Veysel T. Yilmaz

Sonochemical synthesis of nano-scale mixed-ligands lead(II) coordination polymers as precursors for preparation of PbO and PbBr(OH) nano-structures; thermal, structural and X-ray powder diffraction studies

Nano-structures of two new Pb(II) two-dimensional coordination polymers, [Pb(micro-4-pyc)(micro-NCS)(micro-H(2)O)](n) (1) and [Pb(micro-4-pyc)(micro-N(3))(micro-H(2)O)](n) (2), 4-Hpyc=4-pyridinecarboxylic acid were synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and consist of two-dimensional polymeric units. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses and compared. Pb(2)(SO(4))O and PbO nanoparticles were obtained by calcination of the nano-structures of compounds 1 and 2 at 600 degrees C, respectively.

Thermal Studies on Solid Complexes of Saccharin with Divalent Transition Metal Ions

The thermal decompositions of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of saccharin were studied in static air atmosphere. All of the complexes contain four molecules of coordination water and two molecules of crystallization water. The water molecules were removed in a single stage, except from the Zn(II) complex, which exhibited two endothermic effects. The dehydration process was usually accompanied by a sharp colour change. The anhydrous complexes exhibited a phase transition and the decomposition or combustion of saccharin occurred in the second and subsequent stages. The final decomposition products were identified by XRPD as the respective metal oxides. The kinetic parameters, such as the order of reaction and energy of activation for the dehydration stage, were evaluated and the thermal stabilities of the complexes are discussed.

Different coordination modes of saccharin in the metal complexes with 2-pyridylmethanol: synthesis, spectroscopic, thermal and structural characterization

The reaction of [M(sac)2(H2O)4]/2H2O, where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II), and sac is the saccharinate anion, with 2-pyridylmethanol (mpy) result in the formation of the new complexes, which have been characterized by elemental analyses, magnetic measurements, FT-IR spectroscopy, thermal analysis and X-ray diffraction methods. The [Co(sac)2(mpy)2 ]( 3) and [Ni(sac)2(mpy)2 ]( 4) complexes are isomorphous with the triclinic space group the two sac ligands in both 3 and 4 exhibit unusual and non-equivalent coordination. One of them coordinates to the metals through the imino nitrogen atom, while the other is bonded to the metals with the carbonyl oxygen atom behaving as an ambidentate ligand. The [Cu(sac)2(mpy)2 ]( 5) complex is centrosymmetric and crystallizes in orthorhombic space group and both sac ligands in (5) are N coordinated. [Hg2(sac)4(mpy)2 ]( 8) crystallizes in monoclinic space group P 21/n .I n8, the mpy ligands acts as a bridge between the mercury two mercury(II) centres and the complex 8 consists of one-dimensional chains in which dimeric [Hg2(sac)4(mpy)2] units are sequentially bridged by bis-bidentate sac ligands forming a coordination polymer. In all cases, the metal atoms are six-coordinate. The mpy molecules act as a bidentate N - and O-donor ligand in 1/7. Thermal decomposition of the complexes in air results in removal of mpy ligands and formation of stable metal saccharinates as intermediates, which also decompose at higher temperatures to give the corresponding metal oxides. # 2002 Elsevier Science Ltd. All rights reserved.

Saccharin complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with ethanolamine and diethanolamine: synthesis, spectroscopic and thermal characteristics. Crystal structures of [Zn(ea)2(sac)2] and [Cu2(μ-dea)2(sac)2]

