Does decarboxylation make 2,5-dihydroxybenzoic acid special in matrix-assisted laser desorption/ionization?

RATIONALE Among the six positional isomers of dihydroxybenzoic acid (DHB), 2,5-DHB is a more favorable matrix for use in matrix-assisted laser desorption/ionization (MALDI) than the other isomers because of its high ion-generation efficiency at 337 and 355 nm. The generation of hydroquinone or p-benzoquinone through the decarboxylation of 2,5-DHB has been suggested to play a crucial role in the ion-generation efficiency of 2,5-DHB. METHODS The mass spectra of desorbed neutrals generated from MALDI were measured using electron impact ionization (70 eV) and a quadrupole mass spectrometer and vacuum ultraviolet (118 nm) photoionization and a time-of-flight mass spectrometer. The mass spectra of desorbed ions generated from MALDI were investigated using a time-of-flight mass spectrometer. The dissociation barrier height and dissociation rate of decarboxylation were calculated by an ab initio method and RRKM theory. RESULTS Decarboxylation of neutral 2,5-DHB and 2,5-DHB cations was not observed. Theoretical calculations indicated that decarboxylation of neutral 2,5-DHB and 2,5-DHB cations is too slow to occur. CONCLUSIONS The high ion-generation efficiency of the 2,5-DHB matrix at 337 and 355 nm is not related to decarboxylation. Copyright (c) 2014 John Wiley & Sons, Ltd.