A general, most basic rule for ion dissociation: Protonated molecules

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dc.contributor.authorReis A.
dc.contributor.authorAugusti R.
dc.contributor.authorEberlin M.N.
dc.date.accessioned2024-05-01T06:12:12Z
dc.date.available2024-05-01T06:12:12Z
dc.date.issued2024
dc.description.abstract© 2024 John Wiley & Sons Ltd.Contrary to the common but potentially misleading belief that when a protonated molecule is excited, it is its most stable protomer that will mandatorily dissociate, we demonstrate herein that, when rationalizing or predicting the chemistry of such ions, we should always search for the most labile protomer. This “most labile protomer” rule, based on the mobile proton model, states therefore that when a protonated molecule is heated, during ionization or by collisions for instance, the loosely bonded proton (H+) can acquire enough energy to detach itself from the most basic site of the molecule and then freely “walk through” the molecular framework to eventually find, if available, another protonation site, forming other less stable but more labile protomers, that is, protomers that may display lower dissociation thresholds. To demonstrate the validity of the “most labile protomer” rule as well as the misleading nature of the “most stable protomer” rule, we have selected several illustrative molecules and have collected their ESI(+)-MS/MS. To compare energies of precursors and products, we have also performed PM7 calculations and elaborated potential energy surface diagrams for their possible protomers and dissociation thresholds. We have also applied the “most labile protomer” rule to reinterpret—exclusively via classical charge-induced dissociation cleavages—several dissociation processes proposed for protonated molecules. In an accompanying letter, we have also applied a similar “most labile electromer” rule to ionized molecules.
dc.description.issuenumber3
dc.description.volume59
dc.identifier.doi10.1002/jms.5003
dc.identifier.issnNone
dc.identifier.urihttps://dspace.mackenzie.br/handle/10899/38582
dc.relation.ispartofJournal of Mass Spectrometry
dc.rightsAcesso Restrito
dc.subject.otherlanguageelectrospray ionization
dc.subject.otherlanguageion chemistry
dc.subject.otherlanguageprotomers
dc.subject.otherlanguageprotonated molecules
dc.subject.otherlanguagetandem mass spectrometry
dc.titleA general, most basic rule for ion dissociation: Protonated molecules
dc.typeArtigo
local.scopus.citations2
local.scopus.eid2-s2.0-85186771062
local.scopus.subjectBasic rules
local.scopus.subjectDissociation threshold
local.scopus.subjectEnergy
local.scopus.subjectIon chemistry
local.scopus.subjectIon dissociations
local.scopus.subjectProtomers
local.scopus.subjectProtonated molecules
local.scopus.subjectRule based
local.scopus.subjectTandem mass spectrometry
local.scopus.subjectTandem-mass spectrometry
local.scopus.updated2025-04-01
local.scopus.urlhttps://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85186771062&origin=inward
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