Analytical and Bioanalytical Chemistry

, Volume 389, Issue 5, pp 1429–1437

Comparison of collision-induced dissociation and electron-induced dissociation of singly protonated aromatic amino acids, cystine and related simple peptides using a hybrid linear ion trap–FT-ICR mass spectrometer

Original Paper


The gas-phase fragmentation reactions of singly protonated aromatic amino acids, their simple peptides as well as simple models for intermolecular disulfide bonds have been examined using a commercially available hybrid linear ion trap–Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Low-energy collision-induced dissociation (CID) reactions within the linear ion trap are compared with electron-induced dissociation (EID) reactions within the FT-ICR cell. Dramatic differences are observed between low-energy CID (which occurs via vibrational excitation) and EID. For example, the aromatic amino acids mainly fragment via competitive losses of NH3 and (H2O+CO) under CID conditions, while side-chain benzyl cations are major fragment ions under EID conditions. EID also appears to be superior in cleaving the S–S and S–C bonds of models of peptides containing an intermolecular disulfide bond. Systematic studies involving fragmentation as a function of electron energy reveal that the fragmentation efficiency for EID occurs at high electron energy (more than 10 eV) compared with the low-electron energy (less than 0.2 eV) typically observed for electron capture dissociation fragmentation. Finally, owing to similarities between the types of fragment ions observed under EID conditions and those previously reported in ultraviolet photodissociation experiments and the electron-ionization mass spectra, we propose that EID results in fragmentation via electronic excitation and vibrational excitation. EID may find applications in analyzing singly charged molecular ions formed by matrix-assisted laser desorption ionization.


Fragmentation of singly protonated aromatic amino acids and peptide models under electron induced dissociation (EID) conditions is observed to yield complementary fragmentation to collision induced dissociation (CID), with abundant product ions are formed from bond cleavages from the sidechain


Fourier transform ion cyclotron resonance mass spectrometer Linear ion trap Collision-induced dissociation Electron-induced dissociation Protonated peptide fragmentation 

Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  1. 1.School of ChemistryUniversity of MelbourneMelbourneAustralia
  2. 2.Bio21 Institute of Molecular Science and BiotechnologyThe University of MelbourneMelbourneAustralia
  3. 3.ARC Centre of Excellence in Free Radical Chemistry and BiotechnologyMelbourneAustralia

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