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From the mobile proton to wandering hydride ion: mechanistic aspects of gas‐phase ion chemistry
Author(s) -
Bouchoux Guy
Publication year - 2013
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.3204
Subject(s) - chemistry , protonation , mass spectrometry , fragmentation (computing) , mass spectrum , ion , electron ionization , deprotonation , dissociation (chemistry) , hydride , collision induced dissociation , computational chemistry , ionization , hydrogen , tandem mass spectrometry , organic chemistry , chromatography , computer science , operating system
Structural characterization of molecular species by mass spectrometry supposes the knowledge of the type of ions generated and the mechanism by which they dissociate. In this context, a need for a rationalization of electrospray ionization(+)(−) mass spectra of small molecules has been recently expressed. Similarly, at the other end of the mass scale, efforts are currently made to interpret the major fragmentation processes of protonated and deprotonated peptides and their reduced forms produced in electron capture or electron transfer experiments. Most fragmentation processes of molecular and pseudo‐molecular ions produced in the ion source of a mass spectrometer may be described by a combination of several key mechanistic steps: simple bond dissociation, formation of ion‐neutral complex intermediates, hydrogen atom, hydride ion or proton migrations and nucleophilic attack. Selected crucial aspects of these elementary reactions, occurring inside positively charged ions, will be recalled and illustrated by examples taken in recent mass spectrometry literature. Emphasis will be given on the protonation process and its consequence in terms of structure and energetic. Copyright © 2013 John Wiley & Sons, Ltd.