Conformational Preference of Flavonols and Its Effect on the Chemical Properties Involved in Radical Scavenging Activity
Conformational Preference of Flavonols and Its Effect on the Chemical Properties Involved in Radical Scavenging Activity
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DOI：
10.3390/chemistry4040076
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发表时间：
2022-09
期刊：
影响因子：
--
通讯作者：
Hiroko X. Kondo;Yukari Takano
中科院分区：
文献类型：
--
作者：
Hiroko X. Kondo;Yukari Takano
黄酮醇是具有自由基清除活性的化合物，可以防止自由基的有害影响。它们的自由基清除活性引起了极大的关注。最近，基于量子化学的方法由于计算能力和软件改进的显著增加而显着提高了对活性的理解。提出了一种评价自由基清除活性的标准化分析方法--基于量子力学的总自由基清除活性测定法（QM-ORSA）。将QM-ORSA方案应用于黄酮醇的障碍是大量的构象异构体和用于分析的羟基。在这项研究中，我们专注于它，并分析了三个黄酮醇（杨梅素，槲皮素，山奈酚）的化学性质：键离解能，pKa，电离能的构象依赖性。因此，所有的化学性质是不敏感的构象差异。由于主要构象异构体（各构象异构体的相对数量）的差异，应分别在气相和水溶液中进行构象搜索。这些结果表明，它是重要的，分别在水和气相中进行构象搜索，并确定一个代表性的结构分析自由基清除活性。
Flavonols are compounds with radical-scavenging activities that can prevent the harmful effects of free radicals. Their radical-scavenging activity has attracted significant attention. Recently, quantum chemistry-based methodologies have significantly improved the understanding of the activity due to dramatic increases in computational power and software improvements. A standardized analysis method for estimating radical scavenging activity, the quantum mechanics-based test for overall free radical scavenging activity (QM-ORSA), has been proposed. An obstacle in applying the QM-ORSA protocol to flavonols is the large number of conformers and hydroxy groups for analysis. In this study, we focused on it and analyzed the conformational dependences of three flavonols (myricetin, quercetin, and kaempferol) on their chemical properties: bond dissociation energy, pKa, and ionization energy. As a result, all chemical properties were insensitive to conformational differences. The conformational search should be performed separately for each in the gas phase and in aqueous solution because of the differences in the major conformer (relative population of each conformer). These results suggest that it is important to perform the conformational search separately in water and in the gas phase and to determine one representative structure for analyzing radical scavenging activity.