Arnó Manuel, Domingo Luis R
Instituto de Ciencia Molecular, Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain.
Org Biomol Chem. 2003 Feb 21;1(4):637-43. doi: 10.1039/b209636f.
A theozyme for antibody aldolases has been studied at the MP2/6-31G** computational level. Formation of two cooperative hydrogen-bonds between the acidic hydrogen atoms of the enamine and of a methanol molecule with the oxygen atom of the aldol acceptor markedly favors the C-C bond-formation associated with the aldol reaction. A comparative analysis of the geometry, the charge distribution and the shape of the molecular electrostatic potential of the transition structure (TS) with the covalent adduct, resulting from the reaction of methylamine and the beta-diketone used as a hapten allows us to characterize the transition-state analogue (TSA) generated at immunization. This finding allows us to propose a hapten based on a chiral beta-ketosulfoxide that could give the formation of a TSA that addresses the tetrahedral geometry of the TS.
已在MP2/6 - 31G**计算水平上研究了抗体醛缩酶的理论酶。烯胺的酸性氢原子与甲醇分子的酸性氢原子和醛醇受体的氧原子之间形成两个协同氢键，这明显有利于与醛醇反应相关的碳 - 碳键形成。对过渡结构（TS）与共价加合物的几何结构、电荷分布和分子静电势形状进行比较分析，该共价加合物由甲胺与用作半抗原的β - 二酮反应产生，这使我们能够表征免疫时产生的过渡态类似物（TSA）。这一发现使我们能够提出一种基于手性β - 酮亚砜的半抗原，它可以形成一种TSA，该TSA符合TS的四面体几何结构。
