氟虫腈及其代谢物氟虫腈砜中主要有机杂质的定性及定量
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摘要
建立了一种氟虫腈及其代谢物氟虫腈砜标准物质候选物中的主要有机杂质定性、定量分析方法。采用高效液相色谱-三重四极杆串联质谱法(HPLC-MS/MS)成功鉴别出氟虫腈中杂质分别为氟虫腈砜和氟虫腈硫化物,而氟虫腈砜中杂质为氟虫腈硫化物,推导出氟虫腈砜的结构式。HPLC-MS/MS外标法测定氟虫腈中杂质氟虫腈砜和氟虫腈硫化物的含量分别为0. 18%、0. 47%,相对标准偏差分别为0. 73%、0. 87%;氟虫腈砜中杂质氟虫腈硫化物的含量为0. 25%,相对标准偏差为8. 05%。该方法的研究对食品安全检验中氟虫腈及氟虫腈砜的准确测定具有重要意义。
Qualitative and quantitative analysis of the major organic impurities in pure fipronil and its metabolite fipronil sulfone was performed.The organic impurities were qualitatively determined by high performance liquid chromatography-triple quarupole tandem mass spectrometry( HPLC-MS/MS).Full scan of LC/MS in positive ion mode was firstly executed to obtain the m/z values of the molecules.Then LC-MS/MS was carried out on target compounds to obtain structural information.Impurities in fipronil were successfully identified as fipronil sulfone and fipronil sulphide,respectively. The molecular structure of fipronil sulfone was derived and impurity in fipronil sulfone was successfully identified as fipronil sulphide. HPLC-MS/MS external standard method was used to determine the content of the organic impurities.There are 0. 18% fipronil sulfone with the RSD of 0. 73% and 0. 47%fipronil sulphide with the RSD of 0. 87% in pure fipronil material.The content of impurity in fipronil sulfone material was 0. 25%with the RSD of 8. 05%. Moreover,this method has instructive significance to the qualitative and quantitative analysis of pure fipronil and fipronil sulfone and other pure organic substances.
Qualitative and quantitative analysis of the major organic impurities in pure fipronil and its metabolite fipronil sulfone was performed.The organic impurities were qualitatively determined by high performance liquid chromatography-triple quarupole tandem mass spectrometry( HPLC-MS/MS).Full scan of LC/MS in positive ion mode was firstly executed to obtain the m/z values of the molecules.Then LC-MS/MS was carried out on target compounds to obtain structural information.Impurities in fipronil were successfully identified as fipronil sulfone and fipronil sulphide,respectively. The molecular structure of fipronil sulfone was derived and impurity in fipronil sulfone was successfully identified as fipronil sulphide. HPLC-MS/MS external standard method was used to determine the content of the organic impurities.There are 0. 18% fipronil sulfone with the RSD of 0. 73% and 0. 47%fipronil sulphide with the RSD of 0. 87% in pure fipronil material.The content of impurity in fipronil sulfone material was 0. 25%with the RSD of 8. 05%. Moreover,this method has instructive significance to the qualitative and quantitative analysis of pure fipronil and fipronil sulfone and other pure organic substances.
引文
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[2]GOMES J O,BORGES N W,MACHADO A E,et al.Optimization of fipronil degradation by heterogeneous photocatalysis:identification of transformation products and toxicity assessment[J].Water Res.,2016,110:133-140.
[3]TOFFOLI A L,DA M K,BISINOTI M C,et al.Development,validation,and application of a method for the GCMS analysis of fipronil and three of its degradation products in samples of water,soil,and sediment[J]. J. Environ.Sci.Hea.B,2015,50(11):753-759.
[4]BONMATIN J M,GIORIO C,GIROLAMI V,et al.Environmental fate and exposure; neonicotinoids and fipronil[J].Environ.Sci.Pollut.R.,2015,22(1):35-67.
[5]时逸吟,李优,伊雄海,等.液相色谱-串联质谱法测定蛋及蛋制品中氟虫腈及其代谢物的残留量[J].检验检疫学刊,2017,5(27):1-7.
[6]WU X H,YU Y,XU J,et al.Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry[J].Plos One,2017,12(3):1-12.
[7]CHEN H P,GAO G W,LIU P X,et al.Development and validation of an ultra performance liquid chromatography q-exactive orbitrap mass spectrometry for the determination of fipronil and its metabolites in tea and chrysanthemum[J].Food Chem.,2018,246:328-334.
[8]叶倩,邓义才,梁应坤,等.气相色谱-质谱法(GC-MS)测定蔬菜水果中氟虫腈及其代谢物残留[J].农药,2017,56(3):203-206.
[9]堵燕钰,罗漪涟,王洁琼,等.在线净化-液相色谱串联质谱技术测定蔬菜中氟虫腈及其代谢物残留[J].环境化学,2017,36(4):928-930.
[10]郭德华,时逸吟,李优,等.固相萃取-液相色谱-四极杆飞行时间质谱法快速筛查禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 216-1 223.
[11]沈伟健,柳菡,张睿,等.气相色谱-负化学源质谱法测定禽蛋及蛋制品中氟虫腈及其代谢物[J].色谱,2017,35(12):1 224-1 228.
[12]胡贵祥,夏祥,朱惠芳,等.Qu Ch ERS线凝胶色谱-气相色谱/质谱联用法测定水果蔬菜中氟虫腈农药残留[J].化学试剂,2017,39(5):509-512.
[13]ZHANG M Y,BIAN K,ZHOU T,et al.Determination of residual fipronil in chicken egg and muscle by LC-MS/MS[J].J.Chromatogr.B,2016,1 014:31-36.
[14]PARAMASIVAM M,CHANDRASEKARAN S. Determination of fipronil and its major metabolites in vegetables,fruit and soil using quechers and gas chromatography-mass spectrometry[J]. Int. J. Environ. An. Ch.,2013,93(11):1 203-1 211.
[15]LI M H,LI P Y,WANG L,et al.Determination and dissipation of fipronil and its metabolites in peanut and soil[J].J.Agr.Food Chem.,2015,63(18):4 435-4 443.