Amphiphilic Molecules in Aqueous Solution
The aim of this thesis was to investigate amphiphilic molecules in aqueous solution. The work was divided into two parts. In the first part the effects of different counterions on phase behavior was investigated, while the second part concerns the 1-monooleoyl-rac-glycerol (MO)/n-octyl-?-D-glucoside (OG)/2H2O-system. The effects of mixing monovalent and divalent counterions were studied for two surfactant systems, sodium/calcium octyl sulfate, and piperidine/piperazine octanesulfonate. It was found that mixing monovalent and divalent counterions resulted in a large decrease in cmc already at very low fractions of the divalent counterion. Moreover, the degree of counterion binding for piperidine in the piperidine/piperazine octanesulfonate system was much higher than predicted, probably due to the larger hydrophobic moiety of piperidine.The effects of hydrophobic counterions were studied for eight alkylpyridinium octanesulfonates (APOS). The results were discussed in terms of packing constraints. The anomalous behavior of the 2H2O quadrupolar splittings in the lamellar phases was explained by the presence of two or more binding sites at the lamellae surface. The MO/OG/water system was studied in general and the MO-rich cubic phases in particular. When mixing MO and OG it was found that OG-rich structures (micelles, hexagonal and cubic phase of space group Ia3d) could solubilize quite large amounts of MO, while the MO-rich cubic structures where considerable less tolerant towards the addition of OG. The micelles in the OG-rich L1 phase were found to remain rather small and discrete in the larger part of the L1 phase area, but at low water concentration and high MO content a bicontinuous structure was indicated. Only small fractions of OG was necessary to convert the MO-rich cubic Pn3m structure to an Ia3d structure, and upon further addition of OG a lamellar (La) phase formed. Since the larger part of the phase diagram contains a lamellar structure (present either as a single La phase or as a dispersion of lamellar particles together with other phases), the conclusion was that introducing OG in the MO structures, forces the MO bilayer to become more flat. Upon heating the cubic phases, structures with more negative curvature were formed. The transformation between the cubic structures required very little energy, and this resulted in the appearance of additional peaks in the diffractograms.
Source Type:Doctoral Dissertation
Keywords:NATURAL SCIENCES; Chemistry; Physical chemistry; Physical chemistry; liquid crystal; phase diagrams; counterions; alkylpyridinium octanesulfonates; 1-monooleoyl-rac-glycerol; n-octyl-?-D-glucoside; cubic phases; Fysikalisk kemi; Physical Chemistry; fysikalisk kemi
Date of Publication:01/01/2003