Micellar versus hydro-organic mobile phases for retention-hydrophobicity relationship studies with ionizable diuretics and an anionic surfactant

Abstract

Logarithm of retention factors (logk) of a group of 14 ionizable diuretics were correlated with the molecular (logPo/w) and apparent (logPapp) octanol–water partition coefficients. The compounds were chromatographed using aqueous–organic (reversed-phase liquid chromatography, RPLC) and micellar–organic mobile phases (micellar liquid chromatography, MLC) with the anionic surfactant sodium dodecyl sulfate (SDS), in the pH range 3–7, and a conventional octadecylsilane column. Acetonitrile was used as the organic modifier in both modes. The quality of the correlations obtained for logPapp at varying ionization degree confirms that this correction is required in the aqueous–organic mixtures. The correlation is less improved with SDS micellar media because the acid–base equilibriums are shifted towards higher pH values for acidic compounds. In micellar chromatography, an electrostatic interaction with charged solutes is added to hydrophobic forces; consequently, different correlations should be established for neutral and acidic compounds, and for basic compounds. Correlations between logk and the isocratic descriptors logkw, logkwm (extrapolated retention to pure water in the aqueous–organic and micellar–organic systems, respectively), and ϕ0 (extrapolated mobile phase composition giving a k=1 retention factor or twice the dead time), and between these descriptors and logPapp were also satisfactory, although poorer than those between logk and logPapp due to the extrapolation. The study shows that, in the particular case of the ionizable diuretics studied, classical RPLC gives better results than MLC with SDS in the retention hydrophobicity correlations.