Microgel-MediatedCrosslinking 290
12.2.3.1 Initiator-GraftedMicrogels 290
12.2.3.2 Surface-PolymerizableMicrogels 291
12.2.3.3 Surface-ReactiveMicrogels 293
12.2.4 PhysicalMicrogelEntrapment 295
12.2.4.1 EntrapmenttoForm3DHydrogels 295
12.2.4.2 EntrapmenttoForm2DFilms 299
12.3 ApplicationsofMicrogelNetworks 301