新型功能三脚架配合物的合成及性能研究
摘要
在发现配合物cis-[Pt(NH_3)_2Cl_2]具有抗癌作用以后,金属配合物与生命体系相互作用的研究成为功能配位化学的主要研究热点之一。金属配合物与生物大分子,特别是与DNA相互作用的方式和机理的研究,对探索配合物在抗肿瘤药物、分子生物学、生物工程技术及其它相关领域的应用具有非常重要的作用。由于三脚架化合物是一种半刚性的化合物,它通过三条侧链的自由翻转形成大小合适的空腔与不同的金属离子结合,加之侧链取代基的多样性,使其具有丰富多变的立体配位结构,在电化学,生物化学,功能材料等领域有着重要作用。因此选择三脚架化合物为配体设计合成配合物,研究配合物与DNA的作用具有重要意义。并通过改变三脚架配体上的侧链取代基,及取代基的位置对DNA的研究对药物的设计起指导作用。本文选择性合成并表征了三种席夫碱型配体与它的稀土配合物,并且采用紫外光谱法、溴化乙锭荧光分析法、研究了配合物与DNA的相互作用。
1介绍了三脚架配合物的研究进展,及金属配合物与DNA的作用方式和影响因素。并总结了目前较为常用的研究配合物与DNA相互作用的方法,和金属配合物在生物方面的应用领域和前景。
2以1,1,1.三(2-氨基乙基)胺(tren)为骨架引入3,4-二羟基苯甲醛、2,4-二羟基苯甲醛、香草醛为末端基,合成,并表征三个席夫碱型三脚架配体L~1、L~2、L~3及其与La~(3+)、、Sm~(3+)、Eu~(3+)、Gd~(3+)、Yb~(3+)形成的稀土配合物。通过结构表征发现L~1采用了两个相邻的酚羟基和稀土离子参与配位,而L~2,L~3采用席夫碱CH=N中的氮原子和苯环上邻近的氧原子和稀土离子参与配位。L~1的配合物的稀土离子配位数为8,L~2,L~3的配合物的配位数为9,配体和稀土离子的配比均是1:1(Ln/L)。
3采用紫外可见光谱、溴化乙锭荧光分析法研究了在pH=7.08的Tris—Hcl缓冲溶液中上述各个配体的稀土配合物与小牛胸腺DNA的作用机制,探讨了其相互作用的模式。结果发现,当加入一定量的配合物时, DNA的紫外光谱的最大吸收峰产生增色效应。同时配合物也能较大程度地猝灭DNA-EB体系的荧光强度。所有这些研究都表明配合物可能与DNA发生了相互作用,而且主要是以插入方式相结合。并且求出了配合物对DNA-EB的猝灭方式和猝灭常数。以及配体对配合物与DNA结合力大小的影响。
Since the antineoplastic activity of cis-[Pt(NH_)_2Cl_2] complex was discovered, the studies on the interaction of metal complexes with DNA have been attracting great interest in the field of coordination chemistry. The studies on interaction models and mechanism of metal complexes with DNA are of great importance in the fields of antineoplastic Pharmaceuticals, molecular biochemistry and bioengineering technology. Tripodal compound is a unique class of complex agents, which can privide hosts of appropriate size by the chains rotating freely to encapsulate the metal ions. And because of the different terminal groups in chains, it can forms different sturcture, which can give birth to the effect in electrochemistry, biochemistry, and functional material. So it is significant to synthesize functional tripodal complex, and study the interaction of complex with DNA. And by changing the groups in chains, or the situation of groups, studying the effect on the interaction of complex with DNA may guide the design of new medicine. So we synthesized and characterized three Schiff-base type tripodal ligands and five series of rare earth complexes, and studied the interaction of complexes with DNA by spectral analyse.
1 A brief review of the research of the tripodal complexes, and the interaction mechanisms of complexes with DNA had been described . At the same time, the methods used to study the interaction between complexes and DNA had been summarized. Also the development prospects of complexes in biochemistry had been expatiated.
2 Using tren as framework, 3,4-Dihydroxybenzaldehyde, 2,4-Dihydroxybenzaldehydeand 4-Hydroxy-3-methoxybenzaldehyde as terminal groups, respectively, we synthesized three schiff-base type tripodal ligands L~1, L~2, L~3,and their La~(3+), Sm~(3+),Eu~(3+), Gd~(3+)and Y~(3+)complexes. By characterizing these complexes, we reveal that the ligand L~1 coordinate to Ln~(3+) by the two hydroxy, but the ligand L~2, L~3 using the nitrogen atom and the hydroxy in the neighborhood to coordinate with Ln~(3+).The ration of Ln~(3+)/L is 1:1,and the coordinate number of Ln~(3+)-L~1 is 8,but the number of Ln~(3+) to L~2 and L~3 is 9.
