Fragmentation pathways have been studied on the monoanions formed during electrospray ionization of a wide range of aliphatic dicarboxylic acids and their monoesters. All negative ion spectra were obtained from alcoholic or aqueous methanolic solutions without buffers or adjustment of pH, using either a Finnigan LCQ ion trap or a VG-Micromass Quattro triple quadrupole mass spectrometer. Fragmentation pathways were studied using collision-induced dissociation and isotopic-labelling techniques. Two primary fragmentation pathways of the dicarboxylic acid monoanions were observed, namely decarboxylation of the non-ionized carboxyl group and loss of water from this group. The fragmentations were strongly dependent on the chain lengths of the diacids. In the case of a monoester anion, loss of a molecule of alcohol paralleled the loss of water from the diacid monoanion. Losses of water or alcohol were shown to lead to formation of reactive ynolate anions (HOOC(CH2)xC≡CO, x = 39), which in the ion trap spectrometer engaged in complex ion molecule reactions consistent with the chemistry of these anions. For the longer chains (x > 6), the interactions between the ionized and non-ionized carboxyl groups led to readily formed ionneutral complexes, which are described as a neutral molecule (ROH, R = H or alkyl) held by a pair of molecular tweezers.Key words: ESI-MS/MS on negative ions, fragmentation pathways of acyclic carboxylic acid monoanions, ionmolecule reactions in an ion trap mass spectrometer, hydrogendeuterium exchange in a gas-phase anionneutral complex.
