In forensic science, glyphosate (GLYP) and glufosinate (GLUF), a class of non-selective broad-spectrum herbicides, have been frequently encountered in many fatal poisoning and suicide cases due to their widespread availability. Therefore, it is essential to develop an effective method for detecting these compounds. Some conventional methods, such as gas chromatography–mass spectrometry (GC–MS) or liquid chromatography–mass spectrometry (LC–MS), have been reported to detect these compounds. However, these methods are not ideal for their time-consuming and non-sensitive feature. Herein, probe electrospray ionization (PESI) tandem mass spectrometry (MS/MS), a fast and sensitive technique, was applied for the determination of GLYP and GLUF in human blood, which can obtain analytical results within 0.5 min without derivatization and chromatographic separation. After protein precipitation of blood samples, the supernatant was mixed with isopropanol and ultra-pure water (1:1 v/v). Then, 8 μL of the mixture was introduced into the plastic sample plate for PESI-MS/MS analysis. The limits of detection (LODs) of the method were 0.50 μg/mL and 0.25 μg/mL for two analytes, and the limits of quantitation (LOQs) were both 1.00 μg/mL, which are higher than the concentration of reported poisoning and fatal cases. In the linear range of 1–500 μg/mL, the regression coefficients () for GLYP and GLUF were over 0.99. The matrix effects ranged from 94.8 % to 119.5 %, and the biases were below 4.3 %. The recoveries ranged between 84.8 % and 107.4 %, and the biases were below 7.6 %. Meanwhile, the method was effectively utilized to detect and quantify the blood, urine, and other samples. Consequently, the results suggest that PESI-MS/MS is a straightforward, fast, and sensitive method for detecting GLUF and GLYP in forensics. In the future, PESI-MS/MS will become an indispensable technique for polar substances in grassroots units of public security where rapid detection is essential.

中文翻译：

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探针电喷雾电离串联质谱法快速测定人血液中的草甘膦和草铵膦

在法医学领域，草甘膦（GLYP）和草铵膦（GLUF）是一类非选择性广谱除草剂，由于其广泛使用，在许多致命中毒和自杀案件中经常遇到。因此，有必要开发一种有效的方法来检测这些化合物。据报道，一些常规方法，例如气相色谱-质谱法 (GC-MS) 或液相色谱-质谱法 (LC-MS) 可以检测这些化合物。然而，这些方法由于其耗时且不敏感的特点并不理想。本文采用探针电喷雾电离(PESI)串联质谱(MS/MS)这种快速、灵敏的技术来测定人血液中的GLYP和GLUF，无需衍生化和色谱分离即可在0.5 min内获得分析结果。血样蛋白沉淀后，将上清液与异丙醇和超纯水（1:1 v/v）混合。然后，将 8 μL 混合物引入塑料样品板中进行 PESI-MS/MS 分析。该方法的两种分析物的检测限（LOD）分别为0.50 μg/mL和0.25 μg/mL，定量限（LOQ）均为1.00 μg/mL，均高于报告的中毒和致命浓度。案例。在1-500 μg/mL的线性范围内，GLYP和GLUF的回归系数()超过0.99。基质效应范围为 94.8% 至 119.5%，偏差低于 4.3%。回收率介于 84.8% 至 107.4% 之间，偏差低于 7.6%。同时，该方法还有效地应用于血液、尿液等样本的检测和定量。因此，结果表明 PESI-MS/MS 是一种直接、快速且灵敏的法医学检测 GLUF 和 GLYP 的方法。未来，PESI-MS/MS将成为公安基层快速检测极性物质不可或缺的技术。