摘要
合成大麻素(SCs)是数量最多的一类新精神活性物质(NPS)。我国于2021年7月起对SCs实行了整类列管。然后,经过结构修饰后产生的新型SCs仍然层出不穷,给法庭科学实验室检测分析带来巨大挑战。因此,亟需构建高效、绿色和自动化的分析检测方法为真实案件样品的准确筛查提供技术支持。同时,吲唑类SCs因药效更强,自2013年后数量急剧增加,是SCs中需要重点关注的一个亚类,也是法庭科学实验室检测分析SCs的主要类别。本文开发了在线固相萃取前处理技术结合液相色谱-线性离子阱质谱(online SPE/LC-LIT-MS)从人体尿液和血液中检测51种吲唑类SCs的分析方法。将加入了51种吲唑类SCs混合标准溶液和内标溶液的人血液或尿液试样经乙腈沉淀蛋白后,用含0.1%甲酸的10 mmol/L醋酸铵溶液(pH=4.8)稀释,过滤后直接进样;以含0.1%甲酸(v/v)的乙腈-含0.1%甲酸的10 mmol/L醋酸铵溶液为流动相进行分析。在全扫描模式下,选择目标分析物的分子离子([M+H]^(+))和保留时间监测其二级离子,共实现了51种吲唑类SCs的定量分析;结合色谱和多级质谱数据也实现了的定性筛查(包括5组同分异构体)。各分析物检出限为0.02~1 ng/mL,定量限为0.04~4 ng/mL(尿液)和0.1~4 ng/mL(血液)。采用线性拟合时(权重因子1/x),各分析物在各自的线性范围内线性关系良好。同时在定量限、低、中、高4个水平下考察了方法的回收率和精密度,回收率为83.47%~116.95%,精密度为0.58%~13.79%。本文方法通过阀切换在动态模式下实现样品的提取、富集和分析,不仅操作简单,还实现了样品的自动化和高通量分析;同时,具有较好的灵敏度和更宽的适用范围,为实际案件中SCs的快速筛查和定量分析提供了科学依据和技术支持。
To evade legal controls,new psychoactive substances(NPS),which have been designed as substitutes for traditional and synthetic drugs,are gradually dominating the drug market.Synthetic cannabinoids(SCs),which account for the majority of NPS,are rapidly being derivatized;consequently,controlling increasing abuse by merely listing individual compounds is difficult.Therefore,China has included the entire SC category of SCs listed as legal controlled substances since July 1,2021.However,new SCs obtained through structural modification are still appearing and pose significant analytical challenges for forensic laboratories.Therefore,an efficient,green,and automated detection method is urgently required to provide technical support for the accurate screening actual samples.Meanwhile,the number of indazole-type SCs has increased sharply since 2013,which is ascribable to their stronger psychoactive effects.Indeed,forensic laboratories mainly analyze this key SC subclass.Therefore,in this study,we developed a new method for analyzing 51 indazole-type SCs in human urine and blood,which involves online solid-phase extraction(online SPE)as the preprocessing technology,with analysis performed using liquid chromatography-linear ion trap mass spectrometry.Deproteinization was achieved by adding acetonitrile,with dilution performed using 10 mmol/L ammonium acetate solution(pH 4.8)containing 0.1%formic acid.Samples were then analyzed directly using acetonitrile-10 mmol/L ammonium acetate aqueous solution(containing 0.1%formic acid)as the mobile phase.The mass-to-charge ratios of protonated molecular ions([M+H]^(+))in the mass spectra acquired in full-scan mode,and the retention times in the chromatograms of the analytes were selected with the aim of monitoring the MS^(2) ions of the various compounds.Characteristic fragment ions of the various SC structures were summarized,with five groups of isomers,each containing ten compounds,successfully distinguished using multistage mass spectrometry and their retention times.Multistage MS was used to qualitatively screen 51 indazole-type SCs,which were then quantitatively analyzed using MS^(2) ion pairs(as quantitative ion pairs).The analytes exhibited limits of detection(LODs)of 0.02-1 ng/mL,with limits of quantification(LOQs)of 0.04-4 and 0.1-4 ng/mL in urine and blood,respectively.Linear fitting(weighting factor 1/x)revealed good linearity for each analyte within its respective linear range,with correlation coefficients(R 2)greater than 0.99 in both urine and blood.The validity of the analytical method was tested by determining precision and spiked recovery values(n=6).Recoveries of 83.47%-116.95%were obtained at LOQ levels,with precisions of 2.29%-13.40%.In addition,recoveries of 86.63%-113.38%and precisions of 0.58%-13.79%were obtained at low,medium,and high levels.In contrast to methods reported in the literature for analyzing SCs from human blood and urine,t The method described herein is not only easy to operate but also can be automated.Indeed,high-throughput sample analysis was achieved when sample extraction,enrichment,and analysis were performed in dynamic mode through valve switching.Meanwhile,the method exhibited good sensitivity and is applicable to a wider range of compounds than those previously reported;it also provides a scientific basis and technical support for the rapid screening and quantitative analysis of SCs in actual relevant cases.
作者
罗轩
张珺
朱定姬
黄克建
杨宁
刘晓锋
罗秋莲
LUO Xuan;ZHANG Jun;ZHU Dingji;HUANG Kejian;YANG Ning;LIU Xiaofeng;LUO Qiulian(School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China;Institute of Forensic Science,Public Security Department of Guangxi Zhuang Autonomous Region,Nanning 530021,China;Institute of Forensic Science,Public Security Department of Guangxi Zhuang Autonomous Region,Nanning 500012,China;Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development,Guangxi University,Nanning 530004,China)
出处
《色谱》
北大核心
2025年第2期164-176,共13页
Chinese Journal of Chromatography
基金
广西科技计划项目(桂科AD19259004).
关键词
合成大麻素
吲唑类
尿液
血液
在线固相萃取
液相色谱-线性离子阱质谱
synthetic cannabinoids(SCs)
indazole-type
urine
blood
online solid-phase extraction(online SPE)
liquid chromatography-linear ion trap-mass spectrometry(LC-LIT-MS)
