Chromatographic retention and thermodynamics of adsorption of dipeptides on a chiral crown ether stationary phase

Abstract

The enantioselective adsorption of several dipeptides on the crown ether-based stationary phase ChiroSil RCA(+) was studied by means of the linear chromatography method. The retention of analytes was measured with acidified water-methanol mobile phases with varied concentration of methanol (from 60 to 90%, v/v) at different temperatures. Thermodynamic characteristics of adsorption were determined and analyzed applying extrathermodynamic relationships. A considerable difference in adsorption mechanisms of dipeptides with a chiral and achiral N-terminal fragment was proved. An explanation to this fact was proposed assuming that the enantiorecognition of the dipeptides of the first type occurred through the interaction of side groups of the N-terminus with the chiral cavity formed by the crown ether ring. The enantiorecognition of the dipeptides of the second type occurs through the interaction of the C-terminal residue with the side groups of the crown ether moiety. The study also demonstrates how extrathermodynamic concepts can be used for obtaining additional information about retention mechanisms from a limited amount of chromatographic data.