Physical chemistry of polyelectrolytes 2001 radeva

This Page Intentionally Left Blank ISBN: 0-8247-0463-0 This book is printed on acid-free paper Headquarters Marcel Dekker, Inc 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web 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 ᭧ 2001 by Marcel Dekker, Inc All Rights Reserved Neither this book nor any part may be reproduced or transmitted in any form or by any 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 PRINTED IN THE UNITED STATES OF AMERICA Preface Polyelectrolytes are polymers bearing dissociated ionic groups Their unique 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 macroions 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 has increased in the last few years as evidenced by the first two International Symposiums on Polyelectrolytes, held in 1995 and 1998 The number of papers dealing with polyelectrolytes has also increased substantially This is not surprising considering 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 appearance will stimulate the research efforts toward solving many problems in this interdisciplinary field Practical utilization of these results is beyond doubt The book is addressed to scientists working in the fields of biochemistry, molecular biology, physical chemistry of colloids and ionizable polymers, and their applications in related technical processes The volume consists of three parts The first deals with static and dynamic properties of salt-free polyelectrolyte solutions and of solutions with added salts An extension is presented of the counterion condensation theory to the 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’’ clusters in solutions of polyelectrolytes The origin of counterion-mediated attraction between like-charged chains is also discussed within a charge fluctuation approach that reconciles the thermal fluctuation approach with the ionic crystal one A new criterion for counterion condensation is introduced through molecular dynamics simulations of a cell-like model for stiff polyelectrolytes; the effects considered include polyions overcharging, charge oscillations, and attractive interactions Metropolis Monte Carlo simulation is also applied to calculate counterion distributions, electric potentials, and fluctuation of counterion polarization for model DNA 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 on water or solid surfaces and the role of amphiphilic polyelectrolytes for the emulsion stability are considered Special attention is given to surface force measurements that show how association between polyelectrolytes and surfactants at solid–liquid interfaces influences surface interactions and structure of adsorbed layers The third part discusses polyelectrolyte complex formation and complexation 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 advances are summarized for gel electrophoresis, which is invaluable in predicting conformation and structural changes of biologically significant macromolecules In the following chapters, results are grouped for the stoichiometry, structure, and stability of highly aggregated polyelectrolyte complexes; for the role of hydrophobicity and electric charge of the partners in the protein binding to amphiphilic polyelectrolytes; and for the micellar-like aggregation of surfactants bound to oppositely charged polyelectrolytes I wish to thank first Professor Arthur 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 acknowledge with gratitude the assistance of Ani Pesheva in the correspondence, as well as the efforts of our production editor, Paige Force, and of all my friends who contributed to the production of this volume Tsetska Radeva This Page Intentionally Left Blank Contents Preface Contributors Part I iii xi Structure and Properties of Polyelectrolyte Solutions Structure and Dynamics of Polyelectrolyte Solutions by Light Scattering Maria´n Sedla´k Molecular Dynamics Simulations of the Cylindrical Cell Model Markus Deserno, Christian Holm, and Kurt Kremer Inverted Forces in Counterion Condensation Theory Jolly Ray and Gerald S Manning Polyelectrolyte