Improving the Sensitivity in Chiral Analysis by Capillary Electrophoresis

Chiral analysis plays a relevant role in numerous scientific fields, such as the pharmaceutical, biomedical, agrochemical, environmental, or food science, due to the different properties that stereoisomers may present. Capillary electrophoresis (CE) techniques, mainly electrokinetic chromatography (EKC) and micellar electrokinetic chromatography (MEKC), are well-established techniques to achieve enantiomeric separations owing to its high selectivity, methodological versatility, and low consumption of reagents and samples. In this context, method sensitivity is a critical characteristic, as it determines the capability to detect and quantify enantiomers at trace levels and to assess the enantiomeric purity of raw materials, pharmaceutical or agrochemical formulations, and food ingredients, among others. This article reviews the analytical strategies reported from 2022 to June 2026 aimed at enhancing the sensitivity in chiral CE techniques and to apply them to the analysis of pharmaceutical formulations, and to biological, environmental, and food samples. Off-line and in-capillary preconcentration strategies, as well as their combinations, together with the use of alternative detections systems to UV-Vis detection, are described as the most effective. The most relevant results are presented and critically discussed through the manuscript.