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Determination of atrazine and propazine metabolites deemed endocrine disruptors in human seminal plasma by LC–ESI-MS/MS
Chemical and Biological Technologies in Agriculture ( IF 5.2 ) Pub Date : 2022-02-22 , DOI: 10.1186/s40538-022-00285-4
Virginia Rodríguez-Robledo 1, 2 , Alberto Vendrell 1 , Alicia García-Cifuentes 1 , Noemí Villaseca-González 1 , María Rocío Fernández-Santos 1, 3 , Carmen Guiberteau-Cabanillas 2 , Lydia Luque Martínez 4 , José Julián Garde 3
Affiliation  

The increasing prevalence of male infertility and the declining trend in sperm quality has been associated to compounds known as “endocrine-disruptors”. The proven endocrine-disrupting effects of atrazine and propazine herbicides led us to conduct long-term research based on highly accurate specific analytical methods with a view to confirming the suspected association. Among the proposed developments was a sensitive analytical method for the simultaneous determination of three metabolites of atrazine and propazine. In this work, the method was for first time used for the chromatographic separation and determination of deethyl- and deisopropyl-atrazine (DEA and DIA, respectively) and propazine-2-hydroxy (PP-2OH) in human seminal plasma by LC–ESI-MS/MS using deuterated atrazine (d5-AT) as internal standard (IS). Chromatographic and mass spectrometric conditions such as the mobile phase composition and flow-rate, injected volume, dry gas source temperature and flow-rate, nebulizer pressure and capillary voltage were all carefully optimized. Analytes were identified and quantified by using the multiple reaction monitoring (MRM) mode as applied to positive ions ([M + H]+). Transitions at three different m/z values for each analyte were selected from precursor ions, and the 212.1 → [128]+, 188.1 → [146]+ and 174.1 → [68.1]+ transitions for PP-2OH, DEA and DIA, respectively, were found to be quantitative. The proposed method was validated in terms of precision (repeatability and reproducibility), linear range (10–240 ng mL–1), limit of detection (150–210 pg mL–1), and quantification (500–700 pg mL–1), recovery, accuracy and matrix effects on extracts from variably treated seminal plasma samples. The overall analytical method was successfully applied to human seminal plasma samples from volunteers. PP-2OH was found at concentrations from 1.10 to 11.3 ng mL–1 in four of the six samples, and so was DIA at 9.60 ng mL–1 in one. These results are suggestive of bioaccumulation of the target analytes in humans. Untargeted analytes including suspected parent molecules (atrazine and propazine) and other ions [viz., deethyldeisopropyl-atrazine (DD) and diamino-s-chlorotriazine (DACT)] were also detected under the working conditions used. These results may open up new prospects for as yet very incipient research into the bioaccumulation of endocrine disruptors in seminal plasma.

中文翻译:

LC-ESI-MS/MS 测定人精浆中被认为是内分泌干扰物的阿特拉津和丙嗪代谢物

男性不育症的日益流行和精子质量的下降趋势与被称为“内分泌干扰物”的化合物有关。阿特拉津和丙嗪类除草剂经证实的内分泌干扰作用使我们基于高度准确的特定分析方法进行了长期研究,以期确认疑似关联。提议的开发包括一种灵敏的分析方法,用于同时测定阿特拉津和丙嗪的三种代谢物。本研究首次将该方法用于人精浆中去乙基和去异丙基莠去津(分别为DEA和DIA)和丙嗪-2-羟基(PP-2OH)的LC-ESI色谱分离和测定。 -MS/MS 使用氘代阿特拉津 (d5-AT) 作为内标 (IS)。流动相组成和流速、进样量、干气源温度和流速、雾化器压力和毛细管电压等色谱和质谱条件均经过精心优化。通过使用应用于正离子 ([M + H]+) 的多反应监测 (MRM) 模式来识别和量化分析物。每种分析物的三个不同 m/z 值的离子对选自母离子,PP-2OH、DEA 和 DIA 的离子对分别为 212.1 → [128]+、188.1 → [146]+ 和 174.1 → [68.1]+ , 被发现是定量的。所提出的方法在精密度(重复性和重现性)、线性范围(10-240 ng mL-1)、检测限(150-210 pg mL-1)和定量(500-700 pg mL-1)方面进行了验证), 恢复,对来自不同处理的精浆样品的提取物的准确性和基质效应。整体分析方法成功应用于志愿者的人类精浆样本。在六个样品中的四个样品中发现 PP-2OH 的浓度为 1.10 至 11.3 ng mL-1,一个样品中的 DIA 为 9.60 ng mL-1。这些结果暗示了目标分析物在人体中的生物累积。在使用的工作条件下,还检测到了非靶向分析物,包括可疑的母体分子(阿特拉津和丙嗪)和其他离子 [即去乙基去异丙基-阿特拉津 (DD) 和二氨基-s-氯三嗪 (DACT)]。这些结果可能为目前尚处于初期阶段的内分泌干扰物在精浆中的生物蓄积性研究开辟了新的前景。整体分析方法成功应用于志愿者的人类精浆样本。在六个样品中的四个样品中发现 PP-2OH 的浓度为 1.10 至 11.3 ng mL-1,一个样品中的 DIA 为 9.60 ng mL-1。这些结果暗示了目标分析物在人体中的生物累积。在使用的工作条件下,还检测到了非靶向分析物,包括可疑的母体分子(阿特拉津和丙嗪)和其他离子 [即去乙基去异丙基-阿特拉津 (DD) 和二氨基-s-氯三嗪 (DACT)]。这些结果可能为目前尚处于初期阶段的内分泌干扰物在精浆中的生物蓄积性研究开辟了新的前景。整体分析方法成功应用于志愿者的人类精浆样本。在六个样品中的四个样品中发现 PP-2OH 的浓度为 1.10 至 11.3 ng mL-1,一个样品中的 DIA 为 9.60 ng mL-1。这些结果暗示了目标分析物在人体中的生物累积。在使用的工作条件下,还检测到了非靶向分析物,包括可疑的母体分子(阿特拉津和丙嗪)和其他离子 [即去乙基去异丙基-阿特拉津 (DD) 和二氨基-s-氯三嗪 (DACT)]。这些结果可能为目前尚处于初期阶段的内分泌干扰物在精浆中的生物蓄积性研究开辟了新的前景。60 ng mL–1 合二为一。这些结果暗示了目标分析物在人体中的生物累积。在使用的工作条件下,还检测到了非靶向分析物,包括可疑的母体分子(阿特拉津和丙嗪)和其他离子 [即去乙基去异丙基-阿特拉津 (DD) 和二氨基-s-氯三嗪 (DACT)]。这些结果可能为目前尚处于初期阶段的内分泌干扰物在精浆中的生物蓄积性研究开辟了新的前景。60 ng mL–1 合二为一。这些结果暗示了目标分析物在人体中的生物累积。在使用的工作条件下,还检测到了非靶向分析物,包括可疑的母体分子(阿特拉津和丙嗪)和其他离子 [即去乙基去异丙基-阿特拉津 (DD) 和二氨基-s-氯三嗪 (DACT)]。这些结果可能为目前尚处于初期阶段的内分泌干扰物在精浆中的生物蓄积性研究开辟了新的前景。
更新日期:2022-02-22
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