PNNL

Abstract

We provide a thorough characterization of the low-flow electrospray as an ionization source for mass spectrometry (MS) using solutions typical for reversed-phase liquid chromatography. As expected, the electrospray operating regime strongly affects the MS signal; however, contrary to conventional wisdom, the pulsating regime consistently offers better performance than the cone-jet regime in these experimental conditions. We explain this observation by a highly efficient ionization achieved by the pulsating electrospray at low flow rates, rendering the increased charge generated by a cone-jet electrospray detrimental for transmission from atmospheric pressure to vacuum through a heated capillary interface. Over a wide range of voltages, the pulsating electrospray provides a relatively constant MS signal intensity, which depends significantly on the distance between the emitter and the MS inlet. For cone-jet electrosprays the MS signal decreases slightly with increasing voltage, but the signal is less affected by the emitter-inlet distance. At flow rates up to 100 nL/min the MS signal increases with increasing flow rate due to the larger number of ions supplied into the gas phase. At flow rates greater than 100 nL/min, the signal reaches a plateau due to increasingly unsatisfactory ionization efficiency at larger flow rates.