Practical Effects of Intramolecular Hydrogen Rearrangement in Electron Transfer Dissociation-Based Proteomics.
In: Journal of the American Society for Mass Spectrometry, Jg. 33 (2022-01-05), Heft 1, S. 100-110
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Zugriff:
Ion-ion reactions are valuable tools in mass-spectrometry-based peptide and protein sequencing. To boost the generation of sequence-informative fragment ions from low charge-density precursors, supplemental activation methods, via vibrational and photoactivation, have become widely adopted. However, long-lived radical peptide cations undergo intramolecular hydrogen atom transfer from c-type ions to z • -type ions. Here we investigate the degree of hydrogen transfer for thousands of unique peptide cations where electron transfer dissociation (ETD) was performed and was followed by beam-type collisional activation (EThcD), resonant collisional activation (ETcaD), or concurrent infrared photoirradiation (AI-ETD). We report on the precursor charge density and the local amino acid environment surrounding bond cleavage to illustrate the effects of intramolecular hydrogen atom transfer for various precursor ions. Over 30% of fragments from EThcD spectra comprise distorted isotopic distributions, whereas over 20% of fragments from ETcaD have distorted distributions and less than 15% of fragments derived from ETD and AI-ETD reveal distorted isotopic distributions. Both ETcaD and EThcD give a relatively high degree of hydrogen migration, especially when D, G, N, S, and T residues were directly C-terminal to the cleavage site. Whereas all postactivation methods boost the number of c- and z • -type fragment ions detected, the collision-based approaches produce higher rates of hydrogen migration, yielding fewer spectral identifications when only c- and z • -type ions are considered. Understanding hydrogen rearrangement between c- and z • -type ions will facilitate better spectral interpretation.
Titel: |
Practical Effects of Intramolecular Hydrogen Rearrangement in Electron Transfer Dissociation-Based Proteomics.
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Autor/in / Beteiligte Person: | Peters-Clarke, TM ; Riley, NM ; Westphall, MS ; Coon, JJ |
Zeitschrift: | Journal of the American Society for Mass Spectrometry, Jg. 33 (2022-01-05), Heft 1, S. 100-110 |
Veröffentlichung: | 2020- : Washington, DC : ACS Publications ; <i>Original Publication</i>: New York, NY : Elsevier, c1990-, 2022 |
Medientyp: | academicJournal |
ISSN: | 1879-1123 (electronic) |
DOI: | 10.1021/jasms.1c00284 |
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