Binding of Organophosphorus Nerve Agents and Their Simulants to Metal Salts
Binding of Organophosphorus Nerve Agents and Their Simulants to Metal Salts
复制标题
DOI：
10.1021/acsami.0c05777
复制
发表时间：
2020-07-08
影响因子：
9.5
通讯作者：
Mavrikakis, Manos
中科院分区：
文献类型：
--
作者：
Gold, Jake;Szilvasi, Tibor;Mavrikakis, Manos
神经毒剂（NAs）对社会构成了巨大的威胁，因为它们很容易产生并且在本质上是致命的，这使得开发检测，吸附和摧毁它们的方法至关重要。为了使这些方法的发展，我们报告使用第一原理电子结构计算，以了解金属盐表面上的NAs和NA模拟物的结合性能。我们报告计算吉布斯自由结合能（G（BE））的四个NA（塔崩（GA），沙林（GB），梭曼（GD），和有毒的X（VX））和五个NA模拟物（二甲基甲基膦酸（DMMP），二甲基氯磷酸（DMCP），磷酸三甲酯（TMP），甲基二氯磷酸（MDCP），和二异丙基甲基膦酸（DIMP）的金属过氯酸盐和金属硝酸盐使用密度泛函理论。结果表明，NA和NA模拟物与金属盐表面的结合强度的总体趋势为：MDCP < DMCP < GA < GD近似于GB < TMP < VX近似于DMMP < DIMP。基于它们在盐表面上的结合性质，我们确定了最有效的模拟剂为每个研究的NAs如下：DMCP为GA，TMP为GB和GD，和DMMP为VX。为了说明在我们的研究中计算的结合能的效用，我们解决NA传感器的设计的基础上的竞争性结合的NA和液晶化合物的金属盐。我们将我们的结果与以前的实验结果进行比较，并提供了一个有前途的组合的液晶和金属盐系统选择性和灵敏地检测NAs的列表。我们的研究突出了计算化学的巨大价值，设计选择性和敏感的NA传感器，同时尽量减少涉及NA的非常危险的实验的数量。
Nerve agents (NAs) pose a great threat to society because they are easy to produce and are deadly in nature, which makes developing methods to detect, adsorb, and destroy them crucial. To enable the development of these methods, we report the use of first principles electronic structure calculations to understand the binding properties of NAs and NA simulants on metal salt surfaces. We report calculated Gibbs free binding energies (G(BE)) for four NAs (tabun (GA), sarin (GB), soman (GD), and venomous X (VX)) and five NA simulants (dimethyl methylphosphonate (DMMP), dimethyl chlorophosphate (DMCP), trimethyl phosphate (TMP), methyl dichlorophosphate (MDCP), and di-isopropyl methylphosphonate (DIMP)) on metal perthlorate and metal nitrate salts using density functional theory. Our results indicate a general trend in the binding strength of NAs and NA simulants to metal salt surfaces: MDCP < DMCP < GA < GD approximate to GB < TMP < VX approximate to DMMP < DIMP. Based on their binding properties on salt surfaces, we identify the most effective simulant for each of the studied NAs as follows: DMCP for GA, TMP for GB and GD, and DMMP for VX. To illustrate the utility of the binding energies calculated in our study, we address the design of NA sensors based on the competitive binding of NAs and liquid crystalline compounds on metal salts. We compare our results with previous experimental findings and provide a list of promising combinations of liquid crystal and metal salt systems to selectively and sensitively detect NAs. Our study highlights the great value of computational chemistry for designing selective and sensitive NA sensors while minimizing the number of very dangerous experiments involving NAs.