C对<sub>α</sub> -C <sub>β</sub>键型上羟基芪的自由基清除活性：在气相和液相的理论见解,The Journal of Physical Chemistry A

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C对_α -C _β键型上羟基芪的自由基清除活性：在气相和液相的理论见解
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-02-28 00:00:00 , DOI: 10.1021/acs.jpca.6b11814
Nikolaos Nenadis ₁ , Katholiki Stavra ₁

Affiliation

密度泛函理论/ Becke的三参数混合函数与Lee-Yang-Parr相关函数（DFT / B3LYP）相结合，用于检验白藜芦醇，比卡替诺及其脱氢/二氢对应物的自由基清除潜能。因此，在气相和液相（苯，水）中，计算了预测氢原子转移（HAT）和质子转移之前（SETLET）或之后质子转移（SPLET）的单电子转移的分子描述子的值。据预测，导致分子平面性的双键有利于单氢或电子转移。预测产生线性主链的三键会降低这些转移的难易程度，而导致平面度损失的饱和则有望进一步降低活性。预计饱和的影响对白藜芦醇有害。但是，对于皮卡季诺醇，仅在逐步HAT条件下才建议提高活性，因为烯丙基氢原子在形成醌后可能易于被提取。预测（气相，液相）与白藜芦醇及其衍生物的实验证据一致。亲脂性可能会影响实际系统中的抗氧化活性，并随着分配系数的增加而增加（log P）值如下：二氢sti> >>脱氢sti。根据偶极矩值，没有观察到明显的趋势。

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Effect of Cα–Cβ Bond Type on the Radical Scavenging Activity of Hydroxy Stilbenes: Theoretical Insights in the Gas and Liquid Phase

Density functional theory/Becke’s three-parameter hybrid functional combined with the Lee–Yang–Parr correlation functional (DFT/B3LYP) was used to examine the radical scavenging potential of resveratrol, piceatannol, and their dehydro/dihydro counterparts. For this reason, the values of molecular descriptors predicting the hydrogen atom transfer (HAT) and the single electron transfer preceding (SET-PT) or following a proton transfer (SPLET) were computed in the gas and liquid (benzene, water) phases. The double bond, resulting in molecular planarity, was predicted to favor the single hydrogen or electron transfer. The triple bond, resulting in a linear backbone, was predicted to decrease the ease of these transfers, whereas the saturation, resulting in loss of planarity, was expected to decrease the activity even more. The impact of saturation was predicted to be detrimental for resveratrol. However, for piceatannol, an enhancement of activity was proposed only under stepwise HAT because allylic hydrogen atoms could be prone for abstraction after the formation of quinone. The predictions (gas, liquid phase) were in agreement with experimental evidence for resveratrol and its derivatives. The lipophilicity, which may affect antioxidant activity in real systems, increased according to partition coefficient (log P) values as follows: dihydrostilbene > stilbene > dehydrostilbene. On the basis of dipole moment values, no clear trend was observed.

更新日期：2017-02-28

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