含C、N、O配位原子配合物的合成、结构、超分子组装及其与DNA相互作用研究

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英文题名：Synthesis, Crystal Structure, Supramolecular Assembly and DNA Binding Studies of Complexes Containing C, N, and O Coordination Atoms 作者：董风英 论文级别：博士 学科专业名称：药物化学 中文关键词：金属配合物 ; 晶体结构 ; 超分子作用 ; π-π堆积 ; DNA相互作用 英文关键词：Metal complex ; Crystal structure ; Supramolecular action ; π-πstacking ; DNA binding 学位年度：2008 导师：李延团 学科代码：100701 学位授予单位：中国海洋大学 论文提交日期：2008-06-01

摘要

为了探索DNA的结构信息和生物功能,为药物的设计合成提供理论依据,遴选对肿瘤病毒等细胞具有选择性抑制或杀灭作用的化学药物,本文以过渡金属为核心,选用具有较大芳香体系的双N原子螯合配体邻菲咯啉为主要构筑元件,并辅以其它配体,通过高温高压溶剂热合成和常温液相合成等方法定向合成了十六个含C、N、O配位原子的配合物,用单晶X-射线衍射技术对它们的分子结构、超分子组装进行了表征;用电子吸收光谱和荧光光谱对它们与小牛胸腺DNA的相互作用进行了研究。结果如下:
     1.成功地合成了十六个配合物[Cu(phen)_2]ClO_4 (1)、[Zn(phen)_2(H_2O)Cl]Cl·1.5H_2O (2)、[Zn(phen)_3](ClO_4)2·H_2O·CH_3OH (3)、[Cu(sal)(phen)ClO_4]_2 (4)、[Cu(o-van)(phen)ClO_4]_2 (5)、[Mn(sal)(phen)_2]ClO_4 (6)、[Ni(sal)(phen)_2]NO_3·3H_2O (7)、[Pb(Hsal)_2(phen)]n (8)、[Cu_6(CN)_6(phen)_4]n (9)、[Cu_3(CN)_3(phen)_3]n (10)、Co(NCS)_2(phen)_2 (11)、Mn(NCS)_2(phen)_2 (12)、[Ni(phen)_3][Ni(CN)_4]·3H_2O (13)、{Co(phen)_2[Fe(CN)_4(phen)]_2}·4H_2O (14)、[Cu_2(sal)_2(phen)_2(DMF)](HgI_3)_2 (15)和[Ba(phen)_3(H_2O)][Fe(CN)_5NO]·1.5phen·2H_2O (16),并采用不同的培养方法分别得到了质量较好的单晶,其中十三个配合物未见文献报道。
     2.结构分析表明,配合物4至16是含混合配体的配合物;该类配合物的突出特点是,配体不仅金属中心作用,而且不同的配体之间还相互作用,相互影响,能显著地增加配合物的稳定性和反应选择性。
     3.配合物13至16中分别含有Ni/Ni双金属中心,Fe-Co-Fe三核,2Cu/2Hg双核四金属中心和聚Ba-Fe金属中心。这些体系的合成和性质研究不仅有助于加深对“活性中心”电子与立体结构、结构与功能相关性的理解,而且对于分子生物工程的实施和模型化合物的发展也都具有重要的理论和现实意义。
     4.首次系统研究了邻菲咯啉分子间的π-π堆积作用模式,详细讨论了十六个配合物中三十多种π-π堆积作用。
     5.研究了配合物中丰富的C-H???O、O-H???O、O-H???Cl、O-H???N、C-H???N、O-H???N等氢键作用和S···π弱作用。这些研究有助于人们对药物分子与受体,生物活性小分子与蛋白质,酶与底物等相互识别过程的理解。
     6.光谱结果表明,配合物2和10与DNA的作用是沟槽方式;配合物15为静电与插入方式的协同作用;其它配合物表现为中等强度的插入结合。
     7.十六个配合物都能与DNA发生不同强度的作用,其强弱受金属中心(种类、配位环境、配位数),配体(种类和个数),超分子组装方式等因素的影响。
     研究金属配合物的结构信息以及它们与DNA结合选择性及相互作用机理对进一步探讨不同结构和性质的分子与核酸作用模式及其生物活性具有深远的意义,能使人们从分子水平理解疾病的发病机制,并通过分子设计来寻找有效的治疗药物,对阐明抗肿瘤和抗病毒药物的作用机理、致癌物的致癌机理、药物的筛选等都具有非常重要的意义。
In order to explore structural information and biological function of DNA and to obtain the new effective chemical druggery, a series of complexes containing C, N, and O coordination atoms has been synthesized under the solvothermal conditions or in the solution at room temperature. The complexes are composed of transition metals as the cores and phenanthroline as the principal ligand. Their structures are characterized by elemental analysis and single-crystal X-ray diffraction, and supramolecular assemblies are researched. The interactions of complexes with CT-DNA are studied using absorption and fluorescence spectrum titration measurements. The main results are as follow:
     1. Sixteen complexes [Cu(phen)_2]ClO4 (1)、[Zn(phen)_2(H2O)Cl]Cl·1.5H2O (2)、[Zn(phen)_3](ClO4)_2·H2O·CH3OH (3)、[Cu(sal)(phen)ClO4]2 (4)、[Cu(o-van)(phen)ClO4]2 (5)、[Mn(sal)(phen)_2]ClO4 (6)、[Ni(sal)(phen)_2]NO3·3H2O (7)、[Pb(Hsal)_2(phen)]n (8)、[Cu6(CN)6(phen)4]n (9)、[Cu3(CN)_3(phen)_3]n (10)、Co(NCS)_2(phen)_2 (11)、Mn(NCS)_2(phen)_2 (12)、[Ni(phen)_3][Ni(CN)4]·3H2O (13)、{Co(phen)_2[Fe(CN)4(phen)]2}·4H2O (14)、[Cu2(sal)_2(phen)_2(DMF)](HgI3)_2 (15) and [Ba(phen)_3(H2O)][Fe(CN)5NO]·1.5phen·2H2O (16) have been synthesized successfully, and their single crystals obtained. Thirteen of them have not been reported up to now.
     2. The results show that complexes from 4 to 16 are composed of the mixture ligands. There exist interactions not only between metal ions and ligands, but also among the different ligands, which makes the complexes more stable and more selective.
     3. The two metal centers of Ni/Ni, multiclear of Co-Fe-Co, binuclear of 2Cu/2Hg, and polynuclear of Ba-Fe are found in the complexes from 13 to 16. The research on these metal systems are very important to the biological system.
     4. Theπ-πstacking mode of phenanthroline is firstly constructed, and more than thirty modes are observed and discussed in detailed.
     5. Abundant hydrogen bonds including C-H…O、O-H…O、O-H…Cl、O-H…N、C-H…N、O-H…N bonds and S···πweak interaction are found in complexes.
     6. Electronic absorption spectrum titration studies of the interaction between complexes with DNA show the groove binding mode for 2 and 10, the cooperative modes of electrostatic and intercalative binding for 15, and the typical intercalative binding modes with middle-intensity for other complexes.
     7. All the complexes can interact with DNA, and the interactions are influenced by the metal ions (the type, coordination environment and the coordination number), ligands (the type and the number), the assembly modes and other factors. The results reveal that most of the complexes are good intercalaters to DNA, which is important for designing of antitumor drugs and antivirus drugs.

引文

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