液相色谱-串联质谱法同时测定电子烟油中的102种合成大麻素类物质

Simultaneous determination of 102 synthetic cannabinoids in electronic cigarette oil by liquid chromatography-tandem mass spectrometry

合成大麻素是目前世界上滥用最广泛的新精神活性物质之一,其被伪装成各种形态,以电子烟油的形式贩卖是其中一种主要形式。合成大麻素结构多变,更新迅速,通常单个方法所包含的合成大麻素种类有限。本研究针对电子烟油中102种合成大麻素类物质,建立了液相色谱-三重四极杆质谱法(LC-MS/MS)同时对其进行定性定量分析的方法。实验对质谱条件和液相色谱条件进行了优化,结合外标法定量,实现了对102种合成大麻素的同时定性定量分析。样品用甲醇提取,在多反应监测(MRM)模式下,以0.1%甲酸水溶液和甲醇-乙腈(1∶1,v/v)混合溶液为流动相,采用岛津Shim-pack GIST-HP C18 AQ色谱柱(100 mm×2.1 mm,1.9μm)进行分离,柱温40℃,流速0.4 mL/min,进样量1μL。结果表明,采用该方法,102种合成大麻素可在18 min内分离,在1~100.0μg/L范围内线性关系良好,相关系数(r)≥0.9915,检出限为0.01~0.30μg/L,定量限为0.04~0.99μg/L,满足实际样品的分析需求。采用2、10、50μg/L 3个水平的102种合成大麻素混合标准溶液进行精密度试验,其相对标准偏差(RSD,n=6)为0.3%~6.0%。以空白电子烟油为基质样品,在2、10、50μg/L 3个加标水平下进行加标回收试验,各待测物的加标回收率为80.1%~119.8%。本方法具有准确、快速、灵敏、分离效果好等优点,适用于电子烟油中102种合成大麻素类物质的定性定量测定,可满足相关鉴定工作的要求。

Synthetic cannabinoids(SCs),which are among the most widely abused new psychoactive substances,are much more potent and have greater efficacy than natural cannabis.SCs can be disguised in various ways and are commonly sold in the form of electronic cigarette oil.SCs belong to a large family with structures consisting of a core with substituents,linker,ring with substituents,and tail.New SCs can be developed by adding substituents,such as halogen,alkyl,and alkoxy groups,to the aromatic ring system or by changing the alkyl chain length.Since the emergence of so-called first-generation SCs,subsequent developments have led to eighth-generation indole/indazole amide-based SCs.As of July 1,2021,the entire category of SCs was added to the list of controlled substances,but implementation requires urgent improvements in detection technologies.Typically,each method is limited to a few SCs.Owing to the vast number of chemically diverse SCs and their fast update speed,the determination and identification of various types of SCs using a single method is challenging.Therefore,rapid,sensitive,and accurate quantitative methods that includes various types of SCs must be developed to meet the demand for the qualitative and quantitative analysis of new SCs in seized electronic cigarette oil.In this study,a liquid chromatography-tandem mass spectrometry(LC-MS/MS)method was developed for the simultaneous determination of 102 SCs in electronic cigarette oil.The mass spectrometry and liquid-phase conditions influencing SC separation and determination were optimized.Using the external standard method,102 SCs were successfully identified in electronic cigarette oil.The samples were extracted using methanol.Target analytes were separated on a Shimadzu Shim-pack GIST-HP C18 AQ column(100 mm×2.1 mm,1.9μm)at a column temperature of 40℃.The mobile phases consisted of(A)0.1%formic acid aqueous solution and(B)methanol-acetonitrile(1∶1,v/v).The gradient elution conditions were as follows:0-8 min,55%A-15%A;8-15 min,15%A;15-16 min,15%A-55%A;16-18 min,55%A.The flow rate was 0.4 mL/min and the injection volume was 1μL.Operating in the multiple reaction monitoring mode,the 102 SCs were identified within 18 min.Each SC exhibited a good linear relationship in the range of 1-100.0μg/L with a correlation coefficient(r)≥0.9915.The limits of detection were 0.01-0.30μg/L and the limits of quantification were 0.04-0.99μg/L,which meet the requirements for analyzing SCs in actual samples.Precision was determined using standard solutions with 2,10,and 50μg/L of the SCs.The precisions(n=6)were 0.3%-6.0%.The recoveries of the 102 SCs,as evaluated by spiking electronic cigarette oil at low(2μg/mL),medium(10μg/mL),and high(50μg/mL)levels,were 80.1%-119.8%.Good performance was observed for the analysis of real samples.The developed method is accurate,rapid,sensitive,and effective for the determination of the 102 SCs in electronic cigarette oil,satisfying the requirements for practical qualitative and quantitative analysis.