Effects of ion pairing on the capillary electrophoretic separation and ultraviolet‐absorption detection of quaternary ammonium cations using meso‐octamethylcalix[4]pyrrole as the background electrolyte additive

Five quaternary ammonium cations, including tetramethylammonium, tetraethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, and 1‐butyl‐3‐methylimidazolium, have been separated by capillary electrophoresis. A direct ultraviolet method has been achieved when tetrabutylammonium fluoride was the background electrolyte and meso‐octamethylcalix4]pyrrole was the background electrolyte additive. The ultraviolet spectra of meso‐octamethylcalix4]pyrrole and cation mixtures showed that redshifts can be attributed to the size of cations, and the maximum absorption wavelength shifted from 218 to 230 nm when tetrabutylammonium cation was substituted with tetramethylammonium cation or tetraethylammonium cation. Conductivity measurements were performed to evaluate the ion‐pairing effect of tetrabutylammonium fluoride in a mixture of acetonitrile/ethanol (80:20, v/v), and the ion‐pairing formation constant, K_ip, was calculated (K_ip = 14.8 ± 0.3 L/mol) using the Fuoss extended model. Ion pairing also occurs between cations of the analytes and counterion, a fluoride complex of meso‐octamethylcalix4]pyrrole. The tetramethylammonium cations associate more strongly with this counterion than the tetraethylammonium cation that contributes to the change of selectivity in capillary electrophoresis separation. The effective mobilities of the cations with trimethyl groups, such as tetramethylammonium cation, benzyltrimethylammonium cation, and hexadecyltrimethylammonium cation, decreased faster than others with the increase of meso‐octamethylcalix4]pyrrole concentration, highlighting the fact that the ion‐pairing effect played an important role in this method.