Ambient ion/molecule reactions in low-temperature plasmas (LTP): reactive LTP mass spectrometry

RATIONALE Ion/molecule reactions are commonly used to characterize structures due to their high specificity. Herein, we present ambient ion/molecule reactions performed in the course of low-temperature plasma (LTP) ionization of condensed-phase analytes in order to increase the specificity of LTP-based ambient analysis. METHODS The ion population of the cold plasma is modified by addition of a reagent to the plasma before it is directed at a surface bearing the analyte. Desorbed ions were analyzed using linear ion trap-Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). RESULTS Acylium ions generated from tetramethylurea react with 1,3-dioxane analyte to afford distinctive Eberlin product ions. Reactions of alkylamines, such as n-hexylamine and n-octylamine, with benzaldehyde produce the corresponding imines. Reaction of ruthenocene with trifluoroacetic anhydride forms the unusual trifluoroacetate ruthenocene. CONCLUSIONS A LTP source can be used to generate reagent ions that can undergo ion/molecule reactions in the ambient environment with an analyte at condensed phase on a surface. The experiment is a 'reactive' version of the standard low-temperature plasma (LTP) ambient ionization experiment. This approach provides additional information by combining ion/molecule chemistry with conventional MS and MS/MS data to characterize particular analytes. Copyright (c) 2013 John Wiley & Sons, Ltd.