Solutions with Multivalent Added Salts: Stability, Structure, and Dynamics Maurice Drifford and Michel Delsanti Physical Questions Posed by DNA Condensation Bae-Yeun Ha and Andrea J Liu Conformational Transition in Polyelectrolyte Molecules: Influence of Osmotic Pressure of Counterions Valentina V Vasilevskaya 59 111 135 163 181 vii viii Contents Conductance of Polyelectrolyte Solutions, Anisotropy and Other Anomalies Hans Vink 203 Electrical Polarizability of Polyelectrolytes by Metropolis Monte Carlo Simulation Kazuo Kikuchi 223 Polyelectrolytes in Nonaqueous Solutions Masanori Hara Part II 245 Polyelectrolytes at Interfaces 10 Kinetics of Polyelectrolyte Adsorption Martien A Cohen Stuart and J Mieke Kleijn 11 Electric Light Scattering of Colloid Particles in Polyelectrolyte Solutions Tsetska Radeva 305 Monolayer Assemblies of Poly(L-Glutamic Acid)s at Two-Dimensional Interfaces Nobuyuki Higashi and Masazo Niwa 347 12 281 13 Emulsions Stabilized by Polyelectrolytes Patrick Perrin, Fre´de´ric Millet, and Bernadette Charleux 14 Polyelectrolyte–Surfactant Interactions at Solid–Liquid Interfaces Studied with Surface Force Techniques Per M Claesson, Andra Dedinaite, and Evgeni Poptoshev 447 Fragmentation of Colloidal Aggregates by Polyelectrolyte Adsorption Emile Pefferkorn 509 15 16 Interactions Between Polyelectrolytes and Kaolin Joachim Koătz and Sabine Kosmella Part III 363 567 Polyelectrolyte Complexes and Gels 17 Phase Transitions in Polyelectrolyte Gels Etsuo Kokufuta 18 Anomalous Migration of DNA in Gels and the Polyelectrolyte Nature of DNA Udayan Mohanty and Larry W McLaughlin 591 665 Contents 19 20 ix Complexation Between Amphiphilic Polyelectrolytes and Proteins: From Necklaces to Gels Christophe Tribet 687 Polyelectrolyte Complex Formation in Highly Aggregating Systems: Methodical Aspects and General Tendencies Herbert Dautzenberg 743 21 Surfactant Binding to Polyelectrolytes Ksenija Kogej and Jozˇe Sˇkerjanc 793 22 Metal Complexation in Polyelectrolyte Solutions Tohru Miyajima 829 Index 875 868 FIG 32 Miyajima The variation of log(K 0Ca)int(␣) with ␣ for PMA (From Ref 28.) able for this approach, even though metal ion concentration must be kept as low as possible in order that the perturbation due to complexation on acid dissociation should be negligibly small After this electrostatic correction, unique characteristics of polyion complexations, such as the effect of hydrophobicity of supporting ions, the multicoordinate complexability of polyions, and the effect of polymer conformation, have been extracted Polymer complexes with weak complexing ability predominantly form monodentate complexes Agϩ –PAA and Ca2ϩ –PAA systems are examples of this kind Though the apparent Ca2ϩ complexation with PAA is highly enhanced in the presence of TMAϩ, the complexed species are identified as monodentate, indicating that hydrophobicity of supporting ions does not influence the intrinsic complexation behavior With a much stronger complexing ability, polymer ligands form an appreciable amount of multidentate complexes PAA complexes with Cu2ϩ, Cd2ϩ, and Pb2ϩ, are examples of this kind of coordination They form bidentate and/or chelate complexes at a higher degree of dissociation, but monodentate complexes are formed at a lower degree of dissociation The distribution of the two types of complexes has been revealed to be dependent on the average spacing of free carboxylate Metal Complexation in Polyelectrolyte Solutions 869 FIG 33 Relationship between log(K 0Cd)app and ⌬pK for PMA: (⅙) Cs = 0.01; (᭝) Cs = 0.02; (▫) Cs = 0.05; (छ) Cs = 0.10 mol/dm3 (From Ref 28.) groups fixed on the linear polymer molecules It has been revealed that PVIm ligands with nitrogen atoms show much stronger complexing ability than PAA with oxygen atoms to transition metal ions, such as Agϩ, Cu2ϩ, and Cd2ϩ, due to nitrogen atoms as coordinating metal ions At complete dissociation of PVImHϩ, Agϩ shows a maximum coordination number of 2, whereas Cu2ϩ and Cd2ϩ show with PVIm ligands Similarly with the functionality spacing dependence of PAA molecules, the number of coordinating ligating