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Vanadium compounds are being investigated as potential therapeutic agents in the treatment of many health problems, primarily diabetes. We aimed to provide the effect of N(1)-4-hydroxysalicylidene-N(4)-salicylidene-S-methyl-isothiosemicarbazidato-oxovanadium(IV) (VOL) on small intestinal injury in experimental male diabetic rats. Four groups were created of 3.0-3.5-month-old rats. The rats were made diabetic by a single dose of streptozotocin (STZ) at 65 mg/kg and grouped as follows: control animals, VOL-given control animals, STZ-induced diabetic animals and STZ-induced diabetic animals given VOL. A daily dose of 0.2 mM/kg vanadium complex was administered orally for 12 days after the inducement of diabetes. On the 12th day, small intestine tissue samples were taken. According to the data obtained from the biochemical analysis, reduced glutathione (GSH) level, catalase (CAT), glutathione peroxidase (GPx), glutathione-S-transferase (GST), superoxide dismutase (SOD), Na+/K+-ATPase and paraoxanase (PON) activities were increased, whereas sialic acid (SA), xanthine oxidase (XO) and disaccharidases (maltase and saccharidase) activities were decreased in the small intestine tissue of VOL-treated diabetic rats. Microscopic examinations revealed a remarkable decrease in the mucosal necrotic areas, discontinuity in the brush border, deterioration of the villi integrity and oedema inside the villi, but with a mild decrease in the inflammatory cells, deterioration and loss of integrity of the gland in the small intestine of VOL-treated diabetic rats. Moreover, VOL treatment markedly decreased the proliferation of villus cells and especially inflammatory cells in the small intestine of diabetic rats. According to the obtained data, the administration of VOL is a potentially convenient strategy to reducing small intestine injury in diabetic rats.

Ozdemir, Namik/0000-0003-3371-9874 WOS: 000524498200017 A triazole complex of copper(ii) containing ethylenediamine as a coligand was synthesized using salicylaldehydethiosemicarbazone in the presence of CuCl2. Also, a dinuclear copper(ii) complex was synthesized using the same reagents; however, the order of their addition was different. The structures of these two complexes were characterized via elemental analysis, IR, H-1-NMR, and UV-Vis spectroscopy and mass spectrometry (MS). Furthermore, the molecular structures of complexes I and II were determined via single-crystal X-ray structure analysis. The copper(ii) ion has a distorted square-pyramidal geometry in complex I and a distorted square-planar geometry in complex II. Their fragmentation products were investigated in detail by ESI-MS. Finally, the cytotoxic effects of both complexes were evaluated in MDA-MB-231, MCF-7 and 3T3 fibroblast cell lines via the MTT assay and flow cytometry. Ondokuz Mays UniversityOndokuz Mayis University [PYO.FEN.1906.19.001] This study was supported by Ondokuz Mays University (Project No: PYO.FEN.1906.19.001).

Diabetes mellitus (DM) is chronic and metabolic disorder, which is mainly attributed by hyperglycemia. Vanadium salts and their oxo-complexes have been shown to possess insulin-mimetic and anti-diabetic activities in animal models and diabetic patients. The main goal of this study was to investigate the protective effect of oxovanadium(IV) complex based on thiosemicarbazone (VOL) [L: (N(1)-2,4-dihydroxybenzylidene-N-(4)-2-hydroxybenzylidene-S-methyl-isothiosemicarbazidato-oxovanadium(IV)] on glycoprotein components levels and oxidative lung injury of streptozotocin (STZ)-induced diabetic rats. Male Swiss albino rats were separated into four groups. Group I (

ULKUSEVEN, BAHRI/0000-0001-6342-1505; Ozdemir, Namik/0000-0003-3371-9874; Yaylim, Ilhan/0000-0003-2615-0202; SULEYMANOGLU, MEDIHA/0000-0002-1401-4863 WOS: 000527699700001 PubMed: 32314849 Iron(III) and nickel(II) complexes bearing a thiosemicarbazone framework were synthesized by a one-pot synthesis method. The structures were characterized by elemental analysis, IR, H-1 NMR, APCI Mass, conductivity, magnetic moment measurements. Molecular and crystal structures of the iron(III) complex were obtained from single-crystal X-ray diffraction. The findings showed that the metal atom adopts a slightly distorted square-pyramidal coordination, with the four donor atoms of the thiosemicarbazone ligand defining the basal plane and a chloride atom occupying the apical position. In the crystal lattice, the structure is stabilized by intermolecular O & x2500;H center dot center dot center dot O and C & x2500;H center dot center dot center dot O interactions. The cytotoxic activity was studied by MTT assay, the expression levels of cytochrome P450 (CYP) enzymes by Western blot, and the lipophilicity (LogP) by using the shake-flask method, another pharmacokinetic parameter. The findings showed that the IC50 values decreased with the decrease of the LogP values of the substances. Cytochrome P450 expression levels were found specific for each compound and each cell line. As a result, the pharmacokinetic properties of the newly synthesized thiosemicarbazone compounds are crucial for oral administration and provide us with clues for prospective in vivo studies. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [49111]; Ondokuz Mays UniversityOndokuz Mayis University [PYO.FEN.1906.19.001, 109S188] This study was supported by the Scientific Research Projects Coordination Unit of Istanbul University (Project number: 49111); the Ondokuz Mays University (Project No: PYO.FEN.1906.19.001); and TuBTAK-SBAG (Project Number: 109S188).

