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Structural, theoretical and biological activity of mono and binuclear nickel(II) complexes with symmetrical and asymmetrical 4,6-diacetylresorcinol-dithiocarbazate ligands
Journal of Inorganic Biochemistry ( IF 3.9 ) Pub Date : 2021-08-05 , DOI: 10.1016/j.jinorgbio.2021.111559
Francielle C Lima 1 , Yuri A O Só 2 , Ricardo Gargano 2 , Diêgo M de Oliveira 3 , Claudia C Gatto 1
Affiliation  

The present work reports the synthesis and a structural study of two novel dithiocarbazate, the 4,6-diacetylresorcinol-S-benzyldithiocarbazate (H3L1) and the 4,6-diacetylresorcinol-bis(S-benzyldithiocarbazate) (H4L2), and their Ni(II) complexes, [Ni(HL1)(Py)] (1) and [Ni2(L2)(PPh3)2] (2). Single crystal X-ray analyzes reveal mono and binuclear complexes and the metal centers with distorted square planar geometry. The analyses of the Hirshfeld surface and fingerprints plots revealed intermolecular contacts attributed to the H···H and C···H/H···C bonds. The Density Functional Theory (DFT), with the B3LYP functional and 6–311-G(d,p)/LanL2DZ basis sets, was employed to optimize the geometries of synthesized compounds. From the resulting geometries, the highest occupied and lowest unoccupied molecular orbital maps (HOMO-LUMO), orbital energy gap, electron localization function (ELF), electron density, natural bond orbital (NBO) analysis, and complexation of the ligands with Ni(II) were calculated supporting the experimental data. The ESI (+)-MS/MS data indicated the presence in solution of the characteristic fragmentation with the [H3L1]+ and [H4L2]+ molecular ions for the ligands. The pharmacological potential of the dithiocarbazate ligands and their Ni(II) complexes were evaluated in vitro against MDA-MB-231 human breast cancer cells. A remarkable cytotoxic activity was observed, more evident for free ligands than complexes at low concentrations; however, this latter showed a better dose–response pattern, being more attractive in terms of pharmacokinetics and therapeutic window.



中文翻译:

具有对称和不对称 4,6-二乙酰间苯二酚-二硫代氨基甲酸酯配体的单核和双核镍 (II) 配合物的结构、理论和生物活性

本工作报道了两种新型二硫代氨基甲酸酯的合成和结构研究,即 4,6-二乙酰间苯二酚-S-苄基二硫代氨基甲酸酯 (H 3 L 1 ) 和 4,6-二乙酰间苯二酚-双(S-苄基二硫代氨基甲酸酯) (H 4 L 2 ),以及它们的 Ni(II) 配合物,[Ni(HL 1 )(Py)] (1) 和 [Ni 2 (L 2 )(PPh 3 ) 2] (2)。单晶 X 射线分析揭示了单核和双核配合物以及具有扭曲方形平面几何形状的金属中心。Hirshfeld表面和指纹图的分析揭示了归因于H···H和C···H/H···C键的分子间接触。密度泛函理论 (DFT) 具有 B3LYP 泛函和 6-311-G(d,p)/LanL2DZ 基组,用于优化合成化合物的几何形状。根据所得几何结构,最高占据和最低未占据分子轨道图 (HOMO-LUMO)、轨道能隙、电子定位函数 (ELF)、电子密度、自然键轨道 (NBO) 分析以及配体与 Ni( II) 计算支持实验数据。3 L 1 ] +和[H 4 L 2 ] +分子离子为配体。二硫代氨基甲酸酯配体及其 Ni(II) 配合物的药理潜力在体外针对 MDA-MB-231 人乳腺癌细胞进行了评估。观察到显着的细胞毒活性,游离配体比低浓度的复合物更明显;然而,后者显示出更好的剂量反应模式,在药代动力学和治疗窗口方面更具吸引力。

更新日期:2021-08-12
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