菲咯啉与1-萘甲酸配体共同构筑的多核Ca(Ⅱ)、双核Mn(Ⅱ)配合物的合成、结构及性质  

Synthesis, structure, and properties of multinuclear Ca(Ⅱ) and binuclear Mn(Ⅱ) complexes assembled by 1,10-phenanthroline and 1-naphthalic acid ligands

作　　者：杨婷英 郭丹 胡宇琼 易思佳 谷淑琪 贺霞 朱小明 张复兴 YANG Ting-Ying;GUO Dan;HU Yu-Qiong;YI Si-Jia;GU Shu-Qi;HE Xia;ZHU Xiao-Ming;ZHANG Fu-Xing(Hunan Engineering Research Center for Monitoring and Treatment of Heavy Metals Pollution in the Upper Reaches of Xiangjiang River,Key Laboratory of Functional Metal-Organic Compounds of Hunan Province,Key Laboratory of Organometallic New Materials,College of Hunan Province,College of Chemistry and Material Science,Hengyang Normal University,Hengyang,Hunan 421008,China)

机构地区：[1]衡阳师范学院化学与材料科学学院,金属有机新材料湖南省高校重点实验室,功能金属有机化合物湖南省重点实验室,湘江上游重金属污染监测与治理湖南省工程研究中心,衡阳421008

出　　处：《无机化学学报》2023年第1期117-126,共10页Chinese Journal of Inorganic Chemistry

基　　金：湖南省自然科学青年基金(No.2021JJ40010);湖南省教育厅重点项目(No.19A070);湖南省功能金属有机化合物重点实验室开放基金(No.2021HSKFJJ002);湖南省高校科技创新团队支持计划;2020年衡阳市科技局项目(No.202002042081);2022年度湖南省大学生创新创业训练计划一般项目(No.3798)资助。

摘　　要：设计、合成了2种配合物:[Ca(Phen)(Nap)_(2)]_(n)(1)和[Mn_(2)(Phen)_(2)(Nap)_(4)(H_(2)O)](2)(Phen=菲咯啉,HNap=1-萘甲酸)。通过红外光谱、元素分析、X射线单晶衍射和热重对其进行了结构表征。测定了配合物的激发光谱、发射光谱,以及配合物对人肺癌细胞(NCI-H460)、人乳腺癌细胞(MCF-7)、人肝癌细胞(HepG2)的体外抑制活性;利用紫外吸收光谱、荧光分光光度法研究了配合物与小牛胸腺DNA的相互作用。结果表明:配合物1、2的激发光谱和发射光谱具有很好的镜像关系,且配合物2的斯托克斯位移大于配合物1;配合物对3种癌细胞都有较好的抑制作用,但是2更优于1;配合物1和2与小牛胸腺DNA以静电作用发生沟面结合,结合常数分别为5.83×10^(3)和6.46×10^(3)L·mol^(-1)。Two complexes [Ca(Phen)(Nap)_(2)]_(n)(1) and[Mn_(2)(Phen)_(2)(Nap)_(4)(H_(2)O)](2) were synthesized by calcium acetate monohydrate or manganous acetate reacting with 1,10-phenanthroline(Phen) and 1-naphthoic acid(HNap).Complexes 1 and 2 have been characterized by IR,elemental analysis,and thermogravimetry and the crystal structures have been determined by X-ray diffraction.Both the central calcium ion and the central manganese ion form a six-coordinated twisted octahedral structure.The excitation spectrum and emission spectrum of the two complexes were determined,and the results showed that the excitation and emission spectra of the complexes had a good mirror relationship,and the Stokes shift of complex 2 was greater than that of complex 1.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines,namely human lung cancer cells(NCI-H460),human breast cancer cells(MCF-7),human liver cancer cells(HepG2),and human normal cells(HL7702).It was found that complexes 1 and 2 showed a good inhibitory effect on the three cancer cells,compared to the normal cell.The interactions of the complexes with calf thymus DNA have been studied by UV and fluorescence spectroscopy,and the results show that the binding mode of complexes 1 and 2 with DNA may most likely bind in the groove of the DNA backbone by electrostatic action,and their intrinsic binding constants were 5.83×10^(3) and 6.43×10^(3)L·mol^(-1),respectively.Complex 1 showed no redshift,while complex 2 showed an obvious redshift of 2.0 nm.The subtractive effect,intrinsic binding constants,and the redshift data indicate that the interaction between complex 2 and DNA is greater than that between complex 1 and DNA.CCDC:1409882,1;1409878,2.

关 键 词：多核Ca(Ⅱ)配合物 双核Mn(Ⅱ)配合物 晶体结构 DNA作用 体外抗癌活性 

分 类 号：O614.231[理学—无机化学] O614.711[理学—化学]