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《化学分析计量》 2019年第03期
DOI:10.3969/j.issn.1008-6145.2019.03.011
5 种甲氧基多溴联苯醚与羟基自由基的二级反应速率常数的测定及反应活性分析
贺舒文1,薛伟锋12,姜婷婷1,马玉良1,侯辰侠1,刘水琳1,沈葆真1,曹文军1
1. 大连出入境检验检疫局检验检疫技术中心,辽宁大连 116600; 2. 大连理工大学环境学院,辽宁大连 116100 
Determination of second-order reaction rate constants and analysis of reactivity of five MeO-PBDEs with hydroxyl radical
HEHE Shuwen1, XUE Weifeng1,2, JIANG Tingting1, MA Yuliang1, HOU Chenxia1, LIU Shuilin1, SHEN Baozhen1, CAO Wenjun1
1. Inspection and Quarantine Technical Center of Dalian Entry–Exit Inspection and Quarantine Bureau, Dalian 116600, China; 2. School of Environmental Sciences & Technology, Dalian University of Technology, Dalian 116100, China 
摘要:测定了水环境中检出的4’-MeO-BDE-17,5-MeO-BDE-47,5’-MeO-BDE-99,6-MeO-BDE-47 和6-MeOBDE- 85 5 种甲氧基多溴联苯醚(MeO-PBDEs) 与羟基自由基(·OH) 反应的二级速率常数(kOH)。以BDE-47 为参比化合物,采用竞争动力学方法测定MeO-PBDEs 的kOH。5 种MeO-PBDEs 的kOH 值在(0.531~1.030)×1010 L/(mol ·s)范围内,5 号位置甲氧基取代可以增大母体BDE-47 与·OH 的反应活性,而6 号位置甲氧基取代则降低了反应活性;五溴取代的5’-MeO-BDE-99 和6-MeO-BDE-85 与·OH反应活性分别是四溴取代的5-MeO-BDE-47 和6-MeO-BDE-47与·OH 反应活性的1.1 和1.9 倍。MeO-PBDEs 与·OH 的反应活性受甲氧基和溴取代模式影响显著。 
Abstract:Five MeO-PBDEs including 4'-MeO-BDE-17, 5-MeO-BDE-47, 5'-MeO-BDE-99, 6-MeO-BDE-47 and 6-MeO-BDE-85 detected were selected to determine their second-order reaction rate constants with ·OH (kOH). kOH of MeO-PBDEs was determined by competitive kinetic method with BDE-47 as the reference compound. kOH of five kinds of MeO-PBDEs were (0.531-1.030)×1010 L/mol · s. Methoxyl substituent at No.5 position can increase the reactivity of parent BDE-47 with ·OH, where as this substituent at No.6 position can lead to the reverse effects. Penta-brominated 5'- MeO-BDE-99 and 6-MeO-BDE-85 showed respective 1.1 and 1.9 times stronger reactivity with ·OH than 5-MeO-BDE- 47 and 6-MeO-BDE-47. The reactivities of MeO-PBDEs with ·OH are susceptible to substitution patterns of bromine and methoxyl substituent of MeO-PBDEs.  
关键词:甲氧基多溴联苯醚;羟基自由基;二级反应速率常数 
Keywords:methoxylated polybrominated diphenyl ethers; hydroxyl radical; second-order reaction rate constant 
基金:辽宁省自然科学基金面上项目(20170540025) 
本文引用格式:
贺舒文,薛伟锋,姜婷婷,等. 5 种甲氧基多溴联苯醚与羟基自由基的二级反应速率常数的测定及反应活性分析[J]. 化学分析计量,2019,28(3):42-47.
HE S W,XUE W F,JIANG T T,et al. Determination of second-order reaction rate constants and analysis of reactivity of five MeO-PBDEs with hydroxyl radical[J]. Chemical analysis and meterage,2019,28(3):42-47. 

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