groups, i.e., imidazole groups, decreases with decreasing degree of neutralization It has been revealed that this transition takes place stepwise, i.e., as a function of the degree of dissociation of linear polymer ligands Interestingly, the linear charge spacings that correspond to the transition of coordination for PAA and PVIm ligands for different metal cations are consistent with each other, which may be due to the identical skeletal structure of these two linear polymers Much higher compelxability of Ca2ϩ with PMA is revealed at a lower degree of dissociation rather than at a high degree of neutralization Elucidation of the difference in the complexation behaviors of PAA and PMA 870 Miyajima indicates the significance of the polymer conformation as well as the coordination nature of central metal ions Since PMA forms a compact coiled structure at a lower degree of dissociation, the effective ligand concentration of the polymer domain is increased, which enables multidentate carboxylate complexes with Ca2ϩ Since the linear density of carboxylate groups on protein molecules is much lower than the synthetic carboxylate polymers examined in this study, this peculiar Ca2ϩ complexability seems closely related to the role of Ca2ϩ on conformation change of protein molecules upon complexation ACKNOWLEDGMENTS The present author wishes to express his deep gratitude to Professor Jacob A Marinsky at State University of New York at Buffalo for his valuable suggestions throughout this work He wishes to acknowledge the financial support of a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture of Japan (Nos 08454237 and 07405038) LIST OF SYMBOLS Quantities and symbols with subscript p denote the polyelectrolyte phase ␣ b ␤i Ci Cp Cs ␦M ⌬pK fM ␾p G [i] (K 0M)app (K 0M)int Vp yi Z degree of dissociation of polyacids activity of species i average linear charge separation on a polymer backbone stability constant for ith complex total concentration of species i total concentration of a polymer on monomer basis (monomol/dm3) added salt concentration chemical shift value for a metal ion (ppm) difference between pKapp and pK0 free metal ion fraction of total metal ions practical osmotic coefficient activity coefficient quotient free concentration of species i apparent metal ion binding constant in the presence of a negligible amount of metal ions intrinsic metal ion binding constant in the presence of a negligible amount of metal ions volume of polyelectrolyte phase activity coefficient of species i average charge per functional group, charge of a metal ion Metal Complexation in Polyelectrolyte Solutions 871 REFERENCES 10 11 12 13 14 15 16 Z Alexandrowicz, A Katchalsky Colligative properties of polyelectrolyte 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Ishiguo Analysis of complexation equilibria of polyacrylic acid by a Donnan-based concept J Colloid Interface Sci 187:259– 266, 1997 M Yasuda, K Yamasaki, H Ohtaki Stability of complexes of several carboxylic acids formed with bivalent metals Bull Chem Soc Jpn 23:1067–1070, 1960 P Gerding Thermochemical studies on metal complexes Acta Chem Scand 21:2015–2027, 1967 KH Chung, E Hong, Y Do, C-H Moon Unusual six- and eight-coordinated cadmium(II) malonate complex: relevance to 113Cd NMR probe of metal binding sites on metalloproteins J Chem Soc Chem Commun:2333–2334, 1995 KH Chung, C-H Moon Cadmium-113 nuclear magnetic resonance studies of cadmium(II)-carboxylate complexes in aqueous solution J Chem Soc Dalton Trans:75–78, 1996 T Miyajima, H Nishimura, H Kodama, S Ishiguro On the complexation of Ag(I) and Cu(II) ions with poly(N-vinylimidazole) React Funct Polym 38: 183–195, 1998 DH Gold, HP Gregor Metal–polyelectrolyte complexes VII The poly-N- 874 51 52 53 54 Miyajima vinylimidazole silver(I) complex and the imidazole-silver(I) complex J Phys Chem 64:1461–1463, 1960 DH Gold, HP Gregor Metal–polyelectrolyte complexes VIII The poly-Nvinylimidazole copper(II) complex J Phys Chem 64:1464–1467, 1960 SP Datta, AK Grzybowski Stabilities of the silver complexes of imidazole and tri(hydroxymethyl)-methylamine J Chem