Influence of polarity mode switching and standby times on signal stability and detection of aspirated droplet signatures in electrospray mass spectrometry

Abstract

Electrospray ionization plays a central role in modern analytical chemistry. It is often used in combination with an HPLC system and is able to transfer large molecules, such as proteins and complexes, into the gas phase. A liquid solution containing the analyte is sprayed in a strong electric field. Charged droplets generated by this process release the analyte molecules which can ultimately be analyzed by the mass spectrometer system. However, the exact mechanisms of droplet generation and ion release are still not fully understood and are under investigation. Recent literature puts the focus on droplet disintegration and shows that the analyte ions are not exclusively released from the droplets within the ionization chamber but rather in the whole mass spectrometer system. Previous experiments allow the direct observation of the signatures of fragmented droplets within the analyzer region of a time-of-flight mass spectrometer: An oscilloscope was connected to a secondary electron multiplier which serves as an auxiliary ion detector, located downstream of the orthogonal acceleration stage of a time-of-flight mass spectrometer. The oscilloscope is thus able to monitor the time-resolved ion current in the mass analyzer region. Pulses of extraordinarily high ion currents are observable here which are attributed to aspirated charged droplets.

This work provides insights into long-term experiments with this experimental setup. There is a focus on signal stability, in the presence of such droplet signatures. It is apparent that the standby time of the instrument between individual measurements and the time since a switch of the polarity mode, has a significant influence on the signal stability. There are also indications that the observations of droplet signatures and the MS signal stability are correlated.