The effect of chain packing on surfactant aggregation in aqueous solution
- 1 January 1990
- journal article
- Published by Walter de Gruyter GmbH
- Vol. 62 (1) , 47-55
- https://doi.org/10.1351/pac199062010047
Abstract
Hydro'phobic interactions provide the main driving force for the aggregation of amphiphilic compounds in water. However, the morphology and dynamic properties of the aggregate represent the outcome of a compromise between a variety of partly opposing factors. It is obvious that efficient alkyl chain packing in the interior of the molecular assembly is a prerequisite for stabilisation. Unfortunately, the highly dynamic nature of micelles and smaller aggregates hampers a straightforward experimental approach. Small amphiphilic molecules like t-BuOH, 2-butoxyethanol (2-BE), and N-cyclohexylpyrrolidone (CHP) start to form highly dynamic, small clusters at the critical hydrophobic interaction concentration (chic). In addition to other techniques, the occurrence of a chic can be probed using kinetic studies of suitable model reactions. A detailed study of the aggregation behavior of a series of l-alkyl-4-(Clz-alkyl)pyridinium iodides (1-11) illustrates that the preferred morphology of the aqueous surfactant assemblies is primarily determined by the molecular architecture of the surfactant molecule. Depending on the branching and stiffness of the 4-(Clz-alkyl) moiety, the length of the 1-alkyl substituent and the surfactant concentration, the surfactants form spherical micelles, rod-like micelles or vesicles. These differences in aggregation behavior are rationalized by considering the variation of the packing parameter of the surfactant monomer as a function of surfactant structure. The chain packing in the core of the spherical micelles was probed by an analysis of proton TI relaxation times within the framework of Wennerstrom's two-step model.Keywords
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