Goud D Raghavender, Pardasani Deepak, Purohit Ajay Kumar, Tak Vijay, Dubey Devendra Kumar
Vertox Laboratory, Defence Research and Development Establishment, Jhansi Road, Gwalior 474002, India.
Anal Chem. 2015 Jul 7;87(13):6875-80. doi: 10.1021/acs.analchem.5b01283. Epub 2015 Jun 16.
Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) are important precursors of the extremely toxic chemical warfare agent sulfur mustard and classified, respectively, into schedule 3.B.12 and 3.B.13 of the Chemical Weapons Convention (CWC). Hence, their detection and identification is of vital importance for verification of CWC. These chemicals are difficult to detect directly using chromatographic techniques as they decompose and do not elute. Until now, the use of gas chromatographic approaches to follow the derivatized sulfur chlorides is not reported in the literature. The electrophilic addition reaction of sulfur monochloride and sulfur dichloride toward 3-hexyne was explored for the development of a novel derivatization protocol, and the products were subjected to gas chromatography-mass spectrometric (GC-MS) analysis. Among various unsaturated reagents like alkenes and alkynes, symmetrical alkyne 3-hexyne was optimized to be the suitable derivatizing agent for these analytes. Acetonitrile was found to be the suitable solvent for the derivatization reaction. The sample preparation protocol for the identification of these analytes from hexane spiked with petrol matrix was also optimized. Liquid-liquid extraction followed by derivatization was employed for the identification of these analytes from petrol matrix. Under the established conditions, the detection and quantification limits are 2.6 μg/mL, 8.6 μg/mL for S2Cl2 and 2.3 μg/mL, 7.7 μg/mL for SCl2, respectively, in selected ion monitoring (SIM) mode. The calibration curve had a linear relationship with y = 0.022x - 0.331 and r(2) = 0.992 for the working range of 10 to 500 μg/mL for S2Cl2 and y = 0.007x - 0.064 and r(2) = 0.991 for the working range of 10 to 100 μg/mL for SCl2, respectively. The intraday RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and interday RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S2Cl2 and SCl2, respectively.
一氯化硫（S₂Cl₂）和二氯化硫（SCl₂）是剧毒化学战剂硫芥的重要前体，分别被列入《化学武器公约》（CWC）的3.B.12和3.B.13附表。因此，对它们的检测和鉴定对于《化学武器公约》的核查至关重要。由于这些化学品会分解且不被洗脱，所以很难直接用色谱技术进行检测。到目前为止，文献中尚未报道使用气相色谱方法来追踪衍生化的氯化硫。为开发一种新型衍生化方案，研究了一氯化硫和二氯化硫与3 - 己炔的亲电加成反应，并对产物进行了气相色谱 - 质谱（GC - MS）分析。在各种不饱和试剂（如烯烃和炔烃）中，对称炔烃3 - 己炔被优化为这些分析物的合适衍生化试剂。发现乙腈是衍生化反应的合适溶剂。还优化了从掺有汽油基质的己烷中鉴定这些分析物的样品制备方案。采用液 - 液萃取然后衍生化的方法从汽油基质中鉴定这些分析物。在既定条件下，在选择离子监测（SIM）模式下，S₂Cl₂的检测限和定量限分别为2.6 μg/mL、8.6 μg/mL，SCl₂的检测限和定量限分别为2.3 μg/mL、7.7 μg/mL。对于S₂Cl₂，在10至500 μg/mL的工作范围内，校准曲线呈线性关系，y = 0.022x - 0.331，r² = 0.992；对于SCl₂，在10至100 μg/mL的工作范围内，校准曲线呈线性关系，y = 0.007x - 0.064，r² = 0.991。S₂Cl₂的日内相对标准偏差在4.80%至6.41%之间，日间相对标准偏差在2.20%至7.25%之间；SCl₂的日内相对标准偏差在2.73%至6.44%之间，日间相对标准偏差在2.34%至5.95%之间。
