肼衍生物与Pu（IV）的氧化还原反应定量构效关系研究

摘要

Background: Plutonium was one of the most radionuclides and the reducing of Pu(IV) had been researched extensively. It was one of the main research directions that Pu(IV) was reduced by hydrazine derivatives. Purpose:The direction of the study of the separation of Np(VI) from Pu(IV) could be pointed out and crucial basic data for it could be obtained by the study of the quantitative structure-activity relationships (QSAR) between the half-reaction times of reducing Pu(IV) and their physicochemical parameters. Methods: 3D structure of hydrazine derivatives was optimized and their energy was calculated by density functional theory (DFT) with B3LYP method and 6-311+(3d,3p) basis set and the most stable structure was obtained. The physicochemical parameters such as hydrophobic parameters etc. that can describe the structure were gained by HyperChem. Results: The interconnectedness between the half-reaction times and their physicochemical parameters was analyzed, and the QSAR equation with a good correlation is obtained, finally. Conclusion: The result showed that the hydrophobic parameter was the most important factor affecting the reduction rate of Pu(IV) by hydrazine derivatives, and was negatively correlated with Pu(IV) reduction rate.%钚是最重要的放射性核素之一，Pu(IV)与有机还原的的氧化还原反应一直是核燃料后处理研究的重点之一。通过肼衍生物结构与Pu(IV)还原速率之间构效关系的研究，获得其关键影响因素，为镎钚分离提供关键数据及研究方向指引。采用密度泛函B3LYP方法和6-311+(3d,3p)基组对11种肼衍生物进行了几何优化和能量计算，获得了其最稳定构型。并利用HyperChem软件包计算优化后的分子的疏水性参数等结构描述符。运用数学统计软件SPSS对相应的物理化学参数进行相关性分析及逐步回归分析，最终得到具有良好相关性的构效关系(Quantitative structure-activity relationships, QSAR)方程。方程表明，疏水性参数是影响肼衍生物对Pu(IV)还原速率的主要因素，且与Pu(IV)还原速率呈负相关。