面声波电离便携式离子阱质谱路检唾液鉴定毒驾研究

Drugged driving is a serious public health and safety problem in transportation, and more than 7000 casualties occurred in the traffic accident involving drugged driving since 2013. The lack of reliable road-check methods for drugged driving has prevented drugged driving from being sentenced for the time being. In this project, saliva is used as biological specimens to develop a new method for drugged driving check with portable ion trap mass spectrometry (PITMS). And the new method with PITMS mainly focuses on improving the analytical speed, sensitivity, and accuracy. The project intends to design a dual-concentrated interdigital transducer surface acoustic waveform ionization source for direct ionization of illegal drugs inside of saliva. This new design does not need any sample pretreatment, and dramatically reduces the analysis time. The illegal drug ions obtained under atmospheric pressure are initially enriched by nonlinear electrostatic lens. A segmented quadrupole is designed in the vacuum differential chamber, and the RF voltage amplitude of the head rod and the tail rod is adjustable. High RF voltage on head rod removes low mass-to-charge ions. The low RF voltage amplitude on tail rod reduces pseudopotential, radially compresses the ion beam and improves ion transmission efficiency. Segmented quadrupole rod coupled with two-stage linear ion trap construct a three-stage ion storage, and store all the ions obtained from a small amount of saliva sample in one step to ensure the analytical sensitivity. Two-stage linear ion trap tandem mass spectrometry is used to improve the qualitative accuracy. The first-stage ion trap is designed as oblique structure for tailing rod in combination with the slot-endcap electrode, and the axial ion ejection is used to efficiently inject the ions into the second-stage ion trap for tandem analysis. The quantitative quality control and correction method will be optimized to realize accurate quantification of drugs.

毒驾危害巨大，2013年以来涉及毒驾的交通事故造成约7000人伤亡，缺乏可靠路检方法导致毒驾暂未入刑。本项目以唾液作为检材，发展便携式离子阱质谱毒品检测新方法，解决毒驾分析速度、灵敏度及准确性难题。项目拟设计双聚焦叉指换能器面声波电离源喷雾直接电离唾液中毒品，无需样品前处理提高分析速度。大气压下得到的毒品离子采取非线性静电透镜进行离子的初级富集；真空区设计降压片段四极杆，调节头杆和尾杆射频电压幅值，去除低质荷比离子干扰、降低尾杆赝势阱径向压缩离子束提高传输效率；片段四极杆及两级线性离子阱串联，一次性存储少量样品中得到的所有离子，保障分析灵敏度。采用两级线性离子阱实现串级质谱分析提高定性准确度，第一级离子阱设计尾杆斜切结构结合槽式端盖电极，实施轴向弹射将离子高效注入第二级离子阱，实现少量样品一次性离子进样串级质谱分析。优化定量质量控制、校正方法，实现毒品准确定量。

本项目共研制了光闪热解析脉冲进样离子阱和光热解析-双试剂辅助-低温等离子体电离离子阱质谱仪2类微型离子阱质谱用于毒品现场快速分析。发展可检测毒品及其谱库 1 套包括 37 种常见毒品：海洛因、可卡因、甲基苯丙胺、苯丙胺、MDA、MDMA、四氢大麻酚、大麻二酚、氯胺酮、3-单乙酰吗啡、美沙酮、吗啡、可待因、乙酰可待因、蒂巴因、罂粟碱、那可汀、阿替洛尔，麻黄碱，伪麻黄碱等。建立上述毒品的快速、自动识别串级质谱分析程序，发展了利用便携式离子阱现场检测唾液样品分析方法和流程。. 针对难挥发混合毒品的现场鉴定，设计光闪热加热源，基于丙酮辅助化学电离，结合同步脉冲进样，实现了高沸点差异的多种毒品混合物的同时检测。在3s内光闪热解析将解析池内的焦点附近的毒品加热至290℃，难挥发的毒品那可汀的灵敏度相比提高了60倍。研制的脉冲吹扫将热解析池内挥发出来的难挥发和易挥发样品同时吹入质谱，样品的利用率提高了5倍以上，沸点差异达到300℃的10种毒品混合物通过光闪热解析实现了同时检测，分析时间仅3s。. 针对毒驾唾液路检，基于低温等离子体电离源开发了一种石英四通管结构的电离源，并使用连续进样型便携式离子阱质谱仪实现了对尿液和唾液中药物的高灵敏度和快速检测。电离源装置内体积仅0.05mL，结合光闪热解析，仪器灵敏度相比Nano-ESI提高了4倍，相比APPI提高了2倍。丙酮辅助电离试剂和样品蒸发丁醇辅助试剂的双试剂辅助电阻挡放电化学电离，采用棉签实现液体和固体样品取样，无需任何前处理，进行唾液和尿液样品中毒品的现场分析，灵敏度达到10 ng/ml，满足毒驾唾液路检分析国家标准。. 项目共发表SCI论文9篇，其中 Analytical Chemistry 发表1 篇，Trend in Analytical Chemistry 2篇，Analytica Chimica Acta 1篇，Analyst 1 篇，Talanta 1 篇，Journal of Environmental Sciences 1 篇，Analytical Methods 1篇，分析测试学报1 篇。. 项目申请发明专利 10 项，其中发明专利已授权6项，已授权实用新型2项，已授权软件登记1项。