Knowledge Management System Of Guangzhou Institute of Energy Conversion, CAS
| A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex | |
| Zhang, Xuepeng1; Gao, Hui2; Xu, Huiying1; Xu, Jianqiao1; Chao, Hui1; Zhao, Cunyuan1 | |
| 2013-03-01 | |
| Source Publication | JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
 |
| Volume | 368Pages:53-60 |
| Abstract | Density functional theory (DFT) calculations were used to explore the hydrolysis mechanism of the DNA analog BNPP (BNPP= bis(4-nitrophenyl)phosphate) catalyzed by the mononuclear zinc(II):OH- complex of 1,5,9-triazacyclododecane (Zn:([12] aneN(3))). We present a binding mode in which one terminal phosphoryl oxygen atom as well as the nucleophilic group (hydroxyl anion) binds to zinc center. Two potential mechanisms were found as follows: one is a concerted mechanism with a reaction barrier of 18.1 kcal/mol in liquid phase of implicit solvent and 13.8 kcal/mol in liquid phase of explicit solvent of water molecules; the other is a stepwise mechanism with a hydroxylated phosphate reaction intermediate of a quasi-trigonal bipyramid configuration but is less feasible. Both the concerted reaction pathway and stepwise reaction pathway are S(N)2 manner of nucleophilic substitution reactions. Meanwhile polar protic solvents like water, methanol and ethanol are favored in the catalyst-assisted hydrolysis mechanism. We explore the rationality of deprotonation of mono-anionic phosphates in the transient products and find that it is difficult to dissociate a proton and the ultimate product is NPP- rather than NPP2-. These results are consistent with and systematically interpret the experimental observations, more importantly, provide useful suggestions in the catalyst design and solvent selection. (C) 2012 Elsevier B.V. All rights reserved. |
| Subtype | Article |
| Keyword | Phosphodiester Zinc Hydrolysis Solvent Effect s(n)2 Reaction Deprotonation |
| WOS Headings | Science & Technology ; Physical Sciences |
| DOI | 10.1016/j.molcata.2012.11.025 |
| WOS Subject Extended | Chemistry |
| WOS Keyword | METAL-IONS ; PHOSPHATE DIESTERS ; MODEL SYSTEM ; CLEAVAGE ; METHANOL ; ENZYMES ; BINDING ; SERIES ; ACIDS ; SET |
| Indexed By | SCI |
| Language | 英语 |
| WOS Subject | Chemistry, Physical |
| WOS ID | WOS:000315176600008 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.giec.ac.cn/handle/344007/9142 |
| Collection | 中国科学院广州能源研究所 |
| Affiliation | 1.Sun Yat Sen Univ, MOE Key Lab Bioinorgan & Synthet Chem KLGHEI Envi, Sch Chem & Chem Engn, Guangzhou 510275, Guangdong, Peoples R China 2.Chinese Acad Sci, Key Lab Renewable Energy & Gas Hydrate, Guangzhou Inst Energy Convers, Guangzhou 510640, Peoples R China |
| Recommended Citation GB/T 7714 | Zhang, Xuepeng,Gao, Hui,Xu, Huiying,et al. A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,2013,368:53-60. |
| APA | Zhang, Xuepeng,Gao, Hui,Xu, Huiying,Xu, Jianqiao,Chao, Hui,&Zhao, Cunyuan.(2013).A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex.JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,368,53-60. |
| MLA | Zhang, Xuepeng,et al."A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex".JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 368(2013):53-60. |
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