β-cyclodextrin modified quantum dots as pseudo-stationary phase for direct enantioseparation based on capillary electrophoresis with laser-induced fluorescence detection.

In recent years, quantum dots (QDs) have attracted a tremendous amount of attention due to their compelling features. In this work, a kind of composite QDs based on β-cyclodextrin (β-CD) and its derivatives modification was prepared, and for the first time utilized to separate and determine enantiomers in the combined system of capillary electrophoresis with laser-induced fluorescence detection (CE-LIF). By taking advantages of the inclusion complexation of β-CD and the fluorescence property of QD core, the composite QDs were added into the running buffer as pseudo-stationary phase. The resultant CE-LIF method accomplished enantioseparation for six groups of model analytes without need of capillary preparation and analyte derivatization. The effects of composite QDs concentration, the pH value and concentration of the running buffer on resolution have been investigated individually. The RSDs of interday and intraday repeatability were in the range of 2.7–8.1%, 0.7–3.9%, and 1.5–3.8% for the peak area, migration time and resolution, respectively. The theoretical calculation results of the binding energies and binding constant further validated the interaction mechanism of composite QDs and target analytes. Furthermore, this developed method was successfully applied to the analysis of the active components (catechin and epicatechin) in Chinese herb Catechu, and the recoveries were in the range of 92.2–108%. The experimental results suggested that the preparation strategy of the composite QDs is appropriate for enantioseparation of more enantiomers by adjusting the modifiers on the surface of QDs, which is particularly promising for electrophoretic enantioseparation based on fluorescence detection, especially for those analytes lacking proper derivative functional groups.