@article{Saxena2021,
abstract = {In this study, we have modelled the non-enzymatic hydrolysis of ATP in the gas-phase and the aqueous-phase by performing ab initio molecular dynamics simulations combined with an enhanced sampling technique. In the gas-phase, we studied hydrolysis of fully protonated ATP molecule, and in the aqueous-phase, we studied hydrolysis of ATP coordinated with: a) two H+ ions (H-ATP), b) Mg2+ (Mg-ATP), and c) Ca2+ (Ca-ATP). We show that gas-phase ATP hydrolysis follows a two-step dissociative mechanism via a highly stable metaphosphate intermediate. The Adenine group of the ATP molecule plays a crucial role of a general base; temporarily accepting protons and thus helping in the elimination-addition process. In the aqueous-phase hydrolysis of ATP, we find that the cage of solvent molecules increases the stability of the terminal phospho-anhydride bond through a well-known cage-effect. The nature of the ions has an important effect on the mechanism of the reaction. We find a two-step dissociative-type mechanism for H-ATP, a single-step dissociative-type mechanism for Mg-ATP, and an SN-2 type concerted hydrolysis pathway for Ca-ATP.},
author = {Saxena, Raghav and Avanigadda, V. B.K.Sai Phani Kumar and Singh, Raghvendra and Agarwal, Vishal},
doi = {10.1002/qua.26615},
journal = {International Journal of Quantum Chemistry},
number = {10},
pages = {1--16},
title = {{Ab initio dynamics of gas-phase and aqueous-phase hydrolysis of adenosine triphosphate}},
volume = {121},
year = {2021}
}