密度泛函研究细梗胡枝子提取物中新型抗氧化剂的分子结构和活性氧清除机理

DFT Study on Molecular Structures and ROS Scavenging Mechanisms of Novel Antioxidants from Lespedeza Virgata

采用密度泛函方法研究了从细梗胡枝子中提取的三种新型抗氧化剂的分子结构和活性氧清除机理．研究发现优化后的最优分子构型中都含有分子内氢键，与用二级微扰方法得到的结果一致．根据预测的气相和水相抗氧化剂的键解离能、电离势，以及三种重要活性氧的电子亲和势和氰原子亲和势，详细讨论了三种抗氧化剂的活性氧消除机理并发现其抗氧化活性和实验结果一致．

The molecular structure and radical scavenging activity of three novel antioxidants from Lespedeza Virgata, lespedezavirgatol, lespedezavirgatal, and lespedezacoumestan, have been studied using density functional theory with the B3LYP and BhandHLYP methods. The optimized geometries of neutral, radical cation, radical and anion forms were obtained at the B3LYP/6-31G（d） level, in which it was found that all the most stable conformations contain intramolecular hydrogen bonds. The same results were obtained from the MP2 method. The homolytic O-H bond dissociation enthalpy and the adiabatic ionization potential of neutral and anion forms for the three new antioxidants and adiabatic electron affinity and H-atom affinity for hydroxyl radical, superoxide anion radical, and hydrogen peroxide radical were determined both in gas phase and in aqueous solution using IEF-PCM and CPCM model with UAHF or Bondi cavity. The antioxidant activities and reactive oxygen species scavenging mechanisms were then discussed, and the results obtained from different methods are consistent. Furthermore, the antioxidant activities are consistent with the experimental findings of the compounds under investigation.