Tandem time-of-flight mass spectrometer with high precursor ion selectivity employing spiral ion trajectory and...

In this study, we have developed a tandem time-of-flight mass spectrometry (TOF/TOF) technique involving the use of a matrix-assisted laser desorption/ionization ion source that exhibits high precursor ion selectivity. An ion optical system with a 17 m spiral ion trajectory was used in the first time-of-flight mass spectrometer. High precursor ion selectivity was achieved by realizing a 15 m flight path, which is considerably longer than that of the conventional MALDI-TOF/TOF before the precursor ion selection by an ion gate; monoisotopic ions could be selected properly up to m/z 2500. Furthermore, the first time-of-flight mass spectrometer was composed of electrostatic sectors and could eliminate post-source decay (PSD) ions. Precursor ions with 20 keV kinetic energy were selected and injected into a collision cell, leading to the generation of fragment ions by high-energy collision-induced dissociation (HE-CID). The optimized second time-of-flight mass spectrometer included a post-acceleration region and an offset parabolic reflectron to record product ion spectra in the entire mass range. Our system could generate a simple HE-CID product ion spectrum because each fragment pathway could be observed as a single peak by the selection of monoisotopic ions of all precursor ions and HE-CID fragment pathways could be predominantly observed by the PSD ion elimination.