多溴联苯醚代谢物的色谱保留和质谱特征

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。

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

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 by 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.