Development and Application of Non-Tapered Electrospray Emitters for Nano-ESI Mass Spectrometry

Abstract

Nano-ESI mass spectrometry is an attractive analytical technique due to its high sensitivity and small sample consumption, which is especially important for research areas such as proteomics. However, current nano-ESI emitters become a bottleneck for nano-ESI to be widely applied because of problems such as clogging, poor robustness, large flow resistance, and poor spray efficiency for highly aqueous solutions. The objective of this thesis study is to address the problems associated with tapered emitters and provide alternative solutions by developing advanced nano-ESI emitters. Two strategies that were explored to improve the clogging resistance and robustness while maintaining comparable electrospray performances include the development of emitters with larger apertures and multiple channels. Following these strategies, five types of emitters were fabricated without tapering either internal or external diameters, which include a roughened open tubular emitter, a porous membrane-assisted emitter, a microstructured multiple channel photonic crystal fiber (MSF) emitter, a packed ODS bead emitter, and an entrapped ODS bead emitter. The successful transformation of MSF fibers to nanoelectrospray emitters demonstrates a new practical approach to expand the application of nano-ESI because of its availability, compatibility, precisely controlled channel dimensions, variety of channel patterns, and feasibility for surface modification. The fundamental mechanism of non-tapered emitters was studied at nano flow rates. The fact that a plume of mist, instead of single Taylor cone, is generated from multiple channel emitters at nano flow rates suggests multiple Taylor cones may be formed. The calculated sensitivity gains from a MSF emitter compared to a single-tip tapered emitter are related to the number of the orifices containing on a MSF emitter. The characterization of impacts of operational parameters on nanoelectrospray performances shows that non-tapered emitters are more robust and less dependent on the emitter’s fine positioning. It was also found that unlike tapered emitters, non-tapered emitters can be positioned ten times further from the orifice of a mass spectrometer, which is greatly beneficial to online sample manipulation and purification. Furthermore, the electrospray efficiency of spraying highly aqueous solutions (e.g. 90%) was greatly improved through the hydrophobic modification of a MSF emitter exit.