A new HPLC stationary phase has been synthesized based on the ionic liquid n-butylimidazolium bromide. Imidazolium was covalently immobilized on a silica substrate through an n-alkyl tether and the retention characteristics of the resulting stationary phase were evaluated systematically. Using 28 small aromatic test solutes and reversed phase conditions, the linear solvation energy relationship approach was successfully used to characterize this new phase. The retention characteristics of the test solutes show remarkable similarity with phenyl stationary phases, despite the presence of a positive charge on the new imidazolium phase. Operated in the reversed phase mode, this new stationary phase shows considerable promise for the separation of neutral solutes and points to the potential for a truly multi-modal stationary phase.

Previously, a new HPLC stationary phase based on n-butylimidazolium bromide was investigated using a linear solvation energy relationship (LSER) to systematically evaluate the intermolecular interactions between 32 test solutes and the stationary phase. The results and further comparisons with conventional reversed phase systems revealed that retention properties are similar to phenyl phases in both methanol/water and acetonitrile/water mixtures. In this work, the LSER model is extended by including the degree of ionization molecular descriptor, D, which takes into account the pK a of ionizable analytes and the pH of the mobile phase. The D molecular descriptor has been further divided into D + and D − components that separately account for the ionization of basic and acidic solutes, respectively. This is the first study where the ionization terms for weakly acidic solutes and weakly basic solutes have been separated. LSER results obtained with the expanded solute set with and without the inclusion of the D + and D − solute descriptors were compared. The improved correlation and standard error obtained for the expanded test set in the presence and absence of the D + and D − descriptors (R 2 : 0.987 vs 0.846; se: 0.051 vs 0.163 for 60% MeOH) supports inclusion of these additional terms. Further, the coefficients obtained from the multiple linear regression for the expanded test set with the D + and D − descriptors was more consistent with the coefficients obtained when the test set included just neutral analytes. In addition, the expanded LSER model did a better job of predicting elution order for the ionizable analytes. This work provides further supporting evidence for the multimodal nature of the butylimidazolium stationary phase.

A surface-confined ionic liquid (SCIL) and a commercial quaternary amine silica-based stationary phase were characterized employing the linear solvation energy relationship (LSER) method in binary methanol/water mobile phases. The retention properties of the stationary phases were evaluated in terms of intermolecular interactions between 28 test solutes and the stationary phases. The comparison reveals a difference in the hydrophobic and hydrogen bond acceptance interaction properties between the two phases. The anion exchange retention mechanism of the SCIL phase was demonstrated using nucleotides. The utility of the SCIL phase in predicting logk (IL/water) values by chromatographic methods is also discussed.

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