基于高分辨质谱法测定水产品中地西泮及丁香酚类化合物残留

Determination of diazepam and eugenol residues in aquatic products by high resolution mass spectrometry

中文关键词:  超高效液相色谱-静电场轨道阱高分辨质谱、水产品、地西泮及代谢物、丁香酚类化合物

英文关键词:Ultra high performance liquid chromatography-electrostatic field orbital high resolution mass spectrometry (UPLC-Q Exactive MS)  aquatic products  diazepam and its metabolites  eugenol compounds.

中文摘要:

      目的 建立基于Turboflow在线净化结合超高效液相色谱-静电场轨道阱高分辨质谱法（Ultra-high performance liquid chromatography-electrostatic field orbital high resolution mass spectrometry ,UPLC-Q Exactive MS ）测定水产品中4种地西泮及代谢物和6种丁香酚类化合物的方法。方法 采用Turboflow在线净化，AccucoreTM aQ C18柱(100 mm×2.1 mm，2.6 μm)分离，以水-乙腈为流动相梯度洗脱，全扫描+自动触发二级质谱（Full Scan+ddMS2 ）的正离子扫描监测模式，外标法定量。结果 方法学验证结果表明，地西泮及代谢物和丁香酚类化合物在1.0～100.0 μg/L 范围内线性良好，化合物的相关系数（r2）均大于 0.995；在水产品中的 LOQ 定量限分别为0.5~2.0 μg/kg；对在空白水产品和中进行2.0 μg/kg、10.0 μg/kg和30.0 μg/kg加标回收率分别为 75.3%~110.0%，RSD相对标准偏差分别为4.3%~7.2%。结论 该法操作简便、灵敏度高、检出限低，适用于实际样品的测定。通过调查发现，运输环节中水产品和水样中均检出地西泮和丁香酚类化合物，亟需对水产品中镇静剂或麻醉剂残留情况开展风险监测，加强监管以保障水产品质量安全。

英文摘要:

      A high resolution mass spectrometric method was developed for the determination of four diazepam and its metabolites and six eugenol compounds in aquatic products based on Turboflow on-line purification combined with Ultra high performance liquid chromatography-electrostatic field orbital high resolution mass spectrometry (UPLC-Q Exactive MS). Methods The samples were purified by on-line Turboflow. The analytes were separated on a AccucoreTM aQ C18 column (100mm×2.1mm，2.6μm) by gradient elution with water-acetonitrile solution as the mobile phases. The MS analysis was performed by Full Scan and automatic trigger secondary mass spectrometry(Full Scan+ddMS2)monitoring in the positive ion mode. The external standard method was used for quantification. Results The results showed that the linearity of diazepam, its metabolites and eugenol was good in the range of 1.0-100.0 μg/L, and the correlation coefficient (r2) of all compounds was greater than 0.995.The LOQs in aquatic products were 0.5-2.0 μg/kg. The average recoveries ranged from 75.3%-110.0% at spiked in level of 2.0 , 10.0 and 30.0 μg/kg in blank aquatic products, with their relative standard deviations（RSDs）ranged from 4.3%-7.2%.Conclusion The method is simple in operation, high in sensitivity and low in detection limit and suitable for the determination of real samples. It was found that diazepam and eugenol compounds were detected in aquatic products during transportation. There is an urgent need for risk monitoring of residues of sedatives or anesthetics in aquatic products, strengthen supervision to ensure the quality and safety of aquatic products.