Linear solvation energy relationships in micellar liquid chromatography and micellar electrokinetic capillary chromatography

Abstract

Linear solvation energy relationships (LSERs) were used to evaluate and characterize chemical interactions that influence retention behavior in micellar liquid chromatography (MLC) and micellar electrokinetic capillary chromatography (MEKC). High correlations were found between solutes' capacity factors in MLC and in MEKC, as well as binding constants to micelles and their solvatochromic parameters using two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium cholate (SC), and one cationic surfactant, tetradecyltrimethylammonium bromide (C 14TAB). Surprisingly, in the C 14TAB MLC system capacity factor ( k′) vs. solvatochromic parameters gives better correlation than log k′ vs. solvatochromic parameters, which is an opposite behavior to that observed in the SDS MLC system. The capacity factors in the C 14TAB MLC system were characterized using LSERs with and without organic modifiers. It was found that the addition of a small amount of short-chain alcohols (e.g., 7% 2-propanol or 5% butanol) does not significantly change the high correlations between k′ vs. solvatochromic parameters. The changes in the coefficients with the volume fraction of organic solvents were explained by comparing the differences in chemical natures between mobile phase and stationary phase. Stationary phase shows a significant effect on the chemical interactions in MLC through LSER study using a diphenyl column and a C 8 column. LSERs were also used to characterize retention behavior in MEKC. High correlations between the logarithm of solutes' capacity factors and their solvatochromic parameters were observed for a group of 25 uncharged substituted aromatic compounds and polycyclic aromatic hydrocarbons with SDS and SC micelles. It was found that solutes' size and basicity are the two dominant factors that influence the migration behavior in MEKC.