title: Simultaneous enantioselective determination of phenylpyrazole insecticide flufiprole and its chiral metabolite in paddy field ecosystem by ultra-high performance liquid chromatography/tandem mass spectrometry.
abstract: A novel and sensitive ultra-high performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous enantioselective determination of flufiprole and its hydrolysis metabolite in paddy field ecosystem. The separation and determination were performed using reversed-phase chromatography on a novel cellulose chiral stationary phase, a Lux Cellulose-4 (150 mm × 2.0 mm) column, under isocratic conditions at 0.25 mL/min flow rate. The effects of other four different polysaccharide-based chiral stationary phases (CSPs) on the separation and simultaneous enantioseparation of the two target compounds were also evaluated. The elution orders of the eluting enantiomers were identified by an optical rotation detector. Modified QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the enrichment and cleanup of paddy water, rice straw, brown rice and paddy soil samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under the optimal conditions, the mean recoveries for all enantiomers from the above four sample matrix were ranged from 83.6% to 107%, with relative standard deviations (RSD) in the range of 1.0-5.8%. Coefficients of determination R(2)≥0.998 were achieved for each enantiomer in paddy water, rice straw, brown rice and paddy soil matrix calibration curves within the range of 5-500 μg/kg. The limits of quantification (LOQ) for all stereoisomers in the above four matrices were all below 2.0 μg/kg. The methodology was successfully applied for simultaneously enantioselective analysis of flufiprole enantiomers and their chiral metabolite in the real samples, indicating its efficacy in investigating the environmental stereochemistry of flufiprole in paddy field ecosystem.
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Jing
authors.initials: J
authors.lastname: Li
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Yuting
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Tianjin Agricultural University, Tianjin 300380,China.
authors.forename: Youpu
authors.initials: Y
authors.lastname: Cheng
authors.affiliation: Institute for the Control of Agrochemicals, Ministry of Agriculture, Beijing 100125,China.
authors.forename: Shankui
authors.initials: S
authors.lastname: Yuan
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Lei
authors.initials: L
authors.lastname: Liu
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Hui
authors.initials: H
authors.lastname: Shao
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Hui
authors.initials: H
authors.lastname: Li
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Na
authors.initials: N
authors.lastname: Li
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China.
authors.forename: Pengyue
authors.initials: P
authors.lastname: Zhao
authors.affiliation: Tianjin Institute of Quality Standards and Testing Technology for Agricultural Products, Laboratory of Quality & Safety Risk Assessment for Agro-products, Ministry of Agriculture, Tianjin 300381,China. Electronic address: yongze_guo@163.com.
authors.forename: Yongze
authors.initials: Y
authors.lastname: Guo
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D056148:Chromatography, Reverse-Phase / Q000379:methods; D017753:Ecosystem; D005506:Food Contamination / Q000032:analysis; D007306:Insecticides / Q000737:chemistry*; D057230:Limit of Detection; D012275:Oryza / Q000737:chemistry; D011720:Pyrazoles / Q000737:chemistry*; D012987:Soil / Q000737:chemistry; D052616:Solid Phase Extraction / Q000379:methods; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014230:Triazoles / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000737:chemistry
chemical_list: D007306:Insecticides; D011720:Pyrazoles; D012987:Soil; D014230:Triazoles; D014874:Water Pollutants, Chemical; D014867:Water; C000607325:1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(N-(2-methylprop-2-enyl)amino)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile
keywords: Chiral metabolite; Enantioselective separation; Flufiprole; Paddy field; UPLC–MS/MS