title: Stereoselective separation and pharmacokinetic dissipation of the chiral neonicotinoid sulfoxaflor in soil by ultraperformance convergence chromatography/tandem mass spectrometry.
abstract: Ultraperformance convergence chromatography/tandem triple quadrupole mass spectrometry (UPC(2)-MS/MS) is a novel tool in separation science that combines the advantages of supercritical fluid chromatography with ultraperformance liquid chromatography/MS/MS technology. The use of nontoxic CO2 fluid and a postcolumn additive to complement MS/MS allows better control of analyte retention for chiral separation and high-sensitivity determination with different chiral stationary phases. This paper reports the stereoselective separation and determination of the chiral neonicotinoid sulfoxaflor in vegetables and soil by UPC(2)-MS/MS. Baseline resolution (Rs ≥ 1.56) of and high selectivity (LOQ ≤ 1.83 μg/kg) for the four stereoisomers were achieved by postcolumn addition of 1 % formic acid-methanol to a Chiralpak IA-3 using CO₂/isopropanol/acetonitrile as the mobile phase at 40 °C, 2,500 psi, and for 6.5 min in electrospray ionization positive mode. Rearranged Van't Hoff equations afforded the thermodynamic parameters ΔH (ο) and ΔS (ο), which were analyzed to promote understanding of the enthalpy-driven separation of sulfoxaflor stereoisomers. The interday mean recovery, intraday repeatability, and interday reproducibility varied from 72.9 to 103.7%, from 1.8 to 9.2%, and from 3.1 to 9.4%, respectively. The proposed method was used to study the pharmacokinetic dissipation of sulfoxaflor stereoisomers in soil under greenhouse conditions. The estimated half-life ranged from 5.59 to 6.03 d, and statistically nonsignificant enantioselective degradation was observed. This study not only demonstrates that the UPC(2)-MS/MS system is an efficient and sensitive method for sulfoxaflor stereoseparation, but also provides the first experimental evidence of the pharmacokinetic dissipation of sulfoxaflor stereoisomers in the environment.
authors.affiliation: State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing, 100193, China.
authors.forename: Zenglong
authors.initials: Z
authors.lastname: Chen
authors.forename: Fengshou
authors.initials: F
authors.lastname: Dong
authors.forename: Jun
authors.initials: J
authors.lastname: Xu
authors.forename: Xingang
authors.initials: X
authors.lastname: Liu
authors.forename: Youpu
authors.initials: Y
authors.lastname: Cheng
authors.forename: Na
authors.initials: N
authors.lastname: Liu
authors.forename: Yan
authors.initials: Y
authors.lastname: Tao
authors.forename: Xinglu
authors.initials: X
authors.lastname: Pan
authors.forename: Yongquan
authors.initials: Y
authors.lastname: Zheng
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods; D007306:Insecticides / Q000032:analysis* / Q000302:isolation & purification; D057230:Limit of Detection; D011725:Pyridines / Q000032:analysis* / Q000302:isolation & purification; D015203:Reproducibility of Results; D012987:Soil / Q000737:chemistry*; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000032:analysis* / Q000302:isolation & purification; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014675:Vegetables / Q000737:chemistry*
chemical_list: D007306:Insecticides; D011725:Pyridines; D012987:Soil; D013457:Sulfur Compounds; C560328:sulfoxaflor