resumo
Complexes of iron(II), cobalt(III) and nickel(II) with 4-(4-methoxyphenyl)-2-(2-(1-(pyrazin-2yl)ethylidene)hydrazinyl)thiazole (PyztH) have been synthesized and characterized by elemental analyses, spectroscopic methods, CV measurements and a DFT study. The crystal and molecular structures were determined by the X-ray diffraction method. The complexes have the compositions [Fe(Pyzt)(2)]Br-2 (1), [Co(Pyzt)(2)]PF6 (2) and [Ni(Pyzt)(PyztH)IClO4 (3), with an approximate octahedral environment around the metal centre with NNN donor atoms from the two coordinating ligands. The complexes belong to the triclinic crystal system and crystallize in the space group P-1. Complex 1 is stabilized by strong hydrogen bonds, whereas the stability of complexes 2 and 3 is associated to pi-pi stacking interactions. The chemical reactivity, frontier orbital picture and energies of the HOMO and LUMO of the complexes have been estimated by a DFT study. The complexes are redox active species and respond with a quasi-reversible redox process. The cytotoxicity of the complexes was tested against U-937 human monocytic cells and shows IC50 values of 132 (for 1), 45 (for 2) and 162 mu M (for 3). A LDH release assay indicates that 2 and 3 show apoptosis in the tumour cell. Complex 2 induces apoptosis by disrupting the mitochondrial membrane potential and homeostasis leading to cytotoxicity, as envisaged by PARP cleavage. Complexes 1, 2 and 3 show high binding constants (2.01 x 10(6) M-1 for 1, 1.18 x 10(7) M-1 for 2 and 2.90 x 10(7) M-1 for 3) with CTDNA which attest the groove binding nature of the complexes with DNA. The compounds also exhibit a remarkable zone of inhibition against specific tested bacterial and fungal strains. Based on the results, the cobalt complex (2) shows the best antitumor and antimicrobial activity among the complexes under investigation. (C) 2020 Elsevier Ltd. All rights reserved.
palavras-chave
DENSITY-FUNCTIONAL THERMOCHEMISTRY; TRINUCLEAR COPPER(II) COMPLEX; X-RAY CRYSTALLOGRAPHY; CRYSTAL-STRUCTURES; ETHIDIUM-BROMIDE; DNA; DERIVATIVES; CYTOTOXICITY; CHEMISTRY; POTENT
categoria
Chemistry; Crystallography
autores
Bera, P; Aher, A; Brandao, P; Manna, SK; Mondal, G; Jana, A; Santra, A; Jana, H; Bera, P
nossos autores
Paula Cristina Ferreira da Silva Brandão
Investigador Auxiliaragradecimentos
We gratefully acknowledge the Council for Scientific and Industrial Research (CSIR), Government of India for financial support [grant no. 1(2858)/16/EMR-II]. Panskura Banamali College acknowledges the grants received from Department of Science and Technology (DST), Govt. of India through the FIST program (No.SR-FIST-COLLEGE-295-dt18/11/2015). Also, thanks are given to all members of CRNN, Kolkata and IIEST, Shibpur for help in the characterizations.