Effect of different target gases on low-energy collision-activated dissociation of peptides

Experimental variables affecting the daughter-ion spectra of a series of protonated peptides [MH]+, produced by fast-atom bombardment ionization, using a low energy (0-450 eV) quadrupole collision cell are investigated. The parameters studied include target gas pressure, collision energy, cross-sectional area and acidity of the target gas. The results show that low-mass immonium ions are preferentially formed both at high collision energies (greater than 200 eV) and at target gas pressures greater than 10(-6) mBar (where multiple collisions occur in the gas cell). Positive fragment ion abundance is maximized when acidic gases are used as the target gases, and this is rationalized on the basis of a proton-transfer reaction from the target gas to the amide nitrogen of the peptide bond promoting fragmentation.