Division of International Strategy, Center of Future Chemistry, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Department of Environmental Design, Graduate School of Design, Kyushu University, 4-9-1, Shiobaru, Minami-ku, Fukuoka, 815-8540, Japan.
Anal Chim Acta. 2019 Sep 3;1069:82-88. doi: 10.1016/j.aca.2019.04.012. Epub 2019 Apr 10.
Nerve agent metabolites (NAMs) derived from alkyl methyl phosphonic acids, such as ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), and pinacolyl methylphosphonic acid (PMPA), were extracted from human urine using diethyl ether as an extractant. After exchanging the diethyl ether solvent to acetonitrile, the analytes were derivatized with 2-(bromomethyl)naphthalene (BMN). The reaction products of the BMN and NAMs, i.e., MN-EMPA, MN-IMPA, and MN-PMPA, were separated by gas chromatography (GC) and measured by mass spectrometry (MS) using a femtosecond laser emitting at 267 nm as the ionization source for resonance-enhanced two-photon ionization (RE2PI). The limits of detection (LOD) were <1 ng/mL for these analytes. The use of BMN increased the volatility of the analytes for separation by GC and also increased the ionization efficiency via the RE2PI process as the result of presence of a naphthalene functional group. A two-dimensional GC-MS display can be used for comprehensive analysis of NAMs, by-products, and impurities in the sample. Then, this approach could be used to confirm the use of chemical weapons and for forensic identification.
从烷基甲基膦酸衍生的神经毒剂代谢物（NAMs），如乙基甲基膦酸（EMPA）、异丙基甲基膦酸（IMPA）和频哪基甲基膦酸（PMPA），用人尿液中用二乙醚作为萃取剂提取。在用乙腈交换二乙醚溶剂后，用 2-（溴甲基）萘（BMN）对分析物进行衍生化。BMN 与 NAMs 的反应产物，即 MN-EMPA、MN-IMPA 和 MN-PMPA，通过气相色谱（GC）分离，并使用发射波长为 267nm 的飞秒激光作为共振增强双光子电离（RE2PI）的电离源，用质谱（MS）进行测量。这些分析物的检测限（LOD）均<1ng/mL。BMN 的使用增加了分析物的挥发性，便于通过 GC 进行分离，并且由于萘官能团的存在，通过 RE2PI 过程提高了电离效率。二维 GC-MS 显示可用于对样品中的 NAMs、副产物和杂质进行综合分析。然后，这种方法可用于确认化学武器的使用情况和法医鉴定。
