Two
experiments are described that extend the capabilities of quadrupole
ion trap mass spectrometers operated in the precursor and neutral
loss scan mode. The first experiment, a triple resonance precursor
ion scan, is used to enhance sensitivity, selectivity, and molecular
coverage. This method augments the ion trap precursor ion scan with
the application of a second excitation frequency to selectively activate
first-generation (MS2) product ions as they are formed
and produce second-generation (MS3) product ions, which
are then mass-selectively ejected with a third auxiliary signal and
detected. This single mass analyzer experiment can be equated to performing
the sequential precursor ion scan in a multiple analyzer system (Anal. Chem. 1990, 62 (17), 1809–1818).
The second capability demonstrated is “frequency tagging”,
a method used to differentiate between ions ejected due to inherent
instability under given trapping conditions, which causes artifacts
during these scans, and ions that are resonantly ejected by the product
ion ejection frequency. Beat frequencies are used to modulate resonance
ejection peaks but conveniently do not modulate boundary ejection
peaks. Frequency tagging provides a mechanism to identify the artifact
peaks that are a consequence of operating at a high trapping voltage
(i.e., low mass cutoff) for optimal precursor/product ion selectivity.
The experiment is demonstrated for precursor and for neutral loss
scans.