In attempts to improve the selectivity and sensitivity of steroid separation and to determine their migration order, comparison of the use of anionic and cationic surfactants based on the MEKC and sweeping-MEKC modes was made. A mixture of six steroids (progesterone, 17-hydroxy progesterone, 11-deoxycortisol, corticosterone, cortisone, and cortisol) could be separated and detected by means of the CE/UV-absorption method. The order of migration time for these steroids was compared under various conditions, including acidic/alkaline buffers, anionic/cationic surfactants, and positive/negative applied voltage, causing the direction of the EOF and the migration of micelles to change. The major rules for generally predicting the migration order of steroids are summarized. The detection limits were significantly improved when the sweeping-MEKC mode was applied.
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