Novel fluorescence detection of free radicals generated in photolysis of fenvalerate

Photoinduced decarboxylation via homolytic cleavage of the ester linkage generating two benzyl radicals being recoupled is known to be a major photolytic pathway of the insecticide fenvalerate in aqueous or organic solvents. A highly sensitive and selective fluorescence spectroscopic method was applied to detect these radicals generated under xenon lamp irradiation in organic solvents and aqueous acetonitrile solutions. The short-lived radicals were efficiently trapped by the nitroxide free radical having a primary amino group, and the resultant diamagnetic adducts were instantaneously derivatized with fluorescamine as a fluorescent probe. The highly fluorescent derivatives were successfully separated and detected by a reversed-phase high-performance liquid chromatography equipped with a fluorescence detector, and their structures were individually identified by liquid chromatography/mass spectrometry.