双环八氮杂大环双核铜配合物催化羧酸酯水解研究
Catalytic Hydrolysis of p-Nitrophenyl Picolinate (PNPP) by a Dinuclear Copper(Ⅱ) Complex of an Octaaza Di-macrocyclic Ligand
作者单位
寇兴明 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
胡艳 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
田玉华 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
孟祥光 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
胡常伟 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
曾宪诚 四川大学化学学院四川省绿色化学与技术重点实验室成都 610064 
摘要: 合成了一类新的双环二氧大环四胺双核铜配合物,其组成经元素分析、热重/差热分析、摩尔比法及等物质的量连续变化法所确证。在水溶液中,详细研究了其催化2-吡啶甲酸对硝基苯酚酯(PNPP)水解的动力学和机理,并与相应的单核铜配合物进行了对比。结果表明,此双核铜配合物能有效地催化PNPP的水解;两个金属中心之间具有明显的协同作用,较好的模拟了某些天然水解金属酶的“双功能催化机理”。
关键词: 大环双核铜(Ⅱ)配合物  羧酸酯  模拟酶  水解  催化动力学
基金项目: 
Abstract: A new dinuclear copper(Ⅱ) complex of an octaaza di-macrocyclic ligand (bisdioxocyclam) has been synthesized and characterized by elementary analysis, TG/DTA, molar ratio and Job method. Its ability to catalyze the hydrolysis of PNPP was studied and the kinetics and mechanism for the hydrolysis of PNPP promoted by the dinuclear copper(Ⅱ) complex of bisdioxocyclam was discussed in detail. For comparision, the catalytic activity of the corresponding mononuclear copper(Ⅱ) complex toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic dinuclear copper(Ⅱ) complex of bisdioxocyclam can effectively catalyzed the hydrolysis of PNPP. Apparent cooprativity between two metal ions of the macrocyclic dinuclear copper(Ⅱ) complex was observed, which is similar to the “bifunctional mechanism” operated by some natural hydrolytic metalloenzyme.
Keywords: macrocyclic dinuclear copper(Ⅱ) complex  carboxylic esters  enzyme mimcking  hydrolysis  catalytic kinetics
投稿时间:2004-05-24 修订日期:2004-08-02
摘要点击次数:  1386
全文下载次数:  1991
寇兴明,胡艳,田玉华,孟祥光,胡常伟,曾宪诚.双环八氮杂大环双核铜配合物催化羧酸酯水解研究[J].无机化学学报,2005,21(1):51-58.
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