Altun, Mehmet/0000-0003-2541-0623; Ozdemir, Namik/0000-0003-3371-9874 WOS: 000429184600012 The compound 4'-(2,4-dimethoxyphenyl)-2,2':6',2"-terpyridine (Mtpyr) was synthesized and investigated using X-ray single crystal structure determination, combined with Hirshfeld topology analysis of the molecular packing. In addition, Mtpyr was characterized by experimental and theoretical FT-IR, UV-Vis, H-1 NMR, C-13 NMR and fluorescence emission spectra. The optimized molecular geometry (bond length, bond angle, torsion angle), the complete vibrational frequency and all other theoretical computations were calculated by using density functional theory (DFT) B3LYP method with the help of 6 -311++G(d,p) basis set. From the recorded UV Vis spectrum, the electronic properties such as excitation energies, wavelength and oscillator strength are evaluated by TD-DFT in chloroform solution. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge-independent atomic orbital (GIAO) method and compared with experimental results. The calculated HOMO-LUMO band gap energies confirmed that charge transfer and chemical stability within the molecule. The hyperconjugative interaction energy E-(2) and electron densities of donor (i) and acceptor (j) bonds were calculated using natural bond orbital (NBO) analysis. Besides Mulliken and natural population charges (NPA), non-linear optic properties (NLO), Fukui Function analysis, molecular electrostatic potential (MEP) were also computed which helps to identifying the electrophilic/nucleophilic nature. (C) 2018 Published by Elsevier B.V.

Copper(II) and nickel(II) mixed ligand complexes were synthesized from 4-methoxysalicylaldehyde-N-phenyl-thiosemicarbazone and 3,5-lutidine. The structures of the complexes have been characterized by elemental analysis, IR, UV, 1H NMR and ESI-MS spectra, together with magnetic susceptibility measurements. Complex I was found to have a distorted square planar geometry, with coordination of azomethine nitrogen, thiolate sulfur, phenolate oxygen and pyridyl nitrogen atoms, by the single-crystal X-ray diffraction technique. Quantum chemical DFT calculations have also been carried out using the DFT/HSEH1PBE method with the cc-pVDZ basis set for C, H, N, O and S atoms, and the LANL2DZ basis set for the metal atom. The antioxidant activities of the ligand and its metal complexes were investigated by CUPRAC and DPPH assays and calculated as their trolox equivalent antioxidant capacities (TEAC). Electrochemical properties were performed with cyclic voltammetry and square wave voltammetry. Both the ligand and its metal complexes were found to have antioxidant capacity.

Ozdemir, Namik/0000-0003-3371-9874; Ulkuseven, Bahri/0000-0001-6342-1505; Avcu Altiparmak, Elif/0000-0002-5491-8445; Arsu, Nergis/0000-0002-1362-2517 WOS: 000474734200001 The reaction of salicylaldehyde-S-methylisothiosemicarbazone in the presence of ethylenediamine base and iron (III)chloride generated unforeseen homotopic dinuclear triple-stranded iron (III)helicate. The synthesized helicate was characterized by elemental analysis, IR, UV-Vis spectroscopy, magnetic moment measurement, and evaluated cytotoxic activities against K562, HL-60 and THP-1 leukemia cells. In addition, solid-state structure has been determined by single-crystal X-ray diffraction technique. In the complex, three dinucleating O, N, N, O donor ligands provide three diazine (NN) bridges between the metal ions and facial O3N3 coordination spheres around them. The ligands are folded about the NN single bond and coordinated to the two metal ions in a helical fashion to form the triple helical structure. In the crystal lattice, chains of centrosymmetric R22 >12 rings, which are connected to one another via pi pi stacking interactions, are generated by CH center dot center dot center dot O intermolecular interactions. The results are also confirmed by the density functional theory (DFT) calculations. The results obtained from the cytotoxicity test showed to be effective in low concentrations on the leukemia cells. An intercalative binding mode of helicate-DNA complex was confirmed with the high intrinsic binding constant (K-b = 8x10(6) M-1) and competitive displacement assay of Ethidium bromide with high Ksv value. Ondokuz Mayis UniversityOndokuz Mayis University [PYO.FEN.1906.19.001]; Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [FYL-2017-23739] Ondokuz Mayis University, Grant/Award Number: PYO.FEN.1906.19.001; Scientific Research Projects Coordination Unit of Istanbul University, Grant/Award Number: FYL-2017-23739

Ulkuseven, Bahri/0000-0001-6342-1505; Ozdemir, Namik/0000-0003-3371-9874; SOYLU, SERKAN M/0000-0002-8440-1260 WOS: 000461331500002 Mixed ligand Ni(II) complexes were synthesized from triphenylphosphine and S-methyl- or S-ethyl-isothiosemicarbazone ligands derived from 3-bromo-5-chloro-2-hydroxy-benzaldehyde. The complexes were characterized by physicochemical and spectroscopic methods. In addition, their molecular structures were determined by single-crystal X-ray diffraction. In both complexes, the Ni atom has a near square-planar geometry, being coordinated by the phenolato oxygen, azomethine nitrogen and amine nitrogen atoms of the thiosemicarbazone ligands, together with the phosphorus atom of the triphenylphosphine. The S-methyl complex includes an additional free thiosemicarbazone ligand in the asymmetric unit. X-ray analysis shows that O-HN, N-HN, C-HN and C-HO-type hydrogen bonds and - stacking interactions are responsible for stabilizing the crystal structures. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [BYP-2017-21222] This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University (Project Number: BYP-2017-21222).

