Table Of ContentEditedby
SabuThomas,
DominiqueDurand,
ChristopheChassenieux,and
P. Jyotishkumar
Handbookof
Biopolymer-BasedMaterials
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Edited by Sabu Thomas, Dominique Durand,
Christophe Chassenieux, and P. Jyotishkumar
Handbook of Biopolymer-Based Materials
FromBlendsandCompositestoGelsandComplexNetworks
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V
Contents
Foreword XXIII
ListofContributors XXV
1 Biopolymers:StateoftheArt,NewChallenges,andOpportunities 1
ChristopheChassenieux,DominiqueDurand,Parameswaranpillai
Jyotishkumar,andSabuThomas
1.1 Introduction 1
1.2 Biopolymers:ANicheForFundamentalResearch
inSoftMatterPhysics 3
1.3 Biopolymers:AnEndlessSourceofApplications 4
1.4 TopicsCoveredbytheBook 5
1.5 Conclusions 5
References 6
2 GeneralOverviewofBiopolymers:Structure,Properties,and
Applications 7
CharlesWinkworth-SmithandTimJ.Foster
2.1 Introduction 7
2.2 PlantCellWallPolysaccharides 11
2.2.1 Cellulose 11
2.2.1.1 CelluloseExtraction 12
2.2.1.2 Nanocellulose 13
2.2.1.3 MicrofibrillatedCellulose 14
2.2.1.4 CelluloseNanowhiskers 14
2.2.2 Hemicelluloses 15
2.2.2.1 Galactomannans 15
2.2.2.2 KonjacGlucomannan 19
2.2.2.3 Xylan 19
2.2.2.4 Xyloglucan 20
2.2.3 Pectins 21
2.3 Biocomposites 23
2.3.1 NaturalFiberComposites 23
j
VI Contents
2.3.2 CelluloseComposites 25
2.3.3 Cellulose–PolymerInteractions 26
2.3.4 Semi-SolidComposites 27
2.4 FutureOutlook 28
References 29
3 BiopolymersfromPlants 37
MariaJ.Sabater,TaniaR(cid:1)odenas,andAntonioHeredia
3.1 Introduction 37
3.2 LipidandPhenolicBiopolymers 38
3.2.1 TheBiopolymerCutin 38
3.2.1.1 CutinMonomers:BiosynthesisandPhysicochemical
Characteristics 39
3.2.1.2 MolecularArchitectureofCutin 40
3.2.1.3 CutinBiosynthesis 41
3.2.2 Lignin 42
3.2.2.1 MonomerPrecursorsandChemicalReactivity 42
3.2.2.2 LigninBiosynthesis 43
3.2.3 Suberin 45
3.2.3.1 ChemicalComposition 45
3.2.3.2 BiosynthesisandFineStructure 47
3.3 CarbohydrateBiopolymers:Polysaccharides 48
3.3.1 StructuralPolysaccharides 49
3.3.1.1 Cellulose 49
3.3.1.2 Hemicellulose 54
3.3.1.3 Pectin 57
3.3.2 StoragePolysaccharides 59
3.3.2.1 Starch 59
3.3.2.2 Fructans:Inulin 63
3.3.3 Other:Gums(GuarGum,GumArabic,GumKaraya,
GumTragacanth,andLocustBeanGum) 66
3.4 IsopreneBiopolymers:NaturalRubber 67
3.4.1 cis-Polyisoprene 67
3.4.1.1 Occurrence 67
3.4.1.2 Composition,Structure,andProperties 67
3.4.1.3 cis-1,4-PolyisopreneBiosynthesis 68
3.4.1.4 Applications 73
3.4.2 trans-Polyisoprene 73
3.5 ConcludingRemarks 74
References 75
4 BacterialBiopolymersandGeneticallyEngineeredBiopolymers
forGelSystemsApplication 87
DeeptiSinghandAshokKumar
4.1 Introduction 87
4.1.1 NucleicAcidBiopolymers:CentralDogma 89
j
Contents VII
4.2 MicrobialPolysaccharidesasBiopolymers 90
4.2.1 SynthesisandApplications 90
4.3 MicrobialBiopolymersasDrugDeliveryVehicle 92
4.3.1 e-Poly-L-Lysine(e-PL)andItsApplications 92
4.3.2 PolyhydroxyalkanoatesandItsApplications 92
4.4 Polyanhydrides 93
4.5 RecombinantProteinPolymerProduction 94
4.6 RecombinantGeneticallyEngineeredBiopolymer:Elastin 95
4.7 CollagenasanIdealBiopolymer 97
