Gold at crossroads of radical generation and scavenging at density functional theory level: Nitrogen and oxygen free radicals versus their precursors in the face of nanogold,Journal of Physical Organic Chemistry

当前位置： X-MOL 学术 › J. Phys. Org. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Gold at crossroads of radical generation and scavenging at density functional theory level: Nitrogen and oxygen free radicals versus their precursors in the face of nanogold
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2020-08-24 , DOI: 10.1002/poc.4126
Aliakbar Ahmadi ₁ , Mohamad Z. Kassaee ₁ , Mojgan Ayoubi‐Chianeh ₁ , Alireza Fattahi ₂

Affiliation

In our previous report (J. Phys. Org. Chem., 2017), we discussed the dual behavior of gold nanocluster (Au₃ NC), where it scavenged reactive oxygen species (ROS) while promoted their generation to a lesser extent. Continuing this quest, we investigate the effects of Au₃ NC on common reactive nitrogen species (RNS: ON˙ and ON˙O) and their precursors (ONH and ONOH, respectively), at B3LYP/LACVP+* level of theory. We compare the results with those of prevalent ROS (HO˙ and HOO˙) and their precursors (HOH and HOOH, respectively). To this end, various parameters are probed such as binding energy (E_b), bond dissociation energy (BDE), bond lengths, Mullikan spin density (MSD), critical point (CP) eigenvalues (atoms in molecules [AIM] analysis), and natural bond orbital (NBO) analysis including natural population analysis (NPA) and change of charge transfer energy (ΔE_CT). Our results show that in the presence of Au₃ NC, BDEs of the NH and OH bonds increase in both ONHAu₃ (1) and ONOHAu₃ (2) compared with their free forms (ONH and ONOH, respectively). In other words, the tendency to dissociate these bonds and form their corresponding RNS (1′ and 2′) decreases in the presence of gold. This is exactly the opposite of what is observed for the OH bonds in HOHAu₃ (3), HOOHAu₃ (4), and their corresponding ROS (3′ and 4′). Therefore, we can conclude that gold shows a different behavior in the face of RNS compared with ROS where it is a better scavenger of ROS than RNS.

中文翻译：

处于自由基生成和清除的密度泛函理论水平的十字路口的黄金：面对纳米金，氮和氧自由基与它们的前体

在我们之前的报告（J. Phys。Org。Chem。，2017）中，我们讨论了金纳米团簇（Au ₃ NC）的双重行为，该团簇清除了活性氧（ROS）并在较小程度上促进了它们的生成。继续这个任务，我们研究金的影响，₃ NC上常见的活性氮类（RNS：ON˙和ON˙  O）及其前体（ON  H和ON  Ò  H，分别在理论上达到B3LYP / LACVP + *水平。我们比较结果与那些流行的ROS（H 氧，氢 Ò  O）及其前体（H  Ò  H和H ø  Ò  H，分别地）。为此，探索了各种参数，例如结合能（E _b），键解离能（BDE），键长，穆利坎自旋密度（MSD），临界点（CP）特征值（分子中的原子[AIM]分析），以及自然键轨道（NBO）分析，包括自然种群分析（NPA）和电荷转移能的变化（ΔE _CT）。我们的结果表明，在Au中存在₃ NC，所述N个的二苯醚氢，氧 H键在两个ON增加 ħ 的Au ₃（1）和ON  ö ħ 的Au ₃（2（ON）与它们的游离形式相比 H和ON  ö 分别H，）。换句话说，在金的存在下，使这些键解离并形成其相应的RNS（1'和2'）的趋势降低。这对于将O所观察到的刚好相反 H键H中 ö  ħ 的Au ₃（3），H  ö  ö  ħ 的Au ₃（4）及其相应的ROS（3'和4'）。因此，我们可以得出结论，与ROS相比，金在RNS面前表现出不同的行为，而ROS比ROS更好。

更新日期：2020-08-24

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11