POD模型结合SERS技术快速检测饮料中的四氢大麻酚含量及方法评价

POD Model Combined with SERS Technology for Rapid Detection of Tetrahydrocannabinol Content in Beverages and Method Validation

摘要:

该研究建立了一种检出概率（Probability of Detection, POD）模型结合表面增强拉曼光谱（Surface-enhanced Raman Spectroscopy, SERS）技术快速检测饮料中四氢大麻酚（Tetrahydrocannabinol, THC）含量的方法。针对碳酸饮料、果蔬汁饮料、维生素饮料等不同的样品基质，开发了直接稀释法和萃取法两种前处理方案。实验结果显示542、1 172 cm-1处的拉曼特征峰作为四氢大麻酚的识别峰，结合POD模型，确定出四氢大麻酚在碳酸饮料等基质中的检出限为1 mg/kg，在果蔬汁等基质中的检出限为2 mg/kg。实验中设计多梯度阳性样品（0~10 mg/kg）进行SERS检测，建立检出概率值随质量浓度变化的POD定性模型，从而得出该快检方法的灵敏度≥95%，特异性≥90%，假阴性率≤5%，假阳性率≤10%。同时，该快检方法与参比方法（液相色谱串联质谱法）进行一次性评价分析，在检出限水平以上，该方法与参比方法的检出概率均在95%以上，两种方法具有一致性。该快检方法操作简便、快速准确，从样品前处理开始到测定结果仅需30 min，结合使用POD模型，验证了该方法的有效性，有望应用于海关口岸、市场监管等领域中四氢大麻酚的现场快速检测。

Abstract:

In this study, a rapid method for detecting tetrahydrocannabinol (THC) content in beverages using a probability of detection (POD) model combined with surface-enhanced Raman spectroscopy (SERS) technology was established. Two pre-treatment schemes, direct dilution method and extraction method, were developed for different sample matricessuch as carbonated beverages, fruit and vegetable juices, and vitamin beverages. The experimental results showed that the Raman characteristic peaks at 542 cm-1 and 1 172 cm-1 were used as the peaks for identifying THC. In combination with the POD model, the detection limit (LOD) of tetrahydrocannabinol was determined to be 1 mg/kg in carbonated beverages and other matrices, and 2 mg/kg in fruit and vegetable juices. In the experiment, multiple-concentration-gradient positive samples (0~10 mg/kg) were designed for SERS detection, and a qualitative POD model was established to determine the change in detection probability with mass concentration. The sensitivity of this method was greater than or equal to 95%, with specificity greater than or equal to 90%, false negative rate lower than or equal to 5%, and false positive rate lower than or equal to 10%. Meanwhile, this rapid detection method and the reference method (the method by liquid chromatographytandem mass spectrometry) were analyzed through one-time evaluation. When the concentration of added THC was not lower than LOD, the POD values of this SERS method and the reference method were both higher than 95%, indicating that the two methods showed good consistency. This rapid detection method is easy to operate, fast and accurate, and requires only 30 minutes from sample pretreatment to measurement results. In combination with the POD model, the effectiveness of this method was verified. This method is expected to be applied for rapid on-site detection of THC in customs ports, market supervision and other fields.