Optimization of Reflectron for Kinetic and Mechanistic Studies with Multiplexed Multiple Tandem (MSn) Time-of-flight Mass Spectrometry

Photoexcitation of a precursor ion inside a cell floated at high voltage installed in a tandem, time-or-flight (TOF) mass spectrometer provides triple tandem mass spectrometric information and allows kinetic and mechanistic Studies. IN this work, the factors affecting, or downgrading, the performance of the technique were identified. Ion-optical and computational analyses showed that all optimum Instrument could be designed by utilizing a reflectron with linear-plus-quadratic potential inside. Theoretical predictions were confirmed by tests with instruments built with different ion-optical layout. With optimized instruments,, masses of intermediate ions in the consecutive dissociation of a precursor ion Could be determined with the maximum error of 5 Da. We also observed excellent agreement in dynamical parameters (critical energy and entropy) Cur the dissociation of a model peptide ion determined by instruments with different ion-optical layout operated under optimum conditions. This suggests that these parameters call be determined reliably by the kinetic method developed previously When properly designed and operated tandem TOF instruments are used.