title: Solvolysis of chemical warfare agent VX is more efficient with hydroxylamine anion: a computational study.
abstract: The reaction of the chemical warfare agent VX with hydroxylamine anion (NH(2)O(-)) has been studied using a combination of correlated molecular orbital and density functional theory. It has been found that the hydroxylamine anion leads to predominant formation of non-toxic products for solvolysis of VX. The calculated activation barrier for the rate determining step of hydroxylamine anion with VX was found to be lower than that of hydroperoxidolysis and suggesting a more facile solvolysis with the former alpha-nucleophile. The conformational search was performed for VX using Monte Carlo search method with Merck Molecular force fields (MMFFs), which lead to a more stable conformation than reported. The anomeric effect operates in the lowest energy conformation of VX and contributes towards its stabilization. The reactivity of the alpha-nucleophiles towards VX was correlated well with the corresponding charges on nucleophilic oxygen atoms.
authors.affiliation: Analytical Science Discipline, Central Salt & Marine Chemicals, Research Institute, Council of Scientific and Industrial Research, GB Marg, Bhavnagar 364002, Gujarat, India.
authors.forename: Md Abdul Shafeeuulla
authors.initials: MA
authors.lastname: Khan
authors.forename: Manoj K
authors.initials: MK
authors.lastname: Kesharwani
authors.forename: Tusar
authors.initials: T
authors.lastname: Bandyopadhyay
authors.forename: Bishwajit
authors.initials: B
authors.lastname: Ganguly
mesh_terms: D000838:Anions; D002619:Chemical Warfare Agents / Q000737:chemistry*; D019295:Computational Biology; D019811:Hydroxylamine / Q000737:chemistry*; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D012995:Solubility
chemical_list: D000838:Anions; D002619:Chemical Warfare Agents; D019811:Hydroxylamine