On-line electrochemistry/liquid chromatography/mass spectrometry for the simulation of pesticide metabolism.
On-line electrochemistry/liquid chromatography/mass spectrometry (EC/LC/MS) was employed to mimic the oxidative metabolism of the fungicide boscalid. High-resolution mass spectrometry and MS/MS experiments were used to identify its electrochemical oxidation products. Furthermore, the introduction of a second electrochemical cell with reductive conditions provided important additional information on the oxidation products. With this equipment, hydroxylation, dehydrogenation, formation of a covalent ammonia adduct, and dimerization were detected after initial one-electron oxidation of boscalid to a radical cation. On-line reaction with glutathione yielded different isomeric covalent glutathione adducts. The results of the electrochemical oxidation are in good accordance with previously reported in vivo experiments, showing that EC/LC/MS is a useful tool for studying biotransformation reactions of various groups of xenobiotics.
Westfälische Wilhelms-Universität Münster, Institute of Inorganic and Analytical Chemistry, Münster, Germany.
Wiebke
W
Lohmann
Reinhard
R
Dötzer
Gerald
G
Gütter
Suze M
SM
Van Leeuwen
Uwe
U
Karst
D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D004563:Electrochemistry / Q000379:methods*; D005659:Fungicides, Industrial / Q000032:analysis / Q000737:chemistry* / Q000378:metabolism*; D005978:Glutathione / Q000032:analysis / Q000737:chemistry / Q000378:metabolism; D013058:Mass Spectrometry / Q000379:methods*; D008958:Models, Molecular; D010084:Oxidation-Reduction
D005659:Fungicides, Industrial; D005978:Glutathione