Halogenated phenolic compound determination in plasma and serum by solid phase extraction, dansylation derivatization and liquid chromatography-positive electrospray ionization-tandem quadrupole mass spectrometry
Halogenated phenolic compound determination in plasma and serum by solid phase extraction, dansylation derivatization and liquid chromatography-positive electrospray ionization-tandem quadrupole mass spectrometry
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DOI：
10.1016/j.chroma.2013.10.068
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发表时间：
2013-12-13
影响因子：
4.1
通讯作者：
Letcher, Robert J.
中科院分区：
文献类型：
--
作者：
Chu, Shaogang;Letcher, Robert J.
开发了一种稳健、灵敏且准确的方法，用于同时测定血浆和血清中的卤代酚类化合物 (HPC)，已知有几种卤代酚类化合物在环境中持续存在，并且可提供分析纯标准品。即羟基化多溴二苯醚（OH-PBDEs）的14种同系物、羟基化多氯联苯（OH-PCBs）的6种同系物、五氯苯酚、五溴苯酚和阻燃剂四溴双酚A（TBBPA）。固相萃取 (SPE) 通过强阴离子交换固相 SPE 柱 (Oasis MAX) 的有效吸附，富集了目标化合物并净化了样品。最终净化后，用丹磺酰氯对 HPC 进行衍生化，并通过液相色谱-串联质谱法和正离子模式电喷雾电离 (ESI(+)) 进行分析。在 Luna PFP(2) 柱（2 mm x 100 mm，粒径 3 μm）上进行色谱分离，流动相为水和乙腈（均含有 0.1% 甲酸）。由于电喷雾电离效率的提高，向 HPC 中添加丹酰基部分大大提高了分析物的灵敏度。 HPC LC-ESI(+)-MS/MS 分析的仪器检测限 (ILOD) 范围为 0.01-0.07 ng/mL，定量方法限 (MLOQ) 范围为 0.02-0.15 ng/g。强化牛血清样品的这套 HPC 的回收效率为 64% 至 118%，相对标准偏差为 2% 至 12%。该方法成功应用于代表性北极熊和鳄龟血浆样品中的 HPC 测定。皇冠版权所有 (C) 2013 由 Elsevier B.V. 出版。保留所有权利。
A robust, sensitive and accurate method was developed for the simultaneous determination in plasma and serum of suite a halogenated phenolic compounds (HPCs) for which several are known to persist in the environment and analytically pure standards are available. Namely, 14 congeners of hydroxylated polybrominated diphenyl ethers (OH-PBDEs), six congeners of hydroxylated polychlorinated biphenyls (OH-PCBs), pentachlorophenol, pentabromophenol and the flame retardant tetrabromobisphenol A (TBBPA). Solid phase extraction (SPE) enriched the target compounds and cleaned up the samples as a result of efficient adsorption on a strong anion-exchange solid phase SPE cartridge (Oasis MAX). After final clean-up the HPCs were derivatized with dansyl chloride and analyzed by liquid chromatography-tandem mass spectrometry with electrospray ionization in positive mode (ESI(+)). Chromatographic separation was achieved on a Luna PFP(2) column (2 mm x 100 mm, 3 mu m particle size) with mobile phases of water and acetonitrile (both containing 0.1% formic acid). The addition of the dansyl moiety to the HPCs greatly improved analyte sensitivity as the electrospray ionization efficiency was enhanced. Instrument limits of detection (ILODs) for LC-ESI(+)-MS/MS analysis of the HPCs were in the range of 0.01-0.07 ng/mL and the method limits of quantification (MLOQs) were in the range of 0.02-0.15 ng/g. Recovery efficiencies of the suite of HPCs ranged from 64% to 118% with relative standard deviations from 2% to 12% from fortified bovine serum samples. The method was successfully applied for HPC determination in representative polar bear and snapping turtle plasma samples. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.