An improved classification of stationary phases for ultra-high performance supercritical fluid chromatography

•An improved solvation parameter model is useful to measure ionic interactions.•30 columns based on sub −2μm fully porous or sub −3μm superficially porous particles.•Evaluation is based on neutral and ionizable probe molecules.•A revised classification map is proposed to be used in UHPSFC.•Applicability of this system to real-life samples is demonstrated with drug candidates Supercritical fluid chromatography (SFC) has recently benefited of new instrumentation, together with the availability of many ultra-high performance columns (sub −2μm fully porous particles or sub −3μm superficially porous particles), rendering it more attractive than ever. Most of these columns commonly used in SFC were initially developed for HPLC use, with an increasing number of stationary phases specifically designed for SFC. While the availability of different stationary phase chemistries is an advantage to achieve successful SFC separations, selecting a column for method development remains difficult. For this reason, we have previously developed a classification of stationary phases dedicated to SFC use. It is based on linear solvation energy relationships (LSER) with Abraham descriptors (for neutral species). While current interest in SFC is strong in the pharmaceutical industry, the need to take account of interactions occurring with ionisable species is pressing. We have previously shown how a modified version of the solvation parameter model, adapted to take account of ionic and ionizable species, could be applied to the characterization of SFC systems. In the present paper, based on this modified LSER model, and on the analysis of 109 neutral and ionisable species, we propose an improved classification of 31 ultra-high performance stationary phases to facilitate method development with SFC.