Characterization of Novel Polymer-Based Pyridine Stationary Phases for Supercritical Fluid Chromatography

2-Ethylpyridine-bonded silica is one of the most famous stationary phases employed in supercritical fluid chromatography, especially for the analysis of basic compounds and even without an additive in the mobile phase. In the present paper, we present the synthesis and characterization of three original stationary phases based on poly(vinylpyridine) polymers supported on silica. The position of nitrogen atom relative to the polymer chain was varied to be in the 2, 3, or 4 position. All these phases were prototypes, while the poly(4-vinylpyridine) phase was subsequently commercialized (DCPak P4VP from Daicel Corporation). The stationary phases obtained are characterized in supercritical fluid chromatography with carbon dioxide—methanol mobile phase, with a modified version of the solvation parameter model, to take account of ionic interactions. The three phases are also compared to a 2-ethylpyridine-bonded silica phase and a 2-picolylamine-bonded silica phase. It appears that the polymer-based pyridine phases are significantly more retentive than brush-type pyridine phases and adequately shield residual silanol groups to prevent unwanted interactions with basic compounds. The different selectivities and chromatographic performances are also evidenced with sample applications on pharmaceutical compounds, notably with a selection of 140 drug candidates.