Physical Chemistry of Polyelectrolytes

896 Pages·2001·6.343 MB·English

by  Tsetska Radeva

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ISBN: 0-8247-0463-0
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Preface
Polyelectrolytesarepolymersbearingdissociatedionicgroups.Theirunique
properties, dominated by strong long-range electrostatic interactions, have
been studied over the past few decades. Substantial theoretical and experi-
mental efforts have been made, for example, to understand the origin of
‘‘slow’’ domains or ‘‘loose’’ clusters in semidilute solutions of highly
charged polyelectrolytes. This kind of attractive interaction between macro-
ions is not consistent with the standard theory based on the overlap of the
electrical double layers between charged flat surfaces. Charge-fluctuation
forces between several polyions due to sharing of their counterions or at-
traction by expansion of the condensed layers between charged rods have
been suggested to explain the appearance of these formations. Particular
focus has also been placed on polyion interactions with counterions, since
their condensation on the polyion surface is one of the most characteristic
properties of the polyelectrolytes. The interaction of polyions with other
charged or neutral species and, in particular, the adsorption of ionizable
polymers at interfaces, is the second aspect of the physical chemistry of
polyelectrolytes that has been extensively studied due both to the funda-
mental importance of this phenomenon and to its central role in numerous
industrial processes.
The interest in polyelectrolyte investigations hasincreasedinthelastfew
years as evidenced by the first two International Symposiums on Polyelec-
trolytes, held in 1995 and 1998. The number of papers dealing with poly-
electrolytes has also increased substantially. This is not surprising consid-
ering the wide application of natural and synthetic polymers in medicine,
iii
iv Preface
paper making, mineral separation, paint and food industries, cosmetics and
pharmacy, water treatment processes, and soil remediation. The fabrication
of layer-by-layer assembled multicomposite films, which fall in a category
of novel nanomaterials, presently hold a central place in this area.
The purpose of this volume is to collect results that show the current
understanding of the fundamental nature of polyelectrolytes. I hope that its
appearancewillstimulatetheresearcheffortstowardsolvingmanyproblems
in this interdisciplinary field. Practical utilization of these results is beyond
doubt. The book is addressed to scientists working in the fields ofbiochem-
istry, molecular biology, physical chemistry of colloids and ionizable poly-
mers, and their applications in related technical processes.
Thevolumeconsistsofthreeparts.Thefirstdealswithstaticanddynamic
properties of salt-free polyelectrolyte solutions and of solutions with added
salts.An extension is presented ofthe counterion condensationtheorytothe
calculation of counterion–polyion, coion–polyion, and polyion–polyion
pair potentials and the appearance is predicted of inverted forces leading to
the formation of‘‘loose’’clustersinsolutionsofpolyelectrolytes.Theorigin
of counterion-mediated attraction between like-charged chains is also dis-
cussed within a charge fluctuation approach that reconciles thethermalfluc-
tuation approach with the ionic crystal one. A new criterion for counterion
condensation is introduced through molecular dynamics simulations of a
cell-likemodelforstiffpolyelectrolytes;theeffectsconsideredincludepoly-
ionsovercharging,chargeoscillations,andattractiveinteractions.Metropolis
Monte Carlo simulation is also applied to calculate counteriondistributions,
electricpotentials,andfluctuationofcounterionpolarizationformodelDNA
fragments. Theoretical approaches developed for the description of coil–
globule transition of polyelectrolyte molecules are treated in two limiting
situations—for a single macromolecule at infinite dilution and for a poly-
electrolyte gel. Although emphasis is placed on the recent developments in
the theory of polyelectrolytes, this first part provides a partial review of the
new experimental results that try to explain different aspects of the physical
chemistry of polyelectrolytes.
The second part is devoted to adsorption of polyelectrolytes at interfaces
and to flocculation and stabilization of particles in adsorbing polymer so-
lutions. A recent theory of the electrostatic adsorption barrier, some typical
experimental results, and new approaches for studying the kinetics of poly-
electrolyte adsorption are presented in the first chapter of this part. In the
