Functionalization of Graphene

426 Pages·2014·9.411 MB·English

by  Vasilios Georgakilas (Ed.)

Editedby
VasiliosGeorgakilas
FunctionalizationofGraphene
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Edited by Vasilios Georgakilas
Functionalization of Graphene
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V
Contents
Preface XIII
ListofContributors XV
1 AnIntroductiontoGraphene 1
KonstantinosSpyrouandPetraRudolf
1.1 BriefHistoryofGraphite 1
1.2 GrapheneandGrapheneOxide 2
1.2.1 PreparationofGraphenefromGrapheneOxide 3
1.2.2 IsolationofPristineGrapheneMonolayers 5
1.2.3 LargeScaleProductionofGObyLangmuir-BlodgettMethods 6
1.2.4 OtherMethodsofGrapheneProduction 6
1.3 CharacterizationofGraphene 9
1.3.1 MicroscopicObservation 9
1.3.2 RamanSpectroscopy 11
1.3.3 ThermogravimetricAnalysis 12
1.3.4 OpticalPropertiesofGraphene 13
1.3.5 X-RayDiffractionPattern 17
References 18
2 CovalentAttachmentofOrganicFunctionalGroupsonPristine
Graphene 21
VasiliosGeorgakilas
2.1 Introduction 21
2.2 CycloadditionReactions 22
2.2.1 1,3-DipolarCycloadditionofAzomethineYlide 22
2.2.1.1 ThroughaSubstitutedAldehydePathway 24
2.2.1.2 ThroughSubstitutedαAminoAcidPathway 27
2.2.2 CycloadditionbyZwitterionicIntermediate 28
2.2.3 Diels–AlderCycloaddition 29
2.2.4 NitreneAddition 30
2.2.5 CarbeneAddition 35
2.2.6 AryneAddition 36
2.2.7 BingelTypeCycloaddition 37
VI Contents
2.3 AdditionofFreeRadicals 39
2.3.1 DiazoniumSaltReaction 39
2.3.2 OtherRadicalAdditions 42
2.4 NucleophilicAddition 46
2.5 ElectrophilicAdditiononGraphene 46
2.6 OrganometallicChemistryofGraphene 48
2.7 PostFunctionalizationReactions 50
2.8 Conclusion 55
References 56
3 AdditionofOrganicGroupsthroughReactionswithOxygen
SpeciesofGrapheneOxide 59
VasiliosGeorgakilas
3.1 Introduction 59
3.1.1 Graphene/PolymerNanocomposites 60
3.2 TheRoleofCarboxylicAcidsofGO 61
3.2.1 OrganicFunctionalizationthroughAmideBondFormation 61
3.2.1.1 LipophilicDerivatives 61
3.2.1.2 Hydrophilic–BiocompatibleDerivatives 62
3.2.1.3 AdditionofChromophores 64
3.2.1.4 PolymerGrapheneComposite 69
3.2.2 EsterificationofGO 71
3.2.3 FunctionalizationofGOthroughHeterocyclicRing
Formation 75
3.3 TheRoleofHydroxylGroupsofGO 77
3.4 MiscellaneousAdditions 78
3.4.1 ReactionofCarboxylicAcidandHydroxylGroupswithIsocyanate
Derivatives 78
3.4.2 ReactionofEpoxideswithCarboxylicAcidsorHydroxyl
Groups 78
3.4.3 InteractionofAmmoniawithCarboxylicAcidsandEpoxidesof
GO 80
3.4.4 EnrichmentofGOinCarboxylicAcids 81
3.4.5 AdditionofGallium-Phthalocyanine(Ga-Pc)toGOthroughGa–O
CovalentBond 82
3.5 TheRoleofEpoxideGroupsofGO 83
3.5.1 NucleophilicAdditionofAminetoEpoxides 83
3.5.2 AdditionofChromophores 85
3.5.3 AdditionofPolymers 86
3.6 PostFunctionalizationofGO 87
3.6.1 PostFunctionalizationofOrganicallyModifiedGOviaClick
Chemistry 87
3.6.2 CounterAnionExchange 89
3.7 Conclusions 90
References 92
Contents VII
4 ChemicalFunctionalizationofGrapheneforBiomedical
Applications 95
CinziaSpinato,Ce´ciliaMe´nard-Moyon,andAlbertoBianco
4.1 Introduction 95
4.2 CovalentFunctionalizationofGrapheneNanomaterials 97
4.2.1 SynthesisofGOandrGO 99
