Chemistry and physics of supramolecular systems Organic Chemistry ORC-20806 Ton Marcelis Organic Chemistry Ernst Sudhölter Organic Chemistry CONTENTS CHAPTER 1: INTRODUCTION................................................................................................................................... 3 1.1 ORDERED SYSTEMS................................................................................................................................................... 3 1.2 MOLECULES AND MATERIALS ................................................................................................................................... 4 1.3 SUPRAMOLECULAR SYSTEMS .................................................................................................................................... 6 CHAPTER 2: SURFACTANTS..................................................................................................................................... 7 2.1 INTRODUCTION ......................................................................................................................................................... 7 2.2 SURFACTANT PARAMETER ........................................................................................................................................ 8 2.3 MICELLES ............................................................................................................................................................... 10 2.3.1 Micelle models................................................................................................................................................ 11 2.3.2 Dynamics of micelles ...................................................................................................................................... 11 2.3.3 Counter ion binding........................................................................................................................................ 12 2.4 FACTORS THAT INFLUENCE THE CMC..................................................................................................................... 13 2.5 METHODS FOR DETERMINING THE CMC ................................................................................................................. 14 2.5.1 Surface tension................................................................................................................................................ 14 2.5.2 Conductivity.................................................................................................................................................... 15 2.5.3 Light scattering............................................................................................................................................... 15 2.5.4 Solubilisation .................................................................................................................................................. 15 2.6 APPLICATIONS OF MICELLES ................................................................................................................................... 16 2.6.1 Cleaning agents .............................................................................................................................................. 16 2.6.2 Micellar catalysis............................................................................................................................................ 17 2.6.3 Application of micelles in chiral separations.................................................................................................. 19 2.7 GENERAL PHASE BEHAVIOUR OF SURFACTANTS...................................................................................................... 22 2.8 LYOTROPIC LIQUID CRYSTALS ................................................................................................................................ 24 2.9 SPECIAL AGGREGATES OF SINGLE-TAILED SURFACTANTS. ...................................................................................... 26 CHAPTER 3: VESICLES............................................................................................................................................. 28 3.1 INTRODUCTION ....................................................................................................................................................... 28 3.2 PREPARATION OF VESICLES..................................................................................................................................... 30 3.2.1 Preparation of vesicles by sonication ............................................................................................................. 30 3.2.2 Preparation of vesicles by the alcohol injection method. ............................................................................... 31 3.2.3 The preparation of giant vesicles.................................................................................................................... 31 3.3 VISUALISATION OF VESICLES BY ELECTRON MICROSCOPY ...................................................................................... 32 3.4 PHASE TRANSITIONS IN AMPHIPHILIC BILAYERS...................................................................................................... 33 3.5 TRAPPING OF GUEST MOLECULES IN A VESICLE COMPARTMENT.............................................................................. 34 3.6 FUSION OF VESICLES ............................................................................................................................................... 35 3.7 SOLUBILISATION ..................................................................................................................................................... 36 3.8 APPLICATIONS OF VESICLES.................................................................................................................................... 38 3.8.1 Photodynamic therapy .................................................................................................................................... 38 3.8.2 DNA-transfection............................................................................................................................................ 39 3.8.3 Controlled drug release.................................................................................................................................. 39 3.9 LITERATURE ........................................................................................................................................................... 40 CHAPTER 4: MONOLAYERS ................................................................................................................................... 41 4.1 INTRODUCTION ....................................................................................................................................................... 41 4.2 LANGMUIR TROUGH................................................................................................................................................ 42 4.3 PHASE BEHAVIOUR.................................................................................................................................................. 42 4.4 RELATION BETWEEN STRUCTURE AND MONOLAYER BEHAVIOUR............................................................................ 44 4.5 VISUALISATION OF MONOLAYERS........................................................................................................................... 45 4.6 MOLECULAR RECOGNITION AT MONOLAYERS......................................................................................................... 47 4.6.1 Chiral recognition of taste compounds........................................................................................................... 47 4.6.2 Interactions with chiral amino acids .............................................................................................................. 47 4.6.3 Biotine - streptavidine interactions................................................................................................................. 48 4.7 APPLICATIONS OF MONOLAYERS............................................................................................................................. 49 4.8 LITERATURE ........................................................................................................................................................... 49 4.9 INTERMEZZO: AMPHOTROPES ................................................................................................................................ 50 - 1 - CHAPTER 5: POLYMERS.......................................................................................................................................... 57 5.1 INTRODUCTION ....................................................................................................................................................... 57 5.2 POLYMERISATION REACTIONS................................................................................................................................. 57 5.3 MECHANISMS FOR THE ADDITION POLYMERISATION............................................................................................... 58 5.3.1 Radical polymerisation................................................................................................................................... 59 5.3.2 Ionic polymerisation ......................................................................................................................................