| 2,6-吡啶二甲酰肼2-羟基萘甲醛酰腙-Cu(Ⅱ)-CopC三元配合物的光谱研究 |
| Spectral Studies on Complex of 2,6-Pyridine Diformylhydrazine 2-Hydroxylnaphthene Carboxylic Hydrazone-Cu(Ⅱ)-CopC |
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| 摘要: 以2,6-吡啶二甲酸为原料,经酰化、酯化、胺解、亲和加成合成2,6-吡啶二甲酰肼-2-羟基萘甲酰腙(L1)。用紫外-可见吸收光谱、荧光光谱、荧光寿命方法研究了酸碱对L1互变异构的影响及L1、Cu(Ⅱ)、铜运输蛋白(copper trafficking protein,apoCopC)三者的相互结合。结果表明,在pH=7.4、50 mmol·L-1 Tris-HCl缓冲条件下,L1可分别与Cu(Ⅱ)、apoCopC结合形成1:1的配合物,条件结合常数分别为3.32×106 mol-1·L和4.01×105 mol-1·L;而Cu(Ⅱ)-L1与apoCopC结合形成1:1复合物的条件结合常数为8.09×105 mol-1·L。荧光共振能量转移、分子对接模拟表明,L1结合在apoCopC的N端,光谱滴定证实L1、Cu(Ⅱ)、apoCopC可形成以Cu(Ⅱ)为中心的三元配合物。 |
| 关键词: 2,6-吡啶二甲酰肼2-羟基萘甲醛酰腙 Cu(Ⅱ) 铜运输蛋白 配合物 光谱 |
| 基金项目: 国家自然科学基金(No.20771068,20901048)和高等学校博士学科点专项科研基金(No.20131401110011)资助项目。 |
| Abstract: 2, 6-Pyridine diformylhydrazine 2-hydroxylnaphthene carboxylic hydrazone (L1) was synthesized by acylation, esterification and aminolysis reaction. The effect of pH value on isomerization of L1 and the binding among L1, Cu(Ⅱ) and copper trafficking protein, apoCopC, were studied by using UV-Vis absorption, fluorescence spectra and fluorescence lifetime measurement. The results show that the binding constant is 3.32×106 mol-1·L for Cu(Ⅱ)-L1, 4.01×105 mol-1·L for L1-apoCopC, separately, in pH value of 7.4, 50 mmol·L-1 Tris-HCl. Meanwhile, the binding constant between Cu(Ⅱ)-L1 and apoCopC is 8.09×105 mol-1·L. The average distance between the bound L1 and Trp83 of apoCopC from fluorescence resonance energy transfer was determined and the binding site of L1 in apoCopC, which locats at N-terminal, was shown by an automated public domain software package ArgusLab 4.0.1. The formation of a ternary complex, L1-Cu(Ⅱ)-CopC, is confirmed by the titration of Cu(Ⅱ) to L1-apoCopC in pH value of 7.4 and 50 mmol·L-1 Tris-HCl. |
| Keywords: 2,6-pyridine diformylhydrazine 2-hydroxylnaphthene carboxylic hydrazone copper(Ⅱ) copper trafficking protein complex spectra |
| 投稿时间：2015-05-25 修订日期：2015-07-17 |
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| 任小林,宋珍,杨斌盛.2,6-吡啶二甲酰肼2-羟基萘甲醛酰腙-Cu(Ⅱ)-CopC三元配合物的光谱研究[J].无机化学学报,2015,31(9):1811-1819. |
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