4.2.1.1 SynthesisofGrapheneOxide 99
4.2.1.2 ReductionofGrapheneOxide 99
4.2.2 FunctionalizationofGrapheneOxidewithPolymers 100
4.2.2.1 PEGylated-GOConjugates 100
4.2.2.2 CovalentLinkageofBiopolymers 103
4.2.3 TetheringofAntibodies 105
4.2.4 AttachmentofNucleicAcids 106
4.2.5 GraftingofPeptidesandEnzymes 108
4.2.6 AttachmentofOtherOrganicMoleculesandBiomolecules 108
4.3 Non-covalentFunctionalizationofGraphene 110
4.3.1 Adsorptionviaπ-Stacking 110
4.3.1.1 AdsorptionofDrugs 111
4.3.1.2 AdsorptionofPyreneDerivatives 111
4.3.1.3 Non-covalentInteractionswithNucleicAcidsandAptamers 113
4.3.1.4 ImmobilizationofEnzymes,Proteins,andOther
Macromolecules 116
4.3.2 ElectrostaticandHydrophobicInteractions 116
4.3.2.1 CoatingwithPolymersandBiopolymers 116
4.3.2.2 DepositionofNanoparticles 119
4.3.2.3 AdsorptionofQuantumDots 121
4.4 Graphene-BasedConjugatesPreparedbyaCombinationofCovalent
andNon-covalentFunctionalization 121
4.4.1 Polymer-andBiopolymer-GraftedGrapheneNanomaterialsUsedas
Nanocarriers 121
4.4.1.1 Polymer-FunctionalizedGOforDrugDelivery 122
4.4.1.2 Polymer-FunctionalizedGOforGeneDelivery 123
4.4.1.3 Chitosan-FunctionalizedGO 125
4.4.2 GOFunctionalizedwithTargetingLigandsandAntibodies 125
4.4.2.1 FolicAcid-ConjugatedGO 125
4.4.2.2 Antibody-FunctionalizedGOforRadioimaging
andBiosensing 127
4.5 Conclusions 129
Acknowledgments 130
References 130
5 ImmobilizationofEnzymesandotherBiomoleculesonGraphene 139
IoannisV.Pavlidis,MichaelaPatila,AngelikiC.Polydera,
DimitriosGournis,andHaralamposStamatis
5.1 Introduction 139
VIII Contents
5.2 ImmobilizationApproaches 141
5.3 ApplicationsofImmobilizedBiomolecules 145
5.3.1 Biosensors 145
5.3.1.1 GlucoseOxidase-BasedBiosensors 146
5.3.1.2 HorseradishPeroxidase-BasedBiosensors 150
5.3.1.3 Tyrosinase-BasedBiosensors 151
5.3.1.4 Cytochromec-BasedBiosensors 152
5.3.1.5 OtherProtein/EnzymeBiosensors 152
5.3.1.6 DNASensors 152
5.3.1.7 ImmunosensorsandAptasensors 154
5.3.2 Biocatalysis 155
5.3.3 BiofuelCells 159
5.3.4 DrugandGeneDelivery 161
5.4 InteractionsbetweenEnzymesandNanomaterials 162
5.5 Conclusions 165
Abbreviations 165
References 166
6 HalogenatedGraphenes:EmergingFamilyofTwo-Dimensional
Materials 173
KasibhattaKumaraRamanathaDattaandRadekZborˇil
6.1 Introduction 173
6.2 SynthesisofHalogenatedGraphenes 174
6.2.1 Fluorographene 175
6.2.1.1 MechanicalorChemicalExfoliation–fromGraphiteFluorideto
Fluorographene 175
6.2.1.2 FluorinationofGraphene–fromGraphene
toFluorographene 175
6.2.2 NonstoichiometricFluorinatedGrapheneandFluorinated
GrapheneOxide 175
6.2.3 OtherHalogenatedGraphenes 178
6.3 CharacterizationofHalogenatedGraphenes 179
6.3.1 Fluorographene 179
6.3.2 PartiallyFluorinatedandHalogenatedGraphenes 183
6.4 Chemistry,Properties,andApplicationsofFluorographeneand
FluorinatedGraphenes 184
6.5 ChemistryandPropertiesofChlorinatedandBrominated
Graphenes 190
6.6 OtherInterestingPropertiesofHalogenatedGraphenesandTheir
Applications 190
6.7 HalogenatedGraphene–GrapheneHeterostructures–Patterned
Halogenation 193
6.8 ConclusionandFutureProspects 195
References 195