【摘要】 近年来，多柔比星等蒽环类抗生素被广泛应用于医疗、畜牧业等，其在水中的半衰期较大，对人类健康和环境产生了较大威胁。二氧化氯（ClO₂）因氧化性强且不产生卤代消毒副产物等优点，具有降解抗生素的潜在能力。因此，该研究使用ClO₂降解盐酸多柔比星（DOX），探究了影响降解的因素以及反应动力学，此外，利用高相液相色谱-质谱联用分析了降解产物，使用量子化学计算揭示其反应活性位点，通过将实验结果与理论计算结合阐述其降解机理。结果表明，当ClO₂质量浓度为0.8 mg·L^-1、温度为25℃、pH为7.5时，ClO₂降解DOX效果最好，降解率为94.07%;ClO₂降解DOX符合二级反应动力学模型，反应速率常数为2.41×10^-2 mmol·L^-1·s^-1；反应活化能为Ea=25.46kJ·mol^-1;DOX在碱性条件下比酸性条件下更容易被降解。量子化学计算结果表明，DOX的C—C单键容易受到亲核攻击，O—H键容易受到亲电攻击；O26、O39、C20为亲电反应位点。质谱解析结果发现，DOX被ClO₂氧化后发生了自由基的抽氢及加成反应，反应降解产物分别为M+16、M+32、M-157、M-241、M-396，与计算结果基本一致。通过分析DOX降解过程中毒性的变化发现，存在毒性较强的中间产物。更多还原

【Abstract】 In recent years,anthracyclines antibiotics including doxorubicin have been widely used in medical treatment and animal husbandry,and their half-life in water is relatively long,which poses a great threat to human health and the environment.Chlorine dioxide （ClO₂） has the potential to degrade antibiotics because of its strong oxidation and free of halogenated disinfection byproducts.Therefore,ClO₂ was used to degrade Doxorubicin hydrochloride （DOX）,and the influencing factors and the reaction kinetics were explored;meanwhile,high performance liquid chromatography-mass spectrometry was used to identify its degradation products;quantum chemical calculations were used to reveal its reactive sites;and the degradation mechanism was illustrated through the combination of experimental results and theoretical calculations.The results showed that the best DOX degradation effect of ClO₂ occurred when the concentration of ClO₂ was 0.8mg·L^-1,the temperature was 25℃,and pH was 7.5,and the degradation rate reached 94.07%.DOX degradation by ClO₂conformed to the second-order reaction kinetic model,and the reaction rate constant was 2.41×10^-2 mmol·L^-1·s^-1.The activation energy was 25.46kJ·mol^-1.DOX was more easily degraded under alkaline conditions than under acidic conditions.The quantum chemical calculation results showed that the C-C single bond of DOX is vulnerable to nucleophilic attack,and the O-H bond is vulnerable to electrophilic attack.O26,O39 and C20 are electrophilic reaction sites.The results of mass spectrometry showed that free radical hydrogen extraction and addition reactions occurred after DOX was oxidized by ClO₂,and the reaction degradation products were M+16,M+32,M-157,M-241,and M-396,respectively,which were basically consistent with the calculated results.It is found that there were more toxic intermediate products by analyzing the changes in toxicity during the degradation of DOX.更多还原