Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA.
Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA.
Rapid Commun Mass Spectrom. 2021 Aug 15;35(15):e9123. doi: 10.1002/rcm.9123.
Detection of 3-quinuclidinol (3Q), a marker for the chemical warfare agent 3-quinuclidinyl benzilate, is very difficult by gas chromatography-mass spectrometry (GC/MS), providing low, broad signals even when analyzed in isolated form. Therefore, a method that can convert 3Q into a substrate with enhanced detectability by GC/MS would be an important tool for its analysis.
2,2,2-Trichloroethoxycarbonyl chloride (TrocCl) was used in the derivatization of 3Q in three different soils of varying composition and total organic content (Virginia type A soil, Nebraska EPA standard soil and Ottawa sand) when present at a 10 μg g concentration in each. A direct derivatization protocol and one involving the pre-extraction of the analyte were evaluated for their individual efficiencies and subsequent analysis using electron ionization GC/MS.
The practical derivatization of 3Q, when present at low levels (10 μg g ) in three different soil matrices, was found to be rapid (1 h) and to take place smoothly at ambient temperature (and as low as 4°C). The method detection limit was determined to be 30 ng mL for the Virginia type A soil, 49 ng mL for the Nebraska EPA standard soil and 72 ng mL for the Ottawa sand sample.
An expedient and practical derivatization method for 3Q, a chemical warfare degradation product difficult to detect by GC/MS, has been realized using trichloroethyl chloroformate. The reaction provides 3Q-Troc, a derivative with better detectability than 3Q by electron ionization GC/MS such as peak sharpness and a unique mass spectrum for its unambiguous identification.
通过气相色谱-质谱联用（GC/MS）检测 3-奎宁环醇（3Q）非常困难，即使以分离形式分析，也只能提供低而宽的信号，而 3Q 是化学战剂 3-奎宁环基苯酸的标志物。因此，一种可以将 3Q 转化为 GC/MS 检测性增强的底物的方法，将成为其分析的重要工具。
在浓度为 10μg/g 的情况下，使用 2,2,2-三氯乙氧基甲酰氯（TrocCl）对三种不同组成和总有机含量的土壤（弗吉尼亚 A 型土壤、内布拉斯加 EPA 标准土壤和渥太华砂）中的 3Q 进行衍生化。评估了直接衍生化方案和一种涉及分析物预提取的方案，以评估它们各自的效率，然后使用电子电离 GC/MS 进行后续分析。
在三种不同的土壤基质中，当 3Q 以低浓度（10μg/g）存在时，实际的衍生化过程被发现快速（1 小时），并且在环境温度（低至 4°C）下平稳进行。方法检测限确定为弗吉尼亚 A 型土壤为 30ng/mL，内布拉斯加 EPA 标准土壤为 49ng/mL，渥太华砂样品为 72ng/mL。
使用三氯乙氧基甲酰氯，实现了一种快速、实用的衍生化方法，用于检测 GC/MS 难以检测的化学战降解产物 3Q。该反应提供了 3Q-Troc，其衍生物比 3Q 通过电子电离 GC/MS 具有更好的检测性，如峰尖锐度和独特的质谱，可用于其明确鉴定。
