Microcalorimetry of Chiral Surfactant−Cyclodextrin Interactions

Abstract

The interactions of the chiral surfactants taurodeoxycholate (TDOCA) and deoxycholate (DOCA) with a range of cyclodextrins in aqueous solution have been investigated by isothermal titration microcalorimetry. In the presence of β-cyclodextrin, the apparent critical micelle concentration (cmc) of taurodeoxycholate is increased, and the enthalpy of demicellization decreased, in a manner consistent with 1:1 complexation of TDOCA with β-CD at low concentrations. There is no evidence for direct interaction of cyclodextrins with surfactant micelles. This is confirmed by more direct binding titrations. Below the cmc, TDOCA forms 1:1 host-guest complexes with β-cyclodextrin (ΔH°(bind) = -32 kJ mol(-)(1), K(diss) = 0.38 mM; 25 °C, pH 7), methyl-β-cyclodextrin (ΔH(bind) = -13 kJ mol(-)(1), K(diss) = 0.36 mM), hydroxypropyl-β-cyclodextrin (ΔH°(bind) = -12 kJ mol(-)(1), K(diss) = 0.51 mM), and γ-cyclodextrin (ΔH°(bind) = -7.3 kJ mol(-)(1), K(diss) = 0.08 mM), but not with the smaller α-cyclodextrin. At higher cyclodextrin concentrations, the calorimetric binding data are more ambiguous, suggesting 2:1 cyclodextrin/TDOCA complexation. Similar results are found with DOCA, though experiments here are limited by the tendency of DOCA to form gels in aqueous buffers. Enhanced chromatographic or electrophoretic chiral resolution observed in mixed chiral surfactant/cyclodextrin phases could be the result of increased solubility and/or the multiplicity of chiral complexes in such systems.