Graft copolymerization of anion and cation onto silica and application in mixed-mode of reversed phase/ hydrophilic interaction/ ion exchange chromatography

Ionic liquids (ILs) have turned out to be one of the best choices to fabricate mixed-mode stationary phases, this work aimed to investigate the possibility and merit of copolymerizing cations and anions as modifications. We prepared two ILs stationary phases, one of which was constructed by copolymerizing cation and anion (p-vinylbenzene sulfonate). Two stationary phases were characterized and comprehensively evaluated. The stationary phases showed great repeatability (RSD <0.87%) and high efficiency (up to 83,810 plate/m). Both stationary phases can operate under a mixed mode of reversed phase/hydrophilic interaction/ion exchange chromatography (RPLC/HILIC/IEC). Chromatographic evaluation results revealed that copolymerized anions endow stationary phase superior selectivity under RPLC and HILIC modes, so hydrophobic terphenyls isomer (under ACN/H2O = 35/65) and hydrophilic nucleotides and bases (under ACN/100 mM NH4FA buffer = 90/10) are better separated. Organic and inorganic anions showed entirely different retention behaviors on two stationary phases, and the mechanism was investigated by linear solvation energy relationship (LSER) and thermodynamic analysis. This work proved that copolymerizing cations and anions of ILs could be a promising method to prepare stationary phases, the retention property and mechanism need further research.