Evaluation of the retention dependence on the physicochemical properties of solutes in reversed-phase liquid chromatographic linear gradient elution based on linear solvation energy relationships

This paper describes the results of the evaluation of retention dependence on the physicochemical properties of solutes in linear gradient elution by reversed-phase liquid chromatography (RPLC) based on linear solvation energy relationships (LSERs). Retention time data on Inertsil ODS(3) column by linear gradient elution were collected for both acetonitrile–water and methanol–water binary mobile phases under various gradient steepness. Based on the LSERs, the retention times were linearly correlated with the physicochemical properties (size, dipolarity, and hydrogen bond donor–acceptor acidity and basicity) of solutes. As predicted by LSERs, very acceptable linear relationships are observed for both mobile phases. While the magnitudes of the coefficients are modified by the gradient steepness, their signs are consistent with those obtained by isocratic elution. As obtained for isocratic elution, the dominant factors to retention in linear gradient elution of RPLC are the solutes’ size and hydrogen bond acceptor basicity. The conclusions of the study allow us to predict retention in chromatographic method development by gradient elution.