依托咪酯及其结构类似物的高分辨质谱裂解规律  

High Resolution Mass Spectrometry Fragmentation Rules of Etomidate and Its Structural Analogues

作　　者：范先煜 朱雪妍 王鑫 向平 赵君博 FAN Xian-yu;ZHU Xue-yan;WANG Xin;XIANG Ping;ZHAO Jun-bo(Shanghai Key Laboratory of Forensic Medicine,Key Laboratory of Forensic Science,Ministry of Justice,Shanghai Forensic Service Platform,Academy of Forensic Science,Shanghai 200063,China)

机构地区：[1]司法鉴定科学研究院、上海市法医学重点实验室、司法部司法鉴定重点实验室、上海市司法鉴定专业技术服务平台,上海200063

出　　处：《法医学杂志》2024年第6期557-563,共7页Journal of Forensic Medicine

基　　金：上海市司法鉴定协会课题资助项目(SHSFJD2023-010);司法部司法鉴定重点实验室资助项目;上海市法医学重点实验室资助项目(21DZ2270800);上海市司法鉴定专业技术服务平台资助项目。

摘　　要：目的运用气相色谱-四极杆轨道阱质谱联用(gas chromatography-quadrupole-orbitrap mass spectrometry,GC-Q/Orbitrap MS)和液相色谱-线性离子阱四极杆轨道阱质谱联用(liquid chromatographylinear ion trap quadrupole-orbitrap mass spectrometry,LC-LTQ-Orbitrap MS)技术,探索依托咪酯及其结构类似物的特征碎片离子、离子丰度比信息和质谱裂解规律等,为鉴定和预测依托咪酯结构类似物提供数据支撑。方法利用GC-Q/Orbitrap MS和LC-LTQ-Orbitrap MS技术对美托咪酯、依托咪酯、异丙帕酯和丙帕酯进行分析,获得其气相色谱高分辨质谱图和液相色谱高分辨质谱图。结果依托咪酯、美托咪酯等4个化合物在电子轰击(electron impact,EI)离子源模式下均会产生其分子离子和7个相同的碎片离子(m/z77.0386、79.0542、95.0240、105.0699、143.0730、172.0995和199.0866),其中异丙帕酯和丙帕酯还会产生特征碎片离子m/z 216.0893。依托咪酯、美托咪酯等4个化合物在电喷雾电离(electrospray ionization,ESI)源碰撞池中均会产生3个相同的碎片离子(m/z 95.0240、105.0699和113.0346),同时每个物质均会产生1个特征碎片离子(美托咪酯:m/z 127.0502;依托咪酯:m/z 141.0659;异丙帕酯和丙帕酯:m/z 155.0815)。结论依托咪酯及其结构类似物存在共有的碎片离子,根据其侧链碳数的不同,会生成特征的离子碎片,同时,侧链的结构会影响各碎片离子的丰度比,可为该类化合物的结构鉴定与预测提供依据。Objective To explore the characteristic fragment ions,ion abundance ratios and mass spectrometry fragmentation rules of etomidate and its structural analogues by using gas chromatographyquadrupole/orbitrap mass spectrometry(GC-Q/Orbitrap MS)and liquid chromatography-linear ion trap quadrupole-orbitrap mass spectrometry(LC-LTQ-Orbitrap MS)techniques,providing important data support for the identification and prediction of etomidate structural analogues.Methods GC-Q/Orbitrap MS and LC-LTQ-Orbitrap MS were used to analyze metomidate,etomidate,isopropoxate and propoxate,to obtain their GC high resolution mass spectra and LC high resolution mass spectra.Results Under the electron impact(EI)ion source mode,etomidate,metomidate and the other two analogues all produced their molecular ions and seven identical fragment ions(m/z 77.0386,79.0542,95.0240,105.0699,143.0730,172.0995 and 199.0866),among which isopropoxate and propoxate also produced characteristic fragment ions m/z 216.0893.In the collision cell of the electrospray ionization(ESI)source mode,etomidate,metomidate and the other two analogues all produced three identical fragment ions(m/z 95.0240,105.0699 and 113.0346).Meanwhile,each substance produced one characteristic fragment ion(metomidate:m/z 127.0502;etomidate:m/z 141.0659;isopropoxate and propoxate:m/z 155.0815).Conclusion Common fragment ions exist among etomidate and its structural analogues,and characteristic ion fragments are generated based on the different carbon numbers of their side chains.The structure of side chains can affect the abundance ratio of each fragment ion,providing a basis for the structural identification and prediction of such compounds.

关 键 词：法医学 毒物分析 依托咪酯 美托咪酯 异丙帕酯 丙帕酯 高分辨质谱法 气相色谱法 液相色谱法 裂解规律 

分 类 号：R89[医药卫生—法医学] DF795.1[医药卫生—临床医学] D919.1[政治法律—诉讼法学]