环状磷酸酯碱性水解活化自由能的理论计算

磷酸酯的水解是一种非常重要的化学和生化反应．在众多磷酸酯中，磷酸二酯的性质尤其引起了科学家们的研究兴趣．腺苷3’，5’-磷酸单酯(CAMP)是细胞内的第二信使，在视觉、肌肉收缩、神经传递、细胞生长及变异上起着至关重要的作用．如果体内第二信使的浓度过低，将可能诱发一

First-principle determination of activation free energy for alkaline hydrolysis of cyclic phosphate in aqueous solution

First-principles electronic structure calculations were performed in this study to examine the reaction pathway and corresponding activation free energy for alkaline hydrolysis of trimethylene phosphate. Five self-consistent reaction field(SCRF) methods were used to evaluate the activation free energy and the calculated results were compared with available experimental data. It demonstrated that the results calculated by using a recently developed SCRF method, known as the surface and volume polarization for electrostatics (SVPE) or fully polarizable continuum model (FPCM), was in excellent agreement with available experimentally estimated activation free energy. The SCRF methods using a certain charge renormalization scheme or neglecting the effect of volume polarization overestimated the activation free energy and the relative values of the calculated activation free energy were all significantly different from the SVPE results and available experimental data.