Negative ion electrospray ionization mass spectral study of dicarboxylic acids in the presence of halide ions

The negative ion electrospray ionization (ESI) mass spectra of a series of dicarboxylic acids, a pair of isomeric (cis/trans) dicarboxylic acids and two pairs of isomeric (positional) substituted benzoic acids, including a pair of hydroxybenzoic acids, were recorded in the presence of halide ions (F-, Cl-, Br- and I-). The ESI mass spectra contained [M-H](-) and [M+X](-) ions, and formation of these ions is found to be characteristic of both the analyte and the halide ion used. The analytes showed a greater tendency to form adduct ions with Cl- under ESI conditions compared with the other halide ions used. The isomeric compounds yielded distinct spectra by which the isomers could be easily distinguished. The collision-induced dissociation mass spectra of [M+X](-) ions reflected the gas-phase basicities of both the halide ion and [M-H](-) ion of the analyte. However, the relative ordering of gas-phase basicities of all analyte [M-H](-) and halide ions could not account for the dominance of chloride ion adducts in ESI mass spectra of the analytes mixed with equimolar quantities of the four halides. Copyright (C) 2004 John Wiley Sons, Ltd.