Faculty of Biology, Technion - Israel Institute of Technology, 320003, Haifa, Israel; Department of Chemistry, Lomonosov Moscow State University, 119991, Moscow, Russia.
Institute of Analytical Chemistry, Johannes Kepler University Linz, Altenberger Strasse 69, 4040, Linz, Austria.
J Chromatogr A. 2019 Jul 19;1597:214-219. doi: 10.1016/j.chroma.2019.04.025. Epub 2019 Apr 12.
In this research an accumulation of nerve agent markers in garden cress (Lepidium sativum) as a model plant object was studied using LC-QTOF hybrid system. For the determination of methylphosphonic acid and alkyl methylphosphonates, which are specific markers of sarin, soman, VR and VX, simple and sensitive approach was developed. Direct analysis of aqueous extracts on the reversed phase column with polar endcapping allowed to achieve satisfactory retention factor for methylphosphonic acid, which has high polarity and is usually very weakly retained on the ordinary reversed phase columns. Application of the QTOF mass spectrometer with high mass resolution led to the increase in the accuracy of the conducted measurements. The HPLC-HRMS technique developed exclusively for this study has been validated for linearity, limit of detection, limit of quantification, precision, accuracy and matrix effect prior to the analysis of plant extract samples. Hydroponic growth model was employed to examine accumulation of nerve agent markers in garden cress. It was found that after elimination of nerve agent markers from the plant growth medium, garden cress was able to store these substances for at least 5 weeks providing high retrospectivity of the analysis. Moreover, during the cress growth, no metabolization of alkyl methylphosphonates was observed. This allows not only to reveal the fact of nerve agents release into environment, but also to define its type after a long period of time.
本研究使用 LC-QTOF 混合系统研究了作为模型植物对象的荠(Lepidium sativum)中神经毒剂标志物的积累。为了测定沙林、梭曼、VR 和 VX 的特异性标志物甲基膦酸和烷基甲基膦酸,开发了一种简单灵敏的方法。在带有极性封端的反相柱上直接分析水提取物,可实现甲基膦酸的令人满意的保留因子,甲基膦酸具有高极性,通常在普通反相柱上保留非常弱。应用具有高质量分辨率的 QTOF 质谱仪可提高进行测量的准确性。专门为此研究开发的 HPLC-HRMS 技术在分析植物提取物样品之前已针对线性、检测限、定量限、精密度、准确度和基质效应进行了验证。采用水培生长模型研究了荠中神经毒剂标志物的积累情况。结果发现,在从植物生长介质中消除神经毒剂标志物后,荠至少能够储存这些物质 5 周,从而提供了高回溯性分析。此外,在荠的生长过程中,未观察到烷基甲基膦酸的代谢。这不仅可以揭示神经毒剂释放到环境中的事实,还可以在很长一段时间后确定其类型。