Soc (A):1059–1064, 1966 WL Koltum, RN Dexter, RE Clark, FRN Gurd Coordination complexes and catalytic properties of proteins and related substances I Effect of cupric and zinc ions on the hydrolysis of p-nitrophenylacetate by imidazole J Am Chem Soc 80:4188–4194, 1958 C Tanford, ML Wagner The consecutive constants of the association of cadmium with imidazole J Am Chem Soc 75:434–435, 1953 Index Acid dissociation of weak polyelectrolytes, 832–844 dissociation constants, 833 effect of salts on, 835 hydrophobicity-hydrophilicity effect on, 841 Adsorption of polyelectrolyte–surfactant aggregates, 490 Adsorption of surfactants on proteincoated surface, 486 ␣-Helix, 349 Amphiphilic polyelectrolytes, 687 Anomalies in conductivity of kaolinite particles, 574 Anomalies in polyelectrolyte conductance, 218 Anomalous migration in gels, 665–674 bend-induced retardation of DNA, 668 of DNA, 666 effect of A-tracts on, 668 of protein–DNA complexes, 672 Atomic force microscopy: kinetics of polyelectrolyte adsorption, 299 of polyelectrolyte–surfactant association, 447 A-tracts, 668–672 Attachment barrier in polyelectrolyte adsorption, 295–299 Attraction between polyions: bundle formation, 163 counterion-mediated, 164 inverted forces, 124 many-body, 128 polyion clusters, 127 Bancroft rule, 368 Bjerrum length, 66, 115 Brownian dynamics, 63 Bundle formations, 163 charge fluctuation model, 167 kinetics of, 169 long-range effects in, 166 mechanism of, 173 short-range effects in, 166 size of the bundle, 169 Carboxymethylcellulose adsorption on oxide particles, 283, 315, 318 Carboxypullulan adsorption on polystyrene, 288 875 876 Cell model of polyelectrolyte, 63, 794 cylindrical, 63, 794 hexagonal, 65 Poisson-Boltzmann solution, 67 Charge oscillations, 79 Chemical association in polyelectrolyte solutions, 146 Colloidal aggregates fragmentation, 509, 515 by electric forces, 515 by hydration forces, 518 by polyelectrolyte adsorption, 509 by segregation between hydrophobic and hydrophilic groups, 539 by segregation between positive and negative groups, 547 Complexation behavior in polyelectrolyte solutions, 144, 829 Computer simulations, 59, 224 DNA in, 226 of molecular dynamics, 59 Monte Carlo Brownian dynamics, 224 of osmotic pressure, 80 Conformation of polyions, 183 blob model, 183 necklace model, 186 Conformational transitions, 181, 591 coil-globule, 181 in polyelectrolyte gels, 186, 591 in polyelectrolyte microgels, 197 in polyelectrolyte solutions, 191 of single polymer chain, 184 CONTIN analysis, 265 Coulombic end effects, 674 Counterion condensation: determined by simulation, 234 fraction of condensed ions, 115 inflection point criterion of, 70 inverted forces in, 124 loosely bound counterions, 315 in nonaqueous solutions, 249 partition functions, 116 and Poisson-Boltzmann, 675 in polyion pair, 127 site-bound counterions, 830 Index [Counterion condensation] territorially bound counterions, 830 theory of, 114 tightly bound counterions, 314 Counterion distribution functions, 71, 223, 228 De Gennes-Alexander model for neutral brushes, 404 Dextran sulfate, phase diagram, 140 Diffusion in aqueous polyelectrolyte solutions: fast, 13, 151 medium, 20 slow, 42, 151 very fast, Diffusion in nonaqueous polyelectrolyte solutions, 268 Dispersion of the electro-optical effect, 321–334 effect of counterion charge on, 331 effect of salts on, 329 high-frequency, 327 low-frequency, 321 DNA: computer simulations, 226 condensation of, 173, 190 Coulombic end effects, 674 gel electrophoresis of, 666 ion distribution functions, 90, 228 ionic correlations, 100 mean electrostatic potential, 90 Donnan osmotic pressure in polyelectrolyte solutions, 26 Dynamic light scattering: in aqueous polyelectrolyte solutions, 26 in nonaqueous polyelectrolyte solutions, 265 in polyelectrolyte-multivalent ion solutions, 150 and structure of polyelectrolyte complexes, 781 Dynamic properties of polyelectrolytes: diffusion coefficients, in dilute solutions, 12 Index [Dynamic properties of polyelectrolytes] in polyion mixtures, 20 in semidilute regime, 18 Electric light scattering in colloid-polyelectrolyte suspensions, 