Association morphologies of amphiphilic polyelectrolyte diblock
copolymers
Korobko, Alexander Viktorovitch
Citation
Korobko, A. V. (2006, December 12). Association morphologies of amphiphilic
polyelectrolyte diblock copolymers. Retrieved from https://hdl.handle.net/1887/5568
Version:
Corrected Publisher’s Version
License:
Licence agreement concerning inclusion of doctoral thesis in the
Institutional Repository of the University of Leiden
Downloaded from:
https://hdl.handle.net/1887/5568
Association Morphologies
of Amphiphilic Polyelectrolyte
Diblock Copolymers
Universiteit Leiden
Association Morphologies
of Amphiphilic Polyelectrolyte
Diblock Copolymers
Proefschrift
ter verkrijging van
de graad van Doctor aan de Universiteit Leiden, op gezag van de Rector Magnificus Dr. D. D. Breimer,
hoogleraar in de faculteit der Wiskunde en Natuurwetenschappen en die der Geneeskunde, volgens besluit van het College voor Promoties te verdedigen op dinsdag 12 december 2006
klokke 16.15 uur
door
Alexander Viktorovitch Korobko
Promotiecommissie: Promotores:
Prof. Dr. J.R.C. van der Maarel (National University of Singapore) Prof. Dr. Ir. J.G.E.M. Fraaije
Referent:
Prof. Dr. M.A. Cohen Stuart (Wageningen University)
Overige leden:
Prof. Dr. H.J.M. de Groot
Prof. Dr. H.N.W. Lekkerkerker (Utrecht University) Prof. Dr. S. Picken (TU Delft)
Contents
1 Introduction 1
1.1 General Introduction . . . 1
1.2 Polyelectrolytes . . . 2
1.2.1 Amphiphilic Diblock Copolymers and DNA . . . 2
1.3 Curved Polyelectrolyte Brushes . . . 3
1.3.1 Theoretical Investigations . . . 3 1.3.2 Experimental Results . . . 6 1.4 Polyelectrolyte Vesicles . . . 7 1.4.1 Polymersomes . . . 8 1.4.2 Multilayer Capsules . . . 9 1.5 Thesis Outline . . . 9
2 Do Interacting Spherical Polyelectrolyte Brushes Interdigitate? 19 2.1 Introduction . . . 19
2.2 Theory . . . 20
2.3 Experimental Section . . . 21
2.4 Conclusions . . . 26
3 Structure of strongly interacting polyelectrolyte diblock copolymer mi-celles 29 3.1 Introduction . . . 30
3.2 Scattering Analysis . . . 32
3.2.1 From Intensities to Structure Factors . . . 32
3.2.2 Solution Structure Factor . . . 34
ii CONTENTS
3.3 Corona Chain Statistics . . . 35
3.4 Experimental Section . . . 37
3.4.1 Chemicals and solutions . . . 37
3.4.2 Neutron Scattering . . . 37
3.4.3 X-ray Scattering . . . 39
3.4.4 Rheology . . . 40
3.5 Results and Discussion . . . 40
3.5.1 Core and Corona Structure . . . 40
3.5.2 Counterion Structure . . . 46
3.5.3 Inter-micelle Structure . . . 49
3.5.4 Visco-elastic Behavior . . . 52
3.6 Conclusions . . . 54
4 Encapsulation of DNA by Cationic Diblock Copolymer Vesicles 59 4.1 Introduction . . . 60
4.2 Experimental Section . . . 63
4.2.1 Chemicals and Solutions . . . 63
4.2.2 Imaging . . . 64
4.3 Results and Discussion . . . 65
4.3.1 Production of the vesicles . . . 65
4.3.2 Density distribution and compaction factors . . . 69
4.3.3 Stability of the vesicles . . . 75
4.3.4 Cloning Vector DNA and the “Charge Inverse” System . . . 78
4.4 Conclusions . . . 79
5 DNA-copolymer vesicles for gene delivery 83 5.1 Introduction . . . 84
5.2 Materials and methods . . . 85
5.2.1 Plasmid isolation . . . 85
5.2.2 Copolymer and osmotic agent . . . 86
5.2.3 Growth and transfection media . . . 86
5.2.4 Imaging . . . 87
5.3 Results and discussion . . . 88
5.3.1 Production of the vesicles . . . 88
5.3.2 Stability, density distribution, and compaction . . . 91
CONTENTS iii
5.4 Conclusions . . . 100 5.A Permeability of Membrane . . . 104
6 Conclusions 109
Samenvatting 113
Curriculum Vitae 117
Acknowledgments 119
