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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• 作者：Scott Simpson ; Michael S. Gross ; James R. Olson ; Eva Zurek ; Diana S. Aga
• 刊名：Analytical Chemistry
• 出版年：2015
• 出版时间：February 17, 2015
• 年：2015
• 卷：87
• 期：4
• 页码：2299-2305
• 全文大小：515K
• ISSN：1520-6882

文摘

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鈥搈ass 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鈥?4,4鈥?tetrabromodiphenyl ether (BDE-47) and 2,2鈥?4,4鈥?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鈥?hydroxy-2,3鈥?4,4鈥?tetrabromodiphenyl ether (2鈥?OH-BDE-66) from BDE-47, and 2鈥?hydroxy-2,3鈥?4,4鈥?6-pentabromodiphenyl ether (2鈥?OH-BDE-119) and 4-hydroxy-2,2鈥?3,4鈥?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.