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快速简便地识别饮料和体液中的痕量叠氮化钠,然后进行衍生化和液相色谱-电喷雾串联质谱分析。

Rapid and simple identification of trace amounts of sodium azide in beverages and bodily fluids followed by derivatization and liquid chromatography-electrospray ionization tandem mass spectrometry.

机构信息

Department of Analytical Chemistry, Israel Institute for Biological Research (IIBR), Ness Ziona, Israel.

出版信息

Rapid Commun Mass Spectrom. 2023 Nov 15;37(21):e9624. doi: 10.1002/rcm.9624.

DOI:10.1002/rcm.9624
PMID:37799031
Abstract

RATIONALE

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.

METHODS

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.

RESULTS

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).

CONCLUSIONS

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.

摘要

原理

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。

方法

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。

结果

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。

结论

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。

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