Comparison of methods for characterization of reversed-phase liquid chromatographic selectivity

The goal of the present work is to obtain a better understanding of the chemical factors affecting liquid chromatographic retention. One of the most commonly used formats for liquid chromatographic separations is based on a nonpolar stationary phase, typically an octadecyl-derivatized silica material. A wide variety of these reversed-phase columns are commercially available that differ significantly in their chromatographic retention and selectivity. We seek to quantitatively characterize these differences. Retention data for a range of compounds with many diverse characteristics have been measured on several different octadecyl silica columns (J. Chromatogr. A, submitted for publication). Principal components analysis is used to characterize the different properties of these stationary phases and predict retention factors. The key set factor analysis method and the typical solute method are used in conjunction with the principal components analysis to identify small subsets of solutes that can be used to quantitatively describe the retention of a broad range of compounds. In addition, a quantitative comparison to alternative data analysis methods is made, including linear solvation energy relationships and an iterative subtraction method based on linear regression techniques. Although many earlier studies have reported the application of these methods, this study is the first to make a quantitative comparison of these methods using a highly precise and structurally variable set of test compounds.