Photon-induced dissociation with a four-sector tandem mass spectrometer

The feasibility of using photodissociation of protonated peptide molecules to sequence specific fragment ions with a 193-nm pulsed laser beam in a magnetic deflection tandem mass spectrometer of EBEB configuration was demonstrated. Although the short pulse (15 ns) and low repetition rate (100 Hz) of the excimer laser permitted the irradiation of only ～ 0.02% of the (M + H)⁺ ions exiting MS-1, a photon-induced decomposition spectrum of the heptapeptide angiotensio III (M _r 930.5) was produced that was practically the same (but with better signal-to-noise ratio) as that generated by collision-activated dissociation at the same low duty cycle. Because of the low and pulsed fragment ion currents, an array detector was used to record the spectra. A dependence between laser power and abundance of fragment ions was observed (increased power increases the relative abundance of ions of low mass). Laser power was varied from 6 to 80 mJ. Formation of fragment ions from a large peptide (melittin, M, 2844.75) was also observed. The results permit the design of modifications that may increase the fragment ion yield to 10% or higher, which would make photon-induced decomposition a useful method for magnetic deflection mass spectrometers.