Collision-induced isomerization in tandem mass spectrometry

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Collision-induced dissociation (CID) is widely available method for obtaining structural information with tandem mass spectrometry (MS2). Multiple-collision conditions under low-energy regime are the most commonly used experimental setup and implemented most of the modern tandem mass spectrometers. It's an easy and sensitive method, however, low-energy CID give rather limited structural information; MS2 spectral patterns tend to become rather simple for small molecules and spectral patterns of isomers may become indistinguishable as viable fragmentation pathways are rather limited. Such isomers could be differentiated by using our energy-resolved (ER) MS2 strategy as breakdown diagrams are sensitive to the changes in energetics of fragmentation chemistry caused by subtle structural differences between each isomers. In addition to the change in energetics, isomerization process of precursor ions may be hidden in the CID process. For example, a computer modeling study on CID process of ortho- and para-isomers of coumaric acid, which show common CO2 loss, suggested that fragmentation of para-isomer involves isomerization of [M-H]- to a key intermediate for the CO2 loss. The proposed fragmentation mechanism including the isomerization process was supported by the energetics, which was consistent to the data obtained by ER-MS2 experiments.