Guveli, Sukriye/0000-0001-7384-822X; Ulkuseven, Bahri/0000-0001-6342-1505; Ozdemir, Namik/0000-0003-3371-9874 WOS: 000377728600003 Two nickel(II) complexes containing 5-bromosalicylidene-N-methyl-S-methyl-isothiosemicarbazone (H(2)SMeNMeTsc) and 5-bromosalicylidene-N-methyl-thiosemicarbazone (H(2)NMeTsc) with triphenylphosphine were synthesized. The compounds were characterized by elemental analysis, IR, H-1 NMR and UV-Vis spectroscopies, and their structures were determined by single crystal X-ray diffraction technique. Theoretical characterization of the compounds was carried out using the density functional theory (DFF/B3LYP) method with 6-311G(d,p) basis set for the C, H, Br, N, O, P, S atoms and LANL2DZ pseudo-potential for Ni atom, and the results were checked against the experimental data. Electronic absorption spectra of the compounds have also been obtained using the time-dependent density functional theory (TD-DFT) formalism at the same level. The coordination geometry around Ni-II in the two complexes is distorted square-planar geometry. While the thiosemicarbazone ligand is coordinated to nickel through ONN mode in [Ni(SMeNMeTsc)(PPh3)]center dot PPh3, it is bound to the metal as dianionic ONS donors in [Ni(NMeTsc)(PPh3)]. The consistency between theoretical and experimental values is good in general. (C) 2016 Elsevier Ltd. All rights reserved. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University. We also thank Associate Professor Mustafa Serkan Soylu, Giresun University, Turkey, for his help with the X-ray data collection of complex [Ni(SMeN-MeTsc)(PPh3)]center dot PPh3.

Mixed ligand nickel(II) and ruthenium(II) complexes were synthesized from pyridoxal-N-allyl-thiosemicarbazone hydrochloride and triphenylphosphine. The structures of the complexes have been characterized by elemental analysis, IR, 1H and 31P NMR, conductivity, magnetic moment measurements and single-crystal X-ray diffraction technique. Based on X-ray crystallographic studies, a square-planar structure has been proposed for the Ni(II) complex, in which the thiosemicarbazone ligand acts as dianionic tridentate ONS ligand. In the case of the Ru(II) complex, the thiosemicarbazone is coordinated to metal atom as a monoanionic bidentate NS donor ligand in an octahedral geometry. Antioxidant activities of the ligand and its metal complexes were calculated as their trolox equivalent antioxidant capacities (TEAC) by CUPRAC method and DPPH assay. Both the ligand and its metal complexes were found to be antioxidant and are much more antioxidant at least 2.1 times than trolox, even, ligand is 3.5 times greater than that of trolox according to CUPRAC. A linear correlation (correlation coefficient R2 = 0.9997) appeared between the obtained TEAC values by the two antioxidant assays. © 2019 Elsevier B.V.

Guveli, Sukriye/0000-0001-7384-822X; Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000446286200042 A tridentate Schiff base ligand (5-methyl-2-hydroxy-acetophenone-S-methyl-thiosemicarbazone, H2L) and its mononuclear nickel complex, [NiL(PPh3)], were obtained and characterized by spectroscopic techniques. Structural analysis of the compounds was supported by complementing crystallographic studies. The X-ray data related to molecular geometries was used in the DFT/B3LYP calculations with 6-311G (d, p) and LANL2DZ (for nickel atom) basis sets. Atomic charge distribution data indicated that the negative charges of free thiosemicarbazidato ligand were transferred to nickel (II) by the formation of the metal complex. To understand the nucleophilic or electrophilic reaction capabilities the ligand and nickel complex, the molecular electrostatic potential (MEP) and electrostatic potential (ESP) analyses have performed. (C) 2018 Elsevier B.V. All rights reserved. University Research Fund [F.279]; BAP (The Scientific Research Projects Coordination Unit of Istanbul University (Turkey)) [23552] The authors acknowledge the Scientific and Technological Research Application and Research Center of Sinop University (Turkey) for the use of the Bruker D8 QUEST diffractometer. The authors sincerely thank Ondokuz Mayis University (Turkey) for providing analysis using the STOE IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund). This work was also supported by the BAP (The Scientific Research Projects Coordination Unit of Istanbul University (Turkey), Project Numbers: 23552).

The nickel(II), iron(III), oxovanadium(IV) complexes of the 3-hydroxysalicylidene-S-methyl-thiosemicarbazone (L) were obtained from the 3-hydroxysalicyldehyde-S-methylthiosemicarbazone with the R-1-substituted-salicylaldehyde (R-1: H, 3-OH) in the presence of Ni(II), Fe(III), VO(IV) as template ion. The ligand and its complexes were characterized by elemental analysis, electronic, UV/Vis., H-1 NMR, EPR and IR studies. The free ligand and its metal complexes have been tested for in vitro antioxidant capacity by reduction of copper(II) neocuproine (Cu(II)-Nc) using the CUPRAC method. The ligand exhibited more potent in vitro antioxidant capacity than its complexes. The obtained trolox equivalent antioxidant capacity (TEAC) value of the iron(III) complex (TEAC(CUPRAC) = 3.27) was higher than those of other complexes. Furthermore, the antioxidant activity of the free ligand and its complexes were determined by in vitro methods measuring the scavenging activity of reactive oxygen species (ROS) including hydroxyl radical ((OH)-O-center dot), superoxide anion radical (O-2(center dot-)), and hydrogen peroxide (H2O2), showing that especially the V(IV) and Fe(III) complexes had significant scavenging activity for ROS. (C) 2014 Elsevier B.V. All rights reserved.

