Department of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona, Israel.
Rapid Commun Mass Spectrom. 2023 Nov 15;37(21):e9624. doi: 10.1002/rcm.9624.
Sodium azide (NaN ) is a toxic chemical agent to humans by ingestion and inhalation with a growing number of intentional exposures and accidental cases over the last few decades. Due to its low molecular weight and lack of any chromophore, its retention and detection by reverse-phase liquid chromatography-ultraviolet-mass spectrometry methods are a challenging task.
To be able to confirm azide exposure, we have developed a method to identify azide in both beverages and bodily fluids. The identification of azide (N ) is based on derivatization with N-(2-(bromomethyl)benzyl)-N,N-diethylethanaminium bromide (CAX-B) at 25°C for 15 min followed by LC/ESI-MS/MS analysis, with no other sample preparation.
The azide after derivatization (CAX-N ) was stable, retainable by LC and sensitively detected by selected reaction monitoring. The ESI-MS/MS fragmentation of the M precursor ion produced characteristic product ions at m/z 118, 100, 91 and 86. The calibration curves for CAX-N showed linearity over two orders of magnitude with R value of 0.99. Low limits of identification of 0.1-0.5 ng/mL were obtained in all investigated matrices (drinking water, tea, orange juice, plasma and urine).
Compared with previously reported chromatography-based methods, this method that was based on derivatization and LC/ESI-MS/MS analysis was substantially more sensitive, simpler and faster. The method can be used for forensic investigation to confirm azide exposure from fatal use to much smaller intoxication dose.
叠氮化钠(NaN )通过摄入和吸入对人体有毒,在过去几十年中,故意暴露和意外案例的数量不断增加。由于其分子量低且缺乏任何生色团,因此通过反相液相色谱 - 紫外 - 质谱法保留和检测它是一项具有挑战性的任务。
为了能够确认叠氮化物暴露,我们开发了一种在饮料和体液中鉴定叠氮化物的方法。叠氮化物(N )的鉴定基于在 25°C 下与 N-(2-(溴甲基)苄基)-N,N-二乙乙胺溴化物(CAX-B)衍生化 15 分钟,然后进行 LC/ESI-MS/MS 分析,无需其他样品制备。
衍生化后的叠氮化物(CAX-N )稳定,可通过 LC 保留并通过选择反应监测灵敏检测。M 前体离子的 ESI-MS/MS 碎裂产生了特征产物离子,在 m/z 118、100、91 和 86 处。CAX-N 的校准曲线在两个数量级上呈线性关系,相关系数(R 值)为 0.99。在所有研究的基质(饮用水、茶、橙汁、血浆和尿液)中,均获得了 0.1-0.5ng/mL 的低识别限。
与先前报道的基于色谱法的方法相比,该基于衍生化和 LC/ESI-MS/MS 分析的方法灵敏度更高、更简单、更快。该方法可用于法医调查,以确认从致命使用到更小中毒剂量的叠氮化物暴露。