液相色谱-四极杆/飞行时间质谱法分析29种芬太尼类物质及其碎裂机理
摘要
<p id=C2>Given the wide variety of fentanyl analogs, the test for this entire group tends to be crucial and particularly difficult since all fentanyl-like substances are listed as controlled substances in China. This study meticulously analyzed the fragmentation pathways and mechanisms of 29 fentanyl analogs and summarized the fragmentation pathways and features for the entire group of fentanyl analogs, thus providing a reference for related screening tests. Fentanyl, thiofentanyl, and sufentanil were selected as the representative compounds in this study, and the fragmentation mechanism of their fragment ions was interpreted. The general fragmentation rules for fentanyl analogs were summarized as well. The fragment ions of the three compounds formed by induced cleavage (i) came with high abundance ratios, such as fragment ions of <italic>m/z</italic> 188, 105, 194, 111, and 238, while the induced cleavage was due to the amide and piperidinyl groups. Moreover, the induction ability of amide group was significantly stronger than that of the piperidinyl group, and induced cleavage was the main fragmentation pathway for most of the fentanyl analogs. Furthermore, the fragment ions with <italic>m/z</italic> 281 and 287 for fentanyl and thiofentanyl were formed by loss of the propionyl group after single H rearrangement (rH). The fragment ions with <italic>m/z</italic> 216, 146, and 132 for fentanyl and thiofentanyl were formed by double H rearrangement (r2H). Although their abundance ratios were not high, they still had specificity and regularity. Elimination reaction (re) was also a very common fragmentation pathway for these compounds, leading to fragment ions with <italic>m/z</italic> 134 and 140. Phenylethyl substituents were more prone to the elimination reaction with a higher abundance ratio than thiophenethyl substituents. Compounds such as sufentanil with methoxy substituents at the piperidinyl <italic>para</italic>-position could produce a large number of fragme