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Author Vivekananda, Shetty ♦ Sadílek, Martin ♦ Chen, Xiaohong ♦ Adams, Luke E. ♦ Tureček, František
Source SpringerLink
Content type Text
Publisher Springer-Verlag
File Format PDF
Copyright Year ©2004
Language English
Subject Domain (in DDC) Natural sciences & mathematics ♦ Chemistry & allied sciences
Subject Keyword Analytical Chemistry ♦ Biotechnology ♦ Organic Chemistry ♦ Proteomics ♦ Bioinformatics
Abstract The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (∼56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O-C-2 and C-4-C-5 bond dissociations combined account for ∼42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C$_{2}$H$_{3}$O and C$_{2}$H$_{4}$O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3 $^{+}$) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at ∼590 and ∼400 nm.
ISSN 10440305
Age Range 18 to 22 years ♦ above 22 year
Educational Use Research
Education Level UG and PG
Learning Resource Type Article
Publisher Date 2004-07-01
Publisher Institution The American Society for Mass Spectrometry
Publisher Place New York
e-ISSN 18791123
Journal Journal of The American Society for Mass Spectrometry
Volume Number 15
Issue Number 7
Page Count 12
Starting Page 1068
Ending Page 1079

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Source: SpringerLink