Chemistry, structural insight and applications of β-sheet forming lipopeptides

Chemistry, structural insight and applications of β-sheet forming

lipopeptides

Cavalli, S.

Citation

Cavalli, S. (2007, January 25). Chemistry, structural insight and applications of β-sheet forming lipopeptides. Retrieved from https://hdl.handle.net/1887/9452

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/1887/9452

Note: To cite this publication please use the final published version (if applicable).

To those who never stop seeking beyond the horizon To those who never give up trying

to turn metal into gold

Liebe Leut, gedenkt des End’s Das Wissen flüchtet über die Grenz.

Wir, die wissensdurstig sind Er und ich, wir blieben dahint’.

Hütet nun ihr der Wissenschaften Licht Nutzt es und missbraucht es nicht Daβ es nicht, ein Feuerfall Einst verzehre noch uns all Ja, uns all.

Leben des Galilei, Bertolt Brecht

Table of contents

Chapter 1

Bridging Science: Scope and Applications of Peptide-Based Nanostructures

from Chemistry to Biology, Material Science and Engineering 9 1.1 Amphiphilic Peptides as Building Blocks for the

Bottom-Up Constructions of Nanometre-Scale Assembled Structures 10 1.1.1 Amphiphilic Oligopeptides 11 1.1.2 Lipidated Oligopeptides 15 1.1.3 Peptide-Based Block Copolymers 17 1.2 General Synthetic Strategies 21 1.3 Applications of Peptide-Based Nanostructures 25 1.3.1 Nanoreactors and Catalysts 26 1.3.2 RGD Functionalized Materials 27 1.3.3 Tissue Regeneration Materials 28 1.3.4 Drug-Delivery Vehicles 29 1.3.5 Antimicrobial Biomaterials 30 1.3.6 Templates for Mineralization 31 1.3.7 Photosensitive Switches and Nanowires 33 1.2.9 Molecular Machines 34 1.4 Aim and Outline of the Thesis 35 1.5 References and Notes 37 Chapter 2

Synthesis and Characterization of Two-Dimensional Ordered β-Sheet

Lipopeptide Monolayers 43

2.1 Introduction 44

2.2 Results and Discussion 45 2.2.1 Lipopeptide Design 45 2.2.2 Lipopeptide Synthesis 46 2.2.3 Surface Pressure-Molecular Area (π-A) Isotherms 47 2.2.4 Circular Dichroism (CD) and Attenuated Total

Reflectance Fourier Transform Infrared (ATR FTIR) 49 2.2.5 Brewster Angle Microscopy (BAM) 52

2.2.6 In situ Grazing Incidence X-ray Diffraction (GIXD)

Measurements 53 2.2.7 Molecular Dynamic (MD) Simulations 58

2.3 Conclusions 60

2.4 Experimental Section 62 2.5 References and Notes 67 Chapter 3

Self-Organizing β-Sheet Lipopeptide Monolayers as Templates for the

Mineralization of CaCO3 69

3.1 Introduction 70

3.1.1 Calcium Carbonate (CaCO3) 70 3.1.2 Mineralization of CaCO3 71 3.2 Results and Discussion 72

3.2.1 Monolayers Studies on Milli-Q Water, 10 mM CaCl2

and Saturated CaCO3 72 3.2.2 CaCO3 Crystallization Experiments 76 3.2.2 Crystal Analysis 82 3.2.3 Mechanistic Considerations 84 3.2.4 Flexibility and Adaptation in Other Systems 86

3.3 Conclusions 87

3.4 Experimental Section 88 3.5 References and Notes 91 Chapter 4

Self-Assembly of Amphiphilic Lipopeptides 93

4.1 Introduction 94

4.2 Results and Discussion 96 4.2.1 Fiber Formation at the Air-Water Interface 96 4.2.2 Self-Assembly in Aqueous Solution 98

4.3 Conclusions 104

4.4 Experimental Section 104 4.5 References and Notes 107 Chapter 5

Chemical Modification of Liposome Surface via Copper(I)-Mediated

[3+2] Azide-Alkyne Cycloaddition 109 5.1 Introduction 110

5.2 Colorimetric Assay for Chemical Modification of Liposome

Surface via a Copper-Mediated [3+2] Azide-Alkyne Cycloaddition 112 5.3 β-sheet folding induced by liposome conjugation via

copper(I)-catalyzed [3+2] azide-alkyne cycloaddition 119 5.4 Copper(I)-catalyzed [3+2] azide-alkyne cycloaddition towards

immunoliposomes 123

5.5 Conclusions and Future Prospects 127 5.6 Experimental Section 127 5.7 References and Notes 132 Chapter 6

A Pilot Study towards the Preparation of Antimicrobial Coated Surfaces 135 6.1 Introduction 136 6.2 Synthesis, Langmuir Monolayer Studies and Structural Insight

by Grazing Incident X-ray Diffraction (GIXD) at the Air-Water

Interface 136

6.3 Transferred Monolayers towards the Preparation of Antimicrobial

Coated Surfaces 140

6.4 Conclusions and Future Prospects 141 6.5 Experimental Section 142 6.6 References and Notes 144 Summary and Perspectives 145

Samenvatting 151

Curriculum Vitae 157

List of Publications 159

Acknowledgements 161

Appendix 1 : GIXD DATA 163

Appendix 2: Crystal Systems and Crystallographic Notations 165

Appendix 3: AFM Images 167

Appendix 4: Shape of Self-Assembled Amphiphilic Structures 169