4.7.1 MicrobialRecombinantCollagens:Production
inPichiaPastoris 97
4.8 BiopolymersforGelSystem 99
4.9 HydrogelsofBiopolymersforRegenerativeMedicine 99
4.9.1 PolysaccharideHydrogels 99
4.9.2 Cellulose-DerivedBiopolymers-BasedHydrogels 100
4.9.3 ProteinBiopolymers-BasedHydrogels 100
4.10 SupermacroporousCryogelMatrixfromBiopolymers 100
4.10.1 ProteinCryogel 101
4.11 BiopolymersImpactonEnvironment 102
4.12 Conclusion 103
References 104
5 BiopolymersfromAnimals 109
KhaleelullaSahebShaikandBernardMoussian
5.1 Introduction 109
5.2 ChitinandHyaluronicAcidintheLivingWorld 110
5.3 MilestonesinChitinHistory 110
5.4 FromTrehalosetoChitin 112
5.5 ChitinSynthase 115
5.6 RegulationofChitinSynthesisinFungi 117
5.7 OrganizationofChitinintheFungalCellWall 118
5.8 OrganizationofChitinintheArthropodCuticle 119
5.9 Chitin-OrganizingFactors 123
5.10 SecretionandCuticleFormation 126
5.11 TranscriptionalRegulationofCuticleProduction 128
5.12 ChitinSynthesisInhibitors 130
5.13 NoncuticularChitininInsects 131
5.14 ChitinasaStructuralElement 133
5.15 ApplicationofChitin 134
5.16 Conclusion 135
References 135
6 PolymericBlendswithBiopolymers 143
HeroJanHeeres,FrankvanMaastrigt,andFrancescoPicchioni
6.1 Introduction 143
6.2 Starch-BasedBlends 146
j
VIII Contents
6.2.1 PolymerSelectionforStarchBlending 147
6.2.2 StarchStructure 150
6.2.3 UncompatibilizedBlends 152
6.2.4 Compatibilization 155
6.2.5 Composites 157
6.3 BlendswithChitosan(OneAminoGroupTooMuch . . . ) 158
6.4 FuturePerspectives 161
6.4.1 BiopolymerPlasticization 161
6.4.2 BlendMorphologyandCompatibilization 162
6.4.3 BlendProcessing:TechnologicalAspects 163
References 164
7 Macro-,Micro-,andNanocompositesBasedonBiodegradable
Polymers 173
LucAv(cid:1)erousandEricPollet
7.1 Introduction 173
7.2 BiodegradablePolymers 174
7.2.1 Classification 174
7.2.2 Agro-Polymers:TheCaseofStarch 175
7.2.2.1 NativeStarchStructure 175
7.2.2.2 PlasticizedStarch 176
7.2.3 BiodegradablePolyesters 177
7.2.3.1 PolyestersBasedonAgro-Resources 177
7.2.3.2 Petroleum-BasedPolyesters 179
7.3 Biocomposites 181
7.3.1 Generalities 181
7.3.2 TheCaseofBiocompositesBasedonAgro-Polymers 181
7.3.2.1 CelluloseFiberReinforcement 181
7.3.2.2 LigninandMineralFillers 182
7.3.3 TheCaseofBiocompositesBasedonBiopolyesters 182
7.3.3.1 Generalities 182
7.3.3.2 TheCaseofBiocompositesBasedonAromaticCopolyesters 183
7.4 Nanobiocomposites 186
7.4.1 Generalities 186
7.4.2 NanobiocompositesBasedonAgro-Polymers(Starch) 187
7.4.2.1 Whisker-BasedNanobiocomposites 190
7.4.2.2 StarchNanocrystal-BasedNanobiocomposites 190
7.4.2.3 Nanoclay-BasedNanobiocomposites 190
7.4.3 NanobiocompositesBasedonBiopolyesters 193
7.4.3.1 Poly(lacticacid)-BasedNanobiocomposites 193
7.4.3.2 Polyhydroxyalkanoate-BasedNanobiocomposites 194
7.4.3.3 Polycaprolactone-BasedNanobiocomposites 195
7.4.3.4 BiodegradableAliphaticCopolyester-BasedNanobiocomposites 197
7.4.3.5 AromaticCopolyester-BasedNanobiocomposites 199
References 200
j
Contents IX
8 IPNsDerivedfromBiopolymers 211
FernandoG.Torres,OmarPaulTroncoso,andCarlosTorres
8.1 Introduction 211
8.2 TypesofIPNs 212
8.3 IPNsDerivedfromBiopolymers 214
