Capillary zone electrophoresis of some extremely weak bases in acetonitrile

In water capillary zone electrophoresis cannot be used to investigate basic compounds, which are so weak that their pK(a,HB+) values are less than zero. In acetonitrile the basic strength of such compounds is increased by many orders of magnitude. Accordingly, several extremely weak bases are protonated at low pH in acetonitrile, thus, allowing their investigation by CZE. In this work the CZE separation of thioacetamide, acetamide, thiourea, benzamide, and 4-nitrobenzamide as well as that of N-methylformamide, N,N-dimethylformamide, formamide, and dimethyl sulfoxide is demonstrated in acetonitrile using 10 mmol/L perchloric acid as an electrolyte. The effect of BGE additives, like water and acetic acid, on the CZE performance is discussed. The problem of finding a suitable electroosmotic flow marker at low pH in acetonitrile is addressed, and nitromethane is shown to be a proper marker compound under such extreme conditions. This work demonstrates how organic solvents can enlarge the field of application of CZE.