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Abstract：
BACKGROUND: Nitisinone is a medium-sized organic molecule that is used in treating hereditary tyrosinemia type 1 (HT-1). The structurally analogous mesotrione, however, is used as a pesticide/herbicide. What molecular properties are responsible for the similarity/dissimilarity of these molecules is investigated here. The solvent effect reduces the electron affinity to rather negative values and causes the negative electron affinity which manifests itself in a very high positive absolute reduction potential.
METHODS: B3LYP method was utilized for a geometry optimization of nitisinone and mesotrione in their neural and ionized (L0, L+, L-) forms of 6 structures. The calculations were conducted in water as a solvent using conductor-like polarizable continuum model (CPCM), nitisinone also in vacuo. The complete vibrational analysis at the true energy minimum allows evaluating the thermodynamic functions with focus to the zero-point energy and overall entropic term. The change of the Gibbs energy on reductions and/or oxidation facilitates evaluating the absolute reduction and absolute oxidation potentials. Also, DLPNO-CCSD(T) method that involves the major part of the correlation energy has been applied to nitisinone and mesotrione and their molecular ions.
METHODS: B3LYP method was utilized for a geometry optimization of nitisinone and mesotrione in their neural and ionized (L0, L+, L-) forms of 6 structures. The calculations were conducted in water as a solvent using conductor-like polarizable continuum model (CPCM), nitisinone also in vacuo. The complete vibrational analysis at the true energy minimum allows evaluating the thermodynamic functions with focus to the zero-point energy and overall entropic term. The change of the Gibbs energy on reductions and/or oxidation facilitates evaluating the absolute reduction and absolute oxidation potentials. Also, DLPNO-CCSD(T) method that involves the major part of the correlation energy has been applied to nitisinone and mesotrione and their molecular ions.
摘要：
背景：Nitisinone是一种中等大小的有机分子，用于治疗遗传性酪氨酸血症1型（HT-1）。结构类似的甲基磺草酮，然而,用作杀虫剂/除草剂。这里研究了导致这些分子的相似性/差异性的分子特性。溶剂效应将电子亲和力降低到相当负的值,并导致负电子亲和力,其本身表现为非常高的正绝对还原电势。
方法：B3LYP方法用于对神经和离子化中的Nitisinone和mesotrione进行几何优化（L0，L，L-)6种结构形式。计算是在作为溶剂的水中使用类似导体的可极化连续体模型（CPCM）进行的，nitisinone也在真空中。真实能量最小值的完整振动分析允许评估热力学函数，重点是零点能量和整体熵项。还原和/或氧化时吉布斯能量的变化有助于评估绝对还原和绝对氧化电位。此外，涉及相关能量的主要部分的DLPNO-CCSD（T）方法已应用于nitisinone和mesotrione及其分子离子。
方法：B3LYP方法用于对神经和离子化中的Nitisinone和mesotrione进行几何优化（L0，L，L-)6种结构形式。计算是在作为溶剂的水中使用类似导体的可极化连续体模型（CPCM）进行的，nitisinone也在真空中。真实能量最小值的完整振动分析允许评估热力学函数，重点是零点能量和整体熵项。还原和/或氧化时吉布斯能量的变化有助于评估绝对还原和绝对氧化电位。此外，涉及相关能量的主要部分的DLPNO-CCSD（T）方法已应用于nitisinone和mesotrione及其分子离子。
