Physicochemical and chromatographic characteristics of random amphiphilic copolymer aggregation in electrokinetic chromatography

• Monomer ratio affected microstructure and EKC properties of polymeric aggregations.
• Low CACs could be gained when hydrophobic monomer ratio increased.
• Improve separation window and methylene selectivity by increasing hydrophobic monomer ratio.
• LSER analysis found polymeric aggregations owned more complex interactions than SDS micelle.

The random amphiphilic polymeric aggregation, self-assembled from poly (methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)), was explored as a novel pseudostationary phase (PSP) in electrokinetic chromatography (EKC) in our previous report. This work focused on physicochemical characteristics and PSP performances of the polymeric aggregations. The physicochemical characteristics of polymeric aggregations, including critical aggregation concentration (CAC), zeta potential, hydrodynamic diameter, and micropolarity were determined. Experimental results showed that polymeric aggregations had much lower CAC, which decreased the usage of copolymer in EKC, weakened ionic strength and shortened analysis time. The monomer molar ratio of the copolymer was a key factor for physicochemical characteristics and PSP performances of the polymeric aggregations. With the increase of the hydrophobic monomer molar ratio, CAC, micropolarity and dimension of polymeric aggregation decreased significantly while zeta potentials were similar. Correspondingly, separation window enlarged and methylene selectivity evaluated with six kinds of n-alkylphenone homologous series enhanced. Linear solvation energy relationships (LSER) analysis found that hydrophobic interaction is the most important interaction between analytes and polymeric PSPs. Compared with SDS micelle, polymeric aggregations owned more types of interactions, such as stronger hydrogen bonding and relative larger dipole interaction, which provided a bigger adjustment room to improve PSP selectivity.