An in-depth investigation of supercritical fluid chromatography retention mechanisms by evaluation of a series of specially designed alkylsiloxane-bonded stationary phases based on linear solvation energy relationship

Abstract

Fundamental research on supercritical fluid chromatography (SFC) has gained considerable interest, with many studies focusing on its retention mechanism based on the linear solvation energy relationship (LSER) model. In this paper, a series of alkylsiloxane-bonded stationary phases were specifically designed and synthesized, then evaluated using the mobile phase composed of CO2 with 10% (v/v) methanol. The study demonstrated the close relationship between the interactions (manner and magnitude) of stationary phases and the C-chain length, bonding density and the endcapping treatment. All C8 phases provide positive e, v and negative s, whose magnitude was regularly affected by bonding density. It was worth mentioning the non-endcapped C8 phases could provide H-bonding (positive a and b) by reducing the bonding density of the alkyl chain. Once it was endcapped, the interaction manner did not vary with bonding density adjustment. The non-endcapped C4 phases with higher bonding density could establish additional dispersion interaction (positive v). It can be seen that two synthesis strategies, 1) non-endcapped, long C-chain (C8) combined with low bonding density, and 2) non-endcapped, short C-chain (C4) combined with high bonding density, can obtain the alkylsiloxane-bonded stationary phases (C8-1 and C4-3) to provide both polar and dispersion interactions, showing different separation selectivity. Furthermore, the LSER model with ionic terms was applied to evaluate partial C8 columns, and its rationality was verified. The non-endcapped C8 showed great d+ values, which originated from the silanol groups. C8SCX also possessed a great d+ value due to the benzenesulfonic acid groups. A remarkable result showed that C8SAX exhibited prominent d− and d+ values simultaneously due to the combined effect of silanol and quaternary ammonium groups, which indicates the unique selectivity when separating ionic compounds. This study provides in-depth insights into the retention mechanism of alkylsiloxane-bonded stationary phases in SFC, as well as a reference for the design of SFC stationary phases.