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通过高效液相色谱-串联质谱法监测植物材料中芥子气、一些倍半芥子气和氧芥子气及其他化学战剂的水解产物。

Monitoring of hydrolysis products of mustard gas, some sesqui- and oxy-mustards and other chemical warfare agents in a plant material by HPLC-MS/MS.

作者信息

Baygildiev Timur, Vokuev Mikhail, Braun Arcady, Rybalchenko Igor, Rodin Igor

机构信息

Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.

Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.

出版信息

J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Jan 1;1162:122452. doi: 10.1016/j.jchromb.2020.122452. Epub 2020 Nov 17.

DOI:10.1016/j.jchromb.2020.122452
PMID:33264722
Abstract

At present, there is a real threat of chemical warfare agents being used in terrorist acts and military clashes. Sulfur and nitrogen mustards are blister agents with high lethality and rapid disruption of armed forces. These highly poisonous substances are hydrolyzed to the characteristic marker compounds when released into the environment. Analysis of environmental objects allows to establish the fact of alleged use of chemical warfare agents and to reveal their type. However, water and soil samples are not always reliable for retrospective analysis. The resulting chemical warfare agent markers may be washed out from the application site over time by groundwaters or atmospheric condensations. This study shows the potential for using plants as a convenient material for retrospective analysis. Garden cress (Lepidium sativum) was chosen as a model plant for this purpose, since it can be easily and quickly grown hydroponically. The plants were cultivated in the environment of the selected markers to study an accumulation of these compounds by the plants. An effective and fast method of homogenization with subsequent ultrasonic extraction was applied. The extracts were analyzed using a specially developed and validated HPLC-MS/MS approach. Separation of the hydrophilic markers was carried out on a reversed-phase column with a polar endcapping. Sensitive mass spectrometric detection was performed in the multiple reaction monitoring mode. Achieved limits of detection for most markers were in the range of 2-40 ng mL. It was discovered from the research that after the removal of markers from the growing medium the plants are able to store and concentrate these markers for at least 5 weeks, ensuring a high retrospectivity of the analysis. The obtained results indicate the perspective of using plants as additional objects of analysis during the investigation of incidents related to the use of chemical warfare agents. However, more complex plants and models should be studied in the future.

摘要

目前,化学战剂被用于恐怖袭击和军事冲突存在切实威胁。硫芥和氮芥是具有高致死性且能迅速瓦解武装力量的糜烂性毒剂。这些剧毒物质释放到环境中时会水解为特征性标记化合物。对环境物体进行分析能够确定是否存在疑似使用化学战剂的情况,并揭示其类型。然而,水和土壤样本用于追溯分析并不总是可靠的。随着时间推移,生成的化学战剂标记物可能会被地下水或大气凝结物从施放点冲刷掉。本研究表明利用植物作为追溯分析便捷材料的潜力。为此选择了水芹(独行菜)作为模式植物,因为它能在水培条件下轻松快速生长。将植物种植在所选标记物的环境中,以研究植物对这些化合物的积累情况。采用了一种有效且快速的匀浆及后续超声提取方法。提取物使用专门开发并经过验证的高效液相色谱 - 串联质谱法(HPLC - MS/MS)进行分析。亲水性标记物在带有极性封端的反相柱上进行分离。在多反应监测模式下进行灵敏的质谱检测。大多数标记物的检测限达到2 - 40 ng/mL。研究发现,从生长介质中去除标记物后,植物能够储存并浓缩这些标记物至少5周,确保了分析的高追溯性。所得结果表明在调查与化学战剂使用相关的事件时,利用植物作为额外分析对象具有前景。然而,未来应研究更复杂的植物和模型。

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