Abstract New mixed ligand Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) complexes of saccharin (sac) with ethanolamine (ea) and diethanolamine (dea) were synthesized and characterized by elemental analyses, magnetic moments, UV–Vis and IR spectra. The Co(II)–ea, Co(II)–dea and Cu(II)–dea complexes are dimeric, while all the other complexes of ea and dea are mononuclear. The crystal structures of [Zn(ea)2(sac)2] and [Cu2(μ-dea)2(sac)2] complexes were determined by single crystal X-ray diffraction. In the Zn(II) complex, the Zn(II) ion sits on a center of symmetry and is octahedrally coordinated by two bidentate ea (N, O) and two monodentate sac (N) ligands. The centrosymmetric binuclear Cu(II) complex contains two strongly distorted square-planarly coordinated Cu(II) ions bridged by two alkoxo groups of the deprotonated dea. The dea ligand also coordinates to the Cu(II) ions through its nitrogen, while the other ethanolic group does not involve in coordination. The saccharinate anion coordinates to the Cu(II) ion with its nitrogen. Thermal behavior of the complexes was studied using DTA and TG in nitrogen atmosphere. Endothermic degradation of the ea and dea ligands occurs in the first stages of decomposition and the sac anions decompose at higher temperatures to give corresponding metal oxides or metals.

Thermal decomposition of β-cyclodextrin inclusion complexes of ferrocene and their derivatives

Abstract The thermal decomposition of the solid inclusion complexes of ferrocene and its derivatives with β-CD was studied by DTA, TG and DTG. The inclusion complexes contain crystallization water and the first decomposition stage corresponds to the dehydration of the complexes. The second stage is related to the liberation of the ferrocene and its derivatives, and the degradation of the β-CD structure takes place in the third stage. However, the second and third stages of decomposition for some of the inclusion complexes occur in the same temperature ranges and are impossible to distinguish. The final decomposition products formed around 500°C consist mainly of Fe2O3. The thermal behaviour of physical mixtures of these ferrocene derivatives and β-CD was also investigated. The thermal analysis results show that the interaction of ferrocene and its derivatives with β-CD is a chemical phenomenon. The ferrocene derivatives gain an additional thermal stability after inclusion complexation into the β-CD cavity. Thermal analysis methods can be used satisfactorily for the recognition of inclusion complexation.

trans-Dichloridopalladium(II) and platinum(II) complexes with 2-(hydroxymethyl)pyridine and 2-(2-hydroxyethyl)pyridine: synthesis, structural characterization, DNA binding and in vitro cytotoxicity studies.

Four trans-palladium(II)- and trans-platinum(II)-chlorido complexes, trans-[PdCl(2)(2-hmpy)(2)] (1), trans-[PtCl(2)(2-hmpy)(2)] (2), trans-[PdCl(2)(2-hepy)(2)] (3) and trans-[PtCl(2)(2-hepy)(2)] (4) (2-hmpy = 2-(hydroxymethyl)pyridine and 2-hepy = 2-(2-hydroxyethyl)pyridine), have been synthesized and characterized by elemental analysis, IR, NMR, and X-ray diffraction. The binding properties of these complexes with fish sperm DNA (FS-DNA) were investigated by UV titration, viscosity, thermal denaturation and electrophoresis measurements. The complexes can bind to FS-DNA and complex 4 exhibits the highest binding constant. Gel electrophoresis assay demonstrates that all the complexes can cleave the pCMV-βgal plasmid DNA to a different degree. The cytotoxic activities of the complexes were tested against four different cancer cell lines. In general, the platinum(II) complexes are more effective than the isostructural palladium(II) complexes. Complex 4 shows high anticancer activity, compared to transplatin, cisplatin, carboplatin and oxaliplatin.

Cell death-inducing effect of novel palladium(II) and platinum(II) complexes on non-small cell lung cancer cells in vitro