WOS: 000357106400079, Template reactions of 2-hydroxy-R-benzaldehyde-S-methylisothiosemicarbazones (R = 3-methoxy or 4-hydroxy) with the corresponding aldehydes in the presence of FeCl3 and NiCl2 yielded N-1, N-4-disalicylidene chelate complexes. The compounds were characterized by means of elemental and spectroscopic methods. The structure of complex 1 was determined by X-ray single crystal diffraction. Crystal data (Mo K alpha; 296 K) are as follows: monoclinic space group P2(1)/c, a = 12.9857(8) angstrom, b = 7.8019(4) angstrom, c = 19.1976(12) angstrom, beta = 101.655(5) 1, Z = 4. Cytotoxic effects of the compounds were evaluated by the MTT assay in K562 leukemia, ECV304 endothelial and normal mononuclear cells, and DNA fragmentation analysis using the diphenylamine reaction was performed. The DNA binding capacity of thiosemicarbazones at IC50 and different concentrations was investigated. The DNA fragmentation percentage of compound treated cells was higher than that of non-treated control cells but was higher for compound 3 (84%) compared to the others. The interaction of compounds 1-4 and DNA was investigated voltammetrically by using nucleic acid modified electrodes after the double stranded fish sperm DNA (fsDNA), or poly(dA)center dot poly(dT), was immobilized onto the surface of pencil graphite electrodes (PGEs). Accordingly, the oxidation signals of DNA bases, guanine and adenine, were measured by using differential pulse voltammetry (DPV). The changes in the signals of guanine and adenine were evaluated before and after the interaction process. The results indicated that compound 3 was cytotoxic at very low concentrations in K562 leukemia cells unlike other cells and that could damage the DNA double stranded form, specifically the adenine base. Therefore, it may have a selective antileukemic effect and drug potential., TUBITAK (TUBITAK-SBAG Project)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [109S188]; Istanbul UniversityIstanbul University; Turkish Academy of Sciences (TUBA)Turkish Academy of Sciences; Faculty of Arts and Sciences, Ondokuz Mayis University, TurkeyOndokuz Mayis University [F-279], This study was partly supported by TUBITAK (TUBITAK-SBAG Project number: 109S188) and was supported by the Research Fund of Istanbul University. A.E would like to express her gratitude to the Turkish Academy of Sciences (TUBA) as an Associate member for its partial support. We acknowledge the Faculty of Arts and Sciences, Ondokuz Mayis University, Turkey, for the use of the STOE IPDS II diffractometer (purchased under grant No. F-279 of the University Research Fund).

Aygun, Muhittin/0000-0001-9670-9062; Guveli, Sukriye/0000-0001-7384-822X; Ulkuseven, Bahri/0000-0001-6342-1505; Aygun, Muhittin/0000-0001-9670-9062 WOS: 000403118200001 This work presents a combined experimental and theoretical study on new synthesized ONN and ONS chelating 2-hydroxyacetophenone thiosemicarbazone ligands and their nickel(II) complexes with triphenylphosphine co-ligand. The 5-bromo-2-hydroxyacetophenone thiosemicarbazone ligand (L-1) coordinates to nickel through the phenolic-O, azomethine-N and thiole-S atoms and the complex [Ni(L-1) (PPh3)] (1) is formed an ONSP donor set with P atom of triphenylphosphine ligand. The 5-bromo-2-hydroxyacetophenone-S-methyl-thiosemicarbazone ligand (L-2) is functional a thioamide nitrogen instead of a sulfur atom, so complex [Ni(L-2)(PPh3)] (2) have ONNP donor set. The spectroscopic properties of all compounds have been determined by IR, H-1 NMR and UV-Vis spectroscopy techniques and the crystal structure of L-1, 1 and 2 have also been studied using X-ray diffraction. The molecular geometries obtained by X-ray analyzes in the ground state were compared with the optimized geometries which were calculated using the DFT/B3LYP method. The 6-311G(d,p) basis set for C, H, N, O, P, S atoms and LANL2DZ basis set for Ni atom were chosen in all theoretical calculations. In addition to molecular geometries, the vibrational frequencies, electronic transitions and H-1 NMR chemical shifts of the compounds were computed and compared with the experimental values. The electronic absorption spectra of the both complexes were predicted by using the time-dependent DET method. The HOMO-LUMO analyses were carried out and the chemical reactivity parameters (chemical hardness and softness, electronegativity, chemical potential and electrophilicity index) were calculated for studied compounds. (C) 2017 Elsevier Ltd. All rights reserved. Dokuz Eylul University, TurkeyDokuz Eylul University [2010.KB.FEN.13]; Ondokuz Mayis University, TurkeyOndokuz Mayis University [F.279] The authors acknowledge Dokuz Eylul University, Turkey, for the use of the Agilent Xcalibur Eos diffractometer (purchased under University Research Grant No.: 2010.KB.FEN.13) and Ondokuz Mayis University, Turkey, for the use of the STOE IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

