芬太尼类化合物的质谱特征

Mass Spectral Character of Fentanyl Analogues

目的研究芬太尼及其衍生物在碰撞诱导解离(collision induced dissociation,CID)和电子轰击电离(electron impact ionization,EI)模式下产生的特征离子和主要的碎裂途径,为鉴定未知芬太尼类化合物提供参考。方法利用超高效液相色谱-四极杆飞行时间串联质谱(ultra-high performance liquid chromatography-quadrupole time-of-flight-mass spectrometry,UHPLC-QTOF-MS)和气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)法对9种芬太尼类化合物(2,2’-二氟芬太尼、乙酰芬太尼、芬太尼、丁酰芬太尼、戊酰芬太尼、丙烯酰芬太尼、呋喃芬太尼、4-氟异丁酰芬太尼和卡芬太尼)进行分析,并对所获得的质谱图进行解析,推测该类物质CID和EI的碎裂途径。结果 CID和EI碎裂途径显示出高度的相似性,在CID模式下,哌啶环与N-苯基酰胺之间的碳氮键、哌啶环内的碳氮键、苯乙基与哌啶环间的碳氮键易发生断裂形成特征离子,而在EI模式下,哌啶环的裂解及哌啶环与苯乙基的断裂为主要碎裂途径。结论本研究总结了芬太尼类化合物在CID和EI模式下的主要碎裂途径以及所形成的特征离子,阐明该类物质CID和EI的特征碎裂规律有助于法庭科学实验室在实际工作中正确区分及结构解析芬太尼类新精神活性物质。

Objective To provide the reference for the identification of unknown fentanyl analogues by studying the characteristic ions and main fragmentation pathways of fentanyl analogues in the modes of collision induced dissociation (CID) and electron ionization (EI). Methods Nine fentanyl analogues (2,2’-difluorofentanyl,acetyl fentanyl,fentanyl,butyl fentanyl,valeryl fentanyl,acryloyl fentanyl,furan fentanyl,4-fluorine isobutyl fentanyl,carfentanyl) were selected and analyzed with ultra-high performance liquid chromatography- quadrupole time- of- flight- mass spectrometry (UHPLC- QTOF-MS) and gas chromatography-mass spectrometry (GC-MS). The mass spectrum obtained was analyzed. The CID and EI fragmentation routes of fentanyl analogues were speculated. Results The CID and EI fragmentation pathways were highly similar. In the CID mode,characteristic ions were formed by the carbon- nitrogen bond cleavage between the piperidine ring and the N-phenyl-amide moiety,within the piperidine ring,and between the phenethyl and piperidine ring. While in the EI mode,dissociation of the piperidine ring,as well as cleavage between the piperidine ring and the phenethyl were the main fragmentation pathways. Conclusion This study summarizes the main fragmentation pathways and characteristic ions of fentanyl analogues in the CID and EI modes,which is useful for forensic laboratories to identify and structural analyze fentanyl type new psychoactive substance in practical work.