Investigation of electrospray for a capillary electrophoresis-mass spectrometry interface in reverse polarity and negative ion mode.

Capillary zone electrophoresis (CZE) paired with mass spectrometry (MS) is a powerful analytical technique for examining mixtures of ionic analytes such as glycosaminoglycans. This study examines the mechanics of the electrospray process for a sheath flow CZE-MS interface under reverse polarity negative ionization conditions. Liquid flow in a sheath flow nano-electrospray CZE-MS interface is driven by two mechanisms, electroosmotic flow and electrospray nebulization. The contribution of these two processes to the overall flow of solution to the electrospray tip is influenced by the surface coatings of the sheath flow emitter tip and by the solvent composition. We have investigated the application of this interface to the reverse polarity separation of glycosaminoglycans and find that the role of electroosmotic flow is far less than has been reported previously, and the electrospray process itself is the largest contributor to the flow of the sheath liquid.