Characterization of stationary phases in supercritical fluid chromatography including exploration of shape selectivity

Achiral packed column supercritical fluid chromatography (SFC) has shown an important regain of interest in academic and industrial laboratories in the recent years. In relation to this increased concern, major instrument manufacturers have designed some stationary phases specifically for SFC use. SFC stationary phases have been widely examined over the last two decades, based on the use of linear solvation energy relationships (LSER), which relate analyte retention to its properties and to the interaction capabilities of the chromatographic system. The method provides some understanding on retention mechanisms (normal phase, reversed phase or mixed-mode) and the possibility to compare stationary phases on a rational basis, especially through a spider diagram providing a visual classification. The latter can be used as a primary tool to select complementary stationary phases to be screened for any separation at early stages of method development, before optimization steps. In this context, the characterization of the 14 columns from the Shim-pack UC series (Shimadzu Corporation, Kyoto, Japan), which are dedicated to SFC and more broadly to unified chromatography (UC), was performed, using the LSER methodology. As in previous works, seven descriptors, including five Abraham descriptors (E, S, A, B, V) and two descriptors describing positive and negative charges (D⁻ and D⁺) were first employed to describe interactions with neutral and charged analytes. Secondly, two more descriptors were introduced, which were previously employed solely for the characterization of enantioselective systems and expressing shape features of the analytes (flexibility F and globularity G). They brought additional insight into the retention mechanisms, showing how spatial insertion of the analytes in some stationary phases is contributing to shape separation capabilities and how folding possibilities in flexible molecules is unfavorable to retention in other stationary phases.