Preface 9
Contents 13
Conformations and Solution Properties of Star-Branched Polyelectrolytes 15
1 Introduction 16
2 Solutions of Neutral Star Polymers: Reminder on the Scaling Theory 19
2.1 Star Polymer Conformation in a Dilute Solution 21
2.2 Effects of Concentration and Interactions Between Polymer Stars 23
3 Cell Model of the Salt-Free Solution of Polyelectrolyte Stars 24
3.1 Box-Like Cell Model of a Polyelectrolyte Star 26
3.2 Polyelectrolyte Star Conformation in a Dilute Salt-Free Solution 27
3.3 Charge Renormalization Concept 29
3.4 Effects of Concentration and Interactions in Star Polyelectrolyte Solutions 31
4 Localization of Counterions in Salt-Free Solutions of Branched Polyelectrolytes: Effect of the Polyion Topology 34
4.1 Ionic Dendrimers (Star-Burst Polyelectrolytes) 34
4.2 Randomly Branched Polyelectrolytes and Charged Fractals 35
4.3 Polyelectrolyte Cylindrical (Molecular) Brushes 36
5 Localization of Counterions in a Salt-Free Solution of Polyelectrolyte Stars: Numerical Results 38
5.1 Molecular Dynamics and Monte Carlo Simulations 38
5.2 Self-Consistent Field Poisson--Boltzmann Theory 39
6 Localization of Counterions in a Salt-Free Solution of Star-Like Polyelectrolytes: Experimental Results 41
7 Effects of Ionic Strength and pH on the Polyelectrolyte Star Conformation 43
7.1 The Mean-Spherical Equal Arm Stretching Approximation: General Formalism 44
7.2 Density Profiles 46
7.3 Star Size and Degree of Ionization 50
Quenched Polyelectrolyte Star 50
Annealing Star Polyelectrolyte 52
7.4 Annealing Star Polyelectrolytes: Titration Curves 55
7.5 Effect of Counterion Valency 56
8 Collapse of a Polyelectrolyte Star in Poor Solvent 58
9 Conclusions 61
References 65
Self-Assembled Structures of Amphiphilic Ionic Block Copolymers: Theory, Self-Consistent Field Modeling and Experiment 70
1 Introduction 71
2 Thermodynamic Principles of Micellization 74
2.1 Critical Micelle Concentration and Aggregation Number 74
2.2 Block Copolymer Micelles 78
2.2.1 Corona Domain 79
2.2.2 Core Domain 80
2.2.3 Free Energy 81
3 Scaling Theory of Non-ionic Block Copolymer Micelles 82
3.1 Spherical Non-ionic Micelles 82
3.1.1 Starlike Spherical Non-ionic Micelles 83
3.1.2 Crew-Cut Spherical Non-ionic Micelles 84
3.2 Polymorphism of Aggregates of Non-ionic Block Copolymers 85
4 Scaling Theory of Micelles with Polyelectrolyte Corona 91
4.1 Starlike Micelles with Quenched Polyelectrolyte Corona 91
4.2 Crew-Cut Micelles with Quenched Polyelectrolyte Corona 93
5 Mean-Field Theory of Block Copolymer Micelles: Boxlike Model 94
5.1 Non-ionic Block Copolymer Micelles 96
6 Mean-Field Theory of Block Copolymer Micelles with Quenched Polyelectrolyte Corona 97
6.1 Starlike Micelles with Quenched Polyelectrolyte Corona 98
6.2 Crew-Cut Micelles with Quenched Polyelectrolyte Coronae 99
7 Mean-Field Theory of Block Copolymer Micelles with Annealing Polyelectrolyte Corona 100
7.1 Structural Transitions in Starlike Micelles with Annealing PE Corona 102
7.1.1 Quasi-neutral Micelles 102
7.1.2 Charged Micelles 103
7.1.3 Micelle-to-Micelle Transition 104
7.2 Crew-Cut Micelles with Annealing Polyelectrolyte Coronae 107
8 Micelles with Quenched and Annealing Polyelectrolyte Coronae: Nonlocal Mean-Field Approach 113
9 Self-Consistent Field Modeling of Micelle Formation 114
9.1 Spherical Micelles: Implementation of Numerical SF-SCF Method 115
9.2 Neutral Micelles of Amphiphilic Block Copolymers 117
9.3 Micelles with Quenched Polyelectrolyte Corona 120
9.4 Micelles with Annealing Polyelectrolyte Corona 123
10 Polymorphism of Self-Assembled Aggregates of Block Copolymers with Quenched Polyelectrolyte Blocks 126
