| Résumé | A novel electrocatalytic approach using a chemical reaction and an enzymatic reaction has been developed for the measurement of 18 chlorophenol congeners, including highly chlorinated pollutants such as pentachlorophenol, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol, and several trichlorophenols. Chlorophenols were oxidized to chlorobenzoquinones with very high yields using bis(trifluoroacetoxy)iodobenzene in 0.1 M trichloroacetic acid, pH 1.5, at ambient temperature. UV-visible spectrophotometry, cyclic voltammetry, and HPLC have been used to characterize the reaction products and yields. Together with glucose oxidase immobilized on a working glassy carbon electrode (+0.45 V vs Ag/AgCl), chlorinated benzoquinones have been demonstrated to be efficient mediators in a glucose oxidase/glucose system. In this approach, glucose oxidase was readily reduced by excess glucose to provide a non-rate-limiting source of electron flow toward the electrode. The oxidation products of chlorophenols then recycled the reduced glucose oxidase to its active oxidative state, i.e., mediating the rate-limiting electron transfer from the enzyme to the electrode. At pH 3.5, linear behavior of the current response was observed up to 200 nM for all chlorophenol oxidation products. The detection limit of this method for both pentachlorophenol and 2,3,5,6-tetrachlorophenol was about 4 nM, which is close to the maximum allowable contamination level of pentachlorophenol in water samples (2.7 nM). The detection limit obtained for pentachlorophenol could also be considered superior to the result obtained with the PCP immunoassay technology (13.3 nM). |
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