Allergic contact dermatitis is a critical issue in the development of new chemicals. Minor impurities with strong skin-sensitizing properties can be generated as byproducts. However, it is very difficult to identify these skin sensitizers in product mixtures. In this study, fluorescent nitrobenzoxadiazole-labeled glutathione (NBD-GSH) was synthesized to identify small amounts of skin sensitizers in reaction mixtures. Twelve known skin sensitizers and three nonsensitizers were reacted with NBD-GSH. Adducts formed only with the skin sensitizers, which allowed for their detection by a fluorescence detector. Liquid chromatography-mass spectrometry (LC-MS) analyses showed that NBD-GSH reacted with the skin sensitizers via its thiol and amino groups. An adduct of NBD-GSH with the strong skin sensitizer 1-chloro-2,4-dinitrobenzene was detected with a limit of detection of 6 × 10^–8 mol/L by high-performance liquid chromatography with fluorescence detection. When a reaction mixture from primary alcohol oxidation was incubated with NBD-GSH, a NBD-GSH adduct formed with skin-sensitizing aldehyde impurities and could be specifically detected by LC-MS with fluorescence detection. This method will be useful for detection and identification of small amounts of skin sensitizers in raw materials, intermediates, reaction mixtures, and end products in the chemical industry.

中文翻译：

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用荧光硝基苯并二唑标记的谷胱甘肽鉴定反应混合物中潜在致敏杂质的灵敏方法

过敏性接触性皮炎是开发新化学品的关键问题。具有强烈皮肤致敏特性的少量杂质可以作为副产品产生。然而，很难在产品混合物中识别这些皮肤致敏物。在这项研究中，合成了荧光硝基苯并恶二唑标记的谷胱甘肽 (NBD-GSH)，以识别反应混合物中的少量皮肤致敏物。十二种已知的皮肤致敏剂和三种非致敏剂与 NBD-GSH 发生反应。加合物仅与皮肤致敏剂形成，这允许通过荧光检测器进行检测。液相色谱-质谱 (LC-MS) 分析表明 NBD-GSH 通过其硫醇和氨基与皮肤致敏剂发生反应。NBD-GSH 与强致敏剂 1-chloro-2 的加合物，^–8 mol/L，荧光检测的高效液相色谱法。当来自伯醇氧化的反应混合物与 NBD-GSH 孵育时，NBD-GSH 加合物与皮肤致敏醛杂质形成，可以通过荧光检测的 LC-MS 进行特异性检测。该方法可用于检测和鉴定化学工业中原材料、中间体、反应混合物和最终产品中的少量皮肤致敏剂。