Control of relative migration of small inorganic and organic anions with cyclodextrins in capillary electrophoresis (CE)

The capillary electrophoretic separation of iodide, nitrate, perchlorate, thiocyanate, bromate, iodate, and ethane-, butane-, pentane-, and octanesulphonate was examined in sodium chromate or potassium hydrogen phthalate electrolytes and in the presence of alpha-, gamma-, (0-40 mmol/L) and beta-cyclodextrin (0-10 mmol/L). Largest decreases in electrophoretic mobility were observed for iodide, perchlorate, and thiocyanate, probably due to inclusion of these anions in the cyclodextrin (CD) cavity. Changes in migration patterns and electroosmotic flow were observed, which depended on cyclodextrin type and concentration and on electrolyte-cyclodextrin interactions. Thus for larger cavity cyclodextrins (beta- or gamma-cyclodextrin) or in the presence of chromate, relatively small decreases in electrophoretic mobilities for all the anions were observed? indicating that a good match between analyte and cavity size and minimal cyclodextrin affinity for electrolyte ions are essential for different migration patterns. Separation efficiencies were between 50 000 and 400 000 theoretical plates, and calibration plots for iodide and octanesulphonate were linear; R-2 = 0.998 and 0.9999, respectively, in the concentration range (5 x 10(-5))-(5 x 10(-3)) mol/L.