Macromolecular Self-Assembly

Laurent Billon, PhD, is Professor at Pau University (France) and leader of the polymer group at the Interdisciplinary Institute of Environmental and Material Research (IPREM) in Pau, France.  He is the author of over 90 scientific publications and 12 patents. He received his PhD in Polymer Chemistry from Pau University. Oleg Borisov, PhD, is research director at the Institute of Environmental and Material Research at Pau University, France. He received his PhD in physics and mechanics of polymers in the Institute of Macromolecular Compounds of the Russian Academy of Sciences. He is the author of over 150 scientific publications and received the Friedrich Wilhelm Bessel Research Award (2004) from the Alexander von Humboldt Foundation.

List of Contributors ix

Preface xiii

1 A Supramolecular Approach to Macromolecular Self-Assembly: Cyclodextrin Host/Guest Complexes 1
Bernhard V. K. J. Schmidt and Christopher Barner-Kowollik

1.1 Introduction, 1

1.2 Synthetic Approaches to Host/Guest Functionalized Building Blocks, 3

1.2.1 CD Functionalization, 3

1.2.2 Suitable Guest Groups, 5

1.3 Supramolecular CD Self-Assemblies, 7

1.3.1 Linear Polymers, 7

1.3.2 Branched Polymers, 12

1.3.3 Cyclic Polymer Architectures, 17

1.4 Higher Order Assemblies of CD-Based Polymer Architectures Toward Nanostructures, 17

1.4.1 Micelles/Core-Shell Particles, 17

1.4.2 Vesicles, 19

1.4.3 Nanotubes and Fibers, 20

1.4.4 Nanoparticles and Hybrid Materials, 21

1.4.5 Planar Surface Modification, 22

1.5 Applications, 23

1.6 Conclusion and Outlook, 26

References, 26

2 Polymerization-Induced Self-Assembly: The Contribution of Controlled Radical Polymerization to The Formation of Self-Stabilized Polymer Particles of Various Morphologies 33
Muriel Lansalot, Jutta Rieger, and Franck D’Agosto

2.1 Introduction, 33

2.2 Preliminary Comments Underlying Controlled Radical Polymerization, 36

2.2.1 Introduction, 36

2.2.2 Major Methods Based on a Reversible Termination Mechanism, 37

2.2.3 Major Methods Based on a Reversible Transfer Mechanism, 39

2.3 Pisa Via CRP Based on Reversible Termination, 40

2.3.1 PISA Using NMP, 40

2.3.2 Using ATRP, 46

2.4 Pisa Via CRP Based on Reversible Transfer, 48

2.4.1 Using RAFT in Emulsion Polymerization, 48

2.4.2 Using RAFT in Dispersion Polymerization, 61

2.4.3 Using TERP, 70

2.5 Concluding Remarks, 71

Acknowledgments, 73

Abbreviations, 73

References, 75

3 Amphiphilic Gradient Copolymers: Synthesis and Self-Assembly in Aqueous Solution 83
Elise Deniau-Lejeune, Olga Borisova, Petr Št¡epánek, Laurent Billon, and Oleg Borisov

3.1 Introduction, 83

3.2 Synthetic Strategies for The Preparation of Gradient Copolymers, 86

3.2.1 Preparation of Gradient Copolymers by Controlled Radical Copolymerization, 87

3.2.2 Preparation of Block-Gradient Copolymers Using Controlled Radical Polymerization, 106

3.3 Self-Assembly, 110

3.3.1 Gradient Copolymers, 110

3.3.2 Diblock-Gradient Copolymers, 111

3.3.3 Triblock-Gradient Copolymers, 113

3.4 Conclusion and Outlook, 114

Abbreviations, 115

References, 117

4 Electrostatically Assembled Complex Macromolecular Architectures Based on Star-Like Polyionic Species 125
Dmitry V. Pergushov and Felix A. Plamper

4.1 Introduction, 125

4.2 Core-Corona Co-Assemblies of Homopolyelectrolyte Stars Complexed with Linear Polyions, 127

4.3 Core-Shell-Corona Co-Assemblies of Star-Like Micelles of Ionic Amphiphilic Diblock Copolymers Complexed with Linear Polyions, 130

4.4 Vesicular Co-Assemblies of Bis-Hydrophilic Miktoarm Stars Complexed with Linear Polyions, 133

4.5 Conclusions, 137

Acknowledgment, 137

References, 137

5 Solution Properties of Associating Polymers 141
Olga Philippova

5.1 Introduction, 141

5.2 Structures of Associating Polyelectrolytes, 142

5.3 Associating Polyelectrolytes in Dilute Solutions, 142

5.3.1 Intramolecular Association, 145

5.3.2 Intermolecular Association, 147

5.4 Associating Polyelectrolytes in Semidilute Solutions, 151

5.5 Conclusions, 155

References, 155

6 Macromolecular Decoration of Nanoparticles for Guiding Self-Assembly in 2D and 3D 159
Christian Kuttner, Munish Chanana, Matthias Karg, and Andreas Fery

6.1 Introduction, 159

6.2 Guiding Assembly by Decoration with Artificial Macromolecules, 160

6.2.1 Decoration of Nanoparticles, 161

6.2.2 Distance Control in 2D and 3D, 166

6.2.3 Breaking the Symmetry, 171

6.3 Guiding Assembly by Decoration with Biomacromolecules, 173

6.3.1 DNA-Assisted Assembly, 173

6.3.2 Protein-Assisted Assembly, 177

6.4 Application of Assemblies, 181

6.5 Conclusions and Outlook, 183

References, 184

7 Self-Assembly of Biohybrid Polymers 193
Dawid Kedracki, Jancy Nixon Abraham, Enora Prado, and Corinne Nardin

7.1 Introduction, 193

7.1.1 Amphiphiles, 194

7.1.2 Packing Parameter and Interfacial Tension, 195

7.1.3 Interaction Forces in Self-Assembly, 196

7.2 Self-Assembly of Biohybrid Polymers, 198

7.2.1 Polymer-DNA Hybrids, 198

7.2.2 Polypeptide Block Copolymers, 204

7.2.3 Block Copolypeptides, 205

7.3 Self-Assembly Driven Nucleation Polymerization, 207

7.3.1 Polymer-DNA Hybrids, 209

7.3.2 Polymer-Peptide Hybrids, 209

7.3.3 DNA-Peptide Hybrids, 212

7.4 Self-Assembly Driven by Electrostatic Interactions, 213

7.4.1 DNA/Polymer Bio-IPECs, 216

7.4.2 DNA/Copolymer Bio-IPECs, 216

7.5 Conclusion, 218

References, 219

8 Biomedical Application of Block Copolymers 231
Martin Hrubý, Sergey K. Filippov, and Petr Št¡epánek

8.1 Introduction, 231

8.2 Diblock and Triblock Copolymers, 234

8.3 Graft and Statistical Copolymers, 240

8.4 Concluding Remarks, 245

Acknowledgment, 245

References, 245

Index 251