A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex

doi:10.1016/j.molcata.2012.11.025

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	A density functional theory study of the hydrolysis mechanism of phosphodiester catalyzed by a mononuclear Zn(II) complex
	Zhang, Xuepeng 1; Gao, Hui 2; Xu, Huiying 1; Xu, Jianqiao 1; Chao, Hui 1; Zhao, Cunyuan 1
	2013-03-01
发表期刊	JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷号	368 页码:53-60
摘要	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.
文章类型	Article
关键词	Phosphodiester Zinc Hydrolysis Solvent Effect s(n)2 Reaction Deprotonation
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1016/j.molcata.2012.11.025
研究领域[WOS]	Chemistry
关键词[WOS]	METAL-IONS ; PHOSPHATE DIESTERS ; MODEL SYSTEM ; CLEAVAGE ; METHANOL ; ENZYMES ; BINDING ; SERIES ; ACIDS ; SET
收录类别	SCI
语种	英语
WOS类目	Chemistry, Physical
WOS记录号	WOS:000315176600008
引用统计	被引频次：11[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.giec.ac.cn/handle/344007/9142
专题	中国科学院广州能源研究所
作者单位	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
推荐引用方式 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.