Effects of organic modifiers on solute retention and electrokinetic migrations in micellar electrokinetic capillary chromatography

Influences of seven organic modifiers, including urea, methanol (MeOH), dioxane (DIO), tetrahydrofuran (THF), acetonitrile (ACN), 1-propanol (1-PrOH) and 2-propanol (2-PrOH), on the solute retention and the electrokinetic migrations in micellar electrokinetic capillary chromatography (MEKC) are investigated with sodium dodecyl sulfate (SDS) micelle as pseudostationary phase. It is observed that in the limited concentration ranges used in the MEKC systems the effect of organic modifier concentration on the retention can be described by the equation logk'=logk'(w)-SC for most binary aqueous-organic buffer, but deviations from this retention equation are observed at ACN and particularly THF as organic modifiers. With parameter S as a measure of the elutropic strength, the elutropic strength of the organic modifiers is found to follow a general order urea <MeOH<ACN<2-PrOH<DIO, while THF is found to be the most abundant modifier in selectivity among the organic modifiers studied. The electroosmotic mobility decreases linearly with increasing modifier concentrations. The strength of modifiers to suppress the electroosmotic mobility follows the order urea < MeOH, ACN < DIO, THF, 1-PrOH, 2-PrOH. The addition of ACN affects the electrophoretic mobility of the SDS micelle in different patterns depending on the buffer composition used, while the addition of the other modifiers leads to a rough linear decrease of the electrophoretic mobility of the SDS micelle. The suppressing strength of THF on the electrophoretic mobility of the SDS micelle is strongly related to the buffer composition, whereas the suppressing strength for the other modifiers follows the sequence urea < MeOH < DIO, 1-PrOH, 2-PrOH. The migration time window is expanded by the use of organic modifiers. Urea and MeOH have the least expanding strength while ACN, DIO, THF, 1-PrOH and 2-PrOH have the highest expanding strength on the migration time window.