Ulkuseven, Bahri/0000-0001-6342-1505; Guveli, Sukriye/0000-0001-7384-822X WOS: 000370900600015 A new 5-methyl-2-hydroxy-acetophenone-thiosemicarbazone ligand (L) and its nickel(II) complex [Ni(L)(PPh3)] were synthesized. The crystal structure of free ligand and its complex has been determined by single crystal X-ray diffraction technique. In the complex, thiosemicarbazone ligand is coordinated to nickel through ONS mode. The structures were also characterized by elemental analysis, IR, H-1 NMR and UV-Vis. spectroscopies. In addition, the molecular geometries, vibrational frequencies and gauge independent atomic orbital (GIAO) H-1 NMR chemical shift values of the compounds in the ground state have been calculated using the density functional theory (B3LYP) method with 6-311G(d,p) basis set for C, H, N, O, P, S atoms and LANL2DZ basis set for Ni atom. Electronic transitions were calculated using the time-dependent density functional theory (TD-DFT) formalism and the experimental spectra of the compounds have been discussed. (C) 2015 Elsevier Ltd. All rights reserved. Dokuz Eylill University, TurkeyDokuz Eylul University [2010.KB.FEN.13]; Ondokuz Mayis University, TurkeyOndokuz Mayis University [F.279] The authors acknowledge Dokuz Eylill University, Turkey, for the use of the Agilent Xcalibur Eos diffractometer (purchased under University Research Grant No: 2010.KB.FEN.13) and Ondokuz Mayis University, Turkey, for the use of the STOE IPDS 2 diffractometer (purchased under Grant F.279 of the University Research Fund).

Guveli, Sukriye/0000-0001-7384-822X; Ulkuseven, Bahri/0000-0001-6342-1505; Ozdemir, Namik/0000-0003-3371-9874 WOS: 000375518900024 The cationic thiosemicarbazone complex of nickel containing triphenylphosphine as coligand was synthesized through the isopropanol-assisted hydrogen transfer reaction. The thiosemicarbazone ligand (LH2) and its cationic nickel complex, [Ni(LH)(PPh3)]Cl-+(-)center dot(CH3)(2)CHOH, were characterized by elemental analysis, IR, H-1 NMR and UV-Vis spectroscopies. The molecular structure of the complex was also determined by single crystal X-ray diffraction technique. In addition computational studies at B3LYP/6-311G (d,p) (main group) and LANL2DZ (Ni) level were carried out for theoretical characterization of the ligand and complex. Structural analysis of the complex indicated the presence of square-planar coordination geometry (ONNP) about nickel in which the thiosemicarbazone ligand coordinated as mononegative tridentate. Isopropyl alcohol catalyzed efficiently the transfer hydrogenation and the cationic complex formed through inter conversion azinyl-azinylidene. All spectral data support the formation of the ligand and its nickel complex and the results calculated using theoretical methods coincide well with the experimental findings. The thermal degradation of the complex was investigated using thermogravimetric and differential thermal analyses techniques in nitrogen and oxygen atmosphere. The oxidative-thermal decomposition of the compound showed volatilization of nickel as unexpected behavior unlike nitrogen atmosphere. (C) 2016 Elsevier Ltd. All rights reserved. Istanbul UniversityIstanbul University This work was supported by the Research Fund of Istanbul University.

Ulkuseven, Bahri/0000-0001-6342-1505; Guveli, Sukriye/0000-0001-7384-822X; Ozdemir, Namik/0000-0003-3371-9874; KOCA, ATIF/0000-0003-0141-5817 WOS: 000369070900002 Reactions of [Ni(PPh3)(2)Cl-2] with 3-Bromo-5-chloro-2-hydroxyacetophenone-N-4-hexyl ((LH2)-H-1), cyclohexyl (L2H2) and phenyl ((LH2)-H-3)-thiosemicarbazones resulted in four coordinated (ONSP) nickel(II) complexes, [Ni(L-1)(PPh3)] (1), [Ni((LH)-H-2)(PPh3)]center dot Cl (2) and [Ni(L-3)(PPh3)]center dot C2H5OH (3). The structures of 1-3 were determined by spectroscopic and single crystal X-ray diffraction methods. While formation of complexes 1 and 3 occurs through the doubly deprotonated forms of the thiosemicarbazone ligands (L-1 and L-3), complex 2 consists of mono deprotonated ligand ((LH)-H-2). Cyclic voltammetry and square wave voltammetry studies of the compounds showed that all ligands represented one irreversible reduction and two irreversible oxidation processes. Complexes 1-3 illustrated a metal based reduction and a metal based oxidation processes in addition to the ligand based electron transfer reactions. In situ spectroelectrochemical measurements were employed to determine the spectra of electrogenerated species of the complexes and to assign the redox processes. The influences of the N-4-substituent types on structural and electrochemical features of the compounds were discussed. (C) 2015 Elsevier B.V. All rights reserved. TUBA (The Turkish Academy of Sciences)Turkish Academy of Sciences; BAP (The Scientific Research Projects Coordination Unit of Istanbul University)Istanbul University [YOP 40652, UDP 55762] This work was supported TUBA (The Turkish Academy of Sciences) and BAP (The Scientific Research Projects Coordination Unit of Istanbul University, Project Numbers: YOP 40652, UDP 55762.).

Ulkuseven, Bahri/0000-0001-6342-1505; Ozdemir, Namik/0000-0003-3371-9874 WOS: 000287905100009 Two uranyl complexes having the composition [UO2(L)DMSO] were synthesized using salicyl- and 3,5-dichlorosalicylaldehyde-S-propyl-thiosemicarbazones as starting materials. The S-propyl-thiosemicarbazidato structures in the complexes are N-1-3,5-dichlorosalicylidene-N-4-salicylidene and N-1-salicylidene-N-4-3,5-dichlorosalicylidene. The stable solid complexes were characterized by means of elemental analysis, IR and H-1 NMR spectroscopies, and the single crystal X-ray diffraction technique. The two complexes, with the same formula, crystallize in different space groups. In the title complexes, the uranium atom is seven-coordinated in a distorted pentagonal-bipyramidal geometry involving an ONNO donor set of the thiosemicarbazidato ligand and an oxygen atom of a DMSO molecule. The two apical positions of the pentagonal bipyramid are occupied by the two oxygen atoms of the trans-dioxouranium group. The relative orientations of the DMSO and S-propyl groups in both complexes are somewhat different due to different crystal packing. (C) 2010 Elsevier Ltd. All rights reserved. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [UDP-8502] This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University (Project No: UDP-8502).

