摘要
Thiophonate-methyl(TPM) is one of fungicides and pesticides widely used in agriculture field.However,the residue of its benzimidazole(BZD) metabolites in related agricultural products poses a potential risk to consumers.In this paper,nickel oxide nanoparticle-deposited silica(SiO_2@NiO) composite was used for the selective enrichment and purification of TPM's BZD metabolites in celery cabbage sprayed with TPM.Meanwhile,high-performance liquid chromatography coupled with precursor ion scan-mass spectrometry(HPLC-PIS-MS) and high-resolution MS/MS analysis(HR-MS/MS) was utilized for their qualitative and quantitative analysis.Twenty-one potential TPM's BZD metabolites were found and four of them were identified.One metabolite was discovered for the first time.Besides,a robust and sensitive quantitative method was developed with good linearities(R^2> 0.9972) within a wide range of 10.00-1000 ng/g.The detection limits of three known TPM's metabolites were within the range of 3.20-4.90 ng/g.Relative standard deviations(RSDs) of intra-day and inter-day precisions were less than 18.3%,which showed perfect reproducibility.The method was successfully applied to monitoring TPM's BZD metabolites in celery cabbage sprayed with TPM and the concentration versus time curves of TPM's metabolites in celery cabbage were plotted.This method is expected to be used to monitor BZD residues in various fruits and vegetables.
Thiophonate-methyl（TPM） is one of fungicides and pesticides widely used in agriculture field.However,the residue of its benzimidazole（BZD） metabolites in related agricultural products poses a potential risk to consumers.In this paper,nickel oxide nanoparticle-deposited silica（SiO2@NiO） composite was used for the selective enrichment and purification of TPM’s BZD metabolites in celery cabbage sprayed with TPM.Meanwhile,high-performance liquid chromatography coupled with precursor ion scan-mass spectrometry（HPLC-PIS-MS） and high-resolution MS/MS analysis（HR-MS/MS） was utilized for their qualitative and quantitative analysis.Twenty-one potential TPM’s BZD metabolites were found and four of them were identified.One metabolite was discovered for the first time.Besides,a robust and sensitive quantitative method was developed with good linearities（R2> 0.9972） within a wide range of 10.00-1000 ng/g.The detection limits of three known TPM’s metabolites were within the range of 3.20-4.90 ng/g.Relative standard deviations（RSDs） of intra-day and inter-day precisions were less than 18.3%,which showed perfect reproducibility.The method was successfully applied to monitoring TPM’s BZD metabolites in celery cabbage sprayed with TPM and the concentration versus time curves of TPM’s metabolites in celery cabbage were plotted.This method is expected to be used to monitor BZD residues in various fruits and vegetables.
基金
The National Natural Science Foundation of China(No.31671929,21635006 and 31670373)supported this work。
