Sales Carlos, Poma Giulia, Malarvannan Govindan, Portolés Tania, Beltrán Joaquin, Covaci Adrian
Research Institute for Pesticides and Water, University Jaume I, Av. de Vicent Sos Baynat, s/n, 12071, Castellón, Spain.
Toxicological Centre, Department of Pharmaceutical Sciences, University of Antwerp, Universiteitsplein 1, 2610, Wilrijk, Belgium.
Anal Bioanal Chem. 2017 Jul;409(19):4507-4515. doi: 10.1007/s00216-017-0411-x. Epub 2017 Jun 8.
A sensitive method for the simultaneous quantification of dechloranes, polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) has been developed for gas chromatography (GC) coupled to tandem mass spectrometry operating in electron capture negative ionization (ECNI) mode. The major advance has been achieved by combining selected ion monitoring (SIM) and multiple reaction monitoring (MRM) modes in well-defined time windows, to determine dechloranes, PBDEs and NBFRs at picogram per gram level in one single analysis in complex matrix biological samples. From the chromatographic point of view, efforts were devoted to study several injection modes using multimode inlet (MMI) in order to obtain low instrumental detection limits, necessary for trace compounds such as Dechlorane Plus (DP) isomers. Method performance was also evaluated: calibration curves were linear from 20 fg μL to 100 pg μL for the studied compounds, with method detection limits at levels of 50 fg g for DPs. Repeatability and reproducibility, expressed as relative standard deviation, were better than 5% even in solvent vent mode for the injection of standards. The application to a wide range of complex samples (including food, human and animal serum samples) indicated a sensitive and reliable way to quantify at the picogram per gram level 4 halogenated norbornenes (HNs), Dechlorane Plus (anti-DP and syn-DP) and 2 of their homologues (Dechlorane-602 and Dechlorane-603), 11 PBDE congeners (no. 28, 47, 49, 66, 85, 99, 100, 153, 154, 183 and 209) and 5 novel BFRs, i.e. decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HBB), 2,3,4,5-tetrabromo-ethylhexyl-benzoate (TBB) and tetrabromophthalate (TBPH). Graphical Abstract GC-ECNI-MS/MS chromatograms showing the most sensitive transition for DPs when injecting 2 μL of a 16 fg/μL standard solution of s-DP and a-DP at three different source temperatures.
已开发出一种灵敏的方法，用于同时定量分析脱氯烷、多溴二苯醚（PBDEs）和新型溴化阻燃剂（NBFRs），该方法用于气相色谱（GC）与在电子捕获负离子化（ECNI）模式下运行的串联质谱联用。主要进展是通过在明确的时间窗口内结合选择离子监测（SIM）和多反应监测（MRM）模式来实现的，以便在一次分析中对复杂基质生物样品中的脱氯烷、PBDEs和NBFRs进行皮克/克水平的测定。从色谱角度来看，致力于研究使用多模式进样口（MMI）的几种进样模式，以获得低仪器检测限，这对于诸如十氯联苯（DP）异构体等痕量化合物是必要的。还评估了方法性能：所研究化合物的校准曲线在20 fg μL至100 pg μL范围内呈线性，DPs的方法检测限为50 fg/g。即使在进样标准品的溶剂放空模式下，以相对标准偏差表示的重复性和再现性也优于5%。对多种复杂样品（包括食品、人和动物血清样品）的应用表明，这是一种灵敏且可靠的方法，可在皮克/克水平上定量分析4种卤代降冰片烯（HNs）、十氯联苯（反式-DP和顺式-DP）及其2种同系物（脱氯烷-602和脱氯烷-603）、11种PBDE同系物（第28、47、49、66、85、99、100、153、154、183和209号）以及5种新型溴化阻燃剂，即十溴二苯乙烷（DBDPE）、1,2-双（2,4,6-三溴苯氧基）乙烷（BTBPE）、六溴苯（HBB）、2,3,4,5-四溴-乙基己基-苯甲酸酯（TBB）和四溴邻苯二甲酸酯（TBPH）。图形摘要GC-ECNI-MS/MS色谱图显示了在三个不同源温度下进样2 μL 16 fg/μL的s-DP和a-DP标准溶液时DPs最灵敏的跃迁。
