Ma Zhen, Zhang Bian, Guedes da Silva M Fátima C, Silva Joana, Mendo Ana Soraia, Baptista Pedro Viana, Fernandes Alexandra R, Pombeiro Armando J L
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, P. R. China.
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
Dalton Trans. 2016 Mar 28;45(12):5339-55. doi: 10.1039/c5dt02744f.
Reactions between 4'-phenyl-terpyridine (L) and several Cu(II) salts (p-toluenesulfonate, benzoate and o-, m- or p-hydroxybenzoate) led to the formation of Cu(p-SO3C6H4CH3)L(H2O)2 (1), [Cu(OCOPh)2L] (2), [Cu(o-OCOC6H4OH)2L] (3), [Cu(m-OCOC6H4OH)2L]4·MeOH (·MeOH) and [Cu(p-OCOC6H4OH)2L]5·2H2O (·2H2O), which were characterized by elemental and TG-DTA analyses, ESI-MS, IR spectroscopy and single crystal X-ray diffraction, as well as by conductivimetry. In all structures the Cu atoms present N3O3 octahedral coordination geometries, which, in 2-5, are highly distorted as a result of the chelating-bidentate mode of one of the carboxylate ligands. Intermolecular π···π stacking interactions could also be found in 2-5 (in the 3.569-3.651 Å range and involving solely the pyridyl rings). Medium-strong hydrogen bond interactions lead to infinite 1D chains (in 1 and 4) and to an infinite 2D network (in 5). Compounds 1 and 4 show high in vitro cytotoxicity towards HCT116 colorectal carcinoma and HepG2 hepatocellular carcinoma cell lines. The antiproliferative potential of compound 1 is due to an increase of the apoptotic process that was confirmed by Hoechst staining, flow cytometry and RT-qPCR. All compounds able to non-covalently intercalate the DNA helix and induce in vitro pDNA double-strand breaks in the absence of H2O2. Concerning compound 1, the hydroxyl radical and singlet oxygen do not appear to be involved in the pDNA cleavage process and the fact that this cleavage also occurs in the absence of molecular oxygen points to a hydrolytic mechanism of cleavage.
4'-苯基三联吡啶（L）与几种铜（II）盐（对甲苯磺酸盐、苯甲酸盐以及邻、间或对羟基苯甲酸盐）之间的反应生成了Cu(p-SO3C6H4CH3)L(H2O)2（1）、[Cu(OCOPh)2L]（2）、[Cu(o-OCOC6H4OH)2L]（3）、[Cu(m-OCOC6H4OH)2L]4·MeOH（·MeOH）以及[Cu(p-OCOC6H4OH)2L]5·2H2O（·2H2O），通过元素分析、TG-DTA分析、ESI-MS、红外光谱、单晶X射线衍射以及电导率测定对其进行了表征。在所有结构中，铜原子呈现N3O3八面体配位几何构型，在2 - 5中，由于其中一个羧酸根配体的螯合双齿模式，该构型高度扭曲。在2 - 5中还能发现分子间的π···π堆积相互作用（范围在3.569 - 3.651 Å，且仅涉及吡啶环）。中等强度的氢键相互作用导致形成无限的一维链（在1和4中）以及无限的二维网络（在5中）。化合物１和4对HCT116结肠癌细胞和HepG2肝癌细胞系显示出高体外细胞毒性。化合物1的抗增殖潜力归因于凋亡过程的增加，这通过Hoechst染色、流式细胞术和RT-qPCR得以证实。所有化合物都能够在没有H2O2的情况下非共价插入DNA螺旋并诱导体外质粒DNA双链断裂。关于化合物1，羟基自由基和单线态氧似乎不参与质粒DNA的切割过程，并且这种切割在没有分子氧的情况下也会发生这一事实表明存在水解切割机制。
