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Oxalate/hydrogen peroxide chemiluminescence reaction. A 19 F NMR probe of the reaction mechanism
Author(s) -
Chokshi Hitesh P.,
Barbush Michael,
Carlson Robert G.,
Givens Richard S.,
Kuwana Ted,
Schowen Richard L.
Publication year - 1990
Publication title -
biomedical chromatography
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.4
H-Index - 65
eISSN - 1099-0801
pISSN - 0269-3879
DOI - 10.1002/bmc.1130040304
Subject(s) - chemiluminescence , chemistry , oxalate , hydrogen peroxide , peroxyoxalate , aqueous solution , reaction mechanism , proton nmr , peroxide , photochemistry , inorganic chemistry , catalysis , organic chemistry
The mechanism of the oxalate/hydrogen peroxide chemiluminescence reaction has been examined by magnetic resonance techniques. Investigation of the reactive intermediates involved in chemiluminescence was carried out with bis(2,6‐difluorophenyl)oxalate (DFPO) using 19 F NMR to probe its reactions with aqueous hydrogen peroxide. Formation and reactions of the intermediate hydroperoxy oxalate ester B along with the formation of the half ester product C and difluorophenol D were monitored by 19 F NMR. When the reaction of DFPO and aqueous hydrogen peroxide was carried out in the presence of dansylphenylalanine, a typical fluorescent analyte, the intensity of the resonance due to the intermediate B was diminished in direct proportion to the concentration of the analyte. Comparison of the time/intensity profile of the chemiluminescence emission with that of the 19 F NMR transient suggests that the hydroperoxy oxalate ester B is the likely ‘reactive’ intermediate, capable of participating in a chemically initiated electron exchange luminescence mechanism.