title: How does ammonium dynamically interact with benzene in aqueous media? A first principle study using the Car-Parrinello molecular dynamics method.
abstract: The Car-Parrinello molecular dynamics (CPMD) method was used to study the dynamic characteristics of the cation-pi interaction between ammonium and benzene in gaseous and aqueous media. The results obtained from the CPMD calculation on the cation-pi complex in the gaseous state were very similar to those calculated from the Gaussian98 program with DFT and MP2 algorithms, demonstrating that CPMD is a valid approach for studying this system. Unlike the interaction in the gaseous state, our 12-ps CPMD simulation showed that the geometry of the complex in aqueous solution changes frequently in terms of the interaction angles and distances. Furthermore, the simulation revealed that the ammonium is constantly oscillating above the benzene plane in an aqueous environment and interacts with benzene mostly through three of its hydrogen atoms. In contrast, the interaction of the cation with the aromatic molecule in the gaseous state involves two hydrogen atoms. In addition, the free energy profile in aqueous solution was studied using constrained CPMD simulations, resulting in a calculated binding free energy of -5.75 kcal/mol at an optimum interaction distance of approximately 3.25 A, indicating that the cation-pi interaction between ammonium and benzene is stable even in aqueous solution. Thus, this CPMD study suggested that the cation-pi interaction between an ammonium (group) and an aromatic structure could take place even on surfaces of protein or nucleic acids in solution.
authors.affiliation: Drug Discovery and Design Centre, State Key Laboratory of New Drug Research, Shanghai Institute of Materia Medica, Shanghai Institutes for Biological Sciences, Graduate School, Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai 201203, China
authors.forename: Rongjian
authors.initials: R
authors.lastname: Sa
authors.forename: Weiliang
authors.initials: W
authors.lastname: Zhu
authors.forename: Jianhua
authors.initials: J
authors.lastname: Shen
authors.forename: Zhen
authors.initials: Z
authors.lastname: Gong
authors.forename: Jiagao
authors.initials: J
authors.lastname: Cheng
authors.forename: Kaixian
authors.initials: K
authors.lastname: Chen
authors.forename: Hualiang
authors.initials: H
authors.lastname: Jiang
mesh_terms: D001554:Benzene / Q000737:chemistry*; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D008956:Models, Chemical; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D005740:Gases; D000644:Quaternary Ammonium Compounds; D012996:Solutions; D014867:Water; D001554:Benzene