摘要
利用柱前衍生化耦合气相/质谱/质谱(GC/MS/MS),建立了细胞培养液中13种多溴联苯醚(PB-DEs)、8种甲氧基化多溴联苯醚(MeO-PBDEs)和5种羟基化多溴联苯醚(HO-PBDEs)的分析方法。采用氯甲酸甲酯作为HO-PBDEs的衍生化试剂,相比传统重氮甲烷作为衍生化试剂的方法,其衍生化时间明显缩短。同时,衍生物与PBDEs不必分离即可进行衍生化,缩短了前处理时间。在恒温(20.0℃)、控速(250 r/min)及乙腈-甲醇-水-吡啶(5∶2∶2∶1,V/V)等条件下,26种化合物的回收率在86.1%～112.3%之间,相对标准偏差低于16.9%,方法检出限在0.007～0.440 mg/L之间,仪器检出限在0.134～8.798 mg/L之间;在细胞培养液6个加标浓度下,其相关系数平方均大于0.9955。体外细胞实验发现,经大鼠原代肝细胞暴露后的2,2′,4,4′-四溴联苯醚(BDE-47)和2,2′,4,4′,5-五溴联苯醚(BDE-99),无明显脱溴现象,未检出甲氧基化代谢物,但有羟基化代谢产物生成,此结果通过保留时间、选择反应离子模式(Selected Reaction Mode,SRM)和全扫模式(Fullscan Mode)3种信息同时鉴定。
A pre-eolumn derivatization method coupled with GC/MS/MS was set up to analyze 13 polybrominated diphenyl ethers （PBDEs）, 8 MeO-PBDEs and 5 HO-PBDEs in cell culture. The methyl chloroformate was selected for the derivatization of HO-PBDEs, which greatly reduced the analytical time. The analysis process can be carried out without the separation of PBDEs and their metabolites, which can also reduce the analyze time. Under these conditions （temperature of 20 ℃, shaker speed of 250 r/min, the reaction condition of 5： 2 ： 2 ： 1 acetonitrile/methanol/water/pyridine）, the RSD of this method, established in spiked cell culture, was less than 16.5%. The detection limits varied from 0. 007 to 0. 440μg/L for the method and 0. 134 to 8. 798 μg/L for GC/MS/MS. The response was found to be linear in the validated range, with correlation coefficient （R2） better than 0. 9955 for 26 compounds. After the exposure of BDE-47 and BDE-99 in the cell culture, the hydrolated PBDEs can be detected, while the methoxylated PBDEs can not. The result was supported by retention time, selected reaction mode and full scan mode.
出处
《分析化学》
SCIE
EI
CAS
CSCD
北大核心
2011年第3期361-366,共6页
Chinese Journal of Analytical Chemistry
基金
国家自然科学基金(Nos.20977047,20737001)
国家科技重大专项(No.2008ZX08526-003)资助
关键词
多溴联苯醚
液液萃取
柱前衍生化
大鼠原代肝细胞
Polybrominated diphenyl ethers and their metabolites
Liquid-liquid extraction
Pre-column derivatization method
Cell culture
