Temperature effects on chiral microemulsion electrokinetic chromatography employing the chiral surfactant...

Dodecoxycarbonylvaline (DDCV) microemulsions (1% and 4%, w/v) were employed to evaluate the retention mechanism of a series of enantiomers over a temperature range of 15-35 degrees C. From the acquired retention data, van't Hoff plots were constructed and enthalpy and entropy of transfer were calculated from the slope and intercept, respectively. Resolution, enantioselectivity, distribution coefficients and Gibb's free energy were also calculated, as well as between enantiomer differences in enthalpy, entropy and Gibb's free energy. Finally, comparisons were made between the microemulsion thermodynamic data and a corresponding set of micellar data. While the 4% DDCV microemulsion did not provide a linear van't Hoff relationship, the 1% DDCV microemulsion was linear over a temperature range of 15-30 degrees C. For the 1% DDCV microemulsion, the enthalpic contribution to retention was consistently favorable (deltaH < 0), whereas the entropic contribution varied from compound to compound. Finally, while the achiral attraction of the analytes was greater for the micellar phase, the microemulsion seemed to provide a suitable difference in entropy (and Gibb's free energy) between enantiomers to achieve chiral discrimination.