Identification of polybrominated diphenyl ether metabolites based on calculated boiling points from COSMO-RS, experimental retention times, and mass spectral fragmentation patterns.
Identification of polybrominated diphenyl ether metabolites based on calculated boiling points from COSMO-RS, experimental retention times, and mass spectral fragmentation patterns.
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DOI：
10.1021/ac504107b
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发表时间：
2015-01
影响因子：
7.4
通讯作者：
S. Simpson;Michael S. Gross;J. Olson;E. Zurek;D. Aga
中科院分区：
文献类型：
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作者：
S. Simpson;Michael S. Gross;J. Olson;E. Zurek;D. Aga
现实溶剂的类导体筛选模型 (COSMO-RS) 用于预测几种多溴二苯醚 (PBDE) 和单羟基 BDE (OH-BDE) 代谢物的甲基化衍生物 (MeO-BDE) 的沸点。通过绘制 COSMO-RS 计算的理论沸点与气相色谱-质谱实验确定的保留时间，获得线性相关性，有利于 PBDE 和 OH-BDE 的识别。本文证明了 COSMO-RS 在识别 2,2',4,4'-四溴二苯醚 (BDE-47) 和 2,2',4,4',6-五溴二苯醚 (BDE-100) 的未知 PBDE 代谢物方面的适用性。 BDE-47 和 BDE-100 的代谢物是通过将每种 PBDE 与重组细胞色素 P450 2B6 单独孵育而形成的。利用计算的沸点和 MeO-BDE 位置异构体的特征质谱裂解模式，未知单羟基化代谢物被推测为 BDE-47 中的 2'-羟基-2,3',4,4'-四溴二苯醚 (2'-OH-BDE-66)，并且 来自 BDE-100 的 2'-羟基-2,3',4,4',6-五溴二苯醚 (2'-OH-BDE-119) 和 4-羟基-2,2',3,4',6-五溴二苯醚 (4-OH-BDE-91)。 COSMO-RS 预测的沸点和特征质谱碎片模式的集体使用为鉴定同量异位化合物提供了宝贵的工具。
The COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) was used to predict the boiling points of several polybrominated diphenyl ethers (PBDEs) and methylated derivatives (MeO-BDEs) of monohydroxylated BDE (OH-BDE) metabolites. The linear correlation obtained by plotting theoretical boiling points calculated by COSMO-RS against experimentally determined retention times from gas chromatography-mass spectrometry facilitated the identification of PBDEs and OH-BDEs. This paper demonstrates the applicability of COSMO-RS in identifying unknown PBDE metabolites of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and 2,2',4,4',6-pentabromodiphenyl ether (BDE-100). Metabolites of BDE-47 and BDE-100 were formed through individual incubations of each PBDE with recombinant cytochrome P450 2B6. Using calculated boiling points and characteristic mass spectral fragmentation patterns of the MeO-BDE positional isomers, the identities of the unknown monohydroxylated metabolites were proposed to be 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether (2'-OH-BDE-66) from BDE-47, and 2'-hydroxy-2,3',4,4',6-pentabromodiphenyl ether (2'-OH-BDE-119) and 4-hydroxy-2,2',3,4',6-pentabromodiphenyl ether (4-OH-BDE-91) from BDE-100. The collective use of boiling points predicted with COSMO-RS, and characteristic mass spectral fragmentation patterns provided a valuable tool toward the identification of isobaric compounds.