钼氧转移酶活性因子的仿生合成以及结构性质研究
发布时间：2018-10-20 17:20
【摘要】：钼是动植物及人体所必需的微量生命元素，对生物体内的氮、硫、磷的代谢起重要的作用。微量元素钼进入生命体内后，主要以两种方式参与物质的代谢过程：一是以无机盐的方式，与其他营养物质相互络合；二是作为钼酶的辅助因子，参与许多生化反应。钼在生物体内主要与蛋白结合，构成含钼酶的辅助因子，简称Mo-co。它能与各种酶的底物和抑制剂相结合。自上世纪50年代以来，研究发现除固氮酶以外，生物体内还存在另一类含有金属钼成分的酶，，即钼氧转移酶，包括黄嘌呤氧化酶、硝酸盐还原酶、亚硫酸盐氧化酶和醛氧化酶等。这些酶与碳水化合物、脂肪、蛋白质、含硫氨基酸、核酸(DNA和RNA)及铁蛋白中铁的代谢密切相关。 呈手性八面体配位构型的钼配合物是钼氧转移酶活性结构因子的仿生配合物之一，而且也是著名无机抗癌药物顺铂分子的八面体类构物，而呈手性八面体配位构型的金属配合物具有切割识别DNA以及抗癌抗肿瘤的功能。各类钼氧转移酶活性结构因子的仿生合成以及生化机理研究成为热点。 1 以邻苯二酚为配体，在甲醇乙腈混合溶剂中与(n-Bu_4N_4)_4[Mo_8O_(26)]反应，分别向体系中加入乙二胺、1，2-丙二胺和1，3-丙二胺，得到四种呈手性八面体构型的单核钼配合物，测得了晶体结构，进行了UV-VIS和EPR研究，该类酶的EPR信号与牛奶中的黄质氧化酶呈相似性，UV-VIS图谱与和鸡肝中的黄嘌呤去氢酶呈现相似性。有的配合物具有良好的抗肿瘤活性。 2 以邻苯二酚为配体，在甲醇乙腈混合溶剂中与钼酸钠反应。加入乙二胺时得到两种配合物，其中一种是与前章类似的手性八面体构型的单核钼配合物；另一种是钠与邻苯二酚配位得到二维的结构而不含有钼元素。加入1，2-丙二胺时得到钠原子也参与配位的单核一维钼配合物，对三种配合物进行了结构测定和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.
【学位授予单位】：首都师范大学
【学位级别】：硕士
【学位授予年份】：2006
【分类号】：R341
本文编号：2283849
[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.
【学位授予单位】：首都师范大学
【学位级别】：硕士
【学位授予年份】：2006
【分类号】：R341
【相似文献】
相关硕士学位论文 前2条
1 邓元;钼氧转移酶活性因子的仿生合成以及结构性质研究[D];首都师范大学;2006年
2 裴秀焕;以2，3-二羟基萘为配体的钼氧转移酶的仿生合成、表征及性质研究[D];首都师范大学;2007年
本文编号：2283849
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