Premium
Gas‐phase dissociation of 1,4‐naphthoquinone derivative anions by electrospray ionization tandem mass spectrometry
Author(s) -
Vessecchi Ricardo,
Carollo Carlos A.,
Lopes José N. C.,
Crotti Antonio E. M.,
Lopes Norberto P.,
Galembeck Sérgio E.
Publication year - 2009
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.1600
Subject(s) - chemistry , electrospray ionization , dissociation (chemistry) , tandem mass spectrometry , mass spectrometry , deprotonation , electron ionization , collision induced dissociation , naphthoquinone , chemical ionization , ionization , computational chemistry , analytical chemistry (journal) , ion , chromatography , organic chemistry
Abstract Gas‐phase dissociation pathways of deprotonated 1,4‐naphthoquinone (NQ) derivatives have been investigated by electrospray ionization tandem mass spectrometry (ESI‐MS/MS). The major decomposition routes have been elucidated on the basis of quantum chemical calculations at the B3LYP/6‐31 + G(d,p) level. Deprotonation sites have been indicated by analysis of natural charges and gas‐phase acidity. NQ anions underwent an interesting reaction under collision‐induced dissociation conditions, which resulted in the radical elimination of the lateral chain, in contrast with the even‐electron rule. Possible pathways have been suggested, and their mechanisms have been elucidated on the basis of Gibbs energy and enthalpy values for the anions previously described at each pathway. Copyright © 2009 John Wiley & Sons, Ltd.