Physics of Charged Macromolecules: Synthetic and Biological Systems

526 Pages·2023·40.779 MB·English

by  Murugappan Muthukumar

PhysicsofChargedMacromolecules
Charged molecules percolate all aspects of our modern lives including food, health
care, and water-based technologies. As a concise introduction to the physics of
charged macromolecules, this book covers the basics of electrostatics as well as
cutting-edge modern research developments. This accessible book provides a clear
and intuitive view of concepts and theory, and features appendices detailing mathe-
maticalmethodology.Supportedbyresultsfromreal-worldexperimentsandsimula-
tions,thisbookequipsthereaderwithavitalfoundationforperformingexperimental
research. Topics include living matter and synthetic materials including polyelec-
trolytes,polyzwitterions,polyampholytes,proteins,intrinsicallydisorderedproteins,
andDNA/RNA.Servingasagatewaytothegrowingfieldofchargedmacromolecules
and their applications, this concept-driven book is a perfect guide for students
beginningtheirstudiesinchargedmacromolecules,providingnewopportunitiesfor
researchanddiscovery.
MurugappanMuthukumaristheWilmerD.BarrettProfessorofPolymerScienceand
EngineeringattheUniversityofMassachusettsAmherst.HeisafellowoftheAmer-
ican Physical Society and a recipient of the Dillon Medal and the Polymer Physics
Prize of the American Physical Society, as well as the American Chemical Society
PolymerChemistryAward.
Published online by Cambridge University Press
Published online by Cambridge University Press
Physics of Charged
Macromolecules
Synthetic and Biological Systems
MURUGAPPAN MUTHUKUMAR
UniversityofMassachusettsAmherst
Published online by Cambridge University Press
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Informationonthistitle:www.cambridge.org/9780521864879
DOI:10.1017/9781139046749
©MurugappanMuthukumar2023
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placewithoutthewrittenpermissionofCambridgeUniversityPress&Assessment.
Firstpublished2023
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LibraryofCongressCataloging-in-PublicationData
Names:Muthukumar,Murugappan,author.
Title:Physicsofchargedmacromolecules:syntheticandbiologicalsystems/
MurugappanMuthukumar.
Description:Cambridge;NewYork,NY:CambridgeUniversityPress,2023.|
Includesbibliographicalreferences.
Identifiers:LCCN2022025102|ISBN9780521864879(hardback)|
ISBN9781139046749(ebook)
Subjects:LCSH:Macromolecules–Electricproperties.
Classification:LCCQD381.9.E38M882023|DDC547/.70457–dc23/eng20221123
LCrecordavailableathttps://lccn.loc.gov/2022025102
ISBN978-0-521-86487-9Hardback
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Contents
Preface pagexiii
Acknowledgments xv
1 IntroductiontoChargedMacromolecules 1
1.1 GeneralPremise 1
1.2 ChainConnectivityandLong-RangedTopologicalCorrelation 5
1.3 ScalesofEnergy,Length,andTimeinChargedSystems 6
1.4 ConfluenceofElectrostaticandTopologicalCorrelations 9
1.4.1 SimilarlyChargedMacromoleculesCanAttractEachOther 9
1.4.2 Ordinary–ExtraordinaryTransition 10
1.4.3 ReentrantPrecipitation 11
1.4.4 EncapsulationofDNAviaComplexation 12
1.4.5 GelSwelling 12
1.4.6 Outlook 14
2 ModelsofUnchargedMacromolecules 15
2.1 FlexibleChains 15
2.1.1 MeanSquareEnd-to-EndDistance 17
2.1.2 RadiusofGyration 17
2.1.3 SegmentDensityProfile 17
2.1.4 ProbabilityofEnd-to-EndDistance 18
2.1.5 FormFactor 18
2.1.6 FreeEnergy 19
