Caglar, Sema; Altay, Ahmet; Harurluoglu, Betul; Yeniceri, Esma K. K.; Caglar, Bulent; Şahin, Onur

Two polymeric mixed-ligand silver(I) complexes, [Ag(µ-nif)(4-pic)]n (1) and [Ag4(µ-nap)4(2-pic)2]n (2), where Hnif: niflumic acid, Hnap: naproxen, 4-pic: 4-picoline and 2-pic: 2-picoline, were synthesized and characterized by single-crystal X-ray diffraction, FT-IR and 1H NMR spectroscopies, elemental and thermal analysis techniques. In 1, nif ligand behaves as a µ3-N,O,O' bridge connecting three silver(I) ions and each silver(I) ion exhibits a seesaw geometry. In 2, nap ligands act as a µ-carboxylato-(O,O') bridge between two silver(I) ions and µ3-carboxylato-(O,O,O') bridge linking three silver(I) ions. Each silver(I) ion occurs in trigonal geometry. To uncover the anticancer properties of the complexes, first, their cytotoxic abilities were tested against three cancer cell lines, HT-29 (human colorectal adenocarcinoma), A-549 (human lung carcinoma), and MDA-MB-453 (human breast adenocarcinoma), and normal 3T3-L1 (mouse fibroblast) cell line by XTT tests. Afterwards, the anticancer mechanism of the complexes was tried to be elucidated through the flow cytometry analyzes. XTT assay results showed that the complexes exhibited the highest cytotoxic activity and selectivity on HT-29 cells among all the cell lines. Flow cytometry analyses revealed that both complexes induced the apoptosis through the mitochondrial membrane depolarization and activation of the caspase cascade in HT-29 cells.

Dilek, Esra; Caglar, Sema; Dogancay, Nesrin; Caglar, Bulent; Sahin, Onur; Tabak, Ahmet

The mononuclear six metal(II) complexes ([Co(mef)2(3-pic)2(CH3OH)2] (1), [Ni(mef)2(3-pic)2(CH3OH)2] (2), [Cu(mef)2(3-pic)2] (3), [Co(mef)2(4-pic)2] (4), [Ni(mef)2(4-pic)2] (5), and [Cu(mef)2(4-pic)2] (6) with mefenamic acid and picoline ligands were synthesized, characterized, and their carbonic anhydrase inhibitory activities were evaluated. The six complexes were characterized by elemental analysis, FT-IR spectroscopy, and thermal analyses. The crystal structures of 1, 3, and 6 were determined by X-ray crystallography. The complexes have octahedral geometry. In 1, the mefenamato ligand behaved as monodentate whereas in 3 and 6, the mefenamato ligand acted as a bidentate ligand. Complexes 3 and 6 consist of the mefenamate and 4-picoline ligands. In 1, unlike the other complexes, methanol acted as a ligand and was involved in the coordination. Carbonic anhydrase I and II isoenzymes were purified from human erythrocytes. The in vitro effects of mefenamic acid, 3-picoline, 4-picoline, and the six metal(II) complexes on these isoenzymes were evaluated.

Caglar, Sema; Dilek, Esra; Caglar, Bulent; Adiguzel, Ekrem; Temel, Ersin; Buyukgungor, Orhan; Tabak, Ahmet

Four new neutral diclofenac-based complexes, [Co(dicl)2(2-pyet)2] 1, [Ni(dicl)2(2-pyet)2] 2, [Cu2(dicl)2(2-pyet)2] 3, and [Cu2(dicl)2(2-pypr)2] 4 have been synthesized and characterized by elemental analysis, FT-IR, thermal analysis. Complexes 1, 3, and 4 have also been characterized by X-ray single-crystal structural analysis. The compounds of Co(II) and Ni(II) have octahedral geometry with two diclofenac and two 2-pyridineethanol ligands in the coordination sphere. The compounds of Cu(II) have square-pyramidal geometry and Cu(II) ions are linked via oxygens to the bridging 2-pyridineethanol or 2-pyridinepropanol ligands. The Δν values acquired by FT-IR are in agreement with the single XRD data. Studies on the thermal properties are reported and the complexes are stable to 196, 216, 215, and 201 °C in air, respectively. Two dinuclear Cu(II) complexes have demonstrated catalytic activity on oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone showing saturation kinetics at high substrate concentrations. The diclofenac complexes are investigated as inhibitors of the human cytosolic isoforms hCA I and II. The complexes are good as hCA I inhibitors (Kis of 1.52–55.06 μM) but only moderately efficient as hCA II inhibitors (Kis of 0.23–5.61 μM).

Caglar, Sema; Dilek, Esra; Hamamci Alisir, Sevim; Caglar, Bulent

We report the synthesis of two square-pyramidal copper(II) complexes, [Cu(2,5-pydc)(2-aepy)(H2O)]·H2O, 1, and [Cu(2,5-pydc)(2-ampy)(H2O)]·H2O, 2 (2-aepy = 2-(aminoethyl)pyridine, 2-ampy = 2-(aminomethyl)pyridine, 2,5-pydc = pyridine-2,5-dicarboxylic acid or isocinchomeronic acid). The synthesized complexes have been characterized by X-ray diffraction, FT-IR, elemental, and thermal analysis techniques. The crystal structure of 1 was established by X-ray analysis. Powder X-ray diffraction analysis showed that the complexes are pure. The inhibition of human serum paraoxonase 1 (PON 1, EC 3.1.8.1) enzyme with these complexes were investigated. We used diethyl 4-nitrophenyl phosphate as a substrate to measure the paraoxonase activity of PON 1 enzyme spectrophotometrically. Complexes 1 and 2 decreased the in vitro PON 1 activity with different inhibition mechanisms. Complexes 1 and 2 inhibited paraoxonase activity of this enzyme as competitively and noncompetitively, respectively.

