火锅食品中罂粟壳成分检测结果的假阳性研究

False positive study on detection results of pericarpium papaveris components in hot pot foods

中文关键词:  火锅  罂粟壳  假阳性  液相色谱-质谱法

英文关键词:hot pot  pericarpium papaveris  false positive  liquid chromatography-mass spectrometry

中文摘要:

      目的 采用液相色谱-串联质谱法测定火锅食品中罂粟壳成分, 并对检测结果出现的假阳性判断和确证进行详细分析。方法 样品经盐酸、乙腈溶解后, 采用QuEChERS方法提取和净化, 以WATERS Acquity UPLC BEH HILIC柱(2.1 mm×100 mm, 1.7 μm)为分析柱, 0.1%甲酸-甲酸铵溶液(V:V)和0.1%甲酸-乙腈(V:V)为流动相, 梯度洗脱分离。质谱采用正离子模式, 多反应监测模式(multiple reaction monitoring, MRM)进行检测。高分辨质谱分析同时采用全扫描和平行反应监测模式(parallel reaction monitoring PRM)进行监测。测定23种不同香料样品, 并比较混合样品加入油基质及罂粟壳标准品前后的质谱响应和检出限。结果 麻椒、花椒、草果样品中检出与罂粟碱标准品保留时间接近、丰度比相差较大的干扰峰, 易被误判为阳性结果。从白胡椒、荜拨样品提取蒂巴因定量离子也出现类似干扰峰情况。提取香叶样品中那可丁的定量离子时, 发现了一组保留时间与标准品一致且丰度比相近的干扰峰, 并进行了高分辨质谱的确证分析。当罂粟壳添加水平被稀释到0.8 mg/kg时, 吗啡成分的质谱响应极小, 那可丁和罂粟碱成分的质谱响应仍较高。结论 应用液相色谱-串联质谱法测定火锅食品中罂粟壳成分时需检测样品中有无香叶存在, 为避免出现假阳性检测结果, 应采用高分辨质谱进行确证。

英文摘要:

      Objective To determine the pericarpium papaveris components in hot pot foods by liquid chromatography-tandem mass spectrometry (LC-MS/MS), and to analyze the false positive judgment and confirmation of the detection results in detail. Methods After dissolved with hydrochloric acid and acetonitrile, the spice samples were extracted and purified by QuEChERS method. The analysis was performed on a WATERS ACQUITY UPLC BEH HILIC column (2.1 mm×100 mm, 1.7 μm) and using 0.1% (V:V) formic acid-ammonium formate solution and 0.1% (V:V) formic acid-acetonitrile as the mobile phase, then separated by gradient elution. The samples were determined by mass spectrometry in the positive ion mode with the multiple reaction monitoring mode (MRM). High resolution mass spectrometric analysis was performed using both full MS and parallel reaction monitoring (PRM). Then 23 kinds of spice samples were analyzed respectively, and the mass spectrum response and limits of detection were compared before and after adding edible oil and pericarpium papaveris standard. Results Interference peaks with similar retention time of hemp pepper, Chinese prickly ash and amomumtsao-ko samples were extracted compared to papaverine, but ion ratios were different, so it was easy to be mistaken for positive results. There were similar interference peaks also occurred in white pepper and long pepper samples compared with the baine standard. However, narcotine’s quantitative ion from myrcia was extracted, and the retention time was consistent with the standard and the abundance was similar to that of the interference peaks. The confirmatory analysis of high resolution mass spectrometry was carried out. In addition, when the spiked level of pericarpium papaveris was diluted to 0.8 mg/kg, the mass response of morphine component was minimal, but the mass response of narcotine and papaverine components were still high. Conclusions In the determination of pericarpium papaveris components in hot pot foods using LC-MS/MS, the presence of myrcia in samples should be tested. In order to avoid false positive results, high resolution mass spectrometry should be used to confirm the results.