Macromolecular Self–Assembly

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 systems thus self–assembly continues to be a hot technique in synthetic chemistry.

This book describes self–assembly techniques in the synthesis of biomolecules for developing new compounds and improving functionality of existing ones.  Because self–assembly emulates how nature creates molecules, 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

          Review of principles of cross–scale hierarchical assembly

          Illustration of the assembly of bio–hybrid macromolecules and applications in biomedical engineering

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

1.1 Introduction

1.2 Synthetic Approaches to Host/Guest Functionalized Building Blocks

1.2.1 CD functionalization

1.2.2 Suitable guest groups

1.3 Supramolecular CD Self–Assemblies

1.3.1 Linear polymers

1.3.2 Branched polymers

1.3.3 Cyclic polymer architectures

1.4 Higher Order Assemblies of CD based Polymer Architectures towards Nanostructures

1.4.1 Micelles/Core–Shell Particles

1.4.2 Vesicles

1.4.3 Nanotubes and Fibers

1.4.4 Nanoparticles and hybrid materials

1.4.5 Planar surface modification

1.5 Applications

1.6 Conclusion and Outlook

References

Chapter 2: Polymerization–Induced Self–Assembly: the Contribution of Controlled Radical Polymerization to the Formation of Self–Stabilized Polymer Particles of Various Morphologies
Muriel Lansalot, Jutta Rieger, Franck D Agosto

2.1 Introduction

2.2 Preliminary Comments Underlying Controlled Radical Polymerization

2.2.1 Introduction

2.2.2 Major methods based on a reversible termination mechanism

2.2.3 Major methods based on a reversible transfer mechanism

2.3 PISA via CRP Based on Reversible Termination

2.3.1 PISA Using NMP

2.3.2 Using a TRP

2.4 PISA via CRP Based on Reversible Transfer

2.4.1 Using RAFT in Emulsion Polymerization

2.4.2 Using RAFT in Dispersion Polymerization

2.4.3 Using TERP

2.5 Concluding Remarks

Acknowldgements

Abbreviations

References

Chapter 3: Amphiphilic Gradient copolymers : synthesis and self–assemblyin aqueous solution
Elise Deniau–Lejeune, Olga Borisova, Petr Stepanek, Laurent Billon, Oleg Borisov

Nomenclature

3.1 Introduction

3.2 Synthetic strategies for the preparation of gradient copolymers

3.2.1 Preparation of gradient copolymers by Controlled Radical Copolymerization

3.2.2 Preparation of block–gradient copolymers using controlled radical polymerization

3.3 Self–Assembly

3.3.1 Gradient copolymers

3.3.2 Diblock–gradient copolymers

3.3.3 Triblock–gradient copolymers

3.4 Conclusion and Outlook

References

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

4.1 Introduction

4.2 Core–Corona Co–Assemblies of Homopolyelectrolyte Stars Complexed with Linear Polyions

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

4.4 Vesicular Co–Assemblies of Bis–Hydrophilic Miktoarm Stars Complexed with Linear Polyions

4.5 Conclusions

Acknowledgements

References

Chapter 5: Solution properties of associating polymers
Olga Philippova

5.1 Introduction

5.2 Structures of associating polyelectrolytes

5.3 Associating polyelectrolytes in dilute solutions

5.3.1 Intramolecular association

5.3.2 Intermolecular association

5.4 Associating polyelectrolytes in semidilute solutions

5.5 Conclusions

References

Chapter 6: Macromolecular decoration of nanoparticles for guiding self–assembly in 2D and 3D
Christian Kuttner, Munish Chanana, Matthias Karg, Andreas Fery

6.1 Introduction

6.2 Guiding assembly bydecoration with artificialmacromolecules

6.2.1 Decoration of nanoparticles

6.2.2 Distance control in 2D and 3D

6.2.3 Breaking the symmetry

6.3 Biomacromolecules

6.4 DNA

6.5 Proteins

6.6 Application of assemblies

6.7 Conclusion and outlook

References

Chapter 7: Self–Assembly of Biohybrid Polymers
Dawid Kedracki, Jancy Nixon Abraham, Enora Prado, Corinne Nardin

7.1 Introduction to the Mechanism of Self–Assembly

7.1.1 Amphiphiles

7.1.2 Packing Parameter and Interfacial Tension

7.1.3 Interaction Forces in Self–Assembly

7.2 Self–Assembly of Biohybrid Polymers

7.2.1 Polymer–DNA Hybrids

7.2.2 Polypeptide Block Copolymers

7.2.3 Block Copolypeptides

7.3 Self–Assembly Driven Nucleation Polymerization

7.3.1 Polymer–DNA Hybrids

7.3.2 Polymer–Peptide Hybrids

7.3.3 DNA–Peptide Hybrids

7.4 Self–Assembly Driven by Electrostatic Interactions

7.4.1 DNA/polymer bio–IPECs

7.4.2 DNA/copolymer bio–IPECs

7.5 Conclusion

References

Chapter 8: Biomedical application of block copolymers
Martin Hrubý, SergeyK. Filippov, Petr t pánek

8.1 Introduction

8.2 Diblock and triblock copolymers

8.3 Graft and statistical copolymers

8.4 Concluding remarks

Acknowledgements

References

Laurent Billon, PhD, is research director at the Interdisciplinary Institute of Environmental and Material Research (IPREM) in Pau, France.  He is the author of over 150 scientific publications and received the Friedrich Wilhelm Bessel Research Award (2004) from the Alexander von Humboldt Foundation. He received his PhD in Polymer Chemistry from Pau University (France).

Oleg Borisov, PhD, is research director at the Institute of Environmental and Material Research at Pau University, France. He graduated received his PhD in physics and mechanics of polymers from the Institute of Macromolecular Compounds of the Russian Academy of Sciences. He is the author of over 150 papers.