Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation
Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation
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DOI：
10.1016/j.watres.2010.07.053
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发表时间：
2010-12-01
期刊：
影响因子：
12.8
通讯作者：
Huang, Ching-Hua
中科院分区：
文献类型：
--
作者：
Wang, Pei;He, Yi-Liang;Huang, Ching-Hua
氟喹诺酮类(FQS)是一类被广泛使用的抗生素，在水环境中经常被检测到。研究了7种FQS(环丙沙星(CIP)、恩诺沙星(ENR)、诺氟沙星(NOR)、氧氟沙星(OFL)、洛美沙星(LOM)、吡哌酸(PIP)和氟马喹(Flu))和3种结构相关的胺(1-苯基哌嗪(PP)、N-苯基吗啉(PM)和4-苯基哌啶(PD))在ClO2消毒过程中与二氧化氯(ClO2)的反应动力学和转化。反应动力学与pH高度相关，可以用包含FQS形态的二级动力学模型来描述，并且在反应活性上遵循OFL>；ENR>；CIP与LOM>；>；PIP相似或相似的趋势。FQS与相关胺的比较和产物表征表明，FQS的哌嗪环是ClO2的主要反应中心。ClO2可能攻击FQ的哌嗪N4原子，随后涉及哌嗪N1原子的协同碎裂，导致哌嗪部分的脱烷基化、羟化和分子内环关闭。虽然带有叔基N4的FQS与ClO2的反应速度比与次级N4的FQS快，但哌嗪部分的整体反应活性也强烈依赖于喹诺酮环的电子效应。在清水基质中测得的反应速率常数可用于模拟地表水中ClO2对CIP的衰减，但高估了废水中CIP的衰减。总体而言，在典型的ClO2消毒条件下，FQS的转化是可以预期的，特别是对于那些具有叔胺的FQS。然而，由于喹诺酮环的破坏很小，转化可能不会消除抗菌活性。(C)2010爱思唯尔有限公司。保留所有权利。
Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO2) were investigated to elucidate the behavior of FQs during ClO2 disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP similar to NOR similar to LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs' piperazine ring is the primary reactive center toward ClO2. ClO2 likely attacks FQ's piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO2 than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO2 in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO2 disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring. (C) 2010 Elsevier Ltd. All rights reserved.