【作者】 杜娟；

【导师】 曾宪诚；

【作者基本信息】 四川大学 ， 物理化学， 2003， 博士

【摘要】 本文在电导法的基础上，系统地研究了广泛用于人工酶模型的二价金属离子——Cu(Ⅱ)、Zn(Ⅱ)、Co(Ⅱ)和Ni(Ⅱ)以及两种三价金属离子La(Ⅲ)和Fe(Ⅲ)对离子型表面活性剂CTAB和SDS的临界胶束浓度的影响。在此基础上，推导了一系列描述离子型胶束的临界胶束浓度与外加金属离子浓度的经验关系式，这对定量处理人工酶体系催化反应动力学有一定的参考价值。 设计了一种长链取代吡啶类配体及其铜(Ⅱ)和锌(Ⅱ)的配合物，比较性地探讨了它们在与阳离子表面活性剂CTAB所形成的共胶束溶液中催化羧酸脂水解的机理，并推导了相应的胶束体系催化反应动力学模型。实验结果表明，此类金属胶束体系对于PNPP的催化水解尤为有效，而且毗啶基和羟基的共存在反应过程中起了重要作用。 设计并合成了联吡啶胺的铜(Ⅱ)和锌(Ⅱ)配合物，并研究了其在非离子表面活性剂Brij35胶束溶液中催化磷酸二酯的水解。动力学结果显示，具有顺式二水结构的配合物是磷酸二酯水解的有效的催化剂，这种结构能有效地支持分子内的亲核进攻。 研究了大环同双核(Zn(Ⅱ)-Zn(Ⅱ)和Cu(Ⅱ)-Cu(Ⅱ))及异双核(Zn(Ⅱ)-Cu(Ⅱ))金属配合物模拟磷酸单酯酶催化磷酸单酯的水解。动力学分析表明，磷酸单酯的催化水解经历了双路易斯酸活化和分子内亲核进攻的双功能催化机理。不同金属离子对立体环境的不同要求以及与其配位的亲核剂的不同的亲核性决定了不同配合物的催化效率。配合物结构的刚柔性和两个金属中心的距离决定了催化剂对底物的选择性。 探讨了含特殊功能基肟基的双核(Cu(Ⅱ)-Cu(Ⅱ)及Co(Ⅱ)-Co(Ⅱ))配合物催化磷酸二酯的水解。证实了本身不含亲核剂的磷酸二酯也能通过双路易斯酸活化和配体亲核剂的分子内亲核进攻而水解。更多还原

【Abstract】 In this dissertation, the effects of two-valence metal ions extensively used inartificial enzyme models, Cu(II), Zn(II), Co(II) and Ni(II), and two three-valence metal ions, La(III) and Fe(III), on the critical micellization concentrations(CMC) of ionic surfactants CTAB and SDS have been systematically studied by conductivity method. A series of general empirical expressions describing the relationship between the CMC values for ionic surfactants and the concentrations of added metal ions have been derived, which are the bases for quantitative treatments of catalytic reaction kinetics by artificial enzyme system.A substituted long alkyl pyridine ligand and its Cu(II) and Zn(II) complexes have been designed. The mechanisms of the hydrolysis of carboxylate catalyzed by these complexes in the co-micellar solution with cationic surfactant CTAB have been comparatively investigated, and the catalytic reaction kinetic models of micellar system have been proposed respectively. The experimental results indicate that this type of metallomicellar system is especially effective for the hydrolysis of PNPP, and the co-existence of pyridine and hydroxyl plays an important role in the reaction.The Cu(II) and Zn(II) complexes based on 2,2’-dipyridylamine have been designed and synthesized, and the catalytic hydrolysis of phosphodiester by the complexes in nonionic surfactant Brij35 micellar solution has been studied. The kinetic results show that the complex with cis- diaquo structure is an effectivecatalyst for the hydrolysis of phosphodiester, and this structure can assist theintramolecular nucleophilic attack with effect.The macrocyclic homodinuclear (Zn(II)-Zn(II), Cu(II)-Cu(II)) and heterodinuclear (Zn(II)-Cu(II)) metal complexes simulating phosphomonoesterase-promoted hydrolysis of phosphomonoester have been discussed. The kinetic analysis illustrates that the hydrolysis of phosphomonoester experiences a bifunctional catalytic process including double Lewis acid activation and intramolecular nucleophilic attack. The different stereoscopic requirements between metal ions and the different nucleophilicities of the nucleophiles coordinated to metal ions determine the catalytic efficiencies of the complexes. The rigidity and flexibility of the complex and the distance between two metal centers determine the selectivity of the catalyst towards the substrates.The hydrolysis of phosphodiester promoted by dinuclear complexes (Cu(II)-Cu(II) and Co(II)-Co(II)) bearing special functional oxime group has been studied. The results testify the possibility that the phosphodiester not binding with any nucleophile may also hydrolyze through double Lewis acid activation and intramolecular nucleophilic attack by the nucleophile of ligand.更多还原