Versatile derivatization for GC-MS and LC-MS: alkylation with trialkyloxonium tetrafluoroborates for inorganic anions, chemical warfare agent degradation products, organic acids, and proteomic analysis.

Analytical chemists resort to derivatization for improving the detection performance of certain categories of analytes. Within this context, alkylation reactions are regarded as an important asset for many methods based on GC-MS and LC-MS. Trialkyloxonium tetrafluoroborates (R[Formula: see text][BF4]-) are powerful alkylating agents with ionic liquid properties: they are nonvolatile salts soluble in water which are easier and safer to handle with respect to common alkylating agents like diazomethane. R[Formula: see text][BF4]- can perform the alkylation in both organic and aqueous media at pH conditions ranging from acidic to alkaline. Recent analytical applications of trialkyloxonium derivatizations include the high-precision determination of inorganic anions in complex matrices, the qualitative confirmation of chemical warfare agent degradation products in soils, the profiling of carboxylic acids in urine, and the detection of protein post-translational modifications induced by carbon dioxide. The common denominator for all methods presented can be found in the simplicity of the alkylation protocol which, in most of the cases, requires a single step addition of the reagent directly to the sample. Graphical Abstract Alkylation with trialkyloxonium salts for GC-MS and LC-MS analysis.