SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2021, Vol. 29 ›› Issue (3): 10-16.DOI: 10.1016/j.cjche.2020.08.003

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

Changjie Lu1, Weiqiang Tang1, Zijiang Dou2, Peng Xie2, Xiaofei Xu1, Shuangliang Zhao1,2   

  1. 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
  • Received:2020-05-08 Revised:2020-08-09 Online:2021-05-13 Published:2021-03-28
  • Contact: Xiaofei Xu, Shuangliang Zhao
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (Nos. 21978079, and 21878078).

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

Changjie Lu1, Weiqiang Tang1, Zijiang Dou2, Peng Xie2, Xiaofei Xu1, Shuangliang Zhao1,2   

  1. 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
  • 通讯作者: Xiaofei Xu, Shuangliang Zhao
  • 基金资助:
    This work was supported by the National Natural Science Foundation of China (Nos. 21978079, and 21878078).

Abstract: 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 (RxDFT) 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 post-reaction process. In terms of the driving force for the reaction, the effects of both solvation and water assistance are important.

Key words: Solvent effect, Reaction density functional theory, Pyruvic acid, Tautomerism, Isomerization

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 (RxDFT) 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 post-reaction 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