following chapters, results are collected on the electrical and hydrodynamic
properties of colloid–polyelectrolyte surface layers, giving information on
the structure of adsorbed layers and their influence on the interactions be-
tween colloidal particles; examples and mechanisms are analyzed of poly-
electrolyte-induced stabilization and fragmentation of colloidal aggregates;
Preface v
self-assembled monolayers from synthetic polyelectrolytes onwaterorsolid
surfaces and the role of amphiphilic polyelectrolytes for the emulsion sta-
bility are considered. Special attention is given to surface force measure-
ments that show how association between polyelectrolytes and surfactants
at solid–liquid interfaces influences surface interactions and structureofad-
sorbed layers.
The third part discusses polyelectrolyte complex formation andcomplex-
ation of polyelectrolytes with surfactants and proteins. Mobility of short
chains and dynamic properties of polyelectrolyte gels are also considered.
Phase transitions in ionic gels are explained with simple models in which
polymer–polymer interactions are taken into account at a molecular level.
In the second chapter of this part, recent experimental and theoretical ad-
vances are summarized for gel electrophoresis, which is invaluable in pre-
dicting conformation and structural changes of biologically significant
macromolecules. In the following chapters, results are grouped for the stoi-
chiometry, structure, and stability of highly aggregated polyelectrolytecom-
plexes; for the role of hydrophobicity and electric charge of the partners in
the protein binding to amphiphilic polyelectrolytes; andforthemicellar-like
aggregation of surfactants bound to oppositely charged polyelectrolytes.
I wish to thank first ProfessorArthur Hubbard, who invited me to edit a
volume on this rapidly expanding field. Acknowledgments are due to all
authors for their valuable contributions and willing cooperation. I acknowl-
edge with gratitude the assistance ofAni Pesheva in the correspondence, as
wellastheeffortsofourproductioneditor,PaigeForce,andofallmyfriends
who contributed to the production of this volume.
Tsetska Radeva
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Contents
Preface iii
Contributors xi
Part I Structure and Properties of Polyelectrolyte Solutions
1. Structure and Dynamics of Polyelectrolyte Solutions by
Light Scattering 1
Maria´n Sedla´k
2. Molecular Dynamics Simulations of the Cylindrical
Cell Model 59
Markus Deserno, Christian Holm, and Kurt Kremer
3. Inverted Forces in Counterion Condensation Theory 111
Jolly Ray and Gerald S. Manning
4. Polyelectrolyte Solutions with MultivalentAdded Salts:
Stability, Structure, and Dynamics 135
Maurice Drifford and Michel Delsanti
5. Physical Questions Posed by DNACondensation 163
Bae-Yeun Ha and Andrea J. Liu
6. Conformational Transition in Polyelectrolyte Molecules:
Influence of Osmotic Pressure of Counterions 181
Valentina V. Vasilevskaya
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viii Contents
7. Conductance of Polyelectrolyte Solutions,Anisotropy and
OtherAnomalies 203
Hans Vink
8. Electrical Polarizability of Polyelectrolytes by Metropolis
Monte Carlo Simulation 223
Kazuo Kikuchi
9. Polyelectrolytes in Nonaqueous Solutions 245
Masanori Hara
Part II Polyelectrolytes at Interfaces
10. Kinetics of PolyelectrolyteAdsorption 281
Martien A. Cohen Stuart and J. Mieke Kleijn
11. Electric Light Scattering of Colloid Particles in
Polyelectrolyte Solutions 305
Tsetska Radeva
12. MonolayerAssemblies of Poly(L-GlutamicAcid)s at
Two-Dimensional Interfaces 347
Nobuyuki Higashi and Masazo Niwa
13. Emulsions Stabilized by Polyelectrolytes 363
Patrick Perrin, Fre´de´ric Millet, and Bernadette Charleux
14. Polyelectrolyte–Surfactant Interactions at Solid–Liquid
Interfaces Studied with Surface Force Techniques 447
Per M. Claesson, Andra Dedinaite, and Evgeni Poptoshev
15. Fragmentation of ColloidalAggregates by
PolyelectrolyteAdsorption 509
Emile Pefferkorn
16. Interactions Between Polyelectrolytes and Kaolin 567
Joachim Ko¨tz and Sabine Kosmella
Part III Polyelectrolyte Complexes and Gels
17. Phase Transitions in Polyelectrolyte Gels 591
Etsuo Kokufuta
18. Anomalous Migration of DNAin Gels and the
Polyelectrolyte Nature of DNA 665
Udayan Mohanty and Larry W. McLaughlin
Contents ix
19. Complexation BetweenAmphiphilic Polyelectrolytes and
Proteins: From Necklaces to Gels 687
Christophe Tribet
20. Polyelectrolyte Complex Formation in Highly Aggregating
Systems: MethodicalAspects and General Tendencies 743
Herbert Dautzenberg
21. Surfactant Binding to Polyelectrolytes 793
Ksenija Kogej and Jozˇe Sˇkerjanc
22. Metal Complexation in Polyelectrolyte Solutions 829
Tohru Miyajima
Index 875