10.1 Salt-Free Solution 127
10.2 Salt-Dominated Solution 128
11 Re-entrant Morphological Transitions in Aggregates of Block Copolymers with Annealing Polyelectrolyte Block 131
12 Experiment Versus Theory 134
References 139
Interpolyelectrolyte Complexes Based on Polyionic Species of Branched Topology 143
1 Introduction 145
2 IPECs Based on Polyelectrolyte Stars 147
2.1 Experimental Results 147
2.2 Molecular Dynamics Simulations 151
3 IPECs Based on Cylindrical Polyelectrolyte Brushes 154
3.1 Experimental Results 154
3.2 Molecular Dynamics Simulations 155
4 IPECs Based on Star-like Micelles of Ionic Amphiphilic Block Co- and Terpolymers 158
4.1 IPECs Based on Micelles of Ionic Amphiphilic Diblock Copolymers 158
4.2 IPECs Based on Micelles of Ionic Amphiphilic Block Terpolymers 164
4.3 Polyion Interchange Reactions Involving Micellar IPECs 167
5 Conclusions 170
References 171
Co-assembly Towards Janus Micelles 174
1 Introduction 175
2 Characteristic Features of Complex Coacervate Core Micelles 177
3 Experimental Results 178
3.1 Reversible Janus Micelles 179
3.2 Radial Chain Segregation 181
4 Theory and Modelling 184
4.1 1G SCF Results 186
4.2 2G SCF Results 189
5 Conclusion 194
References 195
Fluorescence Spectroscopy as a Tool for Investigating the Self-Organized Polyelectrolyte Systems 197
1 Introduction 199
2 Principles of the Fluorescence Techniques Used 201
2.1 State Diagram and the Characteristics of Time-Dependent Fluorescence 201
2.2 Time-Resolved Fluorescence Anisotropy 206
2.3 Solvent Relaxation 209
2.3.1 Theoretical Background 209
2.3.2 Specific Features of Solvent Relaxation in Heterogeneous Systems 211
2.4 Fluorescence Quenching and Nonradiative Excitation Energy Transfer 212
2.4.1 Fluorescence Quenching 212
2.4.2 Nonradiative Excitation Energy Transfer 214
2.5 Fluorescence Correlation Spectroscopy 215
3 Fluorescence Studies of Self-Organizing Polymer Systems 218
3.1 Brief Introductory Remarks 218
3.2 Conformational Transition in Weak Polyelectrolyte Systems Studied by Fluorescence Anisotropy 219
3.2.1 Motivation 219
3.2.2 Outline of Experimental Study and the Most Important Observations 221
3.3 Solvent Relaxation Study of Self-Assembled Systems 224
3.3.1 Reversible Aggregation of Block Copolymer Micelles with PVP--PEO Shells in Acid Aqueous Solutions 224
3.4 Study of Shell-Forming Chain Conformations by Nonradiative Energy Transfer 233
3.4.1 Studies of Reference Systems of Nonmodified Weak Polyelectrolyte Shells in Solutions with Low Ionic Strength 233
3.4.2 Nonradiative Energy Transfer Study of Conformations of Hydrophobically Modified Shell-Forming PMA Chains 234
3.5 Comparative Experimental FCS and DLS Study of Polymeric Nanoparticles 237
3.5.1 Motivation 237
3.5.2 Outline of Experimental Studies 238
4 Interpretations of Fluorescence Data with the Help of Computer Simulation 240
4.1 Interpretation of Time-Resolved Fluorescence Anisotropy Data by Molecular Dynamics Simulations 240
4.1.1 The Model 241
4.1.2 Conformational Behavior 242
4.1.3 Comparison of Simulated and Experimental Data 242
4.1.4 Molecular Dynamics Simulations of Annealed Polyelectrolyte Chains 244
4.2 Monte Carlo Simulation of Shell-Forming Chain Conformations 246
4.2.1 Models and Simulation Techniques 246
4.2.2 Results and Discussion: Shell-Forming Chains at Low Ionic Strengths 247
4.2.3 Interpretation of NRET Data: Conformations of Hydrophobically Modified Chains 249
4.3 Monte Carlo Simulation of FCS Data 251
4.3.1 Simulation Results 252
5 Concluding Remarks 254
References 255
Index 260