Studying Charge Migration Fragmentation of Sodiated Precursor Ions in Collision-Induced Dissociation at the Library Scale

J Am Soc Mass Spectrom. 2021 Jan 6;32(1):180-186. doi: 10.1021/jasms.0c00240. Epub 2020 Nov 13.


Interpretation of fragmentation mass spectra depends on our knowledge of collision-induced dissociation mechanisms. Computational methods for the annotation of fragmentation mechanisms operate within the boundaries of recognized fragmentation pathways. The prevalence of charge migration fragmentation (CMF) in sodiated ion fragmentation spectra, which produces nonsodiated fragment ions, is unknown. Here, we investigated the extent of CMF in the fragmentation spectra of sodiated precursors by mining the NIST17 spectral library using a diagnostic mass difference. Our results showed that a substantial amount of fragment ions in sodiated precursor spectra are derived from CMF, indicating that this fragmentation mechanism should be commonly considered by computational methods for compound annotation.

Keywords: Collision-Induced Dissociation; Fragmentation Mechanism; Library-Wide Fragmentation Mining; Tandem Mass Spectrometry.