Authors: Ioan Marginean Keqi Tang Richard D Smith Ryan T Kelly
Publish Date: 2013/10/12
Volume: 25, Issue: 1, Pages: 30-36
Abstract
Electrospray ionization mass spectrometry ESIMS at flow rates below ~10 nL/min has been only sporadically explored because of difficulty in reproducibly fabricating emitters that can operate at lower flow rates Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min Depending on the analyte concentration we observe two types of MS signal response as a function of flow rate At low concentrations an optimum flow rate is observed slightly above 1 nL/min whereas the signal decreases monotonically with decreasing flow rates at higher concentrations For example consumption of 500 zmol of sample yielded signaltonoise ratios ~10 for some peptides In spite of lower MS signal the ion utilization efficiency increases exponentially with decreasing flow rate in all cases Significant variations in ionization efficiency were observed within this flow rate range for an equimolar mixture of peptide indicating that ionization efficiency is an analytedependent characteristic for the present experimental conditions Masslimited samples benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution These findings have important implications for the analysis of trace biological samplesThe authors thank William F Danielson for writing the syringe pump control software and Sarah Rausch Allison Sheen and Levi Broeske for assistance with data processing This research was supported by the William R Wiley Environmental Molecular Sciences Laboratory EMSL intramural program and grants from National Institutes of Health the National Institute of General Medical Sciences grant 8 P41 GM10349310 and the National Cancer Institute 1R33CA155252 The EMSL is a national scientific user facility sponsored by US DOE’s Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory PNNL in Richland WA PNNL is a multiprogram national laboratory operated by Battelle for the DOE under contract no DEAC0576RLO 1830
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