Cetyltrimethylammonium chloride as a surfactant buffer additive for reversed-polarity capillary electrophoresis-electrospray mass spectrometry.

The rapid analysis of picomole quantities of various cationic molecules (laser dyes, tripeptides and larger bioactive peptides) has been achieved by on-line capillary electrophoresis-electrospray mass spectrometry (CE-ES-MS). Use of the cationic surfactant, cetyltrimethylammonium chloride (CTAC) in the CE buffer greatly facilitated the analyses. Under reversed-polarity conditions (negative potential at the source vial), CTAC induces electroosmotic flow towards the mass spectrometer, presumably due to the creation of a cationic layer on the inner surface of the fused-silica capillaries. CTAC diminishes analyte-capillary wall interactions, allowing efficient separations and symmetrical peak shapes. It may be used over a wide range of pH values without loss of electroosmotic flow. Added selectivity, provided by the surfactant properties of CTAC, played a critical role in resolving closely related tripeptides as well as larger (five to thirteen amino acid units) peptides. Above the critical micelle concentration of CTAC, interactions with the pseudostationary micellar phase increased selectivity even for ionic analytes.