中文摘要
本项目围绕含锰金属蛋白的人工设计、合成和生物功能进行了系统研究，取得了以下有创新意义的研究成果：1) 以具有不同功能侧臂的三氮环和四氮环衍生物为配体和锰等过渡金属合成了57个新化合物，确定了其中34个化合物的晶体结构。以元素分析、X射线晶体结构分析、EPR、TGA、电喷雾质谱、电子光谱、循环伏安等多种方法对配合物的组成、结构以及性质进行了研究。重点探索了所得化合物仿水解酶、氧化酶以及核酸酶的催化性质，提出了相应的醇解、水解机理。2）运用盐酸-丁酮法制备了脱辅基牛血红蛋白，并用紫外、CD和MALDI-TOF-MS进行表征；脱辅基血红蛋白对金属离子具有高亲和力，并与锰配合物进行组装，建立了表征重组蛋白的紫外、CD和荧光等方法；含锰金属人造蛋白的水解，氧化和核酸酶等催化性质以及与DNA等生物大分子相互作用的研究正在进行中。3）较系统地研究了锰等过渡金属和砷甲基化酶以及其突变体的相互作用，探讨了金属对砷甲基化酶结构和功能的影响作用。4）制备了多种类型的分子印迹聚合物和稀土氟化物的纳米材料，研究了其对生物活性分子多巴胺、阿司匹林、小肽和牛血红蛋白等的识别。
英文摘要
In this research project, we have achieved the following innovative research results in the design,synthesis and biological function of metalloprotein..1).Fifty-seven complexes were synthesized with triazacyclononanes and tetraazacyclononanes bearing different functional pendant arms and transition metals such as Mn(II), Zn(II), Co(II) and thirty-four of them were structurally characterized. Their compositions, structures and properties were studied by elemental analysis, X-ray crystal structure analysis, EPR, TGA, ESI-MS, electronic spectrum, cyclic voltametry, 1H-NMR and so on. The catalytic properties of bionic hydrolase, oxidase and nuclease of these complexes were studied thoroughly, and possible mechanisms for these metal-mediated reactions were supposed..2).Apo-protein of bovine hemoglobin was prepared by the method of HCl-2-butanone, and characterized by UV-Vis, CD and MALDI-TOF-MS. The apoprotein was assembled with Manganese complexes to form artificial metalloproteins because its high affinity with metals. The recombinant proteins were studied by UV-Vis, CD and fluorescence. The catalytic properties of hydrolase, oxidase and nuclease of the artificial metalloproteins and their interactions with biomacromolecular such as DNA are underway. .3).The interactions between arsenic methyltransferase and its mutants and transition metals (Manganese, cobalt and so on) were studied systematically, and the effects of metals on the structure and function of arsenic methyltransferase were also studied..4) Various types of molecular imprint polymers and nano-materials of rare earth fluoride were prepared to recognize bioactive molecules such as dopamine, aspirin, peptide and bovine hemoglobin.
结题摘要
本项目围绕含锰金属蛋白的人工设计、合成和生物功能进行了系统研究，取得了以下有创新意义的研究成果：1) 以具有不同功能侧臂的三氮环和四氮环衍生物为配体和锰等过渡金属合成了57个新化合物，确定了其中34个化合物的晶体结构。以元素分析、X射线晶体结构分析、EPR、TGA、电喷雾质谱、电子光谱、循环伏安等多种方法对配合物的组成、结构以及性质进行了研究。重点探索了所得化合物仿水解酶、氧化酶以及核酸酶的催化性质，提出了相应的醇解、水解机理。2）运用盐酸-丁酮法制备了脱辅基牛血红蛋白，并用紫外、CD和MALDI-TOF-MS进行表征；脱辅基血红蛋白对金属离子具有高亲和力，并与锰配合物进行组装，建立了表征重组蛋白的紫外、CD和荧光等方法；含锰金属人造蛋白的水解，氧化和核酸酶等催化性质以及与DNA等生物大分子相互作用的研究正在进行中。3）较系统地研究了锰等过渡金属和砷甲基化酶以及其突变体的相互作用，探讨了金属对砷甲基化酶结构和功能的影响作用。4）制备了多种类型的分子印迹聚合物和稀土氟化物的纳米材料，研究了其对生物活性分子多巴胺、阿司匹林、小肽和牛血红蛋白等的识别。