Energy-dependent kinetic method: Application to the multicompetitive fragmentation pathways of protonated peptides

A variation of the kinetic method for the analysis of fragmentation patterns in mass spectra is proposed. The procedure presents three notable features: no evaluation of the effective temperature of the parent ion is required; the ratio of the activation energies for all competitive channels at play are provided; and the measurement is not biased by the mass discrimination of the instrument. The method is based on the analysis of mass spectra recorded as a function of both the excitation energy and the excitation time. Collision-activated dissociation of protonated Leu-enkephalin achieved in a quadrupolar ion trap and analyzed with this method is presented.