论文部分内容阅读
用从头计算方法在RHF/6-31G(d)和MP2/6-31G(d)水平上对甲基乙基亚硝胺代谢产生的b-位硫酸酯按照是否经过邻基参与作用与DNA碱基发生烷基化反应的不同假设机理进行了研究.对所有反应物、产物、中间体和过渡态进行了全几何构型优化,得出反应活化能和内禀反应坐标等参数.结果表明,邻基参与作用有力地促进了b-位硫酸酯化烷基亚硝胺与DNA碱基的烷化反应.在相同水平上用Onsager溶剂效应模型反应场进行了计算,表明在极性溶剂中邻基参与反应的活化能明显降低.
The b-position sulfate produced by methylethylnitrosamine metabolism at the ab initio level at RHF / 6-31G (d) and MP2 / 6-31G (d) Different assumptions about the alkylation reaction have been carried out.All geometrical configurations of all reactants, products, intermediates and transition states were optimized and the parameters such as reaction activation energy and intrinsic reaction coordinate were obtained.The results showed that, The ortho-group participation strongly promoted the alkylation of the b-sulfated alkylated nitrosamines with the DNA bases, and was calculated on the same level using the Onsager solvent effect model reaction field, indicating that the ortho- The activation energy of basal participation in the reaction decreased significantly.