文献类型：期刊文献

英文题名：Photoreductive Debromination of Decabromodiphenyl Ethers in the Presence of Carboxylates under Visible Light Irradiation

作者：Sun, Chunyan[1,2];Chang, Wei[1];Ma, Wanhong[1];Chen, Chuncheng[1];Zhao, Jincai[1]

机构：[1]Chinese Acad Sci, Inst Chem, Key Lab Photochem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China;[2]Shaoxing Univ, Dept Chem, Zhejiang Shaoxing 312000, Peoples R China

年份：2013

卷号：47

期号：5

起止页码：2370

外文期刊名：ENVIRONMENTAL SCIENCE & TECHNOLOGY

收录：SCI-EXPANDED(收录号：WOS:000315844200030)、、EI(收录号：20131116106990)、Scopus(收录号：2-s2.0-84874626606)、WOS

基金：The authors appreciate the financial support by 973 project (2010CB933503, 2013CB632405), by NSFC (No. 21137004, 21277147 and 21107073) and the NSF of Zhejiang province (No. Y5110347). The authors also thank Profs. Bian, W. S., Wang, Y. L., and Dr. Han, Y. C. (ICCAS) for their helpful discussion.

语种：英文

外文关键词：Binding energy - Carboxylation - Electron spin resonance spectroscopy - Electrospinning - Ethers - Irradiation - Light absorption - Magnetic moments - Organic pollutants

外文摘要：Polybrominated diphenyl ethers (PBDEs) have aroused global environmental concerns because of their toxicity and ubiquitousness in the biological and environmental systems. It is important to find an efficient method for their decontamination and to understand their chemical transformation in the environment. Here, we report that decabromodiphenyl ether (BDE209) undergoes efficient reductive debromination reactions under visible-light irradiation (>= 420 nm) in the presence of various carboxylate anions that are common in the environmental media. The debromination reactions occur in a stepwise manner, producing a series of lower brominated PBDE congeners. Solvent-derived radials are observed by spin-trapping electron spin resonance (ESR) experiments during the photoreaction. Further experiments by the UV-vis absorption and isothermal titration calorimetry (ITC), combined with theoretical calculations, reveal a new photochemical debromination pathway based on the halogen binding interaction. According to this pathway, the formation of halogen-binding-based complex between PBDE and carboxylate enables the visible-light absorption and debromination of PBDEs, although neither PBDEs nor carboxylates have visible-light absorption. The halogen-bond-based photochemical debromination could find its application for our better understanding of the transformation process of PBDEs in the environment.