Macromolecular Self-Assembly

This book describes techniques of synthesis and self-assembly of macromolecules for developing new materials and improving functionality of existing ones. Because self-assembly emulates how nature creates complex systems, they likely have the best chance at succeeding in real-world biomedical applications. Employs synthetic chemistry, physical chemistry, and materials science principles and techniques Emphasizes self-assembly in solutions (particularly, aqueous solutions) and at solid-liquid interfaces Describes polymer assembly driven by multitude interactions, including solvophobic, electrostatic, and obligatory co-assembly Illustrates assembly of bio-hybrid macromolecules and applications in biomedical engineering

Auteur

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.

Texte du rabat

Molecular self-assembly, the process by which molecules adopt a defined arrangement without guidance or management, is crucial to the function of cells. It is exhibited in lipids forming membranes, the formation of double helical DNA, and the assembly of proteins to form quaternary structures. Because they occur in nature, it is believed that self-assembled molecules are more compatible in biosystems than other systemsthus self-assembly continues to be a hot technique in nanobiotechnology.

This book describes techniques of synthesis and self-assembly of macromolecules for developing new materials and improving functionality of existing ones. Because self-assembly emulates how nature creates complex systems, they likely have the best chance at succeeding in real-world biomedical applications.

A valuable and comprehensive resource for researchers and graduate students, Macromolecular Self-Assembly offers readers benefits that include:

• Use of synthetic chemistry, physical chemistry, and materials science principles and techniques
• Emphasis on self-assembly in solutions (particularly, aqueous solutions) and at solid-liquid interfaces
• Description of polymer assembly driven by multitude interactions, including solvophobic, electrostatic, and obligatory co-assembly
• Illustration of the assembly of bio-hybrid macromolecules and applications in biomedical engineering

Contenu

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 t!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 ...