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A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers
Recent progress has been made in the reductive debromination of polybrominated diphenyl ethers (PBDEs) by nanoscale zero-valent iron (nZVI). To better understand the mechanism of this reaction, seven selected BDE congeners and their anions were investigated at the density functional theory (DFT) lev...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Molecular Diversity Preservation International (MDPI)
2012
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3430299/ https://www.ncbi.nlm.nih.gov/pubmed/22942768 http://dx.doi.org/10.3390/ijms13079332 |
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author | Hu, Ji-Wei Zhuang, Yuan Luo, Jin Wei, Xiong-Hui Huang, Xian-Fei |
author_facet | Hu, Ji-Wei Zhuang, Yuan Luo, Jin Wei, Xiong-Hui Huang, Xian-Fei |
author_sort | Hu, Ji-Wei |
collection | PubMed |
description | Recent progress has been made in the reductive debromination of polybrominated diphenyl ethers (PBDEs) by nanoscale zero-valent iron (nZVI). To better understand the mechanism of this reaction, seven selected BDE congeners and their anions were investigated at the density functional theory (DFT) level using four different methods, including B3LYP/6-31G(d), B3LYP/6-31+G(d), B3LYP/6-31G(d,p) and B3LYP/6-311G(d,p). The cleaved C–Br bonds observed in the equilibrium structures of anionic PBDEs were adopted as the probe of the susceptible debromination position of PBDEs in the presence of nZVI, and the proposed major reaction pathways based on our calculations can satisfactorily conform to the reported experimental results. The debromination preference is theoretically evaluated as meta-Br > ortho-Br > para-Br. In addition, both the calculated frontier orbital energies and adiabatic electronic affinities were found to be highly related to their experimental reductive debromination rate constants. The highest linear regression coefficient was observed in the case using the energy of lowest unoccupied molecular orbital as the molecular descriptor obtained from B3LYP/6-31G(d) (R(2) = 0.961, n = 7) or B3LYP/6-31G(d,p) (R(2) = 0.961, n = 7). The results clearly showed the evidence of an electron transfer mechanism associated with this reductive debromination reaction. |
format | Online Article Text |
id | pubmed-3430299 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2012 |
publisher | Molecular Diversity Preservation International (MDPI) |
record_format | MEDLINE/PubMed |
spelling | pubmed-34302992012-08-31 A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers Hu, Ji-Wei Zhuang, Yuan Luo, Jin Wei, Xiong-Hui Huang, Xian-Fei Int J Mol Sci Article Recent progress has been made in the reductive debromination of polybrominated diphenyl ethers (PBDEs) by nanoscale zero-valent iron (nZVI). To better understand the mechanism of this reaction, seven selected BDE congeners and their anions were investigated at the density functional theory (DFT) level using four different methods, including B3LYP/6-31G(d), B3LYP/6-31+G(d), B3LYP/6-31G(d,p) and B3LYP/6-311G(d,p). The cleaved C–Br bonds observed in the equilibrium structures of anionic PBDEs were adopted as the probe of the susceptible debromination position of PBDEs in the presence of nZVI, and the proposed major reaction pathways based on our calculations can satisfactorily conform to the reported experimental results. The debromination preference is theoretically evaluated as meta-Br > ortho-Br > para-Br. In addition, both the calculated frontier orbital energies and adiabatic electronic affinities were found to be highly related to their experimental reductive debromination rate constants. The highest linear regression coefficient was observed in the case using the energy of lowest unoccupied molecular orbital as the molecular descriptor obtained from B3LYP/6-31G(d) (R(2) = 0.961, n = 7) or B3LYP/6-31G(d,p) (R(2) = 0.961, n = 7). The results clearly showed the evidence of an electron transfer mechanism associated with this reductive debromination reaction. Molecular Diversity Preservation International (MDPI) 2012-07-24 /pmc/articles/PMC3430299/ /pubmed/22942768 http://dx.doi.org/10.3390/ijms13079332 Text en © 2012 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland. http://creativecommons.org/licenses/by/3.0 This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/). |
spellingShingle | Article Hu, Ji-Wei Zhuang, Yuan Luo, Jin Wei, Xiong-Hui Huang, Xian-Fei A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title | A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title_full | A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title_fullStr | A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title_full_unstemmed | A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title_short | A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers |
title_sort | theoretical study on reductive debromination of polybrominated diphenyl ethers |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3430299/ https://www.ncbi.nlm.nih.gov/pubmed/22942768 http://dx.doi.org/10.3390/ijms13079332 |
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