Quantum chemical evaluation, ELF, LOL analysis, Fukui, herbicide-likeness and molecular docking studies of 4-methyl-phenoxyacetic acid, 4-acetyl-phenoxyacetic acid and 4-tert-butyl-phenoxyacetic acid – a comparative study

IF 2.1 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Structural Chemistry Pub Date : 2024-02-03 DOI:10.1007/s11224-023-02271-4

Karpagavalli K, Daisy Magdaline J, Chithambarathanu T, Vijaya P, Amjesh R

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Abstract

The phenoxyacetic acid and its derivatives have attracted considerable attention as they have proven to be excellent bioactive herbicides. The optimized molecular geometry and the fundamental vibrational frequencies of 4-methyl-phenoxyacetic acid (4MPA), 4-acetyl-phenoxyacetic acid (4APA) and 4-tert-butyl-phenoxyacetic acid (4TBPA) have computed using density functional theory (DFT) method with 6–311++G(d,p) basis set. The theoretically predicted wavenumbers are found to be in close agreement with the experimentally determined one. The band gap energy of HOMO and LUMO depicts the charge transfer interactions occurring within the molecules. Global reactivity descriptors have utilized to assess the chemical reactivity. It has been observed that 4APA exhibits good electrophilic properties with a higher electrophilicity index (ω = 2.993 eV) compared to other compounds such as 4TBPA and 4MPA. The molecular electrostatic potential surface (MESP) has been plotted over the optimized structure to estimate the reactive sites of electrophilic and nucleophilic attacks on the phenoxyacetic acid molecule. Fukui function is also used to analyze their electrophilic and nucleophilic descriptors with Hirshfeld charges. Electron localization function (ELF) and local orbital localizer (LOL) are discussed using the multifunction wavefunction (Multiwfn) analyzer. Using the HerbiPAD tool, the herbicide-likeness parameter has exposed the good herbicide-like behaviour of the title compounds. Additionally, the Tice rule and pK_a are described, providing valuable insights into the herbicidal activity of phenoxyacetic acid compounds. The 4APA compound is highly effective, which exhibits more herbicidal activity when interacting with the auxin receptor TIR1. It demonstrates a strong binding affinity of -8.56 kcal/mol.

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4-甲基苯氧乙酸、4-乙酰基苯氧乙酸和 4-叔丁基苯氧乙酸的量子化学评价、ELF、LOL 分析、Fukui、除草剂相似性和分子对接研究 - 对比研究

摘要苯氧乙酸及其衍生物已被证明是一种极好的生物活性除草剂，因而备受关注。采用 6-311++G(d,p) 基集的密度泛函理论（DFT）方法计算了 4-甲基苯氧乙酸（4MPA）、4-乙酰基苯氧乙酸（4APA）和 4-叔丁基苯氧乙酸（4TBPA）的优化分子几何形状和基本振动频率。结果发现，理论预测的波长与实验测定的波长非常接近。HOMO 和 LUMO 的带隙能描述了分子内发生的电荷转移相互作用。全局反应性描述符用于评估化学反应性。据观察，与 4TBPA 和 4MPA 等其他化合物相比，4APA 具有良好的亲电性，亲电指数较高（ω = 2.993 eV）。在优化结构上绘制了分子静电位面 (MESP)，以估计苯氧乙酸分子上亲电和亲核攻击的反应位点。Fukui 函数还用于分析它们的亲电和亲核描述符与 Hirshfeld 电荷。使用多功能波函数（Multiwfn）分析器讨论了电子定位函数（ELF）和局部轨道定位器（LOL）。利用 HerbiPAD 工具，除草亲和性参数揭示了标题化合物具有良好的除草亲和性。此外，还描述了 Tice 规则和 pKa，为了解苯氧乙酸化合物的除草活性提供了宝贵的信息。4APA 化合物非常有效，在与植物生长素受体 TIR1 相互作用时表现出更强的除草活性。其结合亲和力为 -8.56 kcal/mol。

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来源期刊

Structural Chemistry 化学-化学综合

CiteScore

3.80

自引率

11.80%

发文量

227

审稿时长

3.7 months

期刊介绍： Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.