308 Electric polarizability of polyions, 223, 308 of adsorbed polyelectrolytes, 308 anisotropy of, 238 longitudinal, 238 tensors of, 227 transverse, 238 Electric potential of polyions, 230–237 Electrical properties of polyelectrolytes, 237, 316 in adsorbed state, 316 in solutions, 237 Electrokinetic effects, 567–574 acoustophoresis, 573 electro-osmosis, 570 electrophoretic light scattering, 570 sedimentation potential, 572 streaming potential, 571 Electrokinetic potential, 91, 551, 568 of aluminium oxide-polyacrylic acid complexes, 546 of kaolinite-humic acid complexes, 548, 550 of kaolinite particles, 576 of kaolinite-polyacrylic acid complexes, 582 of kaolinite-polyethylenimine complexes, 583 nonmonotonic, 91 Electro-optical effect, 305 definition of, 305 dispersion of, 321 high-frequency, 315 low-frequency, 314 steady-state, 308 transient, 311 Electro-optics of colloid–polyelectrolyte suspension, 304–345 Electrophoretic mobility of colloids, 313 877 Electrostatic interactions, 287 effect on initial adsorption rate, 287 between polyion and charged surface, 287 Emulsion polymerization, 415–425 amphiphilic polyelectrolytes in, 417 basic principles of, 415 block copolymers in, 422 graft copolymers in, 421 polysoaps in, 421 random copolymers in, 418 Emulsions, 363–445 definition of, 363 elasticity of, 398 high internal phase, 397 monodisperse, 400, 426 stability of, 384 type of, 384 Emulsion stability, 384 basic concepts, 384 electrostatic mechanism of, 386 in high internal phase emulsions, 397 in nonconcentrated systems, 387 steric protection, 386 Emulsion type, 366 direct and inverse emulsions, 366 hydrophilic-lipophilic balance and, 368 polyelectrolyte surfactants and, 373 practical examples, 366 salt concentration and, 369 theories for emulsifier selection, 367 Equilibrium analysis of metal complexation, 844 generalized treatment, 844 Gibbs-Donnan approach, 845, 857, 863 with polyacrylic acid, 846 with polymethacrylic acid, 863 with poly(N-vinylimidazole), 856 Equivalent conductivity in polyelectrolyte solutions, 203, 247 concentration dependence of, 219 ion exchange effects, 208 ionic, 207 limiting, 208, 247 878 Films of amphiphilic polyelectrolytes, 404 diblock copolyelectrolytes, 404 homopolyelectrolytes, 409 polyelectrolyte brushes, 406 random copolyelectrolytes, 412 structure of, 410 Fluctuation effects in polyelectrolyte solutions, 165, 223 of ionic charge, 167, 223 thermal, 165 Fokker-Planck equation, 225 Formation of polyelectrolyte complexes, 744 exchange reactions in, 744 general background of, 744 release of counterions, 749 Friction coefficients in polyelectrolyte solutions, 206 Fuoss equation, 251 Gelation in polymer–protein systems, 716–725 elasticity of gels, 721 sol-gel transitions, 720 Gel electrophoresis, 666–674 of DNA, 666 of intrinsically curved DNA, 668 of protein-DNA complexes, 672 Guinier plot, 31 Highly aggregated polyelectrolyte complexes, 747 composition of, 759 methodical aspects, 748 stoichiometry of, 749 structure of, 769 Impinging jet method, 285 Induced dipole moment, 309 Interaction between adsorbed polyelectrolytes, 464 Interaction between surfaces across polyelectrolyte solutions, 458–464 attractive forces, 459 Index [Interaction between surfaces across polyelectrolyte solutions] effect of polyelectrolyte charge density on, 463 glass surfaces and, 460 long-range repulsion, 458, 461 mica surfaces, 458 Interaction of surfactants with adsorbed polyelectrolytes, 467 dependence on the polyelectrolyte charge density, 469 effect of hydrophobic side chains, 483 effect of polyelectrolyte architecture, 489 electrostatic and hydrophobic, 468 nonequilibrium aspects, 497 Interpolyion correlations, 37, 99 Inverted forces in counterion condensation theory, 124 Ionic oligomers, 668 Ionic velocities in polyelectrolyte solutions, 204 Ionomers, 252 definition of, 252 random, 246 sulfonated polystyrene, 254 Kinetics of aggregate fragmentation, 511 Kinetics of polyelectrolyte adsorption, 281–305 atomic force microscopy and, 299 optical reflectometry and, 300 Kramers theory for reaction rates, 295 Kratky plot, 31 Langevin thermostat, 