Abstract
Early in the development of electrohydrodynamic mass spectrometry (EH‐MS), it was realized that ion source performance improved when the sample liquid was supplied discontinuously to the capillary emitter. Based on this realization, an ion source was designed that operates without an external sample supply system. Its essential part is a metal capillary that serves both as the liquid reservoir and the field anode and is mounted exchangeably on a pushrod. As the liquid flow is field induced, the flow rates are extremely low, in the range of 0.2 nl min^−1^. Thus, in spite of high analyte concentrations needed, sample consumption is only a few picomoles per mass scan. Moreover, the emission of larger droplets is avoided, which contributes to the stability of the ion signal. As the capillary emitter is mounted on a standard emitter carrier known from field desorption (FD) MS, the new ion source is compatible with conventional FD ion sources. EH mass spectra of analytes could be obtained from substances whose solubility in glycerol was>0.5 mol l^−1^. The substances investigated with the new ion source include sugars, amino acids, peptides and an antibiotic. The general characteristics of the mass spectra are essentially the same as those known from other EH ion sources. Besides abundant solvent cluster ions, only cationated or protonated molecules of the analytes could be detected, frequently with one or more solvent molecules attached to the ions. Fragment ions were not observed.