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Studies on the mechanism of the peroxyoxalate chemiluminescence reaction : part 2, further identification of intermediates using 2D EXSY 13C nuclear magnetic resonance spectroscopy
journal contribution
posted on 2008-05-05, 00:00 authored by S Tonkin, Richard Bos, Gail Dyson, Kieran LimKieran Lim, R Russell, S Watson, Christopher Hindson, Neil BarnettNeil BarnettFurther consideration has been given to the reaction pathway of a model peroxyoxalate chemiluminescence system. Again utilising doubly labelled oxalyl chloride and anhydrous hydrogen peroxide, 2D EXSY 13C nuclear magnetic resonance (NMR) spectroscopy experiments allowed for the characterisation of unknown products and key intermediate species on the dark side of the peroxyoxalate chemiluminescence reaction. Exchange spectroscopy afforded elucidation of a scheme comprised of two distinct mechanistic pathways, one of which contributes to chemiluminescence. 13C NMR experiments carried out at varied reagent molar ratios demonstrated that excess amounts of hydrogen peroxide favoured formation of 1,2-dioxetanedione: the intermediate that, upon thermolysis, has been long thought to interact with a fluorophore to produce light.
History
Journal
Analytica chimica actaVolume
614Issue
2Pagination
173 - 181Publisher
Elsevier BVLocation
Amsterdam, The NetherlandsPublisher DOI
ISSN
0003-2670eISSN
1873-4324Language
engPublication classification
C1 Refereed article in a scholarly journalCopyright notice
2008, Elsevier B.V.Usage metrics
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peroxyoxalate chemiluminescencemechanismkey intermediates2D EXSY 13C nuclear magnetic resonance spectroscopyScience & TechnologyPhysical SciencesChemistry, AnalyticalChemistrymechanism key intermediates2D EXSY C-13 nuclear magneticresonance spectroscopyHYDROGEN-PEROXIDECHEMI-LUMINESCENCEFLUORESCENT COMPOUNDS2-DIMENSIONAL NMRKINETICS1,2-DIOXETANEDIONEBIS(PENTACHLOROPHENYL)OXALATEDECOMPOSITIONLIGHT
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