【作者】 谢家庆；

【导师】 胡常伟；

【作者基本信息】 四川大学 ， 物理化学， 2004， 博士

【摘要】 天然酶由于具有高选择性、高活性和反应条件温和而受到化学和生物学者的关注。学者们利用各种各样简单或复杂的化学体系（模拟模型）来模拟天然酶。通过研究模拟酶了解天然酶的结构、性质和功能之间的关系，探索酶催化反应机理，为设计、合成结构简单、高活性、高选择性和反应条件温和的理想催化剂奠定理论基础，开发出具有实用价值的绿色催化剂。 本文以不同类型的功能配合物及其与表面活性剂形成的金属胶束作为水解酶和过氧化物酶的模拟酶模型，分别研究它们对磷酸二酯水解反应和酚类氧化反应的催化作用，取得了创新性的成果。 以不同结构的Schiff碱金属配合物作为磷酸二酯水解酶的模拟酶，催化BNPP水解，在水溶液和胶束溶液中研究发现：（1）两种带支链的Schiff碱Mn³⁺配合物的催化活性高于简单Schiff碱配合物的催化活性。带与不带支链的Schiff碱配合物催化BNPP水解反应都遵循金属——氢氧离子催化机理，但由于配体支链上的羟基或烷氧基与配位于金属离子上的羟基对底物有协同作用，加速了底物的水解；（2）冠醚化Schiff碱Co（Ⅱ）和Mn（Ⅱ）配合物的催化活性高于简单Schiff碱配合物的催化活性。冠醚基的疏水性越强，相应冠醚Schiff碱配合物的催化活性越高。冠醚提供了有利于底物与配合物金属离子结合的微环境，促进中间物种的形成，还协同金属离子活化配位水分子，使其转化为羟基，利于分四川大学博士学位论文石‘百亩亩百奋亩亩亩亩亩亩曰奋亩子内的亲核取代反应。 以草酞胺桥联双核铜配合物及其与表面活性剂形成的金属胶束作为双核金属水解酶的模拟模型，研究该模型物对BNPP水解的催化活性。研究表明该类模型具有较高的催化活性。催化反应遵循Lewis酸活化和金属轻基活化的双功能机理。两金属离子之间具有协同作用，其大小取决于两金属离子的间距。 在催化BNPP水解的过程中，不同的胶束以及由schiff碱过渡金属配合物与不同的表面活性剂胶束组成的金属胶束有不同的活性，催化活性的顺序是Brij35>LSS>CTAB. 研究了多种过氧化物酶的模拟酶对酚类氧化反应的催化作用。研究得到如下新的结果:（l）提出了一种新的热动力学研究法—特征对比参量法，用该法研究了过氧化氢氧化苯酮反应动力学;（2）分别建立了由单核和双核金属配合物与表面活性剂形成的金属胶束催化酚类氧化反应的动力学数学模型;（3）探讨了金属胶束模拟过氧化物酶催化酚类氧化反应的可行性及其机理。 上述不同类型的金属配合物及其金属胶束模拟磷酸酣水解酶和过氧化物酶的研究新结果，为今后设计活性更高的模拟水解酶和过氧化物酶以及研究它的催化机理提供了有价值的信息和依据。关键词:功能配合物，金属胶束，模拟磷酸酣酶和过氧化物酶，催化，动力学。更多还原

【Abstract】 The study of natural enzyme aroused the concern of both chemists and biologists because of its high selectivity, catalytic activity and mild reactive condition in chemical reaction. Various simple or complicated chemical systems have been used as mimic models for natural enzyme. Through investigating mimic enzyme, the mechanism of the enzymatic catalytic reaction and the correlation between the structure, character and function of the enzyme were explored, which should lay a theoretic foundation for designing and synthesizing the catalyst of simple structure, high selectivity, high catalytic activity and mild reactive condition in the chemical reaction; and should be favorable to develop green catalyst with practical value.The catalytic action of various kinds of functional coordination compound and metallomicelles which are made from the complex and micelle, used as mimic hydrolase or peroxidase, have been studied respectively in catalyzing the phosphatic diester hydrolysis and the phenolic derivant oxidation, in the paper. Some new results have been obtained.The studies on BNPP hydrolysis catalyzed by Schiff base transitional metal complexes of various structures (used as the mimic model of the phosphatic diester hydrolase catalyzed BN PP hydrolysis) in aqueous solution and micellar solution discovered the following: 1) the catalytic activity of two Schiff base transitionalmetal complexes containing the side chain are higher than that of the simple Schiff base transitional metal complexes. The BNPP hydrolysis catalyzed by the Schiff base transitional metal complexes with or without a side chain all obey the mechanism of the metal - hydroxide ion, the synergism between the hydroxide or alkyl oxygen group on the side chain of the Schiff base and hydroxide ion coordinated to metal ion in the complex accelerates the rate of the substrate hydrolysis; 2) the activity of the crown Schiff base transitional metal complexes is higher than that of the simple Schiff base complex in aqueous or micellar solution. The higher the hydrophobicity of the crown group is, the higher the catalytic activity of the relevant complex is. In BNPP hydrolysis catalyzed by the Schiff complexes, the crown group not only affords a proper microenvironment which is favorable to the formation of the intermediate between complex and BNPP, but also assists metal ion to transfer a coordinated water molecule to OH-, which is favorable to achieve the nucleophilic substituent reaction inside molecule.The catalytic activity of the oxamido-bridged dinuclear copper(II) complex and the metallomicelle made from the complex and the surfactant, used as the mimic models of the dinuclear metal hydrolase in catalyzing BNPP hydrolysis, has been investigated. The results of the studies indicate that the mimic models have high catalytic activity. These catalytic reactions follow the bifunctional mechanism of Lewis acid activation and metal hydroxide activation. There is synergism between two metal ions inside the complex, its performance is regulated by the distance of two metal ions.Different micelles and metallomicelles made from the Schiff base transitional metal complex and different surfactants have different activities in catalyzing BNPP hydrolysis, the order of the catalytic activities is Brij35> LSS >CTAB.The catalysis of some mimetic models of natural peroxidase in the phenol and phenolic derivant oxidation was investigated. Some new results are obtained from the studies: 1) a novel thermokinetic research method, the characteristic reduced parameter method, has been proposed, and the kinetics of oxidation of benzoquinoneby hydrogen peroxide has also been investigated with this method; 2) the kinetic mathematical models that the metallomicelles made from the mono-nuclear or dinuclear complexes and surfactants catalyze the phenolic derivant oxidation have been established respectively; 3) the feasibility and mechanism that the metallomicelle, a mimetic model of peroxidase, catalyzes the phenolic derivant oxidation has been discussed.The new results obtained更多还原