摘要
本文基于稀土元素与含肽键芳酰腙及另一种配体甘氨酸所形成的混配配合物的生物学意义和应用前景,主要完成了以下工作:
本文用苯做溶剂合成了一种新的芳酰腙有机配体-邻羧基苯甲醛水杨酰腙,探讨了该配体合成的最佳条件。对其进行了元素分析、红外光谱、紫外光谱、质子核磁共振、质谱分析和X-射线单晶衍射,确定了其组成和结构。
用邻羧基苯甲醛水杨酰腙与稀土硝酸盐反应,合成了13种稀土离子与邻羧基苯甲醛水杨酰腙形成的二元配合物。经元素分析、摩尔电导率、化学分析等手段确定了其组成为RE(C_(15)H_(11)N_2O_4)(C_(15)H_(10)N_2O_4)·nH_2O (RE=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Yb、Y,n=2~3),用摩尔电导、红外光谱、紫外可见光谱、荧光光谱、质子核磁共振、X-射线粉末衍射对以上配合物进行了表征,确定了该系列稀土配合物的组成,推测了其结构。
设计合成了8种稀土离子(RE=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb)与邻羧基苯甲醛水杨酰腙、甘氨酸的三元配合物。通过元素分析、摩尔电导、红外光谱、紫外-可见光谱、X-射线粉末衍射对三元配合物的组成和结构进行了分析。
通过DSC-TGA热分析系统测试了配体邻羧基苯甲醛水杨酰腙、邻羧基苯甲醛水杨酰腙和稀土硝酸盐二元配合物和配体邻羧基苯甲醛水杨酰腙、甘氨酸、稀土硝酸盐三元配合物在5K/min、10K/min和15K/min三个不同升温速率下的热分解过程,利用Kissinger法计算了它们的热分解阶段的表观活化能和动力学参数。结果表明,二元配合物较配体和三元配合物具有较高的热分解温度,热稳定性较好。
本文选择了具代表性的镧,镱两种稀土硝酸盐与邻羧基苯甲醛水杨酰腙的二元配合物对金黄色葡萄球菌进行了最小抑菌浓度实验,结果表明,邻羧基苯甲醛水杨酰腙及其二元配合物有较好的抑菌效果;同时进行了邻羧基苯甲醛水杨酰腙及邻羧基苯甲醛水杨酰腙、硝酸镧二元配合物对金黄色葡萄球菌的抗菌实验,发现邻羧基苯甲醛水杨酰腙二元配合物的抗菌活性要优于邻羧基苯甲醛水杨酰腙。
Based on the biological significance and applications of mixed ligand complexes formed by the rare earth elements, aroylhydrazone and glycine, this paper mainly concluded the following work:
A new ligand o-carboxybenzaldehyde salicyloylhydrazone was synthesized in benzene; and the optimization conditions of synthesis were got. The composition and structure of the ligand were determined by elemental analysis, IR, UV, NMR, MS and X-ray diffraction. Thirteen binary complexes had been synthesized by the reaction of o-carboxybenzaldehyde salicyloylhydrazone with rare earth nitrate (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y, n=2~3). The composition RE(C15H11N2O4)(C15H10N2O4)·nH2O was determined by elemental analysis, molar conductivity and chemical analysis, and the structure was characterized by molar conductivity, IR, UV-Vis, FS, NMR and X-ray powder diffraction.
Eight ternary complexes of rare earth ions (RE=La, Ce, Pr, Nd, Sm, Eu, Gd and Tb) with o-carboxybenzaldehyde salicyloylhydrazone and glycine were synthesisd. The composition and structure were analyzed through elemental analysis, molar conductance, IR, UV-Vis and X-ray powder diffraction.
The thermal decomposition of the ligand, binary complexes and ternary complexes were carried out by TG-DTG analysis at 5, 10 and 15 K·min-1, respectively. The Kissinger method was used to calculate the apparent activation energies and kinetics parameters of the thermal decomposition stages of the ligand and the complexes. The results showed that binary complexes and ternary complexes had higher thermal decomposition temperature; and their thermal stability was higher than the ligand.
The binary complexes of La, Yb nitrate with the o-carboxybenzaldehyde salicyloylhydrazone were chosen to investigation their bioactivity to staphylococcus aureus by using the method of the mininal inhibitory concentration. The results showed that the o-carboxybenzaldehyde salicyloylhydrazone and the binary complexes possess better antibacterial effect. The antibacteria experiment of La nitrate with the o-carboxybenzaldehyde salicyloylhydrazone to staphylococcus aureus has also been done. It is shown that the antibacterial activity of the La binary complex is better than the o-carboxybenzaldehyde salicyloylhydrazone.
引文
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