Fragmentation reactions of protonated α,ω-diamino carboxylic acids: The importance of functional group interactions

Protonated members of a homologous series of biologically significant α,ω-diamino carboxylic acids were subjected to collision induced dissociation (CID). The resulting fragmentation patterns were studied using isotopic labeling, quantum mechanical computations, and pseudo MS³ experiments conducted primarily on an ion trap mass spectrometer. Each protonated α,ω-diamino acid showed a primary neutral loss of either ammonia or water; a clear explanation was developed for the observed variation of the two losses within the series. Protonated 2,3-diaminopropanoic acid, 2,4-diaminobutanoic acid, and 2,7-diaminoheptanoic acid gave secondary losses of water, carbon monoxide, and a loss of water plus carbon monoxide, respectively. In the parallel pathways characterized for the fragmentations of protonated ornithine and lysine, the α-nitrogen of the diamino acid was maintained in the cyclic iminium product formed by successive losses of NH₃ and (H₂ O + CO), whereas the side-chain nitrogen was retained by consecutive losses of H₂ O and (CO, NH₃ ). The 1-piperideine ion from protonated lysine was fragmented further, losing ethylene from carbons 4 and 5. Protonated 2,6-diaminopimelic acid fragmented by analogous reactions. Detailed mechanistic schemes for the fragmentation of both protonated 2,3-diaminopropanoic and ornithine were generated from MP2/DFT computations. This work highlights the participation of the side-chain amino group, which distinguishes the gas-phase chemistry of protonated α,ω-diamino acids from the well-documented fragmentation reactions of protonated α-amino acids bearing a hydrogen atom or an alkyl side chain. In general, the results further illustrate the importance of intramolecular separations affecting the specific interactions between functional groups leading to the fragmentation of multifunctional ions.