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Mechanisms of repeller‐induced effects in thermospray liquid chromatography/mass spectrometry
Author(s) -
Heeremans C. E. M.,
van der Hoeven R. A. M.,
Niessen W. M. A.,
van der Greef J.,
Nibbering N. M. M.
Publication year - 1991
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210260528
Subject(s) - thermospray , chemistry , mass spectrometry , dissociation (chemistry) , collision induced dissociation , ion , analytical chemistry (journal) , fragmentation (computing) , mass spectrum , tandem mass spectrometry , chromatography , selected reaction monitoring , organic chemistry , computer science , operating system
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.