Conformational distributions of helical perfluoroalkyl substances and impacts on stability
Conformational distributions of helical perfluoroalkyl substances and impacts on stability
复制标题
螺旋全氟烷基物质的构象分布及其对稳定性的影响
DOI：
10.1002/jcc.26967
复制
发表时间：
2022
影响因子：
3
通讯作者：
Vyas, Shubham
中科院分区：
文献类型：
--
作者：
Mifkovic, Maleigh;Van Hoomissen, Daniel J.;Vyas, Shubham
全氟烷基物质和多氟烷基物质 (PFAS) 由于其化学和热稳定性，在过去 70 年中已广泛应用于众多应用中。由于其强大的稳定性，它们对环境具有抵抗力，这使其成为最持久的环境污染物之一。除了强大的C-F键强度之外，PFAS的疏油性、疏水性和高氧化还原电位导致传统方法降解效率低下。它们结构的一个特点是它们倾向于沿着碳主链采用螺旋构象，这与它们的碳氢化合物类似物相反。这项工作通过全氟烷烃的构象分布研究了全氟烷烃的螺旋性质，特别是作为确定极性头基、杂原子和自由基中心对螺旋构象影响的基准。由于结构控制反应性和分子特性，因此评估结构中的微小化学扰动是否会导致构象变化非常重要。基于密度泛函理论计算和综合构象分布，得出结论：螺旋度是一种局部结构性质，随着全氟烷基链中杂原子的存在以及自由基中心的存在而发生显着变化。
Per‐ and polyfluoroalkyl substances (PFAS) have been widely used the past 70 years in numerous applications due to their chemical and thermal stability. Due to their robust stability, they are environmentally recalcitrant which made them one of the most persistent environmental contaminants. In addition to strong CF bond strength, oleophobicity, hydrophobicity, and high reduction–oxidation (redox) potential of PFAS has led to their inefficient degradation by traditional means. A characteristic of their structure is also their preference to adopt helical conformations along the carbon backbone, contrary to their hydrocarbon analogues. This work investigates the helical nature of perfluoroalkanes through their conformational distributions, especially as a benchmark for determining the impact of polar head groups, heteroatoms, and radical center on helical conformations. Since structure governs reactivity and molecular properties, it is important to assess if minor chemical perturbations in the structure will lead to changes in the conformations. Based on density functional theory calculations and comprehensive conformational distributions, it was concluded that the helicity is a local structural property which changes significantly with the presence of heteroatoms in the perfluoroalkyl chain as well as with the presence of radical centers.
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影响因子：
10.9
作者：
Daniel J. Van Hoomissen;Shubham Vyas
通讯作者：
Daniel J. Van Hoomissen;Shubham Vyas
DOI：
--
发表时间：
1992
期刊：
影响因子：
--
作者：
D. Dixon
通讯作者：
D. Dixon
全氟戊烷的螺旋C(2)结构和全氟丙烷的C(2v)结构。
影响因子：
2.9
作者：
J. Fournier;R. Bohn;J. Montgomery;M. Onda
通讯作者：
M. Onda
全氟正戊烷、全氟正己烷和全氟正庚烷的完整构象分析
DOI：
--
发表时间：
2008
期刊：
影响因子：
--
作者：
W. G. Golden;E. M. Brown;Sadie E. Solem;R. Zoellner
通讯作者：
R. Zoellner