Phosphate monoester hydrolysis at tricopper site: The advantage and disadvantage of closely assembled trimetallic active sites

	Phosphate monoester hydrolysis at tricopper site: The advantage and disadvantage of closely assembled trimetallic active sites
	Ning, Yingying 1; Gao, Meng 1; Zheng, Kunyi 1; Zhang, Zongyao 1; Zhou, Jiang 2; Hao, Xiang 3; Cao, Rui 1,4
刊名	JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
	2015-07-01
卷号	403 页码:43-51
关键词	Trinuclear copper complex X-ray structure Phosphate hydrolysis Inhibition Substrate binding
英文摘要	Two trinucleating ligands N(CH2-m-C6H4-CH(2)tacn)(3) (L1, tacn = 1,4,7-triazacyclononane) and 1,3,5-C6H3(o-C6H4-CH2N(CH(2)py)(2))(3) (L2, py = pyridine) were synthesized, and their tricopper(II) complexes [(CuCl)(3)L1]Cl-3 (1) and [(CuCl)(3)L-2]Cl-3 (2) were investigated as catalysts for the hydrolysis of 4-nitrophenyl phosphate (NPP). Structural analysis revealed that the three Cu(II) ions in L1 are adjacent to each other, while those in L2 lack such features due to the steric hindrance of dipicolylamine (dpa) units. Hydrolysis results indicated that vicinal metal ions within same ligand backbone have high levels of cooperation for substrate recognition and thus high initial catalytic efficiency, but the binding of inorganic phosphate as the hydrolysis product at the tricopper site is a major disadvantage. Significantly, complex [((CuCl)-Cl-II)(3)(HPO4)L1](PF6) (3) was isolated from NPP hydrolysis with 1 and was characterized by single crystal X-ray diffraction. In this structure, the triply bridging phosphate at the tricopper site disorders in two opposite orientations. These results, in collaboration with high-resolution mass spectrometry studies, indicated that NPP was first coordinated at the tricopper site, and was subsequently attacked by a water molecule from the underneath of the tricopper plane, a reaction model that supports the proposed mechanism of biological phosphate hydrolysis at the trimetallic active site of pyrophosphatases. (C) 2015 Elsevier B.V. All rights reserved.
收录类别	SCI
语种	英语
公开日期	2015-11-02
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/28045]
专题	化学研究所_分析测试中心
作者单位	1.Renmin Univ China, Dept Chem, Beijing 100872, Peoples R China 2.Peking Univ, Coll Chem & Mol Engn, Beijing 100871, Peoples R China 3.Chinese Acad Sci, Inst Chem, Ctr Physicochem Anal & Measurement, Beijing 100190, Peoples R China 4.Beijing Univ Technol, Dept Chem & Chem Engn, Beijing 100124, Peoples R China
推荐引用方式 GB/T 7714	Ning, Yingying,Gao, Meng,Zheng, Kunyi,et al. Phosphate monoester hydrolysis at tricopper site: The advantage and disadvantage of closely assembled trimetallic active sites[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,2015,403:43-51.
APA	Ning, Yingying.,Gao, Meng.,Zheng, Kunyi.,Zhang, Zongyao.,Zhou, Jiang.,...&Cao, Rui.(2015).Phosphate monoester hydrolysis at tricopper site: The advantage and disadvantage of closely assembled trimetallic active sites.JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,403,43-51.
MLA	Ning, Yingying,et al."Phosphate monoester hydrolysis at tricopper site: The advantage and disadvantage of closely assembled trimetallic active sites".JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 403(2015):43-51.