不同取代基对酚羟基抗氧化活性影响的计算研究.docVIP

不同取代基对酚羟基抗氧化活性影响的计算研究 【摘要】nbsp; 目的:研究不同取代苯酚类化合物的抗氧化活性。方法:用杂化密度泛函B3LYP方法在6-31+G(d, p)水平上，分别对20种苯酚类化合物及其自由基的几何结构、电子结构、键解离能等性质进行计算比较研究。结果:①所有自由基中C-O键长较分子状态都变短，但其键长与具有真正C=O双键的对苯醌和环己酮相比较又稍长。②由Mulliken原子电荷分析，酚羟基抽氢形成自由基后，羟基氧原子电荷数都减少，同时本位碳上的净电荷数值比抽氢前增加。③由偶极矩数值显示，苯环上取代基分别位于邻位、间位和对位，其偶极矩依次减小；随着对位取代基上氯原子的增多极性减小。④前线轨道组成表明，在抽氢形成自由基后，氧的p-π共轭作用增强，使其自旋电子密度降低，但吸电子基团使氧原子上自旋密度增加。中性分子中当苯环上有供电子的基团时，HOMO和LUMO的能差降低，但相差不大，均比环己醇低，而自由基的能差均比环己酮、对苯醌要低。⑤取代苯酚类化合物抗氧化能力大小直接体现于O-H键强度，当取代基为吸电子基团时，所需解离能大，抗氧化活性相对减弱；相反，当取代基团为供电子基团时其抗氧活性加强。结论:烷烃基类取代物易于抗氧化，卤代烃基或硝基类取代物抗氧化活性差。 【关键词】nbsp; 苯酚化合物 抗氧化 密度泛函 酚羟基 nbsp;nbsp;nbsp; Abstract:nbsp; Objective:To explore antioxidant activity of the different substituted phenols. Methods: The geometrical structures, electronic structures, and O-H bond dissociation energies of neutral and free radicals of 20 phenol and substituted phenols were calculated with hybrid density functional theory B3LYP method at 6-31+G(d,p) level. Results: ①The bond length of C-O bond in all free radicals was shorter than that in their neutral compounds but was longer than that in p-benzoquinone and cyclohexanone with real C=O double bonds. ②The Mulliken population showed that the net charges of O atom decreased in the free radicals, but the charges of connected C atom increased. And different alkanyls had little affected on spin density of O atom in free radicals，however, electron-withdrawing groups such as-CHCl2 led to increase. ③The dipole moments of different alkanyl-phenol compounds were orthogt;metagt;para order, and nearly all the dipole moments of free radicals of different substituted phenols were bigger than that of the neutral substituted phenols, especially the dipole moments of β-naphthol were always bigger than that of α-naphthol. ④The frontier molecular orbitals HOMO and LUMO were comprise of p orbital of O atom, p orbital of benzene, and s or p orbital of substitutes, the gap energies difference values for HOMO and LUMO of free radicals were ne