Department of Laboratory Medicine, West China Hospital, Sichuan University, Chengdu, 610041, Sichuan, China.
Department of Pharmacy, West China Hospital, Sichuan University, Chengdu, 610041, Sichuan, China.
Anal Bioanal Chem. 2024 May;416(12):3073-3083. doi: 10.1007/s00216-024-05257-1. Epub 2024 Mar 22.
Diquat (DQ), paraquat (PQ), glufosinate (GLU), and glyphosate (GLYP) are commonly used herbicides that have been confirmed to be toxic to humans. Rapid and accurate measurements of these toxicants in clinical practice are beneficial for the correct diagnosis and timely treatment of herbicide-poisoned patients. The present study aimed to establish an efficient, convenient, and reliable method to achieve the simultaneous quantification of DQ, PQ, GLU, and GLYP in human plasma using liquid chromatography-tandem mass spectrometry (LC-MS/MS) without using derivatization or ion-pairing reagents. DQ, PQ, GLU, and GLYP were extracted by the rapid protein precipitation and liquid-liquid extraction method and then separated and detected by LC-MS/MS. Subsequently, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, accuracy, extraction recovery, matrix effect, dilution integrity, and stability were evaluated to validate the method based on the FDA criteria. Finally, the validated method was applied to real plasma samples collected from 166 Chinese patients with herbicide poisoning. The results showed satisfactory linearity with low LOD (1 ng/mL for DQ and PQ, 5 ng/mL for GLU, and 10 ng/mL for GLYP, respectively) and low LOQ (5 ng/mL for DQ and PQ, 25 ng/mL for GLU and GLYP, respectively). In addition, the precision, accuracy, extraction recovery, and stability of the method were acceptable. The matrix effect was not observed in the analyzed samples. Moreover, the developed method was successfully applied to determine the target compounds in real plasma samples. These data provided reliable evidence for the application of this LC-MS/MS method for clinical poisoning detection.
敌草快（DQ）、百草枯（PQ）、草甘膦（GLU）和草甘膦（GLYP）是常用的除草剂，已被证实对人体有毒。在临床实践中快速准确地测量这些毒物，有利于正确诊断和及时治疗除草剂中毒患者。本研究旨在建立一种高效、方便、可靠的方法，利用液相色谱-串联质谱法（LC-MS/MS）同时定量检测人血浆中的 DQ、PQ、GLU 和 GLYP，无需使用衍生化或离子对试剂。DQ、PQ、GLU 和 GLYP 采用快速蛋白沉淀和液液萃取法提取，然后用 LC-MS/MS 分离和检测。随后，根据 FDA 标准，对线性、检测限（LOD）、定量限（LOQ）、精密度、准确度、提取回收率、基质效应、稀释完整性和稳定性进行评估，以验证方法。最后，将验证后的方法应用于从 166 名中国除草剂中毒患者采集的真实血浆样本。结果表明，该方法具有令人满意的线性关系，LOD 低（DQ 和 PQ 为 1ng/mL，GLU 为 5ng/mL，GLYP 为 10ng/mL），LOQ 低（DQ 和 PQ 为 5ng/mL，GLU 和 GLYP 为 25ng/mL）。此外，该方法的精密度、准确度、提取回收率和稳定性均令人满意。在分析样品中未观察到基质效应。此外，该方法成功应用于测定真实血浆样品中的目标化合物。这些数据为该 LC-MS/MS 方法在临床中毒检测中的应用提供了可靠的证据。