62 Lennard-Jones potential, 66, 88 Long-range electrostatics in polyelectrolyte solutions, 113 Manning parameter, 68, 115, 328, 798 Many-body interactions, 128, 163 Index Metal ion–polyelectrolyte complexation, 844–867 electrostatic effects in, 844 equilibrium analysis of, 844 hydrophobicity-hydrophilicity effect on, 850 multicoordinated complexes, 847, 862 polymer conformation and, 862 stability constants, 850 Method of cumulants, 265 Microemulsions, 363, 367 Molecular recognition, 347 Molecular weight of a polyelectrolyte, 25 apparent, 28 light scattering and, 26 Monolayers of poly(L-glutamic acid), 349–361 on gold, 359 interaction with amino acids, 354 mixing behavior with D-isomer, 352 secondary structure of the segment, 349 on water, 349, 355 Monte Carlo Brownian dynamics simulation, 224–225 Nonaqueous solutions, 245–274 association behavior, 248 conductance in, 247 desolvation in, 273 dielectric constants, 249 heterogeneities in, 270 intermolecular excluded volume in, 261 intermolecular interactions in, 258 osmotic coefficients in, 271 Nonequilibrium thermodynamics and polyelectrolyte conductance, 204– 208 Optical reflectometry and polyelectrolyte adsorption, 300 879 Osmotic coefficients in polyelectrolyte solutions, 83 of monovalent counterions, 84 of multivalent counterions, 85 Osmotic pressure in polyelectrolyte gels, 593 Osmotic pressure in polyelectrolyte solutions, 80, 191 Overcharging of colloidal particles, 311 Overcharging of polyions, 79 Pair potentials: coion-polyion, 124 counterion-polyion, 118 polyion-polyion, 123 Particle counting, 516 Perrin formula, 311 Persistence length, 35 Phase diagrams, 136 in strong polyelectrolyte solutions, 136 in weak polyelectrolyte solutions, 141 Phase transitions in polyelectrolyte gels, 591–664 charge density and, 614 molecular mechanisms, 600 pH and, 638 salt concentration and, 638 surfactants and, 621, 648 theories of, 592 Polyacrylamide adsorption on oxide particles, 314 Polyacrylate, 141 phase diagrams, 141 surfactant binding to, 798 Polyacrylic acid, 291 adsorption on BaTiO3, 293 adsorption on polystyrene, 291 metal complexation with, 846 Polyelectrolyte adsorption, 281, 334, 567 attachment resistance, 286 effect of ionic strength, 289 equilibrium in, 281 fractionation, 293 hysteresis effects, 291 880 [Polyelectrolyte adsorption] initial rates of, 291 isotherms, 288 on kaolinite particles, 567 kinetics of, 281 new experimental approaches in, 299 on oxide particles, 334 reversibility, 282 transport resistance, 285 Polyelectrolyte complexes, 743 highly aggregated, 747 salt stability of, 746 temperature-sensitive, 781 water-soluble, 746 Polyelectrolyte conductance, 203 anisotropy of, 213 anomalies in, 218 bound ions and, 207, 271 carboxymethyl-hydroxyethyl cellulose, 211 a phenomenological approach, 203 polystyrene sulfonate, 215 Polyelectrolyte gels, 182, 591–664 acid–base equilibrium, 610, 643, 650 degree of cross-linking, 608 experimental methods, 603 hydrophobic interactions in, 601, 636 osmotic pressure in, 593 surfactant uptake, 612, 617, 621 theories for phase transitions, 592– 600 Polyelectrolyte-induced aggregate fragmentation, 509–566 aggregate mass frequency in, 513 hydrophobicity effect, 539 impact of the hydrophobic forces on, 533 role of the surface coverage on, 534 polyvinylpyridine in, 523 scaling lows, 513 Polyelectrolyte microgel, 197 Polyelectrolyte-multivalent ion solutions, 135 complexation behavior, 144 dynamic light scattering and, 150 dynamics in, 150 Index [Polyelectrolyte-multivalent ion solutions] interpolyion correlations, 150 phase diagrams, 136 Polyelectrolyte–protein complexes, 687 enzyme activity in, 730 precipitation of, 727 size of, 701 solubility of, 726 structure of proteins in, 729 Polyelectrolyte–surfactant interactions in solution: conductivity measurements of, 817 critical association concentration, 453, 819 role of the polymer charge density on, 800 stability of aggregates, 456 structure of aggregates, 457 Polyethylenimine adsorption on oxide particles, 318 Polyion clusters, 42, 127, 154, 169 Polyion interactions: attractive, 113, 125 counterion-mediated, 