Premium
Fragmentation induced in atmospheric pressure photoionization of peptides
Author(s) -
Debois D.,
Giuliani A.,
Laprévote O.
Publication year - 2006
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1122
Subject(s) - photoionization , electron transfer dissociation , fragmentation (computing) , dopant , chemistry , dissociation (chemistry) , ion , ionization , protonation , photochemistry , atmospheric pressure , collision induced dissociation , electron transfer , mass spectrometry , doping , tandem mass spectrometry , organic chemistry , materials science , chromatography , oceanography , optoelectronics , computer science , geology , operating system
In this work, the fragmentation of peptides under atmospheric pressure photoionization conditions is investigated. Intensive fragmentations into b/y‐ and c‐sequence ions are reported. Abundance of these c‐ions appeared to be related to the quantity of dopant infused and to the disappearance of the doubly protonated peptide ion. A careful analysis of the role of the dopant indicates that the fragmentations are not dependent on the nature of the dopant but on their ionization efficiencies. This result shows that the fragmentation arises from the reaction of the protonated peptide with photoelectrons released upon ionization of the dopant in an electron capture dissociation/electron transfer dissociation (ECD/ETD) type mechanism. Experiments with peptides bearing a single proton indicate that additional mechanisms are involved. H‐atom transfer reactions are suggested to be responsible for the fragmentations as well. Those atoms could arise either from the dopant ions or from negatively charged solvent nanodroplets. This is the first report of an ECD/ETD mechanism in a dense medium and at atmospheric pressure. Copyright © 2006 John Wiley & Sons, Ltd.