8.3.1 Alginate 215
8.3.2 Agarose 215
8.3.3 Chitosan 215
8.3.4 Starch 216
8.3.5 Dextran 217
8.3.6 GumArabic 217
8.3.7 Fibrinogen 217
8.3.8 CollagenandGelatin 217
8.3.9 CelluloseandCelluloseDerivatives 218
8.3.10 Polyhydroxyalkanoates 218
8.3.11 Lactide-DerivedPolymers 219
8.4 ManufactureofIPNs 220
8.4.1 Casting–EvaporationProcessing 220
8.4.2 EmulsificationCross-LinkingTechnique 220
8.4.3 Miniemulsion/InverseMiniemulsionTechnique 221
8.4.4 FreezeDryingTechnique 222
8.5 CharacterizationofIPNs 222
8.5.1 MorphologicalandStructuralCharacterization 222
8.5.2 FTIRSpectroscopy 223
8.5.3 MechanicalCharacterization 224
8.5.4 RheologicalCharacterization 225
8.5.5 SwellingBehaviorCharacterization 225
8.5.6 ThermalCharacterization 226
8.6 ApplicationsofIPNs 226
8.6.1 DrugDeliveryApplications 226
8.6.2 ScaffoldsforTissueEngineering 227
8.6.3 OtherBiomedicalApplications 227
8.6.4 AntibacterialApplications 228
8.6.5 Sensor,Actuators,andArtificialMuscleApplications 228
8.7 Conclusions 229
References 229
9 AssociatingBiopolymerSystemsandHyaluronateBiomaterials 235
DeborahBlanchardandRachelAuz(cid:1)ely-Velty
9.1 Introduction 235
9.2 SynthesisandSelf-AssociationofHydrophobicallyModifiedDerivatives
ofChitosanandHyaluronicAcidinAqueousSolution 237
9.2.1 GeneralAspectsofAssociationinAmphiphilicPolyelectrolytes 237
9.2.2 SynthesisandBehaviorinAqueousSolutionofHydrophobically
ModifiedWater-SolubleDerivativesofChitosan 239
j
X Contents
9.2.3 SynthesisandBehaviorinAqueousSolutionofHydrophobically
ModifiedWater-SolubleDerivativesofHyaluronicAcid 242
9.3 DesignofNovelBiomaterialsBasedonChemicallyModified
DerivativesofHyaluronicAcid 248
9.3.1 NanoassembliesBasedonAmphiphilicHyaluronicAcid 249
9.3.2 HydrogelsforCellBiologyandTissueEngineering 254
9.3.2.1 StrategiesfortheCross-LinkingofHAtoObtainScaffoldsfor
Cells 254
9.3.2.2 EngineeringBiologicalFunctionalityinHyaluronicAcid-Based
Scaffolds 260
9.3.2.3 PatterningofHyaluronicAcid 261
9.4 Conclusions 271
References 271
10 PolymerGelsfromBiopolymers 279
EsraAlveroglu,AliGelir,andYasarYilmaz
10.1 Introduction 279
10.2 ExperimentalMethods 279
10.3 PolymerizationandGelationKinetics 281
10.3.1 Fluoroprobe–PolymerInteractions 283
10.3.2 Real-TimeMonitoringofMonomerConversion 286
10.4 Sol–GelTransitionandUniversalityDiscussion 287
10.5 ImprintingtheGels 292
10.6 HeterogeneityofHydrogels 301
10.6.1 EffectofIonDopingonSwellingPropertiesandNetwork
StructureofHydrogels 301
10.6.2 CurrentMeasurementsforSearchingtheInternalMorphology
oftheGels 302
10.7 Ionicp-Typeandn-TypeSemiconductingGels 303
10.7.1 ElectricalPropertiesofIonicp-Typeandn-TypeSemiconducting
Gels 304
10.7.2 PolymericGelDiodeswithIonicChargeCarriers 305
10.8 Conclusions 307
References 308
11 ConformationandRheologyofMicrobialExopolysaccharides 317
JacquesDesbrieres
11.1 Introduction 317
11.2 ConformationofPolysaccharides 318
11.3 SecondarySolid-StateStructuresforMicrobialPolysaccharides 318
11.3.1 NoSecondarySolid-StateStructure 319
11.3.2 Single-ChainConformation 319
11.3.3 Simpleor/andDoubleHelices 321
11.3.4 DoubleHelix 323
11.3.5 TripleHelix 323
