Trace Detection Of Pyrethroids And Cytotoxic Metabonomics Of Bifenthrin Enantiomers

Pyrethroid pesticides have been widely uesed in agriculture and daily life,which exposed to human beings,various animals and plants directly or indirectly.Different enantiomers of chiral pesticides have different bioactivities and toxicity effects.Previous studies mainly focused on the enantioselective toxic effects of caquatic organisms.However,little attention has been paid to the effect of human beings.A method based on ultrasound-assisted ionic liquid dispersion liquid-liquid microextraction-high performance liquid chromatography(IL-UA-DLLME)for the direct determination of four pyrethroids residues in traditional Chinese medicine oral liquid was established.The oral liquid of traditional Chinese medicine includes Simotang,kangbingdu and Huaji oral liquid.The types of ionic liquid and dispersant,the volume of ionic liquid and dispersant,and ultrasonic assisted extraction time were investigated.Under the optimum conditions,the recovery ranged from 80.1%to 106.4%.The limits of detection ranged from 0.007 to 0.024 mg L-1,and the limits of quantitation ranged from 0.023 to 0.080 mg L-1.A method was developed for the analysis of three pyrethroid pesticide residues in natural coconut water using Magnetic-assisted in-situ ionic liquid dispersive liquid-liquid microextraction(UA-MIS-DLLME).The volume of ionic liquid and dispersant,the kind of ionic liquid,the amount of Fe3O4 magnetic nanoparticles and ultrasonic time were optimized.The linear range was 0.5-50 mg L-1.The recoveries and the correlation coefficients were 84.8-100.6%and 0.9994-0.9999,respectively.In this study,the separation of bifenthrin racemates were performed by high performance liquid chromatography with Chiralcel OJ-H column and C18 column in normal phase.Optical purity and concentrations of chiral enantiomers were determined respectively.Chiral enantiomers of bifenthrin(BT)acted on L02 cells to assess the enantioselective metabolic perturbations and cytotoxicity.The results showed that the cytotoxicity of 1S-cis-BT was significantly higher than that of 1R-cis-BT by detecting CCK-8 enzyme activity at concentrations of 20,40,80 μM,after treatment with different exposure concentrations(5,10,20,40,80 p.M)of bifenthrin enantiomers.UPLC-TOF/MS was performed to evaluate the enantioselective metabolic perturbations in L02 cells after treatment with bifenthrin enantiomers(20 μM).On the basis of principal component analysis,partitial least-squares discriminant analysis,orthogonal partial least squares discriminant analysis,univariate analysis and hierarchical clustering analysis.167 differential metabolites of 1S-cis-BT and 102 differential metabolites of 1R-cis-BT were detected,respectively.The same concentration of 1S-cis-BT and 1R-cis-BT were enantioselective.Pathway analysis indicated that 1S-cis-BT and 1R-cis-BT mainly affected the 10 and 6 pathways in L02 cells,respectively,implying the perturbed pathways induced by BT enantiomers were also enantioselective.