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  

Determination of second-order reaction rate constants and analysis of reactivity of five MeO-PBDEs with hydroxyl radical

作　　者：贺舒文 薛伟锋 姜婷婷 马玉良 侯辰侠 刘水琳 沈葆真 曹文军 HE Shuwen;XUE Weifeng;JIANG Tingting;MA Yuliang;HOU Chenxia;LIU Shuilin;SHEN Baozhen;CAO Wenjun(Inspection and Quarantine Technical Center of Dalian Entry-Exit Inspection and Quarantine Bureau,Dalian 116600,China;School of Environmental Sciences & Technology,Dalian University of Technology,Dalian 116100,China)

机构地区：[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

出　　处：《化学分析计量》2019年第3期42-47,共6页Chemical Analysis And Meterage

基　　金：辽宁省自然科学基金面上项目(20170540025)

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-855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)×10^10L/(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。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)×10^10 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 

分 类 号：O657.7[理学—分析化学]