Ozdemir, Namik/0000-0003-3371-9874; Andac, Omer/0000-0003-3641-9690; Ulkuseven, Bahri/0000-0001-6342-1505; Guveli, Sukriye/0000-0001-7384-822X WOS: 000280898800002 Reaction of 2-hydroxyacetophenone thiosemicarbazone with [Ni(PPh(3))(2)Cl(2)] in optimized conditions afforded a mixed ligand complex with an isolated triphenylphosphine molecule. The structure was characterized by elemental analysis, IR, NMR and UV-Vis. spectroscopies and single crystal X-ray diffraction technique. In addition, the molecular geometry, vibrational frequencies and gauge including atomic orbital (CIAO) (1)H and (13)C NMR chemical shift values of the title compound in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-31G(d,p) basis set for the C. N, O, S, P. H atoms and LANL2DZ pseudo-potential for the Ni atom, and compared with the experimental data. Besides, atomic charge distributions, molecular electrostatic potential and frontier molecular orbitals (FMO) analysis of the title compound were investigated by theoretical calculations. The thermodynamic properties of the compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained. Atomic charge distributions indicate that during forming the title compound, the free ligand of thiosemicarbazone ion transfers their negative charges to central Ni(II) ion. The effect of different solvents (chloroform, methanol and water) on the geometry, vibrational frequencies, total energies and dipole moments was studied using the density functional theory (DFT/B3LYP) method by applying the Onsager and the Polarizable Continuum Model (PCM). (C) 2010 Elsevier Ltd. All rights reserved. istanbul UniversityIstanbul University; Research Centre of Ondokuz May's UniversityOndokuz Mayis University [F-461] Funding of our research from the Research Fund of istanbul University and the Research Centre of Ondokuz May's University (Project No: F-461) is gratefully acknowledged.

Reactions of salicyl- and 3,5-dichlorosalicylaldehyde-S-propyl-thiosemicarbazones with salicyl- and 3,5-dichlorosalicylaldehyde in the presence of UO2(CH3COO)2 in different alcohols yielded stable solid complexes corresponding to the general formula [UO2(L)ROH] (R: propyl-, butyl-, pentyl-, and octyl-). The complexes were characterized by means of elemental analysis, IR and 1H NMR spectroscopies. The thermal stabilities of the alcohol solvated complexes were investigated in air and nitrogen atm., and determined their decomposition phases. In the crystal structure of the [UO2(L)(C4H9OH)], the U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry involving O,O,N,N atoms of two phenolic and two imine groups and one oxygen atom of alcohol molecule in basal plane and two O atoms of dioxo group in apical positions. The title structure is stabilized by one intramolecular interaction of types C–H⋯Cl and by two intermolecular interactions of types O–H⋯O and C–H⋯π (benzene) leading to the molecular chain along the [0 1 0] direction.

Ozdemir, Namik/0000-0003-3371-9874; Guveli, Sukriye/0000-0001-7384-822X; Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000265835400003 Reactions of 5-bromo-2-hydroxy-benzaldehyde-S-R-4-R-1-thiosemicarbazones, [R, R-1 = H,H (L-1); CH3, H (L-2); H, C6H5 (L-3); CH3, C6H5 (L-4)] with [Ni(PPh3)(2)Cl-2] in 1:1 molar ratio yielded complexes of general formula [Ni(L)(PPh3)]. While the complexes of L-1 and L-3 involve the ONS donor set of the thiosemicarbazone, the L-2 complexes utilize the ONN set. The reaction of L-4 and the nickel salt gave the L-3 complex by loss of the CH3 group from the sulphur. The complexes were characterized by physico-chemical and spectroscopic methods. The structures of the L-1 and L-2 complexes have been determined by single crystal X-ray diffraction and a new coordination mode (ONN) of salicylaldehyde thiosemicarbazones has been identified. Research Fund of Istanbul UniversityIstanbul University [T-957/06102006] This work was supported by the Research Fund of Istanbul University. Project No. T-957/06102006.

Mixed-ligand zinc complexes with N,N,N′,N′-tetramethylethylenediamine (tmen) and R-salicylaldehyde N(4)-allyl thiosemicarbazones (R: 3-OCH3 (L1), 5-Br(L2)), [ZnL1,2(tmen)], were synthesized and the complexes were characterized by elemental analysis, atomic absorption spectrometer, magnetic susceptibility, molar conductivity, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectra and IR, UV–Vis, 1H NMR and 15N spectroscopies. Crystal of [ZnL2(tmen)] have a slightly distorted square pyramid involving O, N, S atoms of thiosemicarbazone and one N atom of tmen in basal plane and the other N atom of tmen in apex of the pyramid. The non-coordinated allyl group is disordered.

Ulkuseven, Bahri/0000-0001-6342-1505; SOYLU, SERKAN M/0000-0002-8440-1260; Ozdemir, Namik/0000-0003-3371-9874 WOS: 000343337700119 PubMed: 25168237 The title thiosemicarbazidatodioxouranium(VI) compound was synthesized and characterized by FT-IR, NMR and UV-vis spectroscopies. Solid state structure of the compound was confirmed by X-ray crystallography. Besides, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) H-1 and C-13 NMR chemical shift values of the compound in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set for the C, H, Cl, N, O, S atoms and SDD pseudo-potential for the U atom, and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the compound have been predicted at same level. As a result, a good agreement is obtained between the experimental and theoretical ones. (C) 2014 Elsevier B.V. All rights reserved.

