Khan Md Abdul Shafeeuulla, Kesharwani Manoj K, Bandyopadhyay Tusar, Ganguly Bishwajit
Analytical Science Discipline, Central Salt & Marine Chemicals, Research Institute, Council of Scientific and Industrial Research, GB Marg, Bhavnagar 364002, Gujarat, India.
J Mol Graph Model. 2009 Sep;28(2):177-82. doi: 10.1016/j.jmgm.2009.06.004. Epub 2009 Jun 27.
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.
利用相关分子轨道和密度泛函理论相结合的方法，研究了化学战剂VX与羟胺阴离子（NH₂O⁻）的反应。研究发现，羟胺阴离子会使VX溶剂解主要生成无毒产物。计算得出，羟胺阴离子与VX反应的速率决定步骤的活化能垒低于氢过氧化物解，这表明与前一种α-亲核试剂的溶剂解更容易。使用默克分子力场（MMFFs）的蒙特卡罗搜索方法对VX进行了构象搜索，得到了比报道中更稳定的构象。异头效应在VX的最低能量构象中起作用，有助于其稳定。α-亲核试剂对VX的反应性与亲核氧原子上的相应电荷密切相关。
