High-energy collision-induced dissociation of histidine ions [His + H]+ and [His - H]- and histidine dimer [His2 + H]

Abstract

Rationale: Histidine (His) is an essential amino acid, whose side group consists of an aromatic imidazole moiety that can bind a proton or metal cation and act as a donor in intermolecular interactions in many biological processes. While the dissociation of His monomer ions is well known, information on the kinetic energy released in the dissociation is missing.

Methods: Using a new home-built electrospray ionization (ESI) source adapted to a double-focusing mass spectrometer of BE geometry, we investigated the fragmentation reactions of protonated and deprotonated His, [His + H]⁺ and [His - H]^- , and the protonated His dimer [His₂ + H]⁺ , accelerated to 6 keV in a high-energy collision with helium gas. We evaluated the kinetic energy release (KER) for the observed dissociation channels.

Results: ESI of His solution in positive mode led to the formation of His clusters [His_n + H]⁺ , n = 1-6, with notably enhanced stability of the tetramer. [His + H]⁺ dissociates predominantly by loss of (H₂ O + CO) with a KER of 278 meV, while the dominant dissociation channel of [His - H]^- involves loss of NH₃ with a high KER of 769 meV. Dissociation of [His₂ + H]⁺ is dominated by loss of the monomer but smaller losses are also observed.

Conclusions: The KER for HCOOH loss from both [His + H]⁺ and [His - H]^- is similar at 278 and 249 meV, respectively, which suggests that the collision-induced dissociation takes place via a similar mechanism. The loss of COOH and C₂ H₅ NO₂ from the dimer suggests that the dimer of His binds through a shared proton between the imidazole moieties.