Four new oxovanadium(IV) compounds were prepared by template reaction of salicyl-, 5-bromosalicyl-and 3-methoxysalicyl-aldehyde S-methylthiosemicarbazones with 2-hydroxy-, 5-bromo-2-hydroxy-and 3-methoxy-2-hydroxy-benzaldehyde in various combinations. The compounds were isolated as stable solid compounds with general formula [VO(L)] and characterized by elemental analysis, conductivity and magnetic measurements, electronic, IR and EPR spectroscopy. The X-band EPR signals recorded from powder forms of all samples have a single asymmetric line shape and theoretical fit studies proved the presence of axial symmetry around the paramagnetic vanadium ions. The anisotropic Lande splitting factors take values of g‖ < g⊥ < ge = 2.0023. Orbital energy levels for magnetic electrons were determined from theoretically well fitted Spin Hamiltonian parameters. The EPR spectra recorded from solution forms almost have isotropic character.

Guveli, Sukriye/0000-0001-7384-822X; Ozdemir, Namik/0000-0003-3371-9874; KOCA, ATIF/0000-0003-0141-5817; Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000343922800061 Mixed ligand nickel(II) complexes of 5-chloro-2-hydroxybenzophenone-N-R-thiosemicarbazone (R: -CH3 (L-1), -CH2-CH=CH2 (L-II)) and triphenylphosphine were synthesized. The structures of the complexes were characterized by elemental analysis, IR, H-1 and P-31 NMR spectroscopy, conductivity, electrochemical and magnetic moment measurements, and single-crystal X-ray diffraction technique. The two nickel(II) complexes have a square planar geometry containing O, N, and S atoms of the thiosemicarbazone, and the P atom of triphenylphosphine. The electrochemical behaviors of the thiosemicarbazone ligands and the nickel complexes were studied using cyclic voltammetry and square wave voltammetry. The redox processes of the compounds were significantly influenced by the central metal ions and the nature of the substituents on the thiosemicarbazones, which are the important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of the electro-generated species of the complexes. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [BAP 16682, UDP-26770] This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University (Project Numbers: BAP 16682 and UDP-26770).

The nickel(II), iron(III) and oxovanadium(IV) complexes of the N2O2 chelating thiosemicarbazones were synthesized using 4-hydroxysalicyladehyde-S-methylthiosemicarbazone and R-1-substitute-salicylaldehyde (R-1: 4-OH, H) in the presence of Ni(II), Fe(III), VO(IV) ions by the template reaction. The structures of the thiosemicarbazone complexes were characterized by FT-IR, H-1 NMR, elemental, ESI-MS and APCI-MS analysis. The synthesized compounds were screened for their antioxidant capacity by using the cupric reducing antioxidant capacity (CUPRAC) method. Trolox equivalent antioxidant capacity (TEAC) of iron(III) complex, 1c, was measured to be higher than that of the other complexes. Other parameters of antioxidant activity (scavenging effects on OH, O-2(-) and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities. (c) 2014 Elsevier B.V. All rights reserved.

Ozdemir, Namik/0000-0003-3371-9874; Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000327421300002 Three alkylated thiosemicarbazones (1-3) substituted on sulfur were synthesized using 5-bromosalicylaldehyde as starting material. The template reactions of the S-alkyl-thiosemicarbazones in the presence of dioxouranium(VI) were investigated. Six dioxouranium(VI) (1a-3b) complexes were synthesized. Propyl or allyl alcohol used as second ligand completed the seventh coordination site of UO22+. The synthesized thiosemicarbazones and template complexes were characterized by elemental analysis, UV-visible, FTIR, and H-1 NMR. The structure of the dioxouranium(VI) complex, [UO2L(allylalcohol)], was studied by single-crystal diffraction. The uranium is seven-coordinate in a pentagonal-bipyramidal arrangement with two oxo groups occupying the apical positions. Scientific Research Projects Coordination Unit of Istanbul UniversityIstanbul University [T14/15122006, BYP-12214] This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University (Project No: T14/15122006 and BYP-12214).

KOCA, ATIF/0000-0003-0141-5817; Ozdemir, Namik/0000-0003-3371-9874; Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000283147300026 PubMed: 20922238 The stable uranyl complexes, [UO2(L)C9H19OH], were obtained from 3,5-dichlorosalicyl-(L-I) and salicyl-aldehyde-S-propyl-thiosemicarbazones (L-II) with substituted-salicylaldehyde in nonyl alcohol. The structures of the complexes have been characterized by elemental analysis, IR, H-1 NMR, conductivity, magnetic moment measurements, cyclic voltammetry, thermal gravimetric analysis and single crystal X-ray diffraction technique. The U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry. The relative orientations of the nonyl alcohol and S-propyl group in the title complexes are completely different due to different crystal packing. Electrochemical behaviors of the thiosemicarbazone ligands and the uranyl complexes were studied using cyclic voltammetry and square wave voltammetry. Redox processes of the compounds are significantly influenced by the central metal ions and the nature of substituents on the thiosemicarbazones, which are important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of electro-generated species of the complexes. Istanbul UniversityIstanbul University; Research Centre of Ondokuz Mayis UniversityOndokuz Mayis University [F-461] Funding of our research from the Research Fund of Istanbul University and the Research Centre of Ondokuz Mayis University (Project No: F-461) is gratefully acknowledged.

