水介质中羟基自由基与喹啉草醚和喹乙醇除草剂反应的动力学和机理的理论研究

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-06-03 DOI:10.1002/qua.27430
Hari P. Upadhyaya
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引用次数: 0

摘要

在水介质中,使用各种计算方法对羟基自由基与两种喹啉类除草剂(即喹咯草酮和喹美拉克)反应的动力学和机理进行了研究。使用密度泛函理论(DFT)方法(包括以水为溶剂)进行了几何优化。使用凝聚福井函数预测了这些除草剂对-OH 自由基的局部反应性参数。为了获得更高的精确度,使用双杂交方法(即 B2PLYP-D)计算了各种物种的单点能量。这些酸性除草剂的 pKa 值允许它们在水溶液条件下以去质子形式存在。因此,除中性除草剂外,还对去质子或阴离子形式进行了计算。采用传统的过渡态理论,利用一维隧道修正,评估了-OH 自由基与每个碳原子加成反应的单个速率系数。溶剂对反应的影响是通过柯林斯-金博尔公式实现的。这两种方法,即 Fukui 指数和单个速率常数的测定,都证实了这两种除草剂中 -OH 自由基加成反应最活跃的部位是与 COOH 基团相连的碳原子。这两种除草剂与中性和阴离子形式的 -OH 自由基反应的总速率常数相对较高,且等于其扩散极限值。利用结构-活性关系概念对母体除草剂及其 OH 加合物的生态毒性进行了评估。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Theoretical studies on the kinetics and mechanism of hydroxyl radical reaction with quinclorac and quinmerac herbicides in aqueous media

The kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pKa values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the OH radical addition in these two herbicide is the carbon atom attached to the COOH group. The total rate constant for the OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion-limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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