Application of probe electrospray ionization-tandem mass spectrometry to ultra-rapid determination of glufosinate and glyphosate in human serum
Application of probe electrospray ionization-tandem mass spectrometry to ultra-rapid determination of glufosinate and glyphosate in human serum
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DOI：
10.1016/j.jpba.2019.05.040
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发表时间：
2019-09-10
影响因子：
3.4
通讯作者：
Funayama, Masato
中科院分区：
文献类型：
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作者：
Usui, Kiyotaka;Minami, Eriko;Funayama, Masato
草铵膦和草甘膦是非选择性除草剂，其结构中含有氨基酸部分，在世界范围内经常用于控制不需要的植被。不幸的是，这些容易获得的除草剂也被人们用来自杀，因此代表了临床医学和法医学领域感兴趣的重要化学物质。由于这些除草剂的水溶性较高，大多数检测分析方法都需要衍生化步骤，从而导致分析时间较长。因此，基于衍生化的方法目前无法有助于急诊医学治疗决策的判断。在本研究中，我们通过结合使用探针电喷雾电离 (PESI) 和串联质谱 (MS/MS) 开发一种超快速且简单的分析技术来解决这一限制因素，该技术可在 0.3 分钟内给出定量结果。将除草剂标准品添加到人血清中，然后进行分析（每个浓度 N = 5）。连续八天每天重复分析。草铵膦的检测限 (LOD) 为 0.59 μg/mL，草甘膦的检测限为 0.20 μg/mL。两种除草剂的定量限 (LOQ)，即校准曲线上的最低点，均为 1.56 μg/mL。在三种不同浓度下观察到基质效应（草铵膦在 95.7%-104% 之间，草甘膦在 90.7%-95.7% 之间）。当应用于从实际中毒案例中采集的样品（每种除草剂六个样品）时，本方法给出的定量值与传统的荧光检测高效液相色谱法获得的定量值几乎相同。因此，我们相信 PESI-MS/MS 可以成为临床急诊领域的快速诊断方法。 (C) 2019 Elsevier B.V. 保留所有权利。
Glufosinate and glyphosate, which are non-selective herbicides that include an amino acid moiety in their structures, are frequently used worldwide to control unwanted vegetation. Unfortunately, these readily available herbicides are also used by people to commit suicide, and thus represent important chemicals of interest in the fields of clinical medicine and forensics. Because of the high water solubility of these herbicides, most analytical methods for their detection require a derivatization step, which results in longer analysis times. Therefore, derivatization-based methods do not currently contribute to judgements on treatment decisions in emergency medicine. In this study, we addressed this limiting factor by developing an ultra-rapid and simple analytical technique using a combination of probe electrospray ionization (PESI) and tandem mass spectrometry (MS/MS), which gives quantitative results within 0.3 min. Herbicide standards were added to human serum that was then subjected to analysis (N = 5 per concentration). The analysis was repeated daily over eight consecutive days. The limit of detection (LOD) was 0.59 mu g/mL for glufosinate and 0.20 mu g/mL for glyphosate. The limit of quantitation (LOQ), i.e., the lowest point on the calibration curves, was 1.56 mu g/mL for both the herbicides. The matrix effects were observed at three different concentrations (between 95.7%-104% for glufosinate, and between 90.7%-95.7% for glyphosate). When applied to samples taken from actual poisoning cases (six samples for each herbicide), the present method gave almost the same quantitative values as those obtained by conventional high-performance liquid chromatography with fluorescence detection. Thus, we believe that PESI-MS/MS could emerge as a rapid diagnosis method in the clinical emergency field. (C) 2019 Elsevier B.V. All rights reserved.