基于密度泛函理论及ECOSAR的二氧化氯降解磺胺嘧啶的反应路径及产物风险评价  

Reaction pathways and products risk assessment of sulfadiazine degradation by chlorine dioxide based on density functional theory and ECOSAR

作　　者：陈汉棱 李楠[1,2] 张新颖 张昊瀛 韦安磊 马海霞 宋进喜[1] CHEN Hanling;LI Nan;ZHANG Xinying;ZHANG Haoying;WEI Anlei;MA Haixia;SONG Jinxi(Shaanxi Key Laboratory of Earth Surface System and Environmental Carrying Capacity,Northwest University,Xi’an 710127;Shaanxi Key Laboratory of Environmental Monitoring and Forewarning of Trace Pollutants,Shaanxi Environmental Monitoring Center,Xi’an 710054;School of Chemical Engineering,Northwest University,Xi’an 710127)

机构地区：[1]西北大学,陕西省地表系统与环境承载力重点实验室,西安710127 [2]陕西省环境监测中心站,陕西省环境介质痕量污染物监测预警重点实验室,西安710054 [3]西北大学,化工学院,西安710127

出　　处：《环境科学学报》2025年第1期481-489,共9页Acta Scientiae Circumstantiae

基　　金：国家自然科学基金(No.42230513);陕西省环境介质痕量污染物监测预警重点实验室开放基金重点项目(No.SHJKFJJ 202307)。

摘　　要：磺胺嘧啶(Sulfadiazine,SD)是一种广泛存在于各类水环境中的人工合成抗生素,其降解去除方法已成为国内外研究的热点问题之一.本文结合密度泛函理论计算和HPLC-MS/MS实验分析探究了二氧化氯(ClO_(2))降解去除SD的反应路径和产物,并基于ECOSAR定量预测和评价了反应产物的急性毒性和环境风险水平.结果表明,ClO_(2)降解SD的反应位点主要为嘧啶环的3个双键以及3C–2N单键、磺酰胺基团的C–N、C–S和N–S单键及苯胺基,反应路径为嘧啶环的加成、羟基化、羟基取代、开环和耦合反应、磺酰胺基团的断裂以及苯胺基的氧化反应;发现的反应产物共11种,其中6种产物对3种水生生物的急性毒性为无害,且无环境风险;除产物S-65和S-141对水蚤和绿藻的风险水平为中风险或低风险外,其余产物的风险水平均低于母体化合物.本研究采用的理论模型计算与实验分析相结合的方法便捷可靠,能够为ClO_(2)降解其它复杂结构有机物的研究提供一定的理论依据.Sulfadiazine(SD)is an artificial synthetic antibiotic occurring in various water environments,and its degradation and removal methods have become one of the hot topics worldwide.This study explored the reaction pathways and products of SD degradation by chlorine dioxide(ClO_(2))using a combination of density functional theory calculations and HPLC-MS/MS experimental analysis.Additionally,the acute toxicity and environmental risk levels of the reaction products were quantitatively predicted and evaluated based on ECOSAR.The results showed that the main reaction sites for SD degradation by ClO_(2)were the three double bonds and 3C–2N single bond of the pyrimidine ring,the C–N,C–S,and N–S single bonds of the sulfonamide group,and the aniline group.The reaction pathways included addition,hydroxylation,hydroxyl substitution,ring-opening and coupling reactions of the pyrimidine ring,rupture of the sulfonamide group,and oxidation reaction of the aniline group.A total of 11 reaction products were identified,out of which 6 showed no harm to the three aquatic organisms and posed no environmental risks.The products of S-65 and S-141 presented moderate to low risks to daphnid and green algae.In contrast,all other products exhibited lower risk levels compared to the parent compound.The combination of theoretical model calculation and experimental analysis used in this study is convenient and reliable,which can provide a certain theoretical basis for studying the degradation of other complex organic compounds by ClO_(2).

关 键 词：抗生素 磺胺嘧啶 密度泛函理论 二氧化氯 GAUSSIAN Multiwfn 量子化学 Fukui指数 

分 类 号：X703[环境科学与工程—环境工程] X131.2