"One-shot" analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry.
"One-shot" analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry.
复制标题
使用气相色谱量质谱法对多溴二苯基醚及其在人类母乳和血清中的羟基化和甲氧基化的类似物的“单发”分析。
DOI：
10.1016/j.aca.2015.08.026
复制
发表时间：
2015-09-10
影响因子：
6.2
通讯作者：
Aga DS
中科院分区：
文献类型：
--
作者：
Butryn DM;Gross MS;Chi LH;Schecter A;Olson JR;Aga DS
人体内存在多溴二苯醚及其羟基化（OH-BDE）和甲氧基化（MeO-BDE）类似物，由于其神经毒性和内分泌干扰作用，是公共卫生高度关注的领域。因此，越来越多的人将这三类化合物放在一起研究，以了解它们在环境基质和人体中的生物累积模式。使用液相色谱-质谱法（LC-MS）可以同时分析多溴二苯醚、羟基溴二苯醚和甲氧基溴二苯醚，但LC-MS中多溴二苯醚和甲氧基溴二苯醚的检测限不足以进行痕量定量。因此，通常在样品制备过程中对酚类（OH-BDEs）和中性（PBDEs和MeO-BDEs）化合物进行分级分离，因此可以使用不同的检测技术来实现所需的灵敏度。然而，这种方法涉及多次进样，最终增加了分析时间。在这项研究中，开发了一种分析方法，使用气相色谱串联质谱法（GC-MS/MS）对12种多溴二苯醚、12种羟基溴二苯醚和13种甲氧基溴二苯醚进行“一次性”分析。该总体方法包括通过加压液体提取同时提取所有分析物，然后进行脂质去除步骤以减少基质干扰。使用N-（叔丁基二甲基甲硅烷基）-N-甲基三氟乙酰胺对羟基溴化二苯醚进行衍生化，生成羟基TMDS衍生物，可在25分钟内通过GC-MS/MS“一次”对这些衍生物与多溴二苯醚和甲氧基溴化二苯醚进行分析。总回收率一般大于65%，母乳和血清中的检测限范围为2-14 pg。该方法的适用性成功地验证了四对人母乳和血清样品。母乳中多溴二苯醚、羟基溴二苯醚和甲氧基溴二苯醚的总平均浓度分别为59、2.2和0.57纳克/克。在血清中，平均总浓度分别为79、38和0.96 ng g−1脂质，显示出与母乳中检测到的水平不同的分布特征。这种GC-MS/MS方法将被证明是有用的和具有成本效益的大规模研究，需要进一步了解的分配行为，并最终对人体的这些重要类别的溴化二苯醚的不利健康影响。
The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to public health due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise involving the investigation of these three classes of compounds together in order to understand their bioaccumulation patterns in environmental matrices and in humans. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so different detection techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a “one-shot” analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide, producing OH-TMDS derivatives that can be analyzed with PBDEs and MeO-BDEs by GC-MS/MS in “one shot” within a 25-min run. The overall recoveries were generally greater than 65%, and the limits of detection ranged from 2–14 pg in both breast milk and serum. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g−1 lipid, respectively. In serum, the mean total concentrations were 79, 38, and 0.96 ng g−1 lipid, respectively, exhibiting different distribution profiles from levels detected in the breast milk. This GC-MS/MS method will prove useful and cost-effective in large-scale studies needed to further understand the partitioning behavior and ultimately the adverse health effects of these important classes of brominated diphenyl ethers in humans.