【作者】 张鹏；

【导师】 张亚男；

【作者基本信息】 陕西科技大学 ， 无机化学， 2018， 硕士

【摘要】 金属有机配位聚合物因具有相互交织的结构和潜在应用价值,使得研究者们对其结构的设计及合成产生了浓厚的兴趣。基于羧酸有机配体合成了大量具有新颖结构的配位聚合物。配位聚合物可被应用于陶瓷、医疗设备、日用品等抗菌领域,其具有高的期效性和安全性。本文选用羧酸类有机物作为构建块,成功构筑了 8种的配位聚合物,并对银基配位聚合物的结构及其抑菌活性进行了分析。本文的内容和要点总结如下:(1)在水热条件下,基于有机配体3-(3-竣基-苯氧基)邻苯二甲酸(H3cppa)与硝酸盐(Cd2+,Ni2+,Ce3+)分别合成了 3种配位聚合物,结构式分别为[Cd(Hcppa)(H2O)2(CH3OH)]n(1),[Ni3(cppa)2(bipy)4]n·6nH2O(2),[Ce(cppa)(phen)]n(3)。配合物1是通过氢键连接而形成的三维无限网络状结构,配合物2具有三维孔状框架,配合物3由矩形和平行四边形形成了一维通道结构。此外,3种配位聚合物均具有良好的热稳定性,通过X-射线单晶衍射、傅立叶红外光谱仪、X-射线衍射仪、热重分析仪和荧光热分析仪进行表征。(2)硝酸银与2-(4-羧酸苯氧基)对苯二甲酸(H3cia)和天门冬氨酸分别合成了 5种银基配位聚合物,结构式分别为[Ag(H2cia)(bpa)·2H2O]n(4),[Ag2(cia)(bpp)2·H2O]n·4nH2O(5),[Ag3(D-asp)2(NO3)]n·nH2O(6),[Ag3(L-asp)2(NO3)]n·nH2O(7)and[Ag4(D-asp)(L-asp)(NO3)2]n·2nH2O(8)。配合物4和配合物5是由H3cia和硝酸银通过上下层扩散而得到的,二者均为二维无限网络状结构。配合物6-8是由硝酸银与天门冬氨酸在常温搅拌的条件下得到的。配合物6、7均是由六股螺旋组成的三维框架,螺旋间距为70.6 A。配合物8是由D-天门冬氨酸和L-天门冬氨酸相互交替而形成的具有二维结构的配位聚合物。此外,配合物4-8均具有良好的热稳定性和光稳定性通过X-射线单晶衍射、荧光热释光谱仪、傅立叶红外光谱仪、X-射线衍射仪、热重分析仪进行表征。(3)选用革兰氏阴性菌(大肠杆菌、铜绿假单胞杆菌)和革兰氏阳性菌(金黄色葡萄球菌)对银基配位聚合物4-8的生物抑菌活性进行了研究。根据抑菌圈实验和细菌生长曲线进一步确定配合物8的抑菌效果最佳,最低抑菌浓度(MIC)可达到5-10 ppm。此外利用透射电镜、荧光显微镜、固体紫外可见漫反射光谱和电感耦合等离子体原子发射光谱法(ICP-AES)研究银配位聚合物的抑菌机理。更多还原

【Abstract】 Recently,much interest has been focused on the design and synthesis of coordination polymers,for their various intersting architectures and potential application.People have synthesized a lot of coordination polymers with novel structure by using carboxylic acid ligands.Coordination polymers have been widely applied to antibacterial fields such as ceramics,surgical devices and cosmetics that attributes to their long-range reliability and high safety.In this dissertation,the carboxylates were chosen as main building block,and successfully construct eight coordination polymers.Study focused on the fact that the structures and antibacterial activities have been analyzed for silver-based coordination polymers.The contents and main points in this paper were summarized as follows:(1)A series of Cd(II),Ni(II)and Ce(III)coordination polymers have been synthesized under hydrothermal conditions using 3-(3-carboxy-phenoxy)phthalic acid(H3cppa)organic ligands,namely[Cd(Hcppa)(H2O)2(CH3OH)]n(1),[Ni3(cppa)2(bipy)4]n·6nH20(2),[Ce(cppa)(phen)]n(3).1 forms a 3D supramolecular structure linked by intermolecular hydrogen bonds based on 1D chains.2 structure analysis indicated that it was a 3D porous framework.3 shaped configurations of rectangle and parallelogram shaped 1D channel in structures.Additionally,1-3 had the good thermal stability property and characterized by X-ray single crystal diffraction,FTIR,PXRD,TGA and fluorescence.(2)Silver nitrate react with 2-(4-carboxyl phenoxy)terephthalic acid(H3cia)and aspartic acid,and result five coordination polymers,namely[Ag(H2cia)(bpa)]n·2nH20(4),[Ag2(cia)(bpp)2·H20]n·4nH20(5),[Ag3(D-asp)2(N03)]n·nH20(6),[Ag3(L-asp)2(N03)]n·nH20(7)and[(D-asp)(L-asp)(N03)2]n·2nH20(8).4 and 5 were synthesized constituted silver nitrate and H3cia,forms a 2D wireless network structure by diffusion method.6-8 were obtained by the reaction of AgN03 and aspartic acid,and stirring at room temperature.The 3D framework of the 6 and 7 consists of six-helix bundle with a helical pitch of 70.6 A.A 2D coordination polymer sheet was made up of D/L-aspartic acid chains alternate in the 8.Additionally,4-8 had the good thermal stability property and photostability,characterized by X-ray single crystal diffraction,fluorescence,FTIR,PXRD and TGA.(3)The antibacterial activities of Ag-based coordination polymers(4-8)were investigated against Gram-negative bacteria(E.coli,P.aeruginosa)and Gram-positive bacteria(S.aureus)by determining the minimal inhibitory concentration(MIC)benchmark,the growth inhibition assay of bacteria and using an inhibition zone testing.The study showed that the antibacterial activity of 8 was the best,and MIC could reach 5-10 ppm.In addition,the mechanism of antibacterial activity of Ag-based coordination polymers were also taken into account by using TEM,fluorescent microscopy,solid ultraviolet visible diffuse reflectance spectroscopy and inductively coupled plasma atomic emission spectrometry(ICP-AES).更多还原