164 inverted forces, 124 long-range effects, 113, 166 many-body, 128, 163 in nonaqueous solutions, 258 short-range effects, 138, 166 Poly(L-glutamic acid) monolayers, 348 Polymer–protein association, 687–741 effect of the electric charge, 695 fluorescence and, 692 free ion titration and, 692 gelation phenomena, 716 hydrophobicity effect on, 698 isotherms, 709 role of the hydrogen bonds, 694 turbidity and, 689 viscosity and, 690 Polymethacrylic acid, 13 apparent molecular weight, 28 diffusion coefficient, 13 metal complexation with, 863 Index Poly-N-methyl-2-vinyl pyridinium adsorption on titanium dioxide, 282, 289 Poly(N-vinylimidazole)-metal complexation, 856 Poly(p-phenylene), 61, 95 counterion distribution, 96 osmotic coefficient, 97 Polystyrene sulfonate: adsorption on oxide particles, 319 conductance anisotropy of, 215 diffusion coefficient, 14 light scattering of, 38 phase diagrams, 136 radius of gyration, 34 surfactant binding to, 795 Poly(2-vinylpyridine) viscosity, 253 Poly(4-vinylpyridine) viscosity, 253 Poly(vinyl sulfate) phase diagram, 142 Precipitation of polyelectrolytes, 141 Preparation of gels, 603–606 Preparation of submicron gel particles, 605 Princen plot, 400 Radius of gyration, 34 Relaxation times, 6, 12 in neutral polymer mixture, 23 in polyelectrolyte mixture, 22 Second virial coefficient, 19, 29 Segregation in adsorbed polyelectrolyte layers, 539, 547 Self-assembly in polyelectrolyte monolayers, 348 Self-consistent field method, 295 Self-similarity in aggregate fragmentation, 513 Semidilute solutions with multivalent ions, 153 Separation of polymer–protein mixtures, 725 Solubility of polyelectrolytes, 138 Stability of colloidal suspensions, 312, 336, 579 881 Stabilization of emulsions, 364 by amphiphilic polyelectrolytes, 364 by block and graft copolymers, 364 by homopolymers, 364 microscopic aspects, 404 Static light scattering: in aqueous polyelectrolyte solutions, in nonaqueous solutions, 258 and structure of polyelectrolyte complexes, 770 Stoichiometry of polyelectrolyte complexes, 745, 769 Stokes-Einstein relation, 19 Structure factor, 16 of polyion solution, 37 of polymer chain, 30 Structure of adsorbed polyelectrolyte layer, 334, 458 Structure of polyelectrolyte complexes, 769 dynamic light scattering and, 781 electrophoretic light scattering and, 784 static light scattering and, 770 Structure of polymer–protein complexes, 701, 729 in dilute solutions, 701 in gels, 716 necklaces, 701 Sulfonated polystyrene ionomer, 254 dynamic light scattering of, 265 polyelectrolyte behavior of, 257 static light scattering of, 258 viscosity of, 255 Supermolecular structure of polyelectrolyte complexes, 753, 769 Surface force measurements: bimorph apparatus for, 469 interferometric apparatus for, 469 in polyelectrolyte solutions, 299 of polyelectrolyte–surfactant association, 447 Surfactant binding to adsorbed polyelectrolytes, 447 882 Surfactant binding to polyelectrolytes, 453, 793 enthalpy of, 808 hydrophobicity effect on, 805 isotherms of, 799 viscosity and, 812 volume changes, 815 Surfactant-bound polyelectrolyte gels, 617–627 Swelling characteristics of polyelectrolyte gels, 606, 618, 628 Thermodynamics of polyelectrolytes, 62 Thickness of the adsorbed polymer layer, 314, 335 Index [Thickness of the adsorbed polymer layer] average, 335 hydrodynamic, 314 Transport numbers in polyelectrolyte solutions, 209 of low-charged polyions, 211 of polyions, 209 Two-phase representation of a microion, 192 Wigner crystals, 104–107 Wigner-Seitz cell, 64 Winsor diagrams, 368 Zimm plots, 32, 261 ... Department of Physical Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana, Slovenia Etsuo Kokufuta, Ph.D Institute of Applied Biochemistry, University of Tsukuba,... Institute of Physical and Theoretical Chemistry, University of Potsdam, Potsdam, Germany Joachim Koătz, Ph.D., Dr.rer.nat.habil Department of Colloid Chemistry, Institute of Physical and Theoretical Chemistry, ... Institute for Surface Chemistry, Stockholm, Tsetska Radeva, Ph.D Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria Jolly Ray Department of Chemistry, Rutgers University,