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Peptide dissociation patterns in secondary ion mass spectrometry under large argon cluster ion bombardment
Author(s) -
Gnaser Hubert,
Fujii Makiko,
Nakagawa Shunichirou,
Seki Toshio,
Aoki Takaaki,
Matsuo Jiro
Publication year - 2013
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.6599
Subject(s) - chemistry , ion , fragmentation (computing) , cluster (spacecraft) , mass spectrometry , mass spectrum , dissociation (chemistry) , protonation , collision induced dissociation , analytical chemistry (journal) , tandem mass spectrometry , peptide , secondary ion mass spectrometry , crystallography , chromatography , organic chemistry , computer science , programming language , operating system , biochemistry
RATIONALE The analysis of organic and biological substances by secondary ion mass spectrometry (SIMS) has greatly benefited from the use of cluster ions as primary bombarding species. Thereby, depth profiling and three‐dimensional (3D) imaging of such systems became feasible. Large Ar n + cluster ions may constitute a further improvement in this direction. METHODS To explore this option, large Ar n + cluster ions (with n ~1500 Ar atoms per cluster) were used to investigate the emission of positive secondary ions from two peptide specimens (angiotensin I and bradykinin) by orthogonal time‐of‐flight SIMS using bombarding energies 6, 10 and 14 keV. RESULTS For both peptides, the protonated molecular ion is observed in the mass spectra. In addition, distinct fragmentation patterns were observed; these indicate that fragment ions under Ar cluster irradiation form primarily via cleavage of bonds along the peptide backbone whereas the rapture of side chains occurs much less frequently. These features appear to be similar to low‐energy collision‐induced dissociation pathways. CONCLUSIONS Tentatively, these findings can then be ascribed to the concerted action of the large number of Ar atoms in the impact zone of cluster at the surface: these low‐energy Ar species (with an average energy of few eV) may effect the cleavage of the peptide bonds and lead, eventually, to the emission of the fragment ions. Copyright © 2013 John Wiley & Sons, Ltd.