Fast liquid chromatographic-tandem mass spectrometric method using mixed-mode phase chromatography and solid phase extraction for the determination of 12 mono-hydroxylated brominated diphenyl ethers in human serum.
Fast liquid chromatographic-tandem mass spectrometric method using mixed-mode phase chromatography and solid phase extraction for the determination of 12 mono-hydroxylated brominated diphenyl ethers in human serum.
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DOI：
10.1016/j.chroma.2014.06.048
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发表时间：
2014-08
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通讯作者：
Syrago-Styliani E. Petropoulou;W. Duong;Myrto X Petreas;June-Soo Park
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作者：
Syrago-Styliani E. Petropoulou;W. Duong;Myrto X Petreas;June-Soo Park
羟基多溴二苯醚(OH-PBDEs)是多溴二苯醚(PBDEs)在人、大鼠和小鼠体内氧化代谢形成的产物，但其在人体血液和其他基质中的定量一直是一个挑战。在这项研究中，开发了一种新的分析方法，并验证了一种新的分析方法，仅使用250兆μ的人血清L就可以对12种OH-PBDEs进行定量，在15分钟的分析过程中完全层析分离。该方法包括两种新的方法：酶解过程和使用混合模式色谱柱的层析分离。4‘-OH-BDE17的酶解(EH)是关键的，没有EH是无法检测到的。在样品净化方面，建立了固相萃取分离人血清中12种同系物的方法，并进行了验证。此外，首次实现了两个组分的基线分辨，这两个组分对应于以前确定为6‘-OH-BDE99的单一峰。对方法的线性、准确度、精密度、基质效应、定量限、检出限、样品稳定性和整体效率进行了验证。所有分析物的回收率(绝对和相对)在66%到130%之间，相对标准偏差为21%。方法检出限为4~90pg/mL−1，定量下限为6~120pg/mL−1，无残留效应。该方法被应用于来自美国普通人群的10个商业可获得的人血清样本。在所有样品中检出的同系物的平均值分别为4‘-OH-BDE17(34.2pg/mL−1)、4-OH-BDE42(33.9pg/mL−1)、5-OH-BDE47(17.5pg/mL−1)和4’-OH-BDE49(12.4pg/mL−1)。
Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are formed from the oxidative metabolism of polybrominated diphenyl ethers (PBDEs) in humans, rats and mice, but their quantitation in human blood and other matrices with liquid chromatography–mass spectrometric techniques has been a challenge. In this study, a novel analytical method was developed and validated using only 250 μL of human serum for the quantitation of twelve OH-PBDEs, fully chromatographically separated in a 15 min analytical run. This method includes two novel approaches: an enzymatic hydrolysis procedure and a chromatographic separation using a mixed mode chromatography column. The enzymatic hydrolysis (EH) was found critical for 4′-OH-BDE17, which was not detectable without it. For the sample clean up, a solid phase extraction protocol was developed and validated for the extraction of the 12 congeners from human serum. In addition, for the first time baseline resolution of two components was achieved that correspond to a single peak previously identified as 6′-OH-BDE99. The method was validated for linearity, accuracy, precision, matrix effects, limit of quantification, limit of detection, sample stability and overall efficiency. Recoveries (absolute and relative) ranged from 66 to 130% with relative standard deviations <21% for all analytes. Limit of detection and quantitation ranged from 4 to 90 pg mL−1and 6–120 pg mL−1, respectively, with no carry over effects. This method was applied in ten commercially available human serum samples from the general US population. The mean values of the congeners detected in all samples are 4′-OH-BDE17 (34.2 pg mL−1), 4-OH-BDE42 (33.9 pg mL−1), 5-OH-BDE47 (17.5 pg mL−1) and 4′-OH-BDE49 (12.4 pg mL−1).