WOS: 000273813000014 Mixed-ligand ternary cobalt(III) complexes consisting of N,N,N',N'-tetramethylethylenediamine (tmen), R-salicylaldehyde-N(4)-allyl/methyl thiosemicarbazones (R=3-OMe (L-I/L-II) or H (L-III/L-IV) and azide, of general formula [CoL(tmen)(N-3)], were synthesized and characterized by physico-chemical and spectroscopic methods. The crystal structure of [CoLI(tmen)(N-3)] has a slightly distorted octahedral coordination geometry involving the O, N and S atoms of thiosemicarbazone. Research Fund of Istanbul UniversityIstanbul University This work was supported by the Research Fund of Istanbul University.

The S-methyl-thiosemicarbazones of the 2-hydroxy-R-benzaldehyde (R= H, 3-OH 3-OCH3 or 4-OCH3) reacted with the corresponding aldehydes in the presence of FeCl3 and NiCl2. New ONNO chelates of iron(III) and nickel(II) with hydroxy- or methoxy-substitued N 1,N 4-diarylidene-S-methyl-thiosemicarbazones were characterized by means of elemental analysis, conductivity and magnetic measurements, UV-Vis, IR and 1H-NMR spectroscopies. Cytotoxic activities of the compounds were determined using K562 chronic myeloid leukemia and ECV304 human endothelial cell lines by MTT assay. It was determined that monochloro N 1-4-methoxysalicylidene-N 4-4-methoxysalicylidene-S-methyl-thiosemicarbazidato-iron(III) complex showed selective anti-leukemic effects in K562 cells while has no effect in ECV304 cells in the 0.53 μg/ml (IC50) concentrations. Also, some methoxy-substitued nickel(II) chelates exhibit high cytotoxic activitiy against both of these cell lines in low concentrations. Cytotoxicity data were evaluated depending on cell lines origin and position of the substituents on aromatic rings.

Ulkuseven, Bahri/0000-0001-6342-1505 WOS: 000261912300017 The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone [R: H (L-1); Br (L-2)] with {M-II(PPh3)nCl(2)] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh3)] and [Ru(HL)(2)(PPh3)(2)]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N. S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV-Vis, APCI-MS, H-1 and P-31 NMR spectroscopies. The structures of [Ni(L-2)(PPh3)] (II) and [Ru((LH)-H-1)(2)(PPh3)(2)] (III) were determined by single crystal X-ray diffraction. (C) 2008 Elsevier Ltd. All rights reserved. Istanbul UniversityIstanbul University [233/29042004, 516/050506]; Faculty of Arts and Sciences, Ondokuz Mayis University, TurkeyOndokuz Mayis University [F.279] This work was supported by the Research Fund of Istanbul University. Project number, 233/29042004 and 516/050506. The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayis University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

A new oxovanadium(IV) chelate [VOL] (L: N1-2,4-dihydroxybenzylidene-N4-2-hydroxybenzylidene-S-methyl-thiosemicarbazidato) was synthesized and characterized by elemental analysis, conductivity and magnetic measurements, UV–vis, IR, EPR spectroscopy and mass spectrometry. The biochemical and immunohistochemical effects of the administration of the vanadium complex (VOL) into the pancreas of normal and streptozotocin-induced diabetic rats were profoundly investigated. The animals were randomly divided into four groups. Group I: control (intact) animals. Group II: control animals administered with VOL. Group III: STZ-induced diabetic animals. Group IV: STZ-induced diabetic animals administered with VOL. VOL was given to some of the experimental animals by gavage at a dose of 0.2 mM/kg every day for 12 days. Blood samples were collected from animals, on 0 and 1, 6 and 12 days after STZ injection. On day 12, the pancreatic tissues were taken from the animals. The tissue sections were labelled with streptavidin biotin peroxidase technique for insulin. In the diabetic group, the blood glucose levels, aspartate and alanine transaminases, alkaline phosphatase activities were increased. But, in the diabetic + VOL groups, the blood glucose levels, aspartate and alanine transaminases, alkaline phosphatase activities were reduced. In the diabetic group, a decrease in the pancreatic glutathione levels, glutathione peroxidase and superoxide dismutase activities and an increase in the pancreatic lipid peroxidation level and catalase activities were observed. The administration of VOL to the diabetic rats reversed this diabetic effect due to its insulinomimetic effects. According to the immunohistochemical and biochemical results obtained, it was concluded that VOL can regenerate B cells of the pancreas in experimental diabetes and has an antidiabetic and protective effects on the pancreas.

In this study, in situ monitoring of single lap joint of woven glass fabric reinforced epoxy composites modified with multi-walled carbon nanotubes (MWCNTs) is presented. Woven glass fibre reinforced/epoxy composite plates modified with 3% wt. highly electrically conductive MWCNTs were manufactured by hand lay-up process for obtaining adherends. MWCNTs were used in 1% and 2% by weight in order to investigate the effect of the MWCNTs level on the shear lap joint strength and the self-sensing sensitivity of bonded area. One, four, and seven plies of adhesive woven cloths were employed for bonding adherends to examine the thickness effect on both the shear lap joint strength and the self-sensing sensitivity of bonded area. In order to provide low electrical contact resistance, woven carbon fibres were placed on the top and bottom of the glass fibre layer during production. Results indicate that the health monitoring of lap joints in the woven glass reinforced epoxy composites can be successfully achieved.