Parent ion resolution in linked scans for dissociations occurring in the first field-free region of sector mass spectrometers

Abstract

A frequently employed means of studying reactions of ions under high energy collisional activation conditions involves linked scanning a double-focusing mass spectrometer to detect product ions formed in the first field-free region. Experiments have demonstrated that the effective resolution of the parent ion varies during the course of a product ion scan, and this variation is attributed to the kinetic energy released during dissociation. Carefully generated Lacey-Macdonald ion intensity diagrams accurately reflect the dissociation events occurring in various regions of sector mass spectrometers. Consideration of such diagrams leads to an understanding of the noted phenomena and allows the derivation of an expression for the effective parent ion resolution. Furthermore, the approach predicts that parent ion resolution varies during constant neutral loss scans and that the relatively poor resolution (and its variation) can provide particularly misleading data. Results from product ion scans with stable isotope-labeled compounds and constant neutral loss scans with rubidium bromide and stable isotope-labeled peptide derivatives were consistent with the theoretical predictions