论文总字数：37028字

摘 要

过氧钒配合物指的是 5价的钒与含有氧的配体形成的复杂配合物，其中心原子是基团VO₃^-或 VO₂^-的离子。过渡金属钒(V)能够被过氧化氢(H₂O₂)或者烃基（ROOH）氧化，从而生成相应的过氧基配合物,加入不同配体后可形成不同结构的复合物。过氧钒配合物在多种的领域具有实际应用。它们可以在某些有机化合物的氧化反应中起到氧化剂或催化剂的作用。它们还具有模拟胰岛素的性质，抗肿瘤细胞的活性并刺激或抑制某些酶等作用。已被报道，有些氧钒配合物具有良好的抗肿瘤活性，但其作用机制并不明确。为了进一步了解过氧钒配合物的抗肿瘤机制，本文设计合成了三种过氧钒配合物晶体，获得其单晶结构，并通过细胞生物活性实验，探究了它们的抗视网膜母细胞瘤的活性，进一步揭示了其抗肿瘤机制。

本文研究通过以下几个方面：通过用SciFinder 和Web of Science查找了所有过氧钒配合物及晶体相关的文献，并对其合成方法进行了总结归纳。首先用偏钒酸钾和配体三（羟甲基）甲基氨基酸,乙二胺-N，N’-二乙酸、N-(2-乙酰氨基)-亚氨基二醋酸、草酸，联吡啶、亚氨基二乙酸、三乙烯四胺等原料进行合成实验，后利用结晶生长方法最终获得了三（羟甲基）甲基氨基酸,乙二胺-N，N’-二乙酸、N-(2-乙酰氨基)-亚氨基二醋酸过氧钒的三种未被报道的晶体，测其单晶数据。并对此三种过氧钒做了热重分析、XRD图谱分析以及包括CCK-8，凋亡，活性氧等的细胞毒性实验研究

关键词：过氧钒配合物；晶体的合成与解析；视网膜母细胞瘤

Abstract

The peroxo-vanadium complex is a complex complex of 5 vanadium and oxygen-containing ligand, whose central atom is the group VO₃^- or VO₂^- ion. The transition element vanadium (V) can be oxidized by hydrogen peroxide (H₂O₂) or hydroxyl (ROOH) to generate the corresponding peroxide complexes, which can be added to different ligands to form complex complexes. Peroxide complexes have practical applications in a variety of fields. They can act as an oxidant or catalyst in the oxidation of certain organic compounds. They also mimic the properties of insulin, the activity of anti-tumor cells, and stimulate or inhibit the effects of certain enzymes . It has been reported that some vanadium complexes have good anti-tumor activity, but their mechanism is not clear. In order to further understand the anti-tumor mechanism of vanadium complexes peroxide, this paper designed and synthesized three oxygen vanadium complexes crystal, its single crystal structure, and through the cell biological activity experiment, to explore their activity of retinoblastoma, further reveals its anti-tumor mechanisms.

we have searched through the following aspects: by using SciFinder and Web of Science, we searched all the literatures related to vanadium complexes and crystals, and summarized their synthesis methods. First by partial vanadate potassium and three (hydroxymethyl) methyl amino acid ligand, ethylenediamine - N, N '- iminodiacetic acid, N - (2 - acetyl amino) - the amino diacetate, oxalic acid, pyridine and iminodiacetic acid, triethylene tetramine and other raw materials for synthetic experiment, using the method of crystal growth after winning three (hydroxymethyl) methyl amino acid, ethylene diamine, N, N' - iminodiacetic acid, N- (2 - acetyl amino) - the amino diacetate by vanadium peroxide three go unreported crystal, its single crystal data. The experimental study on the cytotoxicity of three kinds of vanadium peroxide was studied by thermogravimetric analysis, XRD spectrum analysis and MTT colorimetry, apoptosis and other cytotoxicity.

KEY WORDS: peroxo-vanadium complexes; Synthesis and analysis of crystals; Retinoblastoma

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目 录

摘要 II

Abstract III

第一章 绪论 1

1.1过氧钒配合物的研究 1

1.1.1过氧钒配合物的概念 1

1.1.2 过氧钒配合的分类 1

1.1.3 钒过氧配合物的应用 7

1.2视网膜母细胞瘤的研究 8

1.2.1视网膜母细胞瘤的概念 8

1.2.2视网膜母细胞瘤的发病机制 8

1.2.3视网膜母细胞瘤的治疗 9

第二章 过氧钒配合物晶体的制备与表征 12

2.1 实验仪器与试剂 12

2.1.1 实验仪器 12

2.1.2实验试剂 12

2.2 三（羟甲基）甲基氨基酸过氧钒的合成与表征 13

2.2.1 三（羟甲基）甲基氨基酸过氧钒晶体的合成 13

2.2.2结果表征与讨论 13

2.3 N-(2-乙酰氨基)-亚氨基二醋酸过氧钒的合成与表征 17

2.3.1 N-(2-乙酰氨基)-亚氨基二醋酸过氧钒晶体的合成 17

2.3.2结果表征与讨论 18

2.4 乙二胺-N，N’-二乙酸过氧钒晶体的合成与表征 22

2.4.1 乙二胺-N，N’-二乙酸过氧钒晶体的合成 22

2.4.2结果表征与讨论 22

第三章 过氧钒配合物的细胞毒性研究 26

3.1实验仪器与试剂 26

3.1.1 实验仪器 26

3.1.2 实验细胞及试剂 26

3.2 CCK-8细胞增殖及毒性检测^[44] 27

3.2.1 实验方法 27

3.3.2 结果与分析 27

3.3细胞调亡实验^[45] 30

3.3.1 实验方法 30

3.3.2 结果与分析 31

3.4 活性氧（ROS）检测^[46] 33

3.4.1 实验方法 33

3.4.2 结果与分析 33

总结 35

致谢 36

参考文献 37

附录 41

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