UPLC-Q-TOF/MS快速检验17种有机炸药

Analysis of 17 Organic Explosives by UPLC-Q-TOF/MS

本文建立了超高效液相色谱–四级杆串联飞行时间质谱测定涉爆案件中17种有机炸药(TNT、RDX、HMX、PETN、CE、2-Am-DNT、4-Am-DNT、PYX、2-HADNT、4-HADNT、1,2-DNG、1,3-DNG、3,5-DNA、R-SALT、4-NDPA、NTO、4,4’-DNDPA)的快速定性、定量方法。本研究将有机炸药爆炸残留物或原药经有机溶剂直接溶解,用PLD+净化柱或有机微孔过滤膜净化提取,提取液采用超高效液相色谱–四级杆串联飞行时间质谱进行定性、定量检测。分析采用Shim-pack Velox Biphenyl(2.1 mm×100 mm×2.7μm)色谱柱,质谱扫描方式为负离子的全扫描/数据依赖二级质谱扫描(Full MS/DDA-MS2)模式。结果表明17种有机炸药的检出限在0.1~10 ng/mL之间,所有目标物在其相应的浓度范围内线性关系良好,日内相对标准偏差(RSD)为1.6%~5.3%(n=6),日间相对标准偏差(RSD)为1.7%~8.5%(n=24)。应用本方法可同时准确、快速、高效地对涉爆案件中的17种有机炸药进行定性、定量分析。

An analytical method was developed for the simultaneous determination of 17 organic explosives(TNT、RDX、HMX、PETN、CE、2-Am-DNT、4-Am-DNT、PYX、2-HADNT、4-HADNT、1,2-DNG、1,3-DNG、3,5-DNA、R-SALT、4-NDPA、NTO and 4,4’-DNDPA)and its explosive remnants from explosion cases by the ultra-high performance liquid chromatography-quadrupole-time offlight mass spectrometry(UPLC-Q-TOF/MS).The samples were dissolved with the organic solvent,and the solution obtained was purified with a PLD+polymer column or organic microporousfilter membrane.The extract was separated on a Shim-pack Velox Biphenyl column(2.1 mm×100 mm×2.7µm)using acetonitrile–0.05%ammonium chloride as a mobile phase by gradient elution and analyzed under ESI negative ionization Full MS/DDA-MS2 mode.Full scan experiments(TOF/MS&Production)were performed over the m/z range of 40–800 Da.Primary and secondary mass spectrometry information was collected in sequence.The relevant databases about the detected organic explosives was also established.The qualitative screening was performed using Lab Solutions Insight software through a combined score obtained from 4 factors:mass error,retention time error,isotope ratio difference,and library similarity.The quantitative analysis was carried out by extracting peak area with accurate mass.Under the optimal conditions,a good separation and high sensitivity analysis of 17 organic explosives were obtained.We mainly completed the following three parts:(a)We developed Q-TOF high-resolution mass spectrometry for the qualitative analysis and quantification of 17 organic explosives got a fast(10 minutes),high accurate qualitative(resolution 70000 FWHM)detection method.The method was applied to the detection of 17 organic explosives(TNT、RDX、HMX、PETN、CE et al.)and their explosive remnants from explosion cases.(b)The absolute value mass error of this analysis method was below 3.57.The limit of detection(LOD)for 17 organic explosives was 0.1–10 ng/mL.All the compounds had good linearities within their respective linear ranges(r>0.988);The relative standard deviation(RSD)within the day is 1.6%–5.3%,and the daytime RSD is 1.7%–8.5%(n=24).The 17 organic explosives have been tested effectually.(c)We sorted out data and established relevant databases about the detected organic explosives.The method is accurate,rapid,sensitive and efficient,suitable for qualitative and quantitative analysis of 17 organic explosives.The establishment of the screening methods and database realizes targetless screening,which will helpfind more explosive remnants and provide technical support for the nature of the case,therefore capable of being used in daily cases for relevant testing and identification.The method also has good compatibility.If positive and negative ionization mode is used at the same time,the database can be further expanded to achieve rapid screening of more organic explosives.