Formation of Alternating Surfactant-Enriched and Surfactant-Depleted Phases in the Taylor Cone of a Nanoelectrospray.

The electrospray ionization of highly conductive solutions containing Triton X-100, a nonionic surfactant, is found to induce alternating periods of surfactant enrichment and depletion when the concentration of the surfactant is near the critical micelle concentration (CMC) and when the flow rate is on the order of 10 nL/min. Analyzing the surfactant-protein mixture shows that the protein is partially denatured during the surfactant enrichment. The measurement of the phospholipid and oligosaccharide mixture prepared in the surfactant solution shows that the ion signal of the lipid is in phase with, and the hydrophilic oligosaccharide is out of phase with the surfactant signal. The results suggest that this novel phenomenon can be exploited for in situ separation of compounds in ESI-MS. Besides the ion signal, the condition of the alternating phase is also reflected in the spray current and Taylor cone's apex angle. The phase separation is likely related to the formation of a micelle in the Taylor cone and can be selectively triggered by tuning the flow rate with emitter voltage for an on-demand application.