新型直接采样电离方法研究及其毒品快速质谱分析应用

在新型毒品层出不穷的背景下，对毒品进行现场快速检测的需求日益增加。直接采样电离技术与小型质谱系统的结合是对多类型毒品进行现场快速检测的重要途径。针对目前直接电离采样方法对部分毒品分子电离效率低的问题，本工作开发了一种基于快速采样萃取的新型直接毛细管喷雾方法（DCS）及相应的一体化试剂盒。分析流程包括表面采样、溶剂洗涤、直接电离及小型质谱检测，整个分析过程可在1 min内完成。对包装袋表面的麻黄碱、可卡因、氯胺酮、甲基苯丙胺、亚甲基二氧甲基苯丙胺、1-（3-氯苯基）哌嗪、奥芬太尼等进行分析，结果表明，该方法具有良好的稳定性和定性、定量分析能力。以麻黄碱为例，采用DCS试剂盒得到质谱信号的组间和组内相对标准偏差（RSD）均小于20%。甲基苯丙胺的检出限和定量限分别为0.1、0.2 ng/cm²。使用内标法进行定量分析，甲基苯丙胺在0.2~50 ng/cm²范围内呈现良好的线性关系。将该方法用于复杂基质（果汁、可乐、唾液、血液）中可卡因和甲基苯丙胺的检测，最低定量限均低于100 μg/L。该方法适用于环境表面、食品、生物体液等复杂基质中多种毒品的现场、快速检测。

Development of a Novel Direct Capillary Spray Cartridge and its Application in Fast Mass Spectrometry Analysis of Drugs

There is an increasing need for on-site and rapid detection of drugs of abuse, especially with a large number of new designer drugs emerging. The combination of direct sampling ionization and miniature mass spectrometry (MS) system serves as a primary strategy for fast analysis of various drugs. In consideration of low ionization efficiency of current direct sampling techniques for some drugs, a novel direct capillary spray method was developed and a cartridge was designed. The workflow only required an analysis time less than 1 min, including fast sampling, analyte elution and direct MS analysis by a miniature mass spectrometer. The analytical performance was demonstrated by analyzing ephedrine, cocaine, ketamine, methamphetamine, MDMA, 1-(3-chlorophenyl) piperazine (mCPP), and ocfentanil on surfaces of bags, showing good qualitative and quantitative capabilities. The signal stability was tested with the relative standard deviations better than 20%, and the limits of detection (LODs) and the limits of quantitation (LOQs) for methamphetamine were 0.1 ng/cm² and 0.2 ng/cm², respectively. This method was applied to determine cocaine and methamphetamine in complex matrices (juice, cola, saliva, blood), with the LODs better than 100 μg/L. This method is expected to help expand the application in drug analysis using direct sampling ionization MS analysis. It has potential to be used for fast and on-site testing of various drugs in complicated matrices, such as from ambient surfaces, drinks and biofluids.