基于HPLC/Q-TOF MS的4种农药联合暴露人群的代谢组学研究

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采用基于高效液相色谱-飞行时间质谱联用(HPLC-TOF MS)的代谢组学方法,研究了啶虫脒、高效氯氟氰菊酯、联苯菊酯、甲氨基阿维菌素苯甲酸盐4种农药联合暴露所致的施药人群尿液中内源性代谢物的变化。采集30位农民喷洒4种复合农药前和喷洒农药期1,3,5,7 d的尿液进行检测。提取正常尿液中常见代谢物并通过质控样品评价手段进行分析,结果表明该方法具有良好的稳定性和精密度,可用于尿液中代谢物分析。多变量分析结果表明,暴露人群施药前后尿液的代谢物含量存在较大差异。对选取的36个差异离子进行鉴定,确定了8个生物标志物的结构。结果显示联合暴露组人群尿液中多巴胺、5-羟色胺、酪氨酸、色氨酸、牛磺酸和马尿酸的含量显著下降;犬尿素和肌酸的含量显著上升。4种农药联合暴露导致接触人群尿液中色氨酸代谢途径的中间产物含量降低,肝代谢和能量代谢相关的代谢物蓄积,可能与神经系统和肝脏功能的受损有关。 The metabolites of acetamiprid, lambda-cyhalothrin, bifenthrin and emamectin benzoate were studied by using metabolomics based on high performance liquid chromatography-time of flight mass spectrometry (HPLC-TOF MS) Changes of Endogenous Metabolites in Urine of Pesticide Resulting from the Combined Exposure of Four Kinds of Pesticides by Acidic Salt. 30 peasants were collected before spraying 4 kinds of compound pesticides and spraying pesticides 1,3,5,7 d of urine for testing. The common metabolites in normal urine were extracted and analyzed by means of quality control samples. The results showed that this method has good stability and precision, which can be used for metabolite analysis in urine. Multivariate analysis showed that there was a significant difference in the metabolite content of urine before and after administration of the drug. Thirty-six differential ions were identified and the structures of eight biomarkers were determined. The results showed that the urinary excretion of dopamine, serotonin, tyrosine, tryptophan, taurine and hippuric acid in the co-exposed group were significantly decreased; the contents of canine urease and creatine were significantly increased. The combined exposure of four pesticides led to a decrease in the content of intermediates in the tryptophan metabolic pathway in the urine of the exposed population, and the accumulation of metabolites associated with liver metabolism and energy metabolism, which may be related to impaired nervous system and liver function.
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