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

作　　者：任小林[1] 宋珍[1] 杨斌盛[1] 

机构地区：[1]山西大学分子科学研究所,化学生物学与分子工程教育部重点实验室,太原030006

出　　处：《无机化学学报》2015年第9期1811-1819,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20771068,20901048);高等学校博士学科点专项科研基金(No.20131401110011)资助项目

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,apo Cop C)三者的相互结合。结果表明,在p H=7.4、50 mmol·L-1 Tris-HCl缓冲条件下,L1可分别与Cu(Ⅱ)、apo Cop C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apo Cop C结合形成1∶1复合物的条件结合常数为8.09×105mol-1·L。荧光共振能量转移、分子对接模拟表明,L1结合在apo Cop C的N端,光谱滴定证实L1、Cu(Ⅱ)、apo Cop C可形成以Cu(Ⅱ)为中心的三元配合物。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 rno1-1 .L for Ll-apoCopC, separately, in pH value of 7.4, 50 mmol .L-1 Tris-HC1. Meanwhile, the binding constant between Cu（II）-L1 and apoCopC is 8.09×105 mo1-1 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, LI-Cu（Ⅱ）-CopC, is confirmed by the titration of Cu（Ⅱ） to Ll-apoCopC in pH value of 7.4 and 50 mmol. L-1 Tris-HC1.

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 

分 类 号：O614.121[理学—无机化学] O614.4[理学—化学]