Evaluation of the anionic effect on the formation of biologically active {Cu^II-phenx; x=1, 2, 3} fragments- Synthetic and structural variations, antimycobacterial and antiblastoma effects

Kseniya A. Koshenskova, Dmitrii E. Baravikov, Lyudmila A. Kayukova, Elmira M. Ergalieva,Yulia V. Nelyubina,Marina E. Nikiforova,Fedor M. Dolgushin,Matvey V. Fedin,Olga B. Bekker,Victoria O. Shender, Irina K. Malyants,Teimur M. Aliev, Konstantin O. Titov,Igor L. Eremenko,Irina A. Lutsenko

POLYHEDRON（2024）

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摘要

Two cationic and molecular copper(II) complexes - mixed ligand [{Cu(phen)(2)benz}{Cu(phen)(2)Cl}](2+)2Cl(-)benz(-)H3O+4.5H(2)O (1), [Cu(benz)(2)phen] (2) (benz(-) = m-Cl-benzoate anion; phen = 1,10-phenantroline) and [Cu(phen)(3)](2+)2OTf(-)2EtOH (3) (OTf = trifluoromethylsulfonate, triflate anion, CF3SO3-) were synthesized using various synthetic approaches and thoroughly characterized by spectroscopic methods and single crystal X-ray diffraction analysis. The structures of the complexes according to X-ray diffraction data are characterized by a diverse geometric environment of the complexing agent - the cationic form of 1 comprises two structurally nonequivalent moieties: the Cu (1) and Cu (2) complex-forming atoms coordinate, in chelate manner, two phen moieties each and the benz(-) (1)/Cl- (2) anions, respectively, thus forming different-ligand formula units, a trigonal-bipyramidal {Cu(1)N4Cl} and a pseudo octahedral one {Cu(2)N4O2}. The copper(II) ion in the complex 2 coordinates one phen ligand in a bidentate mode and two benz(-) anions to produce a distorted planar square environment {CuN2O2}. In complex 3, the copper(II) cation is surrounded by three phenanthroline fragments {Cu(phen)(3)}(2+) and non-coordinated OTf- ions. The results of an EPR study 1 show that in the solid phase, intermolecular exchange interactions that cause exchange narrowing of the spectrum are efficient, whereas in solutions, resolved spectra of copper(II) ion with rhombic symmetry of the g-tensor are observed. An in vitro study of the biological properties of 1-3 toward nonpathogenic mycobacterial strain Mycolicibacterium smegmatis showed an increase in biological effectiveness depending on the structure of complexes (MIC, 1 (2 nmol/disk) > 3 (5 nmol/disk) > 2 (12.5 nmol/disk)). Complex 1 was also tested for antitumor activity against an ovarian adenocarcinoma SKOV3 demonstrated high efficiency: the IC50 value is almost 9 times higher than the activity of cisplatin.

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copper(II) complexes,10-phenantroline,Crystal structure,EPR,Antiblastoma activity,Non-pathogenic strain

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Evaluation of the anionic effect on the formation of biologically active {CuII-phenx; x=1, 2, 3} fragments- Synthetic and structural variations, antimycobacterial and antiblastoma effects

Evaluation of the anionic effect on the formation of biologically active {Cu^II-phenx; x=1, 2, 3} fragments- Synthetic and structural variations, antimycobacterial and antiblastoma effects