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This Page Intentionally Left Blank ISBN: 0-8247-0463-0 This book is printed on acid-freepaper. Headquarters MarcelDekker,Inc. 270 MadisonAvenue, NewYork, NY10016 tel: 212-696-9000; fax: 212-685-4540 Eastern HemisphereDistribution MarcelDekkerAG Hutgasse 4, Postfach812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 WorldWideWeb http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright(cid:1) 2001 by MarcelDekker,Inc.All Rights Reserved. Neitherthis book norany part may bereproducedortransmittedinanyformorbyany means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTEDINTHE UNITEDSTATES OFAMERICA Preface Polyelectrolytesarepolymersbearingdissociatedionicgroups.Theirunique properties, dominated by strong long-range electrostatic interactions, have been studied over the past few decades. Substantial theoretical and experimental 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 attraction 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 fundamental 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 polyelectrolytes 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 polymers, 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 polyelectrolyte 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 solutions. A recent theory of the electrostatic adsorption barrier, some typical experimental results, and new approaches for studying the kinetics of polyelectrolyte 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 between colloidal particles; examples and mechanisms are analyzed of polyelectrolyte-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 stability 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 This Page Intentionally Left Blank Contents Preface iii Contributors xi Part I Structure and Properties of Polyelectrolyte Solutions 1. Structure and Dynamics of Polyelectrolyte Solutions by Light Scattering 1 Mariań 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 vii 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