VERTOX Laboratory , Defence Research and Development Establishment , Jhansi Road , Gwalior 474002 , Madhya Pradesh , India.
Anal Chem. 2018 Jul 17;90(14):8295-8299. doi: 10.1021/acs.analchem.8b02157. Epub 2018 Jun 27.
Extraction of vesicant class of chemical warfare agents (CWAs) such as sulfur mustard and nitrogen mustards from the environmental matrices is of prime importance, from a forensic and verification viewpoint of the Chemical Weapons Convention (CWC). For extraction of Convention Related Compounds from nonpolar organic medium, commercially available silica cartridges are used extensively, but silica cartridges exhibit limited efficiency toward vesicant classes of compounds. It is expected that sulfur mustard being nonpolar does not retain sufficiently on silica surface, and nitrogen mustards (being basic) are strongly adsorbed on acidic silica surface, resulting in their poor recoveries. Contrary to the expected higher recovery of sulfur mustard over nitrogen mustards, it was observed that the recovery of sulfur mustard was lower than that of nitrogen mustards with the silica based sorbent. The reason for this typical behavior of these agents on silica was investigated. This study was aimed to develop an analytical method for efficient extraction and enrichment of sulfur and nitrogen mustards from hydrophobic matrices. In this work, the polymeric sorbent was synthesized with polar methacrylic acid (MAA) as monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker and used for solid phase extraction (SPE) of sulfur mustard and nitrogen mustards. The extraction efficiency of the polymeric sorbent was optimized and compared with that of silica cartridges. Both classes of analytes were recovered in good amounts from the polymeric sorbent compared to silica. The extraction parameters were optimized for the proposed method which included extraction solvent ethyl acetate and washing solvent n-hexane (1 mL). The recoveries of the analytes ranged from 75 to 87% with relative standard deviations (RSDs) lower than 9%. The limit of detection (LOD) was found to be in the range of 0.075-0.150 μg mL, and limit of quantification (LOQ) was >0.25 μg mL. The linear dynamic range of optimized method was found to be 0.50-20 μg mL ( r = 0.9994) for sulfur mustard and 0.25-20 μg mL ( r = 0.9897-0.9987) for nitrogen mustards, respectively.
从《化学武器公约》（CWC）的法医和核查角度来看，从环境基质中提取芥子气和氮芥等腐蚀性化学战剂（CWA）至关重要。为了从非极性有机介质中提取与公约相关的化合物，商业上可获得的硅胶筒被广泛使用，但硅胶筒对腐蚀性化合物的效率有限。预计芥子气是非极性的，不会在硅胶表面充分保留，而氮芥（碱性）则强烈吸附在酸性硅胶表面，导致回收率差。与预期的氮芥相比，芥子气的回收率更高相反，观察到使用基于硅胶的吸附剂时，芥子气的回收率低于氮芥。研究了这些试剂在硅胶上的这种典型行为的原因。本研究旨在开发一种从疏水性基质中有效提取和富集硫芥和氮芥的分析方法。在这项工作中，合成了含有极性甲基丙烯酸（MAA）作为单体和乙二醇二甲基丙烯酸酯（EGDMA）作为交联剂的聚合物吸附剂，并用于固相萃取（SPE）硫芥和氮芥。优化了聚合物吸附剂的萃取效率，并与硅胶筒进行了比较。与硅胶相比，两种类别的分析物都以良好的量从聚合物吸附剂中回收。优化了用于该方法的萃取参数，包括萃取溶剂乙酸乙酯和洗涤溶剂正己烷（1 mL）。分析物的回收率范围为 75-87%，相对标准偏差（RSD）低于 9%。检测限（LOD）在 0.075-0.150 μg mL 范围内，定量限（LOQ）>0.25 μg mL。优化方法的线性动态范围发现为 0.50-20 μg mL（r = 0.9994）对于芥子气和 0.25-20 μg mL（r = 0.9897-0.9987）对于氮芥，分别。
