【作者】 张秉君；

【导师】 周先礼； 王萃娟；

【作者基本信息】 西南交通大学 ， 生物化工， 2012， 硕士

【摘要】 运用晶体工程原理构建新型高级有序结构分子聚集体如配位聚合物、超分子等逐渐成为当前化学、材料、生物、医学等领域的研究前沿和热点课题之一。这不仅因为对此类课题的研究能够探寻到新颖的拓扑构型、框架结构以及其组装过程中的机理和影响因素,更重要的是因为对此类课题的研究具有潜在的应用前景,如在光、电、磁、吸附、离子交换以及气体储存、生物活性、超分子化学药物等方面的应用前景。目前,该研究课题的核心任务是如何选择和设计合适的构筑基块并通过一定的晶体工程策略来获得具有预期结构与功能的晶体材料,来实现他们在应用方面的价值。本论文在晶体工程组装原理的指导下,考虑选择结构上分别含有杂环N、羧基(-COOH)、羰基(>C=O)三类典型配位基团且共同具有优良生物性能的有机配体(含N多功能咪唑配体、多元羧酸配体、天然产物中黄酮类化学成分),并与适当的生命体系金属基离子为构筑基元,利用它们的加合作用,将生物活性成分与金属基活性作用的机理相结合,构建具有新颖拓扑网络结构且展现特定多功能性质的配位聚合物,并对其性质进行表征,特别是对其可能的生物活性进行了部分研究,以期发挥生物活性成分和金属离子的双功能。系统探讨了配体的几何构型,金属离子的配位趋向,以及有机多羧酸辅助配体的配位能力、骨架长度、柔性程度和溶剂或客体分子调控等因素在目标配位聚合物的形成过程中所起的作用,研究其对配合物的结构及性能的影响。在一定的反应条件下,我们得到了七个具有新颖结构和特定功能的化合物,它们分别是：[Cu2(bcm)2(CH3OH)2]·2CH3OH (1),[Cu2(bcm)2(CH3CH2OH)2]-2CH3CH2OH (2),{[Zn(bbi)3(NO3)]Br·2H2O}n (3),[Zn(oxa)(bbi)]n (4),[Mn(fina)2(bbi)2(H2O)2]n (5),[Cd2(bpdc)2(bbi)2]n (6),{[Co8(cit)4(bbi)6(H2O)10]·7H2O}n (7)。用X-射线单晶衍射等技术对它们的结构进行了表征：1和2是基于π-π堆积作用及氢键弱作用力构筑而成的三维超分子结构；3具有一个三重2D→3D穿插网络结构；4是一个(4,4)拓扑形状的2D结构；5以Mn离子为四连接点,形成3D→3D三重穿插4-节点式的66-dia网络结构；而6是一个由bbi配体连接1D花瓣链状结构形成的3D多孔有机金属框架；7是一个3D多核金属-氧簇化合物,包含以八核金属钴簇为SBUs构筑的2D(4462)网络。其次,以这些在生命体系中具有潜在应用前景的咪唑类功能配合物为研究对象,运用琼脂扩散法、二苯代苦味肼基自由基(DPPH·)法、邻苯三酚自氧化法、α-脱氧核糖法,以及研究与DNA的相互作用,筛选出活性更强、性能更优越,在生命体系中具有潜在应用前景的功能配合物。此外,合成了以天然产物提取物槲皮万寿菊素为主配体的CuⅡ/ZnⅡ/FeⅢ二元配合物,它们较配体具有更强的清除DPPH自由基、超氧阴离子自由基和羟基自由基活性；并且配合物可以以插入模式与CT-DNA结合,影响CT-DNA分子的内部构型,抑制DNA分子的进一步遗传与复制,从而抑制癌细胞的恶性生长以达到抗癌效果。其中,与DNA结合作用的大小顺序为：Que-Fe>Que-Cu>Que-Zn> Que。槲皮万寿菊素金属配合物的制得为配位化学增添了新的内容,良好的生物活性为其在医学上的应用提供了依据,这对寻找新型、高效的金属基抗癌、抗氧化超分子化学药物具有重要意义。更多还原

【Abstract】 The design and construction of metal-organic coordination polymers is of current interest in the fields of supramolecular chemistry and crystal engineering. A major reason for this interest is the promise of being able to generate new materials with intriguing architectures and potential applications in optical, electronic, magnetic, adsorption, gas storage, ion exchange, biology activity and supramolecular chemical drugs. How to obtain materials with prospective structures and function is the prime importance in crystal engineering. It demonstrates that using some specific assembly strategy and choosing suitable building blocks should be the key in constructing target materials. In this paper, with the aim of obtaining novel materials with beautiful architecture and excellent physical, biological properties, we selected multi-functional ligands (N-containing imidazolic ligands, di-or polycarboxylate ligands and flavonoids of natural bioactive ingredients) as building blocks to construct coordination polymers under the intervention of various transition metal ions and auxiliary ligands guided by assembly principle of coordination polymer crystal engineering. The coordination behavior of the ligand completely, the role of solvent and metal ions have been discussed.Under different reaction condition, seven coordination polymers have been synthesized. They are listed as follows:[Cu2(bcm)2(CH3OH)2]·2CH3OH (1),[Cu2(bcm)2(CH3CH2OH)2]·2CH3CH2OH (2),{[Zn(bbi)3(NO3)]Br·2H2O}n (3),[Zn(oxa)(bbi)]n (4),[Mn(fma)2(bbi)2(H2O)2]n (5),[Cd2(bpdc)2(bbi)2]n (6),{[Cog(cit)4(bbi)6(H20)10]·7H20}n (7). These polymers have been characterized by X-ray single crystal diffraction analysis, elemental analysis, thermal analysis and fluorescence spectroscopy to investigate the spectroscopy characters and properties. The results revealed that the conformation of the ligands play an important role in the structure of complexes. The coordination of2is similar to that of1except that ethanol molecules are coordinated instead of methanol molecules. And there-dimensional network structures of1and2are formed through p-p interactions. Compounds3,4and7all exhibit2D layer structures, in which3displays a3-fold interpenetration framework containing2D networks with (6,3) topology and4is a2D structure with (4,4) topology. Compound7contains a2D44grid-like layer with (44.62) topology composed of octanuclear cobalt clusters. Two high-dimensional compounds (3D) with a microporous network containing1D flower-like metal-organic motifs interlinked by bbi ligands for6, and a3-fold interpenetrating network with66-dia topology by considering the manganese ion as a four-connected node for5, are observed. The biological activities of the title compounds have been studied. The results indicate that3-7exhibit certain antimicrobial activities and7exhibits weaker radical-scavenging activities than that of bbi ligand.Furthermore, three kinds of Cu(II), Zn(II), Fe(IlI) complexes of Quercetagetin (Que) were synthesized and characterized by IR spectra, UV spectra and elemental analysis etc. The free radical (DPPH·, O2-·,·OH) scavenging activities of the complexes were investigated in this paper. Then, the mechanism of the interaction between the free ligand and complexes with calf thymus DNA(CT-DNA) were investigated by using means of UV spectra. The results showed that free radical’scavenging activities of the complexes on DPPH·, O2-· and·OH were obviously stronger than that of the quercetagetin. In addition results of spectroscopic measurements suggested that the three complexes bound to DNA via an intercalative mode and calculated DNA-binding action decreased in the order Que-Fe>Que-Cu>Que-Zn>Que. The new metallic complexes of quercetagetin add new contents for coordination chemistry. The well bioactivity of the complexes afford an applied foundation on the medicine.更多还原