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A density functional theory/time-dependent density functional theory study of the structure-related photochemical properties of hydroxylated polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers and metal ion effects

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Abstract

As the derivatives and structural analogs of polybrominated diphenyl ethers (PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have attracted increasing concern. However, knowledge of the photochemical behaviors of OH-PBDEs and MeO-PBDEs in water is limited. Here, we used density functional theory and time-dependent density functional theory to examine the structure-related photochemical properties of OH-PBDEs and MeO-PBDEs in water and the effects of metal ions as environmental factors. Eight 6-OH-PBDEs with 1–8 bromine substituents and eight 6-MeO-PBDEs with 1–8 bromine substituents were selected for this study. The optimized geometries of the selected congeners and their complexes with metals in the lowest excited triplet state (T1) showed that one C–Br bond moderately or significantly elongated. The elongated C–Br bond in the T1 state was shown in the ortho-position for the 6-OH-PBDE congeners and the ortho-position or the meta-position for the 6-MeO-PBDE congeners. For the selected congeners, there were significant positive linear correlations between the number of bromine atoms (NBr) and the calculated average atomic charge of bromine and maximum electronic absorbance wavelength (λmax), and a negative linear correlation between the NBr and average bond dissociation energy of C–O bonds (BDEC–O). The photoreactivities of the 6-OH-PBDEs and 6-MeO-PBDEs increased with an increase in the bromination degree with or without metal ions. The calculated average atomic charge of bromine and BDEC–O of the complexes with Mg2+/Zn2+ was higher and lower than those of the corresponding monomers, respectively, indicating that the presence of Mg2+/Zn2+ increased the photoreactivity (debromination and dissociation of C–O bond) of the selected 6-OH-PBDEs and 6-MeO-PBDEs. The effects of the coordination of Mg2+/Zn2+ may be overestimated due to their missing explicit solvation shell. These results provide vital insight into the photochemical properties of OH-PBDEs and MeO-PBDEs in water.

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Funding

This research was supported by the National Natural Science Foundation of China (41601519) and the Natural Science Foundation of Jiangsu Province (BK20150891).

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Authors and Affiliations

  1. School of Environmental Science and Engineering, Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science and Technology, Nanjing, 210044, China

    Se Wang, Shuwen Wang, Longyan Li & Hao Fang

  2. Department of Chemistry, Karakorum International University, Gilgit, Gilgit-Balitstan, 15100, Pakistan

    Shaheen Shah

  3. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, Liaoning, China

    Ce Hao

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  1. Se Wang
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  2. Shuwen Wang
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  3. Shaheen Shah
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  4. Longyan Li
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  5. Hao Fang
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  6. Ce Hao
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Correspondence to Se Wang.

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Wang, S., Wang, S., Shah, S. et al. A density functional theory/time-dependent density functional theory study of the structure-related photochemical properties of hydroxylated polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers and metal ion effects. Environ Sci Pollut Res 27, 9297–9306 (2020). https://doi.org/10.1007/s11356-019-07538-0

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