ChIP Research Center, School of Science and Technology, University of Camerino, via Madonna delle Carceri Camerino, 62032 Macerata, Italy.
ChIP Research Center, School of Pharmacy, University of Camerino, via Madonna delle Carceri Camerino, 62032 Macerata, Italy.
J Med Chem. 2024 Sep 12;67(17):15676-15690. doi: 10.1021/acs.jmedchem.4c01298. Epub 2024 Sep 2.
The synthesis and characterization of nine Schiff bases of pyrazolone ligands ( = 1-9) and the corresponding zinc(II) complexes - of composition [Zn(L)] ( = 1-9) are reported. The molecular structures of complexes , , , , and were determined by single-crystal X-ray diffraction analysis, highlighting in all cases a distorted tetrahedral geometry around the Zn(II) ion. Density functional theory studies are performed on both the ligands and the derived complexes. A mechanism of dissociation and hydrolyzation of the coordinated Schiff base ligands is suggested, confirmed experimentally by powder X-ray diffraction study and photophysical studies. Complexes were investigated in vitro as anticancer agents, along with mutant p53 (mutp53) protein levels in human cancer cell lines carrying R175H and R273H mutp53 proteins. Only those complexes with the highest Zn(II) ion release via dissociation have shown a significant cytotoxic activity with reduction of mutp53 protein levels.
报告了 9 种吡唑啉酮配体席夫碱(=1-9)的合成和表征,以及相应的锌(II)配合物[Zn(L)](=1-9)的合成和表征。通过单晶 X 射线衍射分析确定了配合物[Zn(L1)]、[Zn(L2)]、[Zn(L3)]、[Zn(L4)]、[Zn(L5)]、[Zn(L6)]、[Zn(L7)]、[Zn(L8)]和[Zn(L9)]的分子结构,在所有情况下,Zn(II)离子周围都呈现出扭曲的四面体型几何结构。对配体和衍生配合物都进行了密度泛函理论研究。提出了配位席夫碱配体的离解和水解的机制,并通过粉末 X 射线衍射研究和光物理研究得到了实验证实。在体外,配合物[Zn(L1)]、[Zn(L2)]、[Zn(L3)]、[Zn(L4)]、[Zn(L5)]、[Zn(L6)]、[Zn(L7)]、[Zn(L8)]和[Zn(L9)]被用作抗癌剂,并在携带 R175H 和 R273H mutp53 蛋白的人癌细胞系中研究了它们对突变型 p53(mutp53)蛋白水平的影响。只有那些通过离解释放出最高量 Zn(II)离子的配合物表现出显著的细胞毒性活性,并降低了 mutp53 蛋白水平。