Early Events in the Reductive Dehalogenation of Linear Perfluoroalkyl Substances
Early Events in the Reductive Dehalogenation of Linear Perfluoroalkyl Substances
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DOI：
10.1021/acs.estlett.9b00116
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发表时间：
2019-04
影响因子：
10.9
通讯作者：
Daniel J. Van Hoomissen;Shubham Vyas
中科院分区：
文献类型：
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作者：
Daniel J. Van Hoomissen;Shubham Vyas
这项工作详细介绍了全氟烷基物质（PFASs）的还原脱附的早期事件，并提出了一个简单的方法来预测的全氟烷基酸（PFAAs）的还原行为，使用电子结构计算。与直链全氟羧酸的电子连接通常发生在α-碳上，并且在能量上与链长无关，与直链全氟烷基磺酸盐的情况相反，其中电子通常插入其他位置。因此，全氟辛烷磺酸和全氟辛酸这两种被广泛研究和仔细审查的全氟辛酸预计将通过不同的途径减少。我们的协议可以预测PFAAs的标准还原电位，提供了一个合理的基础上探测反应中间体，建立自由能关系，并占PFASs的内在结构多样性超出线性基板。
This work details the early events in the reductive defluorination of perfluoroalkyl substances (PFASs) and presents a straightforward methodology for predicting the reduction behavior of the perfluoroalkyl acids (PFAAs) using electronic structure calculations. Electron attachment to linear perfluorocarboxylic acids generally occurs at the α-carbon and is energetically not correlated to chain length, contrary to the case for linear perfluoroalkanesulfonates, where electrons generally insert into other positions. Perfluorooctanesulfonate and perfluorooctanoic acid, two widely studied and scrutinized PFAAs, are therefore predicted to be reduced through diverging pathways. Our protocol can predict the standard reduction potentials of PFAAs, provides a rational basis for probing reaction intermediates, establishes free energy relationships, and accounts for PFASs’ inherent structural diversity beyond the linear substrates.