A neutral marker of the EOF can gain a nonzero effective mobility because of its possible interaction with a charged complexing agent, such as a chiral selector in CE. We determined effective mobilities of four compounds often used as EOF markers (dimethyl sulfoxide, mesityl oxide, nitromethane, and thiourea) in the BGE-containing sulfated β-CD (60 g/L). All the compounds studied were measurably mobilized by their interaction with the selector. The highest effective mobility (-3.0·10(-9) m(2) s(-1) V(-1)) was observed for thiourea and the lowest (-1.5·10(-9) m(2) s(-1) V(-1)) for dimethyl sulfoxide and nitromethane. The mobilities were determined by a new two-detector pressure mobilization method (2d method), which we propose, and the results were confirmed by standard CE measurements. In the 2d method, one marker zone is situated in the BGE containing the charged selector, while the second marker zone is surrounded with a selector-free BGE, which prevents its complexation. The initial distance between the two marker zones equals the capillary length from the inlet to the first detector. After a brief voltage application, the final distance between the marker zones is determined based on known capillary length from the first to the second detector. The difference between these two distances determines the effective mobility.

Faculty of Science Department of Physical and Macromolecular Chemistry Charles University Prague Prague Czech Republic

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