Caglar, Sema; Aydemir, Ismihan E.; Cankaya, Murat; Kuzucu, Mehmet; Temel, Ersin; Buyukgungor, Orhan

Cobalt(II) and nickel(II) complexes with diclofenac (dicl) in the presence of nitrogen-donor 3-picoline (3-pic) and 1-(2-aminoethyl)pyrrolidine (2-aepyr), [Co(dicl)2(3-pic)2] (1), [Ni(dicl)2(3-pic) 2(H2O)2] (2), [Co(dicl)2(2-aepyr) 2] (3), and [Ni(dicl)2(2-aepyr)2] (4), have been synthesized and characterized by FT-IR, UV-Vis, elemental and thermal analysis. The crystal structures of 1 and 3 have been determined by single-crystal X-ray diffraction; phase purity of complexes has been proved by powder X-ray diffraction analysis. Structural analyses have demonstrated that 1 and 3 are mononuclear and Co(II) ions have distorted octahedral environments. In 1, dicl is bidentate, whereas in 2, 3, and 4 dicl is monodentate. Dicl ligands are coordinated to metal(II) ions with O of carboxylate. Therefore, IR spectra of all complexes display {(OCO)asym and (OCO)sym} of dicl. The calculated Δ(OCO) values are consistent with the presence of monodentate (>200) and bidentate (<200) carboxylate. Compounds 2, 3, and 4 exhibit inhibition effects on human carbonic anhydrase-I. Compounds 3 and 4 show high thermal stability compared with 1 and 2.

Caglar, Sema; Adiguzel, Ekrem; Sariboga, Bahtiyar; Temel, Ersin; Buyukgungor, Orhan

Mononuclear and dinuclear copper(II) complexes [Cu2(-nap) 4(3-pic)2] (1) and [Cu(nap)2(H 2O)(4-pic)2] (2) have been synthesized in the presence of 3-picoline and 4-picoline. Two complexes were characterized by FT-IR, UV-vis spectroscopic methods and their thermal stabilities were determined by TG/DTA/DTG techniques. The crystal structures of 1 and 2 were established by X-ray analysis. X-ray structure analysis has shown that copper(II) has a distorted square-pyramidal geometry. Naproxenate is a bridging ligand in 1 and monodentate in 2. Two complexes have shown catalytic activity on oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone exhibiting saturation kinetics at high substrate concentrations. The complexes were also screened for antimicrobial activity against pathogenic bacteria and fungi. The complexes exhibited antimicrobial activity against Entrococcus faecalis and Candida albicans.

Caglar, Sema; Heren, Zerrin; Büyükgüngör, Orhan

Four 2-benzoylbenzoate (bba) complexes, [Co(bba)2(H 2O)2(3-pic)2] (1), [Ni(bba)2(H 2O)2(3-pic)2] (2), [Cu(bba)2(3-pic) 2] (3), and [Hg(bba)2(3-pic)2] (4), have been synthesized and characterized by IR spectra, thermal (TG, DTG, and DTA) analysis, and single crystal X-ray diffraction. All the complexes consist of neutral monomeric units with 1 and 2 crystallizing in the orthorhombic (P n a 21), 3 in triclinic (P1), and 4 in monoclinic (P2 1/c) crystal systems. The metal(II) ions exhibit distorted octahedral coordination for 1, 2, and 3 and mercury(II) exhibits distorted trigonal prism coordination. In 1 and 2, bba is monodentate, whereas in 3 and 4 bba is bidentate. 3-Picoline (3-pic) is a classical N-monodentate ligand. Bba are coordinated to metal(II) with carboxylates and IR spectra of all complexes display characteristic absorptions of carboxylate {υ(OCO)asym and υ(OCO)sym}. Thermogravimetric (TG) analyses show that 1 and 2 are thermally stable (Tdecomp.>60°C) and 3 and 4 are thermally stable (Tdecomp.>120°C).

Caglar, Sema; Heren, Zerrin; Büyükgüngör, Orhan

Aquabis(2-benzoylbenzoato)(1,10-phenanthroline)cobalt(II) and aquabis(2-benzoylbenzoato) (butanol)(1,10-phenanthroline)nickel(II) have been prepared and characterized by elemental analyses, IR and electronic spectroscopy, magnetic measurements, and single-crystal X-ray diffraction. [Co(bba)2(H2O)(phen)] (1) and [Ni(bba)2(H 2O)(butOH)(phen)] (2) consist of neutral monomeric units and crystallize in the monoclinic (P2(1)) and triclinic (P1) crystal systems, respectively. The cobalt(II) and nickel(II) sit on inversion centres and exhibit distorted octahedral coordination. Phen is bidentate chelating. In 1, bba is both monodentate and bidentate, whereas in 2 bba is only monodentate. bba ligands are coordinated to metal(II) with carboxylates and IR spectra of both complexes display characteristic absorptions of carboxylate anions {ν(OCO)asym and ν(OCO)sym} of bba. Thermal analysis shows that mass losses of 1 from 105°C to 456°C correspond to decomposition of phen and bba, while for 2 these occur at 271-529°C.