Fluorescence Studies of Polymer Containing Systems (eBook)

Preface 8
Contents 10
Conformational and Dynamic Behavior of Polymer and Polyelectrolyte Chains in Dilute Solutions 11
1 Neutral Chains 12
2 Comments on the Differences Between Dilute and Concentrated Solutions 20
3 Polyelectrolyte Chains 21
4 Comments on Computer Studies of Polymer Conformations and Dynamics 27
5 The Persistence Length 29
References 32
Self-Assembly of Amphiphilic Block Copolymers in Selective Solvents 37
1 Introduction 39
2 Amphiphilic Block Copolymer Micelles 40
2.1 General Features 40
2.2 Micelle Preparation 41
2.3 Micellar Morphology 42
2.3.1 Spherical Micelles 42
2.3.2 Cylindrical Micelles 45
2.3.3 Polymersomes 46
2.3.4 Other Morphologies 50
2.4 Micelle Characterisation: Experimental Techniques 52
2.4.1 Microscopy Techniques 52
2.4.2 Scattering Techniques 52
2.4.3 Spectroscopic Techniques 53
2.4.4 Other Techniques 54
2.5 Theoretical Aspects of Micellisation 54
3 Representative Amphiphilic Block Copolymer-Selective Solvent Systems 57
3.1 Amphiphilic Copolymers in Organic Solvents 57
3.2 Amphiphilic Block Copolymers in Aqueous Solutions 59
3.2.1 Nonionic Amphiphilic Block Copolymers 60
3.2.2 Ionic Amphiphilic Block Copolymers 61
4 Potential Applications and Conclusions 63
References 64
Electrostatically Driven Assembly of Polyelectrolytes 74
1 Electrostatically Driven Self- and Co-assembly 75
1.1 Nomenclature 75
2 Fundamentals of Electrostatically Driven Assembly 77
2.1 Thermodynamics 77
2.2 Stoichiometry 79
2.3 Composition 81
2.4 Morphology 82
2.5 Stability 84
2.6 Exchange Dynamics and Formation/Dissolution Kinetics 85
3 Applications of Electrostatically Driven Assembly 86
3.1 Responsive Materials 87
3.2 Multicompartment Micelles 88
References 89
Theoretical Principles of Fluorescence Spectroscopy 99
1 Introduction 100
2 The Jablonski Diagram and Characteristics of Time-Dependent Fluorescence 101
3 Fluorescence Quenching 109
4 Resonance Energy Transfer 110
5 The Solvent Relaxation Method 114
6 Solvent Relaxation in Heterogeneous Systems 118
7 Time-Resolved Fluorescence Anisotropy 120
8 Models of Rotational Diffusion (RD) and Their Advanced Variants 122
9 Fluorescence Anisotropy in a System of Flexible Fluorescent Molecules 127
10 Rigid Molecules in Anisotropic Medium 132
11 Excimers and Exciplexes 135
12 The Effect of Ground-State Aggregation on Fluorescence Spectra 140
Appendix: Simple Quantum Mechanics Explanation of Nondegenerate Transitions Between Energy Levels in ``J´´ and ``H´´ Dimers 148
References 150
Historical Perspective of Advances in Fluorescence Research on Polymer Systems 158
1 Introduction 159
2 Fluorescence Resonance Energy Transfer Studies of Polymer Systems 160
3 Excimer Studies of Polymer Miscibility 167
4 Fluorescence Depolarization Studies of the Dynamics of Dilute Polymer Solutions 168
5 Dynamics of Concentrated Solutions and Polymer Melts 172
6 Fluorescence Depolarization Studies of Chain Conformations in Dilute Solutions 174
7 Comments on Self-Assembly Studies 182
8 Comments of Fluorescence Studies of pi-Conjugated Polymers 189
References 196
Fluorescence Spectroscopy Studies of Amphiphilic Block Copolymer Micelles in Aqueous Solutions 210
1 Introduction 210
2 Polarity-Sensitive Fluorescent Probes 212
3 Fluorescence Quenching 216
4 Fluorescent pH Indicators 219
5 Conclusions 220
References 220
Pyrene-Labeled Water-Soluble Macromolecules as Fluorescent Mimics of Associative Thickeners 223
1 Introduction 224
2 Fluorescence Decay Analysis 227
3 Applications of the FBM and MFA 231
4 Conclusions 255
References 256
Fluorescence Correlation Spectroscopy Studies of Polymer Systems 260
1 Introduction 261
2 FCS Measurements and Analysis 262
2.1 FCS Setup 262
2.2 Autocorrelation Analysis 262
2.3 Analysis of Translational Diffusion 265
2.4 Analysis of Anomalous Diffusion 266
2.5 Full Correlation FCS to Detect Triplet Kinetics, Rotational Diffusion, and Fluorescence Antibunching 268
3 Technical Variations of FCS 269
3.1 Dual-Focus FCS 270
3.2 Total Internal Reflection FCS: Investigation of Interfaces 270
3.3 Superresolution in FCS 271
3.4 Temperature Control in FCS 271
4 Limitations of FCS 272
4.1 Refractive Index Changes 272
4.2 Spatial Resolution 273
4.3 Choice of the Fluorescent Probes 273
5 FCS in Polymer Solutions 274
6 Diffusion of Small Molecular Probes 276
7 Diffusion of Macromolecular Probes 277
8 Diffusion of Nanoparticles in Polymers 279
9 FCS in Polymer Gels 280
10 FCS in Charged Polymer Systems 282
11 FCS in Responsive Polymers 282
12 FCS in Polymeric Systems Near Interfaces 286
13 FCS in Polymeric Micellar Systems 287
14 Comparison of FCS with Other Methods 291
15 FCS and Simulations 292
16 Conclusion and Outlook 293
References 294
Index 303