关于乙腈中阴极条件下酰肼异解键裂解的 DFT 研究。

IF 2.1 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY
Mark A. W. Lawrence
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引用次数: 0

摘要

背景:人们研究了肼酮的多种化学和物理化学特性,如传感器、螯合剂和多种生物活性。实验数据表明,肼酮在阴极电位下不稳定,与溶剂无关。肼酮的单电子还原产生的自由基阴离子会导致不稳定的物种以异性分解的方式裂解 N-N 键。文献提出的机理倾向于亚胺分子上的自由基,但在本研究中,DFT 计算表明,键裂解时胺产物上的自由基更有可能产生。这对电化学机制以及生物研究中的活性分子(即向目标区域输送的方法)都有影响:方法:使用 GAMESS 软件包进行密度泛函理论计算。在气相(B3LYP/6-31G(d,p))和 CH3CN(B3LYP/6-31G(d,p)/SMD)条件下对结构进行了优化,前者以 Hessian 中没有虚频为标志,后者以 Pople 极化函数为标志。作为比较,在气相和 CH3CN 中分别使用 PBE0/6-31G(d,p) 和 PBE0/6-31G(d,p)/SMD 以及 Pople 极化函数对所选路径进行了全面优化。结果表明
本文章由计算机程序翻译,如有差异,请以英文原文为准。

A DFT study on the heterolytic bond cleavage of hydrazones under cathodic conditions in acetonitrile

A DFT study on the heterolytic bond cleavage of hydrazones under cathodic conditions in acetonitrile

A DFT study on the heterolytic bond cleavage of hydrazones under cathodic conditions in acetonitrile

Context

Hydrazones have been studied for a myriad of chemical and physiochemical properties, such as sensors, chelators and numerous biological activities. Experimental data indicates that hydrazones are unstable under cathodic potentials irrespective of the solvent. The single electron reduction of hydrazones to produce radical anions result in unstable species that cleaves at the N–N bond in a heterolytic manner. The literature has proposed a mechanism favouring the radical on the imine moiety, however in this study DFT calculations suggest the radical on the amine product is more likely upon bond cleavage. This has implications on electrochemical mechanisms, and the active molecule in biological studies viz the method of delivery to target areas.

Methods

Density functional theory calculations were carried out using the GAMESS software package. The structures were optimized in the gas phase (B3LYP/6-31G(d,p)) as indicated by the absence of imaginary frequencies in the Hessian, and in CH3CN (B3LYP/6-31G(d,p)/SMD) with the Pople polarization functions. As a comparison, selected pathways were fully optimized using PBE0/6-31G(d,p) and PBE0/6-31G(d,p)/SMD for gas phase and CH3CN, respectively with the Pople polarization functions. The values were not significantly different (< 5% difference). As such only the B3LYP is evaluation is discussed.

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来源期刊
Journal of Molecular Modeling
Journal of Molecular Modeling 化学-化学综合
CiteScore
3.50
自引率
4.50%
发文量
362
审稿时长
2.9 months
期刊介绍: The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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