Thermodynamics of micelle formation of the ephedrine-based chiral cationic surfactant DMEB in water, and the intercalation of DMEB in montmorillonite

The solubility and the micelle formation of the chiral cationic surfactant (IR,2S)-(-)-N-dodecyl-N-methylephedrinium bromide (DMEB) in aqueous solution were investigated by conductometry and titration microcalorimetry in the temperature range of 278-328 K. The Krafft temperature of DMEB is T-K = 280 K and the solubility of the surfactant at this point is 4.5 mM. The cmc versus T curve passes through a shallow minimum close to room temperature. The micelle formation changes from endothermic to exothermic at this characteristic temperature. The apparent degree of dissociation of the micelles alpha(app) increases slightly as the temperature is raised. The isosteric enthalpies of micelle formation, Delta H-st mic, are close to the calorimetrically measured enthalpies, Delta H-mic, provided that the real degree of dissociation, alpha(st) = 1, is used in the calculations. Delta H-mic and the temperature dependence Delta H-mic of DMEB are markedly similar to those of sodium dodecylsulfate and dodecyltrimethylammonium bromide. The micelle formation of DMEB is favored by both enthalpy and entropy at and above room temperature. The enthalpy-entropy compensation results in a slight decrease in the Gibbs free energy on increase of the temperature. Sodium montmorillonite (M) was rendered organophilic by DMEB via ion-exchange to produce the clay/organocomplex DME-M. The swelling properties of the organoclay were investigated by XRD measurements in a variety of organic solvents. The basal spacing of DME-M varied from 1.8 to 3.5 nm, depending on the nature of the solvent. DME-M is a heterogenized ephedrine derivative, which may be regarded as a potential catalyst for enantioselective organic syntheses. (c) 2007 Elsevier B.V. All rights reserved.