Self-Assembly

An introduction to the state-of-the-art of the diverse self-assembly systems

Self-Assembly: From Surfactants to Nanoparticles provides an effective entry for new researchers into this exciting field while also giving the state of the art assessment of the diverse self-assembling systems for those already engaged in this research. Over the last twenty years, self-assembly has emerged as a distinct science/technology field, going well beyond the classical surfactant and block copolymer molecules, and encompassing much larger and complex molecular, biomolecular and nanoparticle systems. Within its ten chapters, each contributed by pioneers of the respective research topics, the book:

• Discusses the fundamental physical chemical principles that govern the formation and properties of self-assembled systems

• Describes important experimental techniques to characterize the properties of self-assembled systems, particularly the nature of molecular organization and structure at the nano, meso or micro scales.

• Provides the first exhaustive accounting of self-assembly derived from various kinds of biomolecules including peptides, DNA and proteins.

• Outlines methods of synthesis and functionalization of self-assembled nanoparticles and the further self-assembly of the nanoparticles into one, two or three dimensional materials.

• Explores numerous potential applications of self-assembled structures including nanomedicine applications of drug delivery, imaging, molecular diagnostics and theranostics, and design of materials to specification such as smart responsive materials and self-healing materials.

• Highlights the unifying as well as contrasting features of self-assembly, as we move from surfactant molecules to nanoparticles.

Written for students and academic and industrial scientists and engineers, by pioneers of the research field, Self-Assembly: From Surfactants to Nanoparticles is a comprehensive resource on diverse self-assembly systems, that is simultaneously introductory as well as the state of the art.

Autorentext

RAMANATHAN NAGARAJAN, Emeritus Professor of Chemical Engineering at the Pennsylvania State University, served on the faculty from 1979 until 2005. His research interests cover the broad areas of molecular self-assembly, colloids, polymers and nanomaterials. Currently he serves as the Army's Senior Research Scientist in nanomaterials-based technologies to address Soldier domain problem areas at the Natick Soldier Research, Development and Engineering Center.

Inhalt
List of Contributors xi

Preface xv

Acknowledgments xxi

**1 Self-Assembly from Surfactants to Nanoparticles Head vs. Tail 1
**Ramanathan Nagarajan

1.1 Introduction 1

1.2 Classical Surfactants and Block Copolymers 4

1.2.1 Tanford Model for Surfactant Micelles 4

1.2.2 de Gennes Model for Block Copolymer Micelles 11

1.2.3 Surfactant Self-Assembly Model Incorporating Tail Effects 13

1.2.4 Star Polymer Model of Block Copolymer Self-Assembly Incorporating Headgroup Effects 15

1.2.5 Mean Field Model of Block Copolymer Self-Assembly Incorporating Headgroup Effects 17

1.2.6 Tail Effects on Shape Transitions in Surfactant Aggregates 20

1.2.7 Headgroup Effects on Shape Transitions in Block Copolymer Aggregates 22

1.3 Self-Assembly of Nonclassical Amphiphiles Based on HeadTail Competition 24

1.3.1 Dendritic Amphiphiles 25

1.3.2 DNA Amphiphiles 27

1.3.3 Peptide Amphiphiles 29

1.3.4 ProteinPolymer Conjugates 31

1.3.5 Amphiphilic Nanoparticles 34

1.4 Conclusions 37

Acknowledgments 37

References 38

**2 Self-Assembly into Branches and Networks 41
**Alexey I. Victorov

2.1 Introduction 41

2.2 Rheology and Structure of Solutions Containing Wormlike Micelles 44

2.2.1 Viscoelasticity of Entangled Wormlike Micelles 44

2.2.2 Growth of Nonionic Micelles 50

2.2.3 Growth of Ionic Micelles 51

2.2.4 Persistence Length of an Ionic Micelle 52

2.2.5 Networks of Branched Micelles 53

2.2.6 Ion-Specific Effect on Micellar Growth and Branching 55

2.3 Branching and Equilibrium Behavior of a Spatial Network 56

2.3.1 The Entropic Network of Chains 56

2.3.2 The Shape of Micellar Branch and the Free Energy 61

2.4 Conclusions 66

Acknowledgments 69

References 69

**3 Self-Assembly of Responsive Surfactants 77
**Timothy J. Smith and Nicholas L. Abbott

3.1 Introduction 77

3.2 Redox-Active Surfactants 77

3.2.1 Reversible Changes in Interfacial Properties 78

3.2.2 Reversible Changes in Bulk Solution Properties 82

3.2.3 Control of Biomolecule-Surfactant Assemblies 84

3.2.4 Spatial Control of Surfactant-Based Properties 87

3.3 Light-Responsive Surfactants 90

3.3.1 Interfacial Properties 90

3.3.2 Bulk Solution Properties 90

3.3.3 Biomolecule-Surfactant Interactions 91

3.3.4 Spatial Control of Surfactant-Based Properties Using Light 93

3.4 Conclusion 93

Acknowledgments 96

References 96

**4 Self-Assembly and Primitive Membrane Formation: Between Stability and Dynamism 101
**Martin M. Hanczyc and Pierre-AlainMonnard

4.1 Introduction 101

4.2 Basis of Self-Assembly of Single-Hydrocarbon-Chain Amphiphiles 104

4.2.1 van derWaals Forces and Hydrophobic Effect 104

4.2.2 Headgroup-to-Headgroup Interactions 105

4.2.3 Interactions Between the Amphiphile Headgroups and Solute/Solvent Molecules 106

4.3 Types of Structures 106

4.3.1 Critical Aggregate Concentration 107

4.3.2 Packing Parameter 108

4.4 Self-Assembly of a Single Type of Single-Hydrocarbon-Chain Amphiphile 109

4.4.1 Single Species of Single-Hydrocarbon-Chain Amphiphile 109

4.4.2 Mixtures of Single-Hydrocarbon-Chain Amphiphiles 110

4.4.2.1 Mixtures of Amphiphiles with the Same Functional Headgroups 111

4.4.2.2 Mixtures of Single-Hydrocarbon Chain Amphiphiles and Neutral Co-surfactants 111

4.4.2.3 Mixtures of Charged Single Hydrocarbon Chain Amphiphiles 112

4.4.2.4 Mixtures of Single-Chain Amphiphiles and Lipids 113

4.4.3 Mixtures of Single-Hydrocarbon-Chain Amphiphiles and Other Molecules 114

4.4.4 Self-Assembly on Surfaces 115 4.5 Catalysis Compartmentalization with Single-Hydrocarbon-Chain Amphiphiles 116</p&g...