Departamento de Química Física, Universidade de Vigo, Campus Universitario Lagoas-Marcosende 36310 Vigo, Spain.
J Phys Chem A. 2009 Dec 17;113(50):13937-42. doi: 10.1021/jp9056048.
This work aims at describing the electronic features of cocaine and how they are modified by the different substituents present in its metabolites. The QTAIM analysis of B3LYP and MP2 electron densities obtained with the 6-311++G** 6d basis set for cocaine and its principal metabolites indicates: (i) its positive charge is shared among the amino hydrogen, those of the methylamino group, and all of the hydrogens attached to the bicycle structure; (ii) the zwitterionic structure of benzoylecgonine can be described as two partial charges of 0.63 au, the negative one shared by the oxygens of the carboxylate group, whereas the positive charge is distributed among all the hydrogens that bear the positive charge in cocaine; (iii) its hydrogen bond is strengthened in the derivatives without benzoyloxy group and is also slightly strengthened as the size of the alkyl ester group at position 2 increases.
这项工作旨在描述可卡因的电子特性，以及其代谢物中存在的不同取代基对其电子特性的影响。用 B3LYP 和 MP2 电子密度对可卡因及其主要代谢物进行 6-311++G** 6d 基组的 QTAIM 分析表明：（i）其正电荷由氨基氢、甲基氨基氢和与自行车结构相连的所有氢原子共享；（ii）苯甲酰古柯碱的两性离子结构可以描述为两个 0.63 au 的部分电荷，负电荷由羧酸盐组的氧原子共享，而正电荷分布在可卡因中带正电荷的所有氢原子上；（iii）在没有苯甲酰氧基的衍生物中，氢键增强，而随着 2 位烷基酯基团的增大，氢键也略有增强。
