多溴联苯醚代谢物的色谱保留和质谱特征  

Chromatographic Retention and Mass Spectrometric Characteristics of Hydroxylated and Methoxylated Polybrominated Diphenyl Ethers

作　　者：余益军[1] 毛丽[1] 林汉华[2] 于红霞[1] 

机构地区：[1]南京大学环境学院,污染控制与资源化国家重点实验室,南京210093 [2]香港城市大学生物与化学系

出　　处：《分析化学》2008年第8期1029-1034,共6页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(No.20730017);香港研究资助局联合基金(No.20518002/N_CityU110/05)资助项目

摘　　要：研究了多溴联苯醚(PBDEs)代谢物中常见的18种羟基PBDEs(HO-BDEs)、15种甲氧基PBDEs(MeO-BDEs)的气相色谱、反相液相色谱分离和质谱碎片特征。MeO-BDEs在反相液相色谱(RPLC)的保留行为受疏水作用支配,而HO-BDEs则还受到除疏水作用以外的特殊作用影响。LC/MS中大气压化学电离(APCI)源适用于HO-BDEs检测,而APCI源以及电喷雾离子源(ESI)对MeO-BDEs都没有响应。质谱碎片具有显著取代位效应:在LC/APCI-MS中,邻位取代HO-BDEs的碎片离子基峰均为脱一个溴的结构[M-H]--HBr,而对位取代的基峰则为准分子离子[M-H]-;在电子电离(EI)源质谱仪下,邻位取代MeO-BDEs有脱溴甲烷碎片离子(M.+-BrCH3),对位取代有特征的脱甲基自由基结构(M.+-.CH3),间位取代则无上述两种碎片离子。Behaviors of eighteen hydroxylated polybrominated diphenyl ethers （HO-BDEs） and fifteen methoxylated polybrominated diphenyl ethers （MeO-BDEs） in chromatography and mass spectrometry were characterized. High performance liquid chromatography with diode array detector and mass spectrometric detector, and gas chromatography （GC） with electron capture detector （ECD） and electron ionization （EI） mass spectrometric detector were employed. Retention of MeO-BDEs in reversed phase liquid-chromatography was governed hy hydrophobic interaction, while the retention of HO-BDEs was affected by other specific interactions besides hydrophobic interaction. Both of atmospheric pressure chemical ionization （APCI） and electrospray ionization （ESI） were used in LC/MS. LC/APCI-MS was suitable to detect HO-BDEs, while both of APCI and ESI gave no response to MeO-BDEs. The position of the hydroxy and methoxy substituent （ortho, meta and para） relatives to the diphenyl ether oxygen in HO-BDEs and MeO-BDEs determined the compositions of mass spectrometric fragments in EI-MS and APCI-MS.

关 键 词：多溴苯联 色谱保留 大气压化学电离源 电子电离源 

分 类 号：X132[环境科学与工程—环境科学]