3 The mechanism of the interaction between complexes and calf thymus (CT DNA) in tris buffer (pH=7.08) had been studied by electronic absorption and ethidium bromide(EB) fluorescence spectroscopy. The results show that the absorptivity of the DNA solution increases considerably, with the addition of complexes, and the addition of complexes caused the quenching fluorescence of the DNA-EB system, which reveal that all the complexes can bind to DNA, and have strong binding affinity with DNA. Also by studying ethidium bromide(EB) fluorescence spectroscopy, we obtained the model of complexes to DNA, and the binding constant of the reaction. The effect of ligand to the binding affinity had also been studied.
1介绍了三脚架配合物的研究进展,及金属配合物与DNA的作用方式和影响因素。并总结了目前较为常用的研究配合物与DNA相互作用的方法,和金属配合物在生物方面的应用领域和前景。
2以1,1,1.三(2-氨基乙基)胺(tren)为骨架引入3,4-二羟基苯甲醛、2,4-二羟基苯甲醛、香草醛为末端基,合成,并表征三个席夫碱型三脚架配体L~1、L~2、L~3及其与La~(3+)、、Sm~(3+)、Eu~(3+)、Gd~(3+)、Yb~(3+)形成的稀土配合物。通过结构表征发现L~1采用了两个相邻的酚羟基和稀土离子参与配位,而L~2,L~3采用席夫碱CH=N中的氮原子和苯环上邻近的氧原子和稀土离子参与配位。L~1的配合物的稀土离子配位数为8,L~2,L~3的配合物的配位数为9,配体和稀土离子的配比均是1:1(Ln/L)。
3采用紫外可见光谱、溴化乙锭荧光分析法研究了在pH=7.08的Tris—Hcl缓冲溶液中上述各个配体的稀土配合物与小牛胸腺DNA的作用机制,探讨了其相互作用的模式。结果发现,当加入一定量的配合物时, DNA的紫外光谱的最大吸收峰产生增色效应。同时配合物也能较大程度地猝灭DNA-EB体系的荧光强度。所有这些研究都表明配合物可能与DNA发生了相互作用,而且主要是以插入方式相结合。并且求出了配合物对DNA-EB的猝灭方式和猝灭常数。以及配体对配合物与DNA结合力大小的影响。
Since the antineoplastic activity of cis-[Pt(NH_)_2Cl_2] complex was discovered, the studies on the interaction of metal complexes with DNA have been attracting great interest in the field of coordination chemistry. The studies on interaction models and mechanism of metal complexes with DNA are of great importance in the fields of antineoplastic Pharmaceuticals, molecular biochemistry and bioengineering technology. Tripodal compound is a unique class of complex agents, which can privide hosts of appropriate size by the chains rotating freely to encapsulate the metal ions. And because of the different terminal groups in chains, it can forms different sturcture, which can give birth to the effect in electrochemistry, biochemistry, and functional material. So it is significant to synthesize functional tripodal complex, and study the interaction of complex with DNA. And by changing the groups in chains, or the situation of groups, studying the effect on the interaction of complex with DNA may guide the design of new medicine. So we synthesized and characterized three Schiff-base type tripodal ligands and five series of rare earth complexes, and studied the interaction of complexes with DNA by spectral analyse.
1 A brief review of the research of the tripodal complexes, and the interaction mechanisms of complexes with DNA had been described . At the same time, the methods used to study the interaction between complexes and DNA had been summarized. Also the development prospects of complexes in biochemistry had been expatiated.
2 Using tren as framework, 3,4-Dihydroxybenzaldehyde, 2,4-Dihydroxybenzaldehydeand 4-Hydroxy-3-methoxybenzaldehyde as terminal groups, respectively, we synthesized three schiff-base type tripodal ligands L~1, L~2, L~3,and their La~(3+), Sm~(3+),Eu~(3+), Gd~(3+)and Y~(3+)complexes. By characterizing these complexes, we reveal that the ligand L~1 coordinate to Ln~(3+) by the two hydroxy, but the ligand L~2, L~3 using the nitrogen atom and the hydroxy in the neighborhood to coordinate with Ln~(3+).The ration of Ln~(3+)/L is 1:1,and the coordinate number of Ln~(3+)-L~1 is 8,but the number of Ln~(3+) to L~2 and L~3 is 9.
3 The mechanism of the interaction between complexes and calf thymus (CT DNA) in tris buffer (pH=7.08) had been studied by electronic absorption and ethidium bromide(EB) fluorescence spectroscopy. The results show that the absorptivity of the DNA solution increases considerably, with the addition of complexes, and the addition of complexes caused the quenching fluorescence of the DNA-EB system, which reveal that all the complexes can bind to DNA, and have strong binding affinity with DNA. Also by studying ethidium bromide(EB) fluorescence spectroscopy, we obtained the model of complexes to DNA, and the binding constant of the reaction. The effect of ligand to the binding affinity had also been studied.
引文
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