Advancements in Multiple‐Step On‐Line Preconcentration Techniques for Enhanced Sensitivity in Capillary Electrophoresis

ABSTRACT Multiple‐step on‐line preconcentration, a combination of at least two stacking techniques has been developed to increase the sensitivity in capillary electrophoresis (CE) for analytes in various samples. It is usually conducted sequentially, or in some cases, synergistically, where different stacking modes occur simultaneously. Multiple‐step techniques allow simultaneous preconcentration and separation of various kinds of analytes in different complex samples in a single CE run. This review aims to provide recent advances in multiple‐step on‐line preconcentration techniques in CE. We critically review technical papers published for the last 7 years up until July 2024, subsequently organized according to the combination of the main stacking techniques, that is, field amplification, large volume sample stacking, transient isotachophoresis, micelle to solvent or micelle to cyclodextrin stacking, and others. The procedures, fundamental mechanism, analytical figures of merits achieved, and their feasibility for complicated sample matrices are reviewed.