2.1.7 TensileForce 20
2.2 SemiflexibleChains 21
2.3 OtherArchitectures 22
2.3.1 BranchedMacromolecules 22
2.3.2 CircularMacromolecules 23
2.4 ExcludedVolumeInteractions 23
2.5 ChainSwelling 27
2.6 Coil–GlobuleTransition 30
2.7 SwellingofRandomlyBranchedMacromolecules 31
2.8 SummaryofSizeExponents 32
2.9 ExperimentalDeterminationofSizeExponent 33
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vi Contents
3 Water,Oil,andSalt 35
3.1 BasicsofElectrostaticsinVacuum 35
3.1.1 ForceandElectricField 36
3.1.2 ElectricPotential 37
3.1.3 ElectrostaticPotentialEnergy 37
3.2 DielectricMedia 38
3.2.1 HomogeneousIsotropicLinearDielectrics 39
3.2.2 EntropyofDielectrics 40
3.3 Water 41
3.4 DissolutionofSaltandOilinWater 44
3.4.1 Salt 44
3.4.2 OilandHydrophobicEffect 45
3.5 IonSolvationandBornFreeEnergy 46
3.6 Ion-PairFormationandBjerrumLength 49
3.6.1 ReleaseofBoundWaterDrivesAttraction 49
3.6.2 BjerrumLength 51
3.6.3 EffectofIonSize 52
3.7 Dipoles 53
3.7.1 PropertiesofSimpleDipoles 54
3.8 DiluteSolutionsofStrongElectrolytes 58
3.8.1 Poisson–BoltzmannFormalism 59
3.8.2 Debye–HückelTheory 61
3.8.3 ElectrostaticScreeningLength(DebyeLength) 62
3.8.4 IonSizeandExtendedDebye–HückelTheory 64
3.8.5 SizeandShapeofIonCloud 66
3.8.6 FreeEnergy 67
3.8.7 OsmoticPressure 68
4 ChargedInterfacesandGeometricalObjects 70
4.1 PlanarInterfaces 71
4.1.1 Salt-FreeSolutions 72
4.1.2 SolutionswithSalt 74
4.2 ChargedSphericalParticles 79
4.3 ChargedCylindricalAssemblies 81
4.3.1 CounterionDistributioninSalt-FreeSolutions 81
4.3.2 CounterionDistributioninSolutionswithSalt 84
4.4 LineChargeandManningCondensation 87
4.5 DielectricMismatch 89
5 DiluteSolutionsofChargedMacromolecules 92
5.1 Introduction 92
5.2 TitrationCurvesandChargeRegularization 95
5.3 PolyelectrolyteModelChainandBasicConcepts 100
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Contents vii
5.3.1 ExcludedVolumeInteraction(HydrophobicInteraction) 102
5.3.2 ElectrostaticInteraction 102
5.3.3 ElectrostaticPersistenceLength 109
5.4 ExperimentalResults 111
5.5 SimulationResults 113
5.5.1 RadiusofGyration 114
5.5.2 CounterionAdsorptionandEffectiveCharge 116
5.6 ElectrostaticSwellingwithFixedPolymerCharge 119
5.6.1 HighSaltLimit 119
5.6.2 LowSaltLimit 121
5.6.3 ElectrostaticBlob 123
5.6.4 CrossoverFormula 124
5.6.5 ElectrostaticStretchingofSemiflexibleChains 125
5.7 Self-regularizationofPolymerCharge 126
5.8 Coil–GlobuleTransitioninPolyelectrolytes 130
5.9 ApparentMolarMass,ApparentRadiusofGyration,andStructure
Factor 134
5.9.1 ApparentMolarMass 136
5.9.2 CorrelationHoleandApparentRadiusofGyration 138
5.9.3 InternalStructure 139
5.10 OsmoticPressureandDonnanEquilibrium 140
5.10.1 OsmoticPressureofaDilutePolyelectrolyteSolution 142
5.10.2 DonnanEquilibrium 144
5.10.3 DonnanMembranePotential 145
5.11 Polyampholytes,Polyzwitterions,andProteins 146
5.11.1 Polyampholytes 147
5.11.2 Polyzwitterions 149
5.11.3 IntrinsicallyDisorderedProteins 153
6 StructureandThermodynamicsinHomogeneousPolyelectrolyteSolutions 159
6.1 Introduction 159
6.2 SolutionsofUnchargedMacromolecules 162
6.2.1 Flory–HugginsTheory 162
6.2.2 ConcentrationFluctuations 166
6.2.3 ScalingLaws 174
6.3 SemidiluteandConcentratedPolyelectrolyteSolutions 177
6.3.1 EssentialsofDoubleScreeningTheory 177
6.3.2 EffectiveInteractionandAttractionatIntermediateDistances 180
6.3.3 CorrelationLengthinPolyelectrolyteSolutions 182
6.3.4 ScatteringFunction 182
