A reaction density functional theory study of solvent effects on keto-enol tautomerism and isomerization in pyruvic acid  

作　　者：Changjie Lu Weiqiang Tang Zijiang Dou Peng Xie Xiaofei Xu Shuangliang Zhao 

机构地区：[1]State Key Laboratory of Chemical Engineering and School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China [2]Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology and School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China

出　　处：《Chinese Journal of Chemical Engineering》2021年第3期10-16,共7页中国化学工程学报（英文版）

基　　金：National Natural Science Foundation of China(Nos.21978079,and 21878078).

摘　　要：It is important to study the solvent effect on keto-enol tautomerism that has applications in many areas of chemical engineering.In this work,we use a multiscale reaction density functional theory(Rx DFT)to study the keto-enol tautomerism and isomerization of pyruvic acid.The results show that both effects of solvation and water assistance could reduce the reaction barriers.The water molecule participates the reaction as a catalyst to accept/give the protons with forming a hexagonal ring in the transition state.As a result of this temporary and intermediate hexagonal ring,the solute configuration undergoes a small variation during the reaction,giving a diminished contribution to the intrinsic reaction free energy.The solvent distribution shows a local ordering behavior near the solute that also reduces the contribution of solvation effect to the reaction barrier.Water assistance plays a major role in both pre-reaction and postreaction process.In terms of the driving force for the reaction,the effects of both solvation and water assistance are important.

关 键 词：Solvent effect Reaction density functional theory Pyruvic acid TAUTOMERISM ISOMERIZATION 

分 类 号：O621.25[理学—有机化学]