Electrophoretic focusing on an inverse electromigration dispersion profile is a relatively new electrophoretic separation method for the analysis of ionisable analytes. Although it offers alternative selectivity, powerful concentration capability and high sensitivity, so far only several systems for the analysis of anionic compounds were reported. This work describes for the first time a functional electrolyte system for the separation of cationic analytes by this method. Based on computer simulations and calculations, a functional electrolyte system was designed, based on 1-ethylpiperazine and pivalic acid. It is suitable for the analysis of weak bases with pK values between 4.5 and 6 and due to the volatility of both components, it can be operated in combination with ESI-MS detection. Its practical applicability is demonstrated on direct analysis of four 2-hydroxy-s-triazines in waters. Separation in an uncoated capillary with application of negative pressure at the inlet provides very satisfactory results with good reproducibility of peak areas, peak heights and detection times, and with LODs at the 0.5-1 nM (100 ngL) level. The robustness of the method is shown on analyses of real tap and river water samples used without any pretreatment.
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