Electron Impact Excitation of Ions from Organics on Singly Protonated Peptides with and without Post-Translational Modifications

J Am Soc Mass Spectrom. 2022 Sep 7;33(9):1723-1732. doi: 10.1021/jasms.2c00146. Epub 2022 Aug 10.

Abstract

We report on the dissociation of singly protonated peptides by electrons using electron-activated dissociation (EAD), which comprises electron impact excitation of ions from organics (EIEIO), electronic-excitation dissociation (EED), and electron ionization dissociation (EIoD). Various singly protonated peptides were dissociated using a recently reported fast EAD device. The dissociation can be induced through two pathways: (i) vibrational dissociation similar to collision-activated dissociation (CAD, or collision-induced dissociation, CID) by relaxation from a molecular electronic excited state to high vibrational states; and (ii) radical-induced dissociation where molecular electronic excitation is followed by homolytic cleavage. EAD is complementary to CAD as additional molecular information can be obtained; e.g., fragile PTM moieties, such as glycosylation and sulfation, can be localized. Simultaneously, the energetic production of radical z fragments enables Leu and Ile discrimination, like in a hot ECD process. Using the fast EAD device, LC-EIEIO-time-of-flight mass spectrometry was applied to a tryptic monoclonal antibody digest containing short singly protonated peptides.

MeSH terms

  • Electrons*
  • Ions / chemistry
  • Mass Spectrometry / methods
  • Peptides* / chemistry
  • Protein Processing, Post-Translational

Substances

  • Ions
  • Peptides