Poladian, Qumars; İlhan-Ceylan, Berat; Bölükbaşı-Yalçınkaya, Olcay; Türkmenoğlu, Burçin; Kurt, Yasemin

Two new complexes, [Ni (L)] (1) and [Fe (L)Cl] (2), were synthesized through template condensation of 2-hydroxy-5-ethoxyacetophenone S-methylthiosemicarbazone (H2L1) with 2-hydroxy-4-methoxybenzaldehyde in the presence of nickel(II) and iron(III) ions. The complexes were characterized using elemental analysis, magnetic measurements, FT-IR, UV–Vis, ESI-MS and 1H NMR spectra. In order to gain further insights into their structural features, Density Functional Theory (DFT) calculations were employed to optimize the geometries and predict vibrational frequencies of the complexes, providing valuable insights into their structural stability and bonding interactions. The frontier molecular orbital (HOMO and LUMO) analyses were conducted for the optimized geometries to evaluate the electronic properties and chemical reactivity. The computational results confirmed the proposed square-planar geometry for (1) and square-pyramidal geometry for (2). TD-DFT analyses predicted the theoretical UV–Vis spectra and compared with experimental spectra. Molecular docking analyses were performed with EGFR (PDB ID: 4HJO) and B-DNA (PDB ID: 1BNA). Binding parameters and ADME analyses were also conducted. The antioxidant capacity of the compounds were examined using the CUPRAC (cupric reducing antioxidant capacity) method, and their radical scavenging activity was determined by the DPPH (1,1-Diphenyl-2-picrylhydrazyl) assay. [Ni(L)] exhibited higher antioxidant activity compared to [Fe(L)Cl] and the ligand (H2L1) in the CUPRAC assay.

Sogukomerogullari, Hatice Gamze; Sarıoğlu, Ahmet Oral; Kepekçi, Remziye Aysun; Türkmenoğlu, Burçin; Morcali, Mehmet Hakan

This study details the synthesis and characterization of new metal complexes formed by combining 2-((2-mercaptophenylimino)methyl)-4-methoxy-6-nitrophenol (L1) and 1,10-phenantroline (L2) ligands. The ligand (L1) and its mixed-ligand complexes with Co (II), Cu (II), Fe (II), and Ni (II) salts was analyzed using elemental analysis, FT-IR, UV–Vis, mass spectrometry, 1H and 13C NMR, magnetic susceptibility, and molar conductivity studies. The development of non-electrolytic compounds in a 1:1:1 M (L1:M:L2) ratio was verified by elemental analysis and conductance measurements. The complexes displayed an octahedral configuration. Biological uses of newly synthesized complexes were suggested by their antibacterial and antioxidant properties. Especially, the Fe (II) complex exhibited higher antimicrobial activity than free ligand on all the tested microbial strains according to the results of agar disc difffusion assay (inhibition zones ranging from 09.50 ± 0.70 and 19.50 ± 0.70 mm) and broth microdilution test (MIC values ranging between 97.66 and 781.25 μM) The highest antioxidant activity, among ligand and its metal complexes, were recorded for Ni (II) complex with IC50 value 59.17 ± 01.94 μM. The compounds with antimicrobial and antioxidant effects were further investigated via in silico approaches. The binding parameter values were calculated for the effectiveness of [FeL1L2H2O].3H2O complexes on the antimicrobial target and [NiL1L2H2O].2H2O complexes on the antioxidant target in molecular docking.

Altay, Ahmet; Caglar, Sema; Caglar, Bulent; Sahin, Zarife Sibel

Two Ag(I) complexes [Ag2(μ-mef)2(2-pymet)2] 1, [Ag2(μ-mef)2(2-pyet)2] 2 containing mefenamic acid, 2-pyridinemethanol and 2-pyridineethanol were synthesized and characterized by using SCXRD, FT-IR, elemental and thermal analysis techniques. The complex 1 was synthesized as a single crystal whereas the complex 2 was obtained as a microcrystalline powder. The complex 1 consists of binuclear structure. The argentophilic interaction occurs among silver(I) ions due to the short Ag⋯Ag distance (2.8710(10) Å). Two Ag(I) centers are connected by carboxylato oxygen-bridge to form the binuclear metal core. The FT-IR spectra and thermal analysis studies confirmed that both complexes exhibited similar structures. In vitro antiproliferative activity of both complexes were evaluated against MCF-7, HT-29 and HepG2 cancer cell lines. The apoptotic effects and intracellular ROS generation from both complexes were investigated in MCF-7 cell line by flow cytometry analysis. The XTT and LDH assays revealed that both complexes showed strong antiproliferative activity with higher selectivity towards cancer cells compared to the normal cells. In addition, Annexin V/propidium iodide assay exhibited that apoptotic cell number was increased in MCF-7 cells with increasing concentrations of Ag(I) complexes. Furthermore, both complexes induced the ROS generation considerably in MCF-7 cells suggesting the possible pro-oxidant activity of the novel synthesized Ag(I) complexes. Taken together, these findings provide a notable support for potential utility of Ag(I) complexes as novel anticancer agents against numerous kind of carcinogenesis.

Caglar, Sema; Aydemir, Ismihan E.; Adigüzel, Ekrem; Caglar, Bulent; Demir, Serkan; Buyukgungor, Orhan

Four novel mononuclear copper(II) complexes [Cu(dicl)2(2-pic) 2] 1, [Cu(dicl)2(3-pic)2] 2, [Cu(dicl) 2(4-pic)2] 3 and [Cu(dicl)2(2-ampy) 2] 4 have been synthesized. The crystal structures of the complexes 2 and 3 have been determined by X-ray crystallography. X-ray structure analysis has shown that copper(II) ions have distorted octahedral geometry in 2 and 3 and diclofenac coordinates to Cu(II) ion as a deprotonated ligand through carboxylato oxygens. Four complexes have been characterized by elemental analysis and IR spectroscopy. Their thermal stabilities have been determined by TG/DTA/DTG techniques. Four mononuclear complexes have shown catalytic activity on the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone exhibiting saturation kinetics at high substrate concentrations.

Caglar, Sema; Adigüzel, Ekrem; Caglar, Bulent; Saykal, Tuba; Sahin, Ertan; Büyükgüngör, Orhan

Two novel copper(II) complexes, mononuclear [Cu(bba)2(pypr) 2] 1 and dinuclear [Cu2(bba)2(pypr) 2] 2, have been synthesized by reactions of 2-pyridilpropanol with CuSO4·5H2O or Cu(CH3COO) 2·2H2O metal salt in the presence of 2-benzoylbenzoic acid. The copper(II) ion has a distorted octahedral geometry in 1 and distorted square pyramidal geometry in 2. 1 crystallizes in space group P1̄, while 2 crystallizes in the monoclinic crystal system with the space group P21/n. 2-Benzoylbenzoate behaves as a monodentate in 1, bidentate in 2. 2-pyridilpropanol ligand acts as a bidentate in 1 and bridging in 2. Both complexes were characterized by elemental analysis, mass and IR spectroscopy. Their molecular structures were determined by X-ray crystal structure analysis and their thermal stabilities were confirmed by TG/DTA/DTG techniques. Dinuclear compound shows high catalytic activity regarding the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone exhibiting saturation kinetics at high substrate concentrations. In addition, dinuclear compound demonstrates significantly catalase-like activity. But mononuclear complex shows neither catalase-like nor catechol oxidase activity.