Polymeric micelle as the pseudostationary phase in electrokinetic chromatography

► Amphiphilic random copolymer self-assembled to form micelle via neutralization. ► Spherical micelles with monodispersity were obtained. ► The polymeric micelle was firstly used as PSP in EKC. ► EKC using the polymeric micelle as PSP has reverse phase interaction mechanism. A simple, green, and novel approach to prepare polymeric micelle with amphiphilic random copolymer P (MMA- co -MAA) via neutralization in aqueous medium has been developed, and the polymeric micelle was firstly applied as a pseudostationary phase (PSP) in electrokinetic chromatography (EKC) in the present work. Three structurally similar corticosteroids namely hydrocortisone, prednisolone, and prednisone were separated with EKC using polymeric micelle as PSP to assess the separation performance. The effects of polymeric concentration and pH on micellar microstructure including size, morphology, surface charge density and EKC performances have been investigated. TEM showed that amphiphilic random copolymers were self-assembled via neutralization to form micelles with well-defined size and shape. The size and shape of the micelle depended on the P (MMA- co -MAA) concentration and pH. At the concentration of 0.048 mM and pH 9.2, the polymeric micelles were of monodispersity and perfect spheres. DLS showed the size of micelle was almost equal as polymer concentration in the range of 0.0096–0.048 mM, and then enlarged sharply at the concentration larger than 0.048 mM. However, the zeta potentials of micelle were nearly unchanged. The polymer concentration is also the key parameter for EKC separation. Under the optimum conditions, three analytes could be baseline separated within 7.4 min. Compared with typical MEKC, MEEKC, and MEKC modified with IL ([Bmim]BF 4 ), the developed method was more rapid, efficient, and higher selective. The separation mechanism using polymeric micelle as PSP was reverse-phase interaction. The actual cosmetic samples were analyzed with recoveries between 97.3% and 113%.