Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability

作     者：Xiaohua Jiang William AJefferson Dean Song Hanyang Cheng Fengmin Li Zhimin Qiang Aiqian Zhang Huijuan Liu Jiuhui Qu Xiaohua Jiang;William A.Jefferson;Dean Song;Hanyang Cheng;Fengmin Li;Zhimin Qiang;Aiqian Zhang;Huijuan Liu;Jiuhui Qu

作者机构：College of Environmental Science and EngineeringOcean University of ChinaQingdao 266100China The State Agriculture Ministry Laboratory of Quality&Safety Risk Assessment for TobaccoTobacco Research InstituteChinese Academy of Agricultural SciencesQingdao 266101China Key Laboratory of Drinking Water Science and TechnologyResearch Center for Eco-Enuironmental SciencesChinese Academy of SciencesBeijing 100085China 

出 版 物：《Journal of Environmental Sciences》 (环境科学学报（英文版）)

年 卷 期：2020年第32卷第1期

页      面：281-288页

核心收录：

学科分类：083002[工学-环境工程] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 08[工学] 

基　　金：supported by the National Key R&D Program of China(No.2018YFC0406304) the Central Public-Interest Scientific Institution Basal Research Fund(No.1610232019005) the Agricultural Science and Technology Innovation Program(No.ASTIPTRIC06) 

主　　题：Permanganate oxidation of tetracycline Regioselective reactivity Rate-limiting hydroxylation step Altered susceptible moiety Increased electronegativity 

摘      要：Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental ***,few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target ***,we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich *** second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants,yielding kTC0=11.7(mol/L)^-1 sec^-1,kTC-=35.7(mol/L)^-1 sec^-1,kTC2-=43.1(mol/L)^-1 sec^-1 for individual reaction *** products were then identified as the hydroxylated and demethylated *** result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties,while the demethylation should be caused by the unavoidably formed manganese oxide via single electron *** is supported by the DFT calculation,indicating the primary oxidation of phenolic group of TC0 with activation barrier of 44.5 kcal/mol and of alkene group of TC-and TC2-with activation barriers of 44.0 and 43.4 kcal/mol,*** is in agreement with the experimental results,implying the alternation of regioselectivity associated with the deprotonation *** result was further supported by performing the Fukui function and electrostatic potential analysis,reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.