Does deprotonated benzoic acid lose carbon monoxide in collision-induced dissociation?

Decarboxylation is known to be the major fragmentation pathway for the deprotonated carboxylic acids in collision-induced dissociation (CID). However, in the CID mass spectrum of deprotonated benzoic acid ( m/z 121) recorded on a Q-orbitrap mass spectrometer, the dominant peak was found to be m/z 93 instead of the anticipated m/z 77. Based on theoretical calculations, 18 O-isotope labeling and MS 3 experiments, we demonstrated that the fragmentation of benzoate anion begins with decarboxylation, but the initial phenide anion ( m/z 77) can react with trace O 2 in the mass analyzer to produce phenolate anion ( m/z 93) and other oxygen-containing ions. Thus oxygen adducts should be considered when annotating the MS/MS spectra of benzoic acids.