Effects of amino acid-derived chiral ionic liquids on cyclodextrin-mediated capillary electrophoresis enantioseparations of dipeptides

Abstract

The synergistic effect of chiral ionic liquids composed of tetraalkylammonium ions and the amino acids Asn, Asp or Pro on the enantioseparations of dipeptides mediated by β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin in capillary electrophoresis was studied. Addition of a chiral ionic liquid resulted in a concentration-dependent increase in the enantioresolutions compared to the sole presence of a cyclodextrin in the background electrolyte. The extent varied with the tetraalkylammonium cation (tetramethylammonium versus tetrabutylammonium) as well as the amino acid component of the ionic liquid. The presence of a chiral ionic liquid did not counteract the pH-dependent reversal of the enantiomer migration order of the dipeptides Ala-Phe, Ala-Tyr and Phe-Phe when increasing the pH of the background electrolyte from 2.5 to 3.5. Comparing the effect of a chiral ionic liquid based on Asp with the addition of equimolar concentrations of the individual components of the ionic liquid, a diverse picture was observed. In some cases, higher resolution values were obtained with the chiral ionic liquid, while for other cases superior enantioseparations were obtained upon separate addition of the amino acid component and a tetraalkylammonium chloride. With regard to the stereochemistry of the amino acid, a superior effect was typically observed using the l-configured amino acid, but in some cases higher resolution values were found in the presence of d-Asp. The rationale for the diverse observations is not obvious and may be due to the zwitterionic nature of analytes as well as the amino acid component of the chiral ionic liquid.