Modeling and Characterization of Microfabricated Emitters: In Pursuit of Improved ESI-MS Performance

Abstract

Electrospray ionization (ESI) has been an invaluable technique to mass spectrometry (MS) especially for analyzing large bio-molecules with unparalleled sensitivity, robustness, and simplicity. Great effort in the development of ESI technique has been devoted in the emitter design, as its shape and geometry have proved pivotal to the electrospray performance and further MS detection. Intrinsic problems for the traditional single-hole emitters including clogging and low throughput limit the applicability of the technique. To address this issue, the current project is focused on developing multiple electrospray (MES) emitters for improved ESI-MS analysis. In this thesis, joint work of both computational fluid dynamic (CFD) simulations for electrospray and offline electrospray experiments for spray current measurement were performed. Numerical simulations were used to test the effect of various emitter designs on electrospray performance and the laboratory results serve as a guide and validation. The CFD code was based on Taylor-Melcher leaky dielectric model (LDM) and the transient electrospray process was successfully simulated. The method was first validated via a 750 μm inner diameter (i.d.) emitter and further applied to a 20 μm i.d. model. Different stages of the electrospray process were visually demonstrated and the quantitative investigations for the change of spray current under various applied electric fields and flow rates share good agreement with previous simulations and measurements. Based on the single-aperture prototype, MES simulations were performed with 2-hole and 3-hole emitters. Simulation predictions compared favorably with the experimental results. Evidence from this work has proved that CFD simulation can be used as an effective numerical tool to test emitter designs for MES. The benchmarking result on the successful simulation of a microscale emitter electrospray achieved in this work is believed to be the smallest scale of the dynamic simulation for electrospray published to date.