Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: an experimental and theoretical evaluation.
Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: an experimental and theoretical evaluation.
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DOI：
10.1371/journal.pone.0121276
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发表时间：
2015
期刊：
影响因子：
3.7
通讯作者：
Liang G
中科院分区：
文献类型：
--
作者：
Chen Y;Xiao H;Zheng J;Liang G
酚酸及其衍生物具有潜在的生物学功能，但迄今为止，这些酚酸的构效关系和潜在的作用机制知之甚少。本文采用DPPH·清除实验、密度泛函理论B3 LYP/6-311++G（d，p）水平计算和定量构效关系（QSAR）模型，研究了20种天然酚酸及其衍生物的结构-热力学-抗氧化性关系。在气相、苯、水和乙醇四种微环境下，探讨了三种主要的工作机理（HAT、SETPT和SPLET）。计算的热力学参数（BDE、IP、PDE、PA和埃特）与实验结果进行了比较。现有的理论和实验研究表明，扩展的离域和分子内氢键是自由基稳定性的两个主要贡献。COOH、COOR、C = CCOOH和C = CCOOR基团中的C = O或C = C以及邻苯二酚官能团被示出有利地稳定特定自由基物种以增强自由基清除活性，而COOH基团的邻位中的单个OH的存在不利于活性。HAT是气相和苯中的优先反应机理，而SPLET在水和乙醇中是优先反应机理。此外，我们的QSAR模型稳健地代表了这些探索的化合物在极性介质中的结构-活性关系。
Phenolic acids and derivatives have potential biological functions, however, little is known about the structure-activity relationships and the underlying action mechanisms of these phenolic acids to date. Herein we investigate the structure-thermodynamics-antioxidant relationships of 20 natural phenolic acids and derivatives using DPPH• scavenging assay, density functional theory calculations at the B3LYP/6-311++G(d,p) levels of theory, and quantitative structure-activity relationship (QSAR) modeling. Three main working mechanisms (HAT, SETPT and SPLET) are explored in four micro-environments (gas-phase, benzene, water and ethanol). Computed thermodynamics parameters (BDE, IP, PDE, PA and ETE) are compared with the experimental radical scavenging activities against DPPH•. Available theoretical and experimental investigations have demonstrated that the extended delocalization and intra-molecular hydrogen bonds are the two main contributions to the stability of the radicals. The C = O or C = C in COOH, COOR, C = CCOOH and C = CCOOR groups, and orthodiphenolic functionalities are shown to favorably stabilize the specific radical species to enhance the radical scavenging activities, while the presence of the single OH in the ortho position of the COOH group disfavors the activities. HAT is the thermodynamically preferred mechanism in the gas phase and benzene, whereas SPLET in water and ethanol. Furthermore, our QSAR models robustly represent the structure-activity relationships of these explored compounds in polar media.
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