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Ni(II) and Co(II) complexes of an asymmetrical aroylhydrazone: synthesis, molecular structures, DNA binding, protein interaction, radical scavenging and cytotoxic activity

机译:不对称芳酰hydr的Ni(II)和Co(II)配合物:合成,分子结构,DNA结合,蛋白质相互作用,自由基清除和细胞毒活性

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Two new nickel(II) and cobalt(II) benzhydrazone complexes having the general formula [ML2phen·3CH3OH] (where M = Ni and Co, L = 2-acetonaphthonebenzoylhydrazone, phen = 1,10-phenanthroline) have been synthesized via the reaction of Ni(OAc)2·4H2O and CoCl2·6H2O with 2 equivalents of HL and 1 equivalent of phen ligands in a MeOH/THF mixed medium. Both complexes have been characterized by single-crystal X-ray crystallography methods, which reveals a distorted octahedral coordination environment around the metal center with an MN4O2 chromophore [M = Ni(II) and Co(II)], with the hydrazone ligand acting as a monoanionic bidentate N,O-donor. These complexes exhibit quasi-reversible one-electron reduction responses (NiII–NiI, CoII–CoI) within the E1/2 at ?0.808 and ?0.767 V versus Ag/AgCl reference. The DNA-binding interactions of the complexes with herring sperm DNA have been investigated by UV-vis absorption, emission and viscosity measurements, which reveal that the complexes could interact with DNA via intercalation. The protein binding interactions of the complexes with BSA were investigated by UV-vis, fluorescence and synchronous fluorescence methods, which indicate strong binding of the complexes with BSA and a static quenching mechanism was observed. The Ni(II) complex displays higher DNA and BSA-binding affinity than the corresponding Co(II) analogue, which is expected of its smaller size. Moreover, the potential for free-radical scavenging of all the complexes was also determined using DPPH, hydroxyl and nitric oxide radicals under in vitro conditions, showing that the complexes are more effective in arresting the formation of hydroxyl than nitric oxide or DPPH radicals. Cytotoxicity experiments reveal that the two complexes both exhibit cytotoxic effects against human hepatocellular carcinoma cell line SMMC-7721 and human lung adenocarcinoma cell line A549.
机译:两种新的通式为[ML 2 phen·的镍( II )和钴( II )苯并zone配合物通过通过 3 OH](其中M = Ni和Co,L = 2-乙酰萘苯甲酰hydr,phen = 1,10-菲咯啉) Ni(OAc) 2 ·4H 2 O和CoCl 2的反应 ·6H 2 O在MeOH / THF混合介质中具有2个当量的HL和1个当量的phen配体。两种配合物均已通过单晶X射线晶体学表征,揭示了金属中心周围扭曲的八面体配位环境,其中MN 4 O 2 发色团[M = Ni( II )and Co( II )],配体起单阴离子双齿N的作用, O捐助者。这些配合物表现出准可逆的单电子还原反应(Ni II –Ni I ,Co E 1/2 <中的 II –Co I ) / sub> (相对于Ag / AgCl参考),相对于<0.8> V和<0.767 V 。通过紫外-可见吸收,发射和粘度测量研究了复合物与鲱鱼精子DNA的DNA结合相互作用,这表明该复合物可以通过嵌入与DNA相互作用。通过紫外可见,荧光和同步荧光方法研究了配合物与牛血清白蛋白的蛋白质结合相互作用,这表明配合物与牛血清白蛋白有很强的结合力,并观察到了静态猝灭机理。 Ni( II )配合物比相应的Co( II )类似物显示出更高的DNA和BSA结合亲和力,而Co( II )类似物的尺寸较小。此外,还使用DPPH,羟基和一氧化氮自由基在体外条件下测定了所有配合物的自由基清除潜能,表明该配合物在阻止羟基形成方面比在其他条件下更有效。一氧化氮或DPPH自由基。细胞毒性实验表明,这两种复合物均对人肝癌细胞系SMMC-7721和人肺腺癌细胞系A549均具有细胞毒性作用。

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