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|Title:||Studies on the mechanism of the peroxyoxalate chemiluminescence reaction - Part 2. Further identification of intermediates using 2D EXSY C-13 nuclear magnetic resonance spectroscopy|
|Citation:||Analytica Chimica Acta, 2008; 614(2):173-181|
|Publisher:||Elsevier Science BV|
|Sarah A. Tonkin, Richard Bos, Gail A. Dyson, Kieran F. Lim, Richard A. Russell, Simon P. Watson, Christopher M. Hindson and Neil W. Barnett|
|Abstract:||Further 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 (13)C 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. (13)C 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.|
|Keywords:||Peroxyoxalate chemiluminescence; Mechanism; Key intermediates; 2D EXSY 13C nuclear magnetic resonance spectroscopy|
|Rights:||© 2008 Published by Elsevier B.V.|
|Appears in Collections:||Adelaide Graduate Centre publications|
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