Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA.
Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA.
Sci Rep. 2021 Nov 18;11(1):22489. doi: 10.1038/s41598-021-01896-x.
The one-step breakdown and derivatization of a panel of nine fentanyls to yield uniquely tagged products that can be detected by Electron Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS) is presented. The method involves the treatment of the synthetic opioids with 2,2,2-trichloroethoxycarbonyl chloride (TrocCl) at 60 °C for 3 h in dichloromethane and furnishes two products from one fentanyl molecule that can be used to retrospectively identify the original opioid. Parameters that were studied and fully optimized for the method included temperature, solvent, nature of scavenging base and reaction time. One of the two resulting products from the reaction bears the trichloroethoxycarbonyl (Troc) tag attached to the norfentanyl portion of the original opioid and greatly aids in the opioid detection and identification process. The methodology has been applied to the chemical modification of a panel of nine fentanyls and in all cases the molecular ion peak for the Troc-norfentanyl product bearing the distinctive trichloroethyl isotopic signature can be clearly observed. The method's LLOD was determined to be 10 ng/mL while its LLOQ was found to be 20 ng/mL. This methodology represents the first application of chloroformates in the chemical modification of this class of synthetic opioids that are notoriously inert to common derivatization strategies available for GC-MS analysis.
本文介绍了一种将九种芬太尼类药物一步分解并衍生化，生成独特标记产物，可通过电子电离气相色谱-质谱联用（EI-GC-MS）检测的方法。该方法涉及用 2,2,2-三氯乙氧羰基氯（TrocCl）在二氯甲烷中于 60°C 下处理合成阿片类药物 3 小时，从一个芬太尼分子中生成两种产物，可用于追溯鉴定原始阿片类药物。对该方法进行了研究和全面优化的参数包括温度、溶剂、清除碱的性质和反应时间。反应生成的两种产物之一带有三氯乙氧羰基（Troc）标记，附着在原始阿片类药物的去甲芬太尼部分，极大地有助于阿片类药物的检测和鉴定过程。该方法已应用于九种芬太尼类药物的化学修饰，在所有情况下，都可以清楚地观察到带有独特三氯乙基同位素特征的 Troc-去甲芬太尼产物的分子离子峰。该方法的 LLOD 为 10ng/mL，LLOQ 为 20ng/mL。该方法代表了氯甲酸酯在这一类对常见 GC-MS 分析衍生化策略惰性的合成阿片类药物的化学修饰中的首次应用。
