Straight nano-electrospray ionization and its coupling of mobility capillary electrophoresis to mass spectrometry

Abstract Mobility capillary electrophoresis (MCE) was developed previously in our group, which has the capabilities of ion separation and biomolecule hydrodynamic radius analysis. The coupling of MCE with mass spectrometry (MS) would greatly improve complex sample identification capability as well as system detection sensitivity. In the present study, a simple and robust ionization source, named as straight nano-electrospray ionization (nanoESI) source was developed, which was applied to couple MCE with MS. A stainless-steel needle attached directly at the end of an MCE capillary was used as the nanoESI emitter, and the connection between this emitter to the liquid flow in the MCE separation channel was established through a liquid bridge. After optimization, this straight nanoESI source enhanced the ion signal intensity by ∼10 times when compared with a commercial nanoESI source. The MCE-straight nanoESI-MS system was also characterized in terms of mixture separation and peptide hydrodynamic radius measurements. Compared to our previous work when a UV detector was used in a commercial Lumex CE system (model Capel 105 M, St. Petersburg, Russia), peptides with much lower concentrations could be analyzed (from ∼1 mg/mL to ∼20 μg/mL) in terms of radius measurement.