Solvolysis Mechanisms of RNA Phosphodiester Analogues Promoted by Mononuclear Zinc(II) Complexes: Mechanisic Determination upon Solvent Medium and Ligand Effects

doi:10.1021/ic501084a

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	Solvolysis Mechanisms of RNA Phosphodiester Analogues Promoted by Mononuclear Zinc(II) Complexes: Mechanisic Determination upon Solvent Medium and Ligand Effects
	Zhang, Xuepeng 1; Zhu, Yajie 1; Gao, Hui 2; Zhao, Cunyuan 1
	2014-11-17
发表期刊	INORGANIC CHEMISTRY
卷号	53 期号:22 页码:11903-11912
摘要	The solvolysis mechanisms of RNA phosphodiester model 2-(hydroxypropyl)-4-nitrophenyl phosphate (HpPNP) catalyzed by mononuclear zinc(II) complexes are investigated in the paper via a theoretical approach. The general-base-catalyzed (GBC) and specific-base-catalyzed (SBC) mechanisms are thoroughly discussed in the paper, and the calculations indicate a SBC mechanism (also named as the direct nucleophilic attack mechanism) when the cyclization of HpPNP is promoted by the Zn:[12]aneN(3) complex ([12]aneN(3) = 1,5,9-triazacyclododecane). The ligand effect is considered by involving two different catalysts, and the results show that the increasing size catalyst provides a lower energy barrier and a significant mechanistic preference to the SBC mechanism. The solvent medium effect is also explored, and reduced polarity/dielectric constant solvents, such as light alcohols methanol and ethanol, are more favorable. Ethanol is proven to be a good solvent medium because of its low dielectric constant. The computational results are indicative of concerted pathways. Our theoretical results are consistent with and well interpret the experimental observations and, more importantly, provide practical suggestions on the catalyst design and selection of reaction conditions.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1021/ic501084a
研究领域[WOS]	Chemistry
关键词[WOS]	DINUCLEAR ZN(II) COMPLEX ; ACTIVATED PHOSPHATE DIESTER ; METAL-IONS ; ARTIFICIAL METALLONUCLEASES ; COBALT(III) COMPLEX ; FUNCTIONAL-GROUPS ; DNA HYDROLYSIS ; CLEAVAGE ; MODEL ; REACTIVITY
收录类别	SCI
语种	英语
WOS类目	Chemistry, Inorganic & Nuclear
WOS记录号	WOS:000345264100010
引用统计	被引频次：14[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/344007/10774
专题	中国科学院广州能源研究所
作者单位	1.Sun Yat Sen Univ, Sch Chem & Chem Engn, MOE Key Lab Bioinorgan & Synthet Chem, Guangzhou 510275, Guangdong, Peoples R China 2.Chinese Acad Sci, Guangzhou Inst Energy Convers, Key Lab Renewable Energy & Gas Hydrate, Guangzhou 510640, Guangdong, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Xuepeng,Zhu, Yajie,Gao, Hui,et al. Solvolysis Mechanisms of RNA Phosphodiester Analogues Promoted by Mononuclear Zinc(II) Complexes: Mechanisic Determination upon Solvent Medium and Ligand Effects[J]. INORGANIC CHEMISTRY,2014,53(22):11903-11912.
APA	Zhang, Xuepeng,Zhu, Yajie,Gao, Hui,&Zhao, Cunyuan.(2014).Solvolysis Mechanisms of RNA Phosphodiester Analogues Promoted by Mononuclear Zinc(II) Complexes: Mechanisic Determination upon Solvent Medium and Ligand Effects.INORGANIC CHEMISTRY,53(22),11903-11912.
MLA	Zhang, Xuepeng,et al."Solvolysis Mechanisms of RNA Phosphodiester Analogues Promoted by Mononuclear Zinc(II) Complexes: Mechanisic Determination upon Solvent Medium and Ligand Effects".INORGANIC CHEMISTRY 53.22(2014):11903-11912.