Table of contents

VII

Table of contents

Chapter I:

General Introduction ... 1

1 Supramolecular chemistry ... 1

2 Transmembrane transport ... 2

2.1 Model membranes and methodologies ... 3

2.2 Chloride transport with synthetic systems – state of the art ... 6

3 Outline of the thesis ... 18

4 References ... 20

Chapter II:

Transmembrane transport of chloride and organic ion pairs with

calix[6]arene-based receptors ... 29

1 Introduction ... 29

2 Calixarenes and transport ... 29

3 Development of the NMR methodology used ... 34

3.1 NMR and paramagnetic compounds ... 34

3.2 Setting up of NMR methodologies ... 36

4 Summary of published results ... 39

5 Additional data ... 42

6 Conclusions ... 45

7 Materials and methods ... 47

7.1 Synthesis of H8DOTP ... 47

7.2 Synthesis of calixarene 12 ... 49

7.3 Synthesis of calixarene 13 ... 50

VIII

Chapter III:

Binding of chloride to receptors embedded in lipid membranes 61

1 Introduction ... 61

2 Binding studies with liposomes and micelles by 1_{H and} 31_{P NMR ... 63}

2.1 State of the art ... 63

2.2 Results and discussions ... 66

3 35_{Cl NMR binding studies with liposomes and micelles ... 71}

3.1 Chemical exchange effects ... 73

3.2 35_{Cl NMR to monitor chloride binding in aqueous media ... 75}

3.3 State of the art ... 77

3.4 Results and discussions ... 78

4 Conclusions ... 96

5 Materials and methods ... 98

5.1 Materials ... 98

5.2 1_{H NMR titrations ... 98}

5.3 35_{Cl NMR titrations ... 99}

5.4 ITC experiments ... 100

6 References ... 102

Chapter IV:

Conclusions ... 107

Chapter V:

Appendices ... 111

1 Publication in Angewandte Chemie – International Edition. ... 111

2 Appendices to Chapter III ... 143

2.1 Binding studies with liposomes and micelles by 1_{H and} 31_{P NMR ... 143}