Sai Sachin L, Karthikraj R, Kalyan Kumar K, Sony T, Prasada Raju N, Prabhakar S
National Centre for Mass Spectrometry, CSIR-Indian Institute of Chemical Technology, Hyderabad- 500 007, Telangana, India.
Eur J Mass Spectrom (Chichester). 2015;21(6):791-800. doi: 10.1255/ejms.1398.
Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verification of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1-7) and chloroethyl vinylic compounds (8-14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1-7) showed M-SH ions, whereas the chloroethylvinyl compounds (8-14) showed M-Cl and M-CH2CH2Cl ions. Methane/CI mass spectra showed M+H ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verification of the chemical weapons convention and also to participate in official Organization for the Prohibition of Chemical Weapons proficiency tests.
硫芥是一类糜烂性化学战剂，在环境样品中会迅速降解。硫芥最可能的降解产物是氯乙基乙烯基化合物和二乙烯基化合物，它们分别由硫芥分子脱去一个和两个氯化氢分子形成。在环境样品中检测和鉴定这些降解产物是证实使用硫芥的一项重要证据。在本研究中，我们合成了一组硫芥降解产物，即二乙烯基化合物（1 - 7）和氯乙基乙烯基化合物（8 - 14），并在电子电离（EI）和化学电离（CI）（甲烷）条件下使用气相色谱/质谱联用仪（GC/MS）对其进行了表征。所研究化合物的EI质谱主要包括伴随或不伴随氢迁移均裂产生的碎片离子。二乙烯基化合物（1 - 7）显示出M - SH离子，而氯乙基乙烯基化合物（8 -14）显示出M - Cl和M - CH₂CH₂Cl离子。甲烷/CI质谱显示出M + H离子并提供了分子量信息。还计算了所研究化合物的气相色谱保留指数（RI）值。EI和CI质谱数据以及RI值对于《化学武器公约》核查中的场外分析以及参加禁止化学武器组织官方能力验证测试极为有用。