PurposeTreatment for lung cancer is still far from satisfying rates. Therefore, there is a need for novel anticancer agents. For this purpose, novel platinum and palladium complexes {[Pd(sac)(terpy)](sac)·4H2O (Complex 1), [Pt(sac)(terpy)](sac)·5H2O (Complex 2), [PdCl(terpy)](sac)·2H2O (Complex 3), [PtCl(terpy)](sac)·2H2O (Complex 4)} have been tested against three different non-small cell lung cancer cell lines (A549, H1299, PC-3).MethodsGrowth-inhibiting effects have been tested by the MTT and ATP viability assays. Apoptosis has been detected by the caspase-cleaved cytokeratin 18 (M30-antigen) assay. Necrosis has been detected by staining the cells with fluorescent dyes. Mitotic index has been calculated by counting the mitotic figures after staining with hematoxylin.ResultsThe complex 3 exhibited significant anti-growth effects, and its anti-growth effect was more powerful than that of cisplatin that is a standard chemotherapeutic agent for this type of cancer. The complexes did not induce apoptosis, while necrosis clearly took place.ConclusionsNovel Pd(II) complex ([PdCl(terpy)](sac)·2H2O) seems to represent a potentially active drug against non-small cell lung cancer cell lines, and further studies in vivo are warranted.

Di- and triethanolamine complexes of Co(II), Ni(II), Cu(II) and Zn(II) with thiocyanate: synthesis, spectral and thermal studies. Crystal structure of dimeric Cu(II) complex with deprotonated diethanolamine, [Cu2(μ-dea)2(NCS)2]

Abstract New mixed ligand Co(II), Ni(II), Cu(II) and Zn(II) complexes of di- (dea) and triethanolamine (tea) with thiocyanate were synthesized and characterized by elemental analyses, magnetic moments, UV–Vis and IR spectra. All the metal complexes of tea, and the Ni(II) and Zn(II) complexes of dea are mononuclear, while the Co(II) and Cu(II) complexes of dea are dimeric. The crystal structure of the bis(μ-diethanolaminato) bis(isothiocyanato)dicopper(II) complex were determined by single crystal X-ray diffraction. The centrosymmetric binuclear complex contains two strongly distorted square-pyramidally coordinated copper ions bound together by two alkoxo bridges. The bridging oxygen is a deprotonated oxygen of the ethanolic group of dea. The dea ligand also coordinates to the Cu(II) ions through its nitrogen, while the other ethanolic group does not involve in coordination. The thiocyanate anion coordinates to the Cu(II) ion with its nitrogen. Thermal reactivity of the complexes was studied using DTA and TG. Degradation of the amine ligands in the complexes occurs in the first stages of decomposition and the thiocyanate anions decompose at higher temperatures to give corresponding metal oxides.

Metal Complexes of Saccharin with the N-(2-hydroxyethyl)-ethylenediamine Ligand: Synthesis, Characterization and Spectroscopic Examination. Crystal Structures of trans- Bis(Saccharinato)Bis{N-(2-hydroxyethyl)-Ethylenediamine} copper(II) and Cadmium(II)

The novel transition metal saccharinato complexes of N-(2-hydroxyethyl)-ethylendiamine (HydEt-en) have been synthesized and characterized by elemental analyses, magnetic moments, UV-Vis and IR spectra. Coordination behaviour of HydEt-en has been studied. The Mn(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) form mononuclear complexes, while the Fe(II) and Co(II) complexes are dimeric. The crystal structures of the [Cu(sac)2(HydEt-en)2] and [Cd(sac)2(HydEt-en)2] complexes, where sac is the deprotonated form of saccharin, were determined by x-ray diffraction. The metal ions are octahedrally coordinated by these ligands. The amine ligand acts as a bidentate N-donor ligand and its ethanol group is not involved in coordination. The sac ions coordinate through the deprotonated N as a monodentate ligand. The NH and OH groups of the amine ligand are involved in intra- and intermolecular hydrogen bonding with the carbonyl and sulphonyl oxygens of the sac ions to form a three-dimensional infinite network.

Synthesis, structural characterization and cell death-inducing effect of novel palladium(II) and platinum(II) saccharinate complexes with 2-(hydroxymethyl)pyridine and 2-(2-hydroxyethyl)pyridine on cancer cells in vitro.

Four palladium(II) and platinum(II) saccharinate (sac) complexes with 2-(hydroxymethyl)pyridine (2-