Tailored-waveform collisional activation of peptide ion electron transfer survivor ions in cation transmission mode ion/ion reaction experiments

摘要

Broadband resonance excitation via a tailored waveform in a high pressure collision cell (Q2) onna hybrid quadrupole/time-of-flight (QqTOF) tandem mass spectrometer has been implemented forncation transmission mode electron transfer ion/ion reactions of tryptic polypeptides. The frequencyncomponents in the broadband waveform were defined to excite the first generation intact electronntransfer products for relatively large tryptic peptides. The optimum amplitude of the arbitrarynwaveform applied has been determined empirically to be 3.0 Vp-p, which is effective for relatively highnmass-to-charge (m/z) ratio precursor ions with little elimination of sequence information for low m/znions. The application of broadband activation during the transmission mode ion/ion reaction obviatesnfrequency and amplitude tuning normally associated with ion trap collision induced dissociation (CID).nThis approach has been demonstrated with triply and doubly charged tryptic peptides with and withoutnpost-translational modifications. Enhanced structural information was achieved by production ofna larger number of informative c- and z-type fragments using the tailored waveform on unmodified andnmodified (phosphorylated and glycosylated) peptides when the first generation intact electron transfernproducts fell into the defined frequency range. This approach can be applied to a wide range of trypticnpeptide ions, making it attractive as a rapid and general approach for ETD LC-MS/MS of trypticnpeptides in a QqTOF instrument.