Sinha Roy Kanchan, Goud D Raghavender, Mazumder Avik, Chandra Buddhadeb, Purohit Ajay Kumar, Palit Meehir, Dubey Devendra Kumar
Vertox Laboratory , Defence Research and Development Establishment , Jhansi Road , Gwalior 474002 , Madhya Pradesh , India.
ACS Appl Mater Interfaces. 2019 May 1;11(17):16027-16039. doi: 10.1021/acsami.9b02354. Epub 2019 Apr 22.
The strict monitoring and precise measurements of chemical warfare agents (CWAs) in environmental and other complex samples with high accuracy have great practical significance from the forensic and Chemical Weapons Convention (CWC) verification point of view. Therefore, this study was aimed to develop an efficient extraction and enrichment method for identification and quantification of toxic agents, especially with high sensitivity and multidetection ability in complex samples. It is the first study on solid-phase extraction (SPE) of CWAs and their related compounds from hydrocarbon backgrounds using covalent triazine-based frameworks (CTFs). This nitrogen-rich CTF sorbent has shown an excellent SPE performance toward sample cleanup by selective elimination of hydrocarbon backgrounds and enrich the CWC related analytes in comparison with the conventional and other reported methods. The best enrichment of the analytes was found with the washing solvent (1 mL of n-hexane) and the extraction solvent (1 mL of dichloromethane). Under the optimized conditions, the SPE method had good linearity in the concentration range of 0.050-10.0 μg mL for organophosphorus esters, 0.040-20.0 μg mL for nerve agents, and 0.200-20.0 μg mL for mustards with correlation coefficients ( r) between 0.9867 and 0.9998 for all analytes. Limits of detection ( S/ N = 3:1) in the SIM mode were found to be in the range of 0.015-0.050 μg mL for organophosphorus esters, 0.010-0.030 μg mL for nerve agents, and 0.050-0.100 μg mL for blister agents. Limits of quantification ( S/ N = 10:1) were found in the range of 0.050-0.200 μg mL for organophosphorus esters, 0.040-0.100 μg mL for nerve agents, and 0.180-0.350 μg mL for blister agents in the SIM mode. The recoveries of all analytes ranged from 87 to 100% with the relative standard deviations ranging from 1 to 8%. This method was also successfully applied for the sample preparation of H NMR analysis of sulfur and nitrogen mustards in the presence of hydrocarbon backgrounds. Therefore, this SPE method provides the single sample preparation for both NMR and GC-MS analyses.
从法医和《化学武器公约》（CWC）核查的角度来看，对环境及其他复杂样品中的化学战剂（CWA）进行严格监测和精确测量具有重大的现实意义。因此，本研究旨在开发一种高效的萃取和富集方法，用于有毒战剂的鉴定和定量分析，尤其是在复杂样品中具有高灵敏度和多检测能力。这是首次使用共价三嗪基框架（CTF）从烃类背景中对CWA及其相关化合物进行固相萃取（SPE）的研究。与传统方法和其他已报道方法相比，这种富含氮的CTF吸附剂通过选择性去除烃类背景，在样品净化方面表现出优异的SPE性能，并能富集与CWC相关的分析物。发现用洗涤溶剂（1 mL正己烷）和萃取溶剂（1 mL二氯甲烷）对分析物的富集效果最佳。在优化条件下，SPE方法对有机磷酸酯的浓度范围为0.050 - 10.0 μg/mL、对战剂的浓度范围为0.040 - 20.0 μg/mL、对芥子气的浓度范围为0.200 - 20.0 μg/mL时具有良好的线性，所有分析物的相关系数（r）在0.9867至0.9998之间。在选择离子监测（SIM）模式下，有机磷酸酯的检测限（S/N = 3:1）在0.015 - 0.050 μg/mL范围内，战剂的检测限在0.010 - 0.030 μg/mL范围内，糜烂性毒剂的检测限在0.050 - 0.100 μg/mL范围内。在SIM模式下，有机磷酸酯的定量限（S/N = 10:1）在0.050 - 0.200 μg/mL范围内，战剂的定量限在0.040 - 0.100 μg/mL范围内，糜烂性毒剂的定量限在0.180 - 0.350 μg/mL范围内。所有分析物的回收率在87%至100%之间，相对标准偏差在1%至8%之间。该方法还成功应用于在烃类背景存在下对硫芥和氮芥进行1H NMR分析的样品制备。因此，这种SPE方法为NMR和GC-MS分析提供了单一的样品制备方法。
