Binding of Organophosphorus Nerve Agents and Their Simulants to Metal Salts.

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 () 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 perchlorate 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 ≈ GB < TMP < VX ≈ 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.