含双核铁活性中心的非血红素蛋白的模拟-无机化学专业论文.docxVIP

南开人学博}：论文 南开人学博}：论文 摘要 中文摘要 毖予非血红素蛋白酶的化学模拟热点，选用n，A(三(2-吡啶甲基)胺)作 为端基配体，分别用酸根和氨基酸作为桥联配体，设计合成了11个氧桥联的双 核铁配合物(其中9个未见文献报道)，运用X．射线单晶衍射方法解析了7个配 合物的晶体结构，用元素分析、红外光谱、紫外．可见光潜、变温磁化率等手段 对配合物进行了表征和性质研究。研究结果表明，所合成的双核铁配合物在结构 和性质上与天然非血红素蛋白酶相近。重点讨论了配合物中双核铁之间反铁磁偶 合参数，值与双核铁中心结构的关系，针对目前关于双核铁之闯磁相互作用与 Fe—D—Fe角之间关系的争论，提出了我们的观点。对两个亚铁配合物进行了分 jf氧加合物的动力学研究，得出分子氧加合物的低温分解反应为～级反应，为研 究非血红素蛋白酶中双核铁中心的载氧机理提供了实验依据。 关键词：非血红素蛋白酶，双核铁；晶体结构?磁性必反应动力学 摘篮 摘篮 南开大学博{?论文 Abstract The design and synthesis of I．t-OXO diiron(III)complexes is an attractive field in the simulation of non如eme protein which is new calss of metal proteins and enzymes．Tris(2-pyridylmethyl)amine WaS used to act the terminal ligand and series of acidic radicals and L-amino acid were used to act the bridged ligands in the synthesized 1 1 complexes in which 9 complexes unreported far we know and 7 complexes were structural characterized by X-ray diffraction analyses．The complexes were character／zed by elemental analyses， IR， UV-vis and variable·temperature magnetic susceptibility．The results showed that the diiron(1lI) structures and properties were similar to those of nonheme proteins．The correlation between J values of the antiferromagnetic coupling parameters and the structures of diiron(1lI)core was discussed detailed．Kinetic studies of the decomposition reaction oftwo dinuclear Fe(1I)／02 adduets at low temperature showed that the reaction was first．order in the experimental conditions．The results were similar to those of other metal complexes and natural enzymes such methane monooxygenase(MMOH)． Keywords：northeme protein，diimn complexes，crystal structure，magnetic property, reaction kinetiCS 南开人学博Ij论文 南开人学博Ij论文 第一章 第一章绪 论 生物体内的天然氧载体具有可逆载氧能力，能