芬太尼类物质制毒原料NPP与4-ANPP的定性检验

Detection of NPP and 4-ANPP by GC-MS and UPLC-Q-TOF MS

目的建立芬太尼类物质制毒原料N-苯乙基4-哌啶酮(NPP)和4-苯胺基-N-苯乙基哌啶(4-ANPP)的气相色谱-质谱(GC-MS)和超高效液相色谱-串联四极杆飞行时间质谱(UPLC-Q-TOF MS)定性检验方法。方法采用GC-MS和UPLC-Q-TOF MS进行分析。结果 GC-MS方法通过程序升温对NPP和4-ANPP进行分离分析,NPP的保留时间为8.49min,以特征碎片离子m/z 112、84、42进行定性分析;4-ANPP的保留时间为12.70min,以特征碎片离子m/z 146、189、44、96、105进行定性分析。UPLC-Q-TOF MS方法通过梯度洗脱对NPP和4-ANPP进行分离分析,NPP的保留时间为1.633min,准分子离子峰为m/z 204.138 2,碰撞诱导解离(CID)模式下二级质谱主要离子有m/z 186.127 5、146.096 6、134.096 5、130.065 1、112.075 5、105.070 1、103.054 4、77.038 4;4-ANPP的保留时间为3.702min,准分子离子峰为m/z 281.200 9,碰撞诱导解离(CID)模式下二级质谱主要离子有m/z 188.143 5、146.096 6、134.096 6、105.070 1。结论该方法具有操作简便、分析快速的特点,可应用于司法鉴定实践中NPP和4-ANPP的定性分析。

Objective To establish two methods by gas chromatography-mass spectrometry(GC-MS) and/or ultraperformance liquid chromatography-quadrupole time-of-flight-mass spectrometry(UPLC-Q-TOF MS) for determining NPP(N-Phenethyl-4-piperidinone) and 4-ANPP(4-anilino-N-phenethylpiperidine), both of the precursor chemicals of fentanyl. Methods The sample was extracted with methanol and formic acid solution, with the supernatant being subjected to GCMS and UPLC-Q-TOF MS for analysis. Results The separation of NPP or 4-ANPP was carried out by GC-MS with the temperature-programmed handling. The NPP was of retention time at 8.49 min, with its characteristic fragment ions at m/z 112, 84 and 42. The 4-ANPP was of retention time at 12.70 min, with its characteristic fragment ions at m/z 146, 189, 44, 96 and 105. For the UPLC-Q-TOF MS analysis, NPP or 4-ANPP was isolated through the gradient elution. The NPP was of retention time at 1.633 min, with its characteristic fragment ion peaks appearing at m/z 204.1382([M+H]+) in the single stage plus the m/z 186.1275, 146.0966, 134.0965, 130.0651, 112.0755, 105.0701, 103.0544, 77.0384 in the tandem(MS/MS) mode. The 4-ANPP was of retention time at 3.702 min, with its characteristic fragment ion peaks showing at m/z 281.2009([M+H]+) in the single stage and m/z 188.1435, 146.0966, 134.0966, 105.0701 in the tandem(MS/MS) mode. Conclusions The method is simple and rapid, suitable for qualitative analysis of both NPP and 4-ANPP.