【摘要】：鉬是動植物及人體所必需的微量生命元素，對生物體內的氮、硫、磷的代謝起重要的作用。微量元素鉬進入生命體內后，主要以兩種方式參與物質的代謝過程：一是以無機鹽的方式，與其他營養(yǎng)物質相互絡合；二是作為鉬酶的輔助因子，參與許多生化反應。鉬在生物體內主要與蛋白結合，構成含鉬酶的輔助因子，簡稱Mo-co。它能與各種酶的底物和抑制劑相結合。自上世紀50年代以來，研究發(fā)現(xiàn)除固氮酶以外，生物體內還存在另一類含有金屬鉬成分的酶，，即鉬氧轉移酶，包括黃嘌呤氧化酶、硝酸鹽還原酶、亞硫酸鹽氧化酶和醛氧化酶等。這些酶與碳水化合物、脂肪、蛋白質、含硫氨基酸、核酸(DNA和RNA)及鐵蛋白中鐵的代謝密切相關。 呈手性八面體配位構型的鉬配合物是鉬氧轉移酶活性結構因子的仿生配合物之一，而且也是著名無機抗癌藥物順鉑分子的八面體類構物，而呈手性八面體配位構型的金屬配合物具有切割識別DNA以及抗癌抗腫瘤的功能。各類鉬氧轉移酶活性結構因子的仿生合成以及生化機理研究成為熱點。 1 以鄰苯二酚為配體，在甲醇乙腈混合溶劑中與(n-Bu_4N_4)_4[Mo_8O_(26)]反應，分別向體系中加入乙二胺、1，2-丙二胺和1，3-丙二胺，得到四種呈手性八面體構型的單核鉬配合物，測得了晶體結構，進行了UV-VIS和EPR研究，該類酶的EPR信號與牛奶中的黃質氧化酶呈相似性，UV-VIS圖譜與和雞肝中的黃嘌呤去氫酶呈現(xiàn)相似性。有的配合物具有良好的抗腫瘤活性。 2 以鄰苯二酚為配體，在甲醇乙腈混合溶劑中與鉬酸鈉反應。加入乙二胺時得到兩種配合物，其中一種是與前章類似的手性八面體構型的單核鉬配合物；另一種是鈉與鄰苯二酚配位得到二維的結構而不含有鉬元素。加入1，2-丙二胺時得到鈉原子也參與配位的單核一維鉬配合物，對三種配合物進行了結構測定和NMR研究。
[Abstract]:Molybdenum is a trace element of life necessary for animals, plants and human bodies, which plays an important role in the metabolism of nitrogen, sulfur and phosphorus in organisms. After the trace element molybdenum entered into the body of life, it mainly participated in the metabolic process of substance in two ways: one is complexing with other nutrients in the way of inorganic salt, the other is taking part in many biochemical reactions as an auxiliary factor of molybdenum enzyme. Molybdenum mainly binds to protein in organism and forms the auxiliary factor of molybdenum-containing enzyme, Mo-co. for short It can be combined with substrates and inhibitors of various enzymes. Since the 1950s, studies have found that in addition to nitrogenase, there is another enzyme containing molybdenum, molybdenum oxide transferase, including xanthine oxidase, nitrate reductase. Sulfite oxidase, aldehyde oxidase, etc. These enzymes are closely related to carbohydrate, fat, protein, sulfur amino acid, nucleic acid (DNA and RNA) and iron metabolism in ferritin. The chiral octahedral molybdenum complex is one of the biomimetic complexes of molybdenum oxygen transferase active structural factors, and is also the octahedral structure of the famous inorganic anticancer drug cisplatin. The metal complexes with chiral octahedral coordination have the functions of cutting and recognizing DNA and anticancer and anti-tumor. Biomimetic synthesis and biochemical mechanism of various molybdenum oxygen transferase active structural factors have become a hot topic. 1 catechol is used as ligand. Four mononuclear molybdenum complexes with chiral octahedral configuration were obtained by the reaction of (n-Bu_4N_4) _ 4 [Mo_8O_ (26)] with (n-Bu_4N_4) _ 4 [Mo_8O_ (26)] in methanol-acetonitrile mixed solvent, and the addition of ethylenediamine, 1h2propylenediamine and 1h3propylenediamine into the system, respectively. The crystal structure was studied by UV-VIS and EPR. The EPR signal of this enzyme is similar to that of xanthine oxidase in milk, and the UV-VIS map is similar to that of xanthine dehydrogenase in chicken liver. Some complexes have good antitumor activity. 2 Catechol was used as ligand to react with sodium molybdate in the mixed solvent of methanol and acetonitrile. Two complexes were obtained by adding ethylenediamine, one of which was a chiral octahedron mononuclear molybdenum complex similar to the previous chapter, the other was that sodium coordinated with catechol to obtain a two-dimensional structure without molybdenum. The mononuclear one-dimensional molybdenum complexes with sodium atoms also coordinated were obtained by adding 1H 2-propylenediamine. The structures of the complexes were determined and NMR studies were carried out.
【學位授予單位】：首都師范大學
【學位級別】：碩士
【學位授予年份】：2006
【分類號】：R341

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1 鄧元;鉬氧轉移酶活性因子的仿生合成以及結構性質研究[D];首都師范大學;2006年

2 裴秀煥;以2，3-二羥基萘為配體的鉬氧轉移酶的仿生合成、表征及性質研究[D];首都師范大學;2007年

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