Journal
EUROPEAN JOURNAL OF MASS SPECTROMETRY
Volume 13, Issue 1, Pages 19-28Publisher
IM PUBLICATIONS
DOI: 10.1255/ejms.837
Keywords
reaction mechanisms; reaction intermediates; tandem mass spectrometry; direct infusion electrospray mass spectrometry; ion chemistry; gas-phase reactions
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Electrospray ionization mass spectrometry (ESI-MS), in conjunction with its tandem version ESI-MS/MS, is now established as a major tool to study reaction mechanisms in solution. This suitability results mainly from the ability of ESI to fish ions directly from solution to the gas phase environment of mass spectrometers. In this review, we summarize recent studies from our laboratory on the use of on-line monitoring by ESI-MS ion fishing of several types of reactions that permitted us to follow how these reactions progress as a function of both time and conditions using the ultra-high sensitivity and speed of ESI-MS to detect and even characterize transient reaction intermediates. We also show that the intrinsic reactivity of each key gaseous speciesfished by ESI can be further investigated via ESI-tandern mass spectrometry experiments, searching for the most active species via gas-phase ion/molecule reactions. In the gas-phase, solvent and counter-ion effects are absent. These studies often permit a detailed overview of major steps via the interception, characterization and reactivity investigation of key reaction players.
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