Mechanisms of repeller-induced effects in thermospray liquid chromatography/mass spectrometry

The application of a high potential at the repeller electrode, positioned opposite to the sampling cone in order to increase the sampling efficiency, can induce fragmentation in thermospray mass Spectrometry. Until now, this fragmentation has been attributed to collision‐induced dissociation. As a result of studies on the changes in the reagent gas composition in the thermospray buffer ionization mode as a function of the repeller potential in the positive‐ion mode, it appears that three different processes are occurring. At low repeller potentials, the thermospray mass spectra of the eluent are determined by the proton affinities and the concentrations of the various solvent constituents, and the stabilities of the formed cluster ions under the ion source conditions. With an increase in the repeller potential, collision‐induced dissociation of the background ions starts to occur. When the kinetic energy of the ions and cluster ions becomes high enough, endothermic proton transfer and solvent‐switching reaction pathways are opened. For the relatively volatile analytes studied, e.g. aniline, acetophenone, benzaldehyde and benzoic acid, similar effects are observed.