6.3.5 SizeofaLabeledPolyelectrolyteChain 183
6.3.6 FreeEnergyandOsmoticPressure 183
6.4 ElectrostaticallyDrivenStructureinSalt-FreePolyelectrolyteSolutions 185
6.5 AggregationofSimilarlyChargedPolymers 192
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viii Contents
7 Dynamics 196
7.1 Introduction 196
7.2 HydrodynamicInteraction 200
7.3 DiluteSolutionsofColloidalParticles,Macroions,andFoldedProteins 202
7.3.1 Einstein’sElectrophoreticMobility 202
7.3.2 HückelTheory 204
7.3.3 HenryTheory 206
7.3.4 Helmholtz–SmoluchowskiTheory 207
7.3.5 ElectroosmoticFlow 208
7.3.6 ZetaPotential 210
7.3.7 MobilitythroughaNanopore 211
7.4 PhenomenologyofDynamicsofPolyelectrolyteSolutions 213
7.4.1 DiffusionandRelaxationTime 214
7.4.2 Ordinary–ExtraordinaryTransition 216
7.4.3 ElectrophoreticMobility 219
7.4.4 Viscosity 219
7.5 ModelsofDynamicsofUnchargedPolymers 222
7.5.1 RouseDynamics 225
7.5.2 ZimmDynamics 230
7.5.3 ReptationModel 233
7.5.4 EntropicBarrierModel 238
7.6 DilutePolyelectrolyteSolutions 242
7.6.1 TranslationalFrictionCoefficient 242
7.6.2 ElectrophoreticMobility 243
7.6.3 CoupledDiffusionCoefficient 245
7.6.4 IntrinsicViscosityandModulus 249
7.7 SemidilutePolyelectrolyteSolutions 250
7.7.1 TracerDiffusionCoefficient 254
7.7.2 ElectrophoreticMobility 254
7.7.3 CooperativeDiffusionCoefficient 255
7.7.4 CoupledDiffusionandOrdinary–ExtraordinaryTransition 256
7.7.5 Viscosity 261
7.8 EntangledSolutions 264
7.9 ConductivityofPolyelectrolyteSolutions 265
7.10 DielectricRelaxation 267
7.11 PolymerTranslocation 269
7.11.1 PolymerCapturethroughaBarrier 273
7.11.2 KineticsofTranslocation 275
7.12 TopologicallyFrustratedNon-diffusiveDynamics 277
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Contents ix
8 Self-AssemblyandPhaseBehaviors 279
8.1 GeneralPremise 279
8.2 Liquid–LiquidPhaseSeparationinSolutionsofUnchargedPolymers 282
8.2.1 ConcentrationFluctuationsandLandau–GinzburgTheory 287
8.3 CoulombCriticalityinElectrolyteSolutions 291
8.3.1 FreeEnergy 292
8.3.2 InstabilityandCriticality 292
8.4 PhaseBehaviorofPolyelectrolyteSolutions 294
8.4.1 Salt-FreePolyelectrolyteSolutions 295
8.4.2 PolyelectrolyteSolutionswithSalt 298
8.4.3 Charge Regularization: Daughter Phases Have Different
ChargeDensities 300
8.4.4 ConcentrationFluctuationsandGinzburgCriterion 302
8.5 KineticsofPhaseSeparation 303
8.5.1 SpinodalDecomposition 304
8.5.2 NucleationandGrowth 307
8.5.3 InterludeofAggregationinPhaseSeparation 308
8.6 MicellizationandMicrophaseSeparation 310
8.6.1 Self-AssemblyofChargedDiblockCopolymesinSolutions 311
8.6.2 MicrophaseSeparation 316
8.7 Isotropic−NematicTransitioninSolutionsofChargedRods 322
8.8 Proteins,Fibrillization,andMembranelessOrganelles 326
8.8.1 Fibrillization 327
8.8.2 MembranelessOrganelles 336
9 Adsorption,Complexation,andCoacervation 339
9.1 Introduction 339
9.2 Adsorption 340
9.2.1 AdsorptionataPlanarSurface 343
9.2.2 AdsorptionatSphericalSurfaces 347
9.3 ChargedBrushes 349
9.3.1 No-SaltLimit 350
9.3.2 High-SaltLimit 352
9.3.3 DisjoiningPressure 353
9.3.4 DensityProfile 353
9.4 GenomePackaginginViruses 354
9.5 IntermolecularComplexation 359
9.5.1 CounterionReleaseDrivesComplexCoacervation 362
9.5.2 CompetitiveSubstitutioninIntermolecularComplexes 363
9.6 Coacervation 366
9.6.1 Voorn–OverbeekTheory 368
9.6.2 DipolarTheoryofCoacervation 370
9.7 MembranelessOrganelles 373
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