title: Analytical method for urinary metabolites of the fluorine-containing pyrethroids metofluthrin, profluthrin and transfluthrin by gas chromatography/mass spectrometry.
abstract: An analytical method was developed for measurement of the major urinary metabolites in rats administered fluorine-containing pyrethroids (metofluthrin, profluthrin and transfluthrin) which are widely used recently as mosquito repellents or mothproof repellents. Eight metabolites, 2,3,5,6-tetrafluorobenzoic acid, 4-methyl-2,3,5,6-tetrafluorobenzoic acid, 2,2-dimethyl-3-(1-propenyl)-cyclopropanecarboxylic acid, 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (carboxylic metabolites), 2,3,5,6-tetrafluorobenzyl alcohol, 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol and 4-hydroxymethyl-2,3,5,6-tetrafluorobenzyl alcohol (alcoholic metabolites), were extracted from enzymatic hydrolyzed urine using toluene and then concentrated. After transformation to their tert-butyldimethylsilyl derivatives for carboxylic metabolites or their trimethylsilyl derivatives for alcoholic metabolites, analysis was conducted by gas chromatography/mass spectrometry in the electron impact ionization mode. The calibration curves for each metabolite were linear over the concentration range of 0-20μg/ml in urine, and the quantification limits were between 0.009 and 0.03μg/ml. The relative errors and the relative standard deviations on replicate assays were less than 6% and 5%, respectively, for all concentrations studied. The measurements were accurate and precise. The collected urine samples could be stored for up to 1 month at -20°C in a freezer. The proposed method was applied to the analysis of several urine samples collected from rats treated with these pyrethroids.
authors.affiliation: Osaka Prefectural Institute of Public Health, 1-3-69, Nakamichi, Higashinari-ku, Osaka 537-0025, Japan. tsyosida@iph.pref.osaka.jp
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Yoshida
mesh_terms: D000818:Animals; D001592:Benzyl Alcohols / Q000737:chemistry / Q000378:metabolism / Q000652:urine*; D002138:Calibration; D003521:Cyclopropanes / Q000737:chemistry / Q000378:metabolism / Q000652:urine*; D004355:Drug Stability; D005464:Fluorobenzenes / Q000737:chemistry / Q000378:metabolism / Q000652:urine*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D007302:Insect Repellents / Q000737:chemistry / Q000378:metabolism / Q000652:urine; D016014:Linear Models; D008297:Male; D011722:Pyrethrins / Q000737:chemistry / Q000378:metabolism / Q000652:urine*; D051381:Rats; D017207:Rats, Sprague-Dawley; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity
chemical_list: C000594831:2,3,5,6-tetrafluoro-4-methylphenyl)methyl 2,2-dimethyl-3-(prop-1-enyl)cyclopropane-1-carboxylate; C000592572:2,3,5,6-tetrafluorobenzyl alcohol; C000601999:4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol; D001592:Benzyl Alcohols; D003521:Cyclopropanes; D005464:Fluorobenzenes; D007302:Insect Repellents; D011722:Pyrethrins; C560613:transfluthrin; C492600:(2,3,5,6-tetrafluoro-4-methoxymethylphenyl)methyl-2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate