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The reaction intermediate spectrum. A new type of experiment in tandem mass spectrometry
Author(s) -
O'Lear John Raymond,
Wright Larry Gene,
Louris John Nathan,
Cooks R. Graham
Publication year - 1987
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210220608
Subject(s) - ion , mass spectrum , chemistry , fragmentation (computing) , mass spectrometry , dissociation (chemistry) , spectral line , tandem mass spectrometry , collision induced dissociation , analytical chemistry (journal) , mass , physics , organic chemistry , chromatography , astronomy , computer science , operating system
A new scan is described which responds to ions that are intermediates in the dissociation of a mass‐selected parent ion (m p ) to give a mass‐selected daughter ion (m d ). The scan gives a simple mass v. abundance output for ions which satisfy this condition. It is implemented here on a BEQQ hybrid mass spectrometer using, in sequence, collision‐induced dissociation occurring at high energy in the first reaction region, and low‐energy collisional activation in the collision quadrupole. The experiment provides information on reaction sequences not available from single scans of other types. In the several cases examined, it is demonstrated that, among many conceivable fragmentation routes connecting a parent ion with a particular fragment ion, only a few are significant. Examination of reaction intermediate spectra also appears to be a fruitful new approach to mechanistic questions, as illustrated by consideration of the behavior of several isomeric octanones. These new spectra also have analytical value: they show good signal‐to‐noise ratios and allow ready distinction between isobaric and isomeric ions. A comparison of the reaction intermediate spectrum with a daughter spectrum obtained by the B/E linked‐scanning technique reveals the contributions of artifact peaks which result from poor parent ion mass resolution in the latter. Reaction intermediate spectra combine information from the daughter spectra of m p and the parent spectra of m d and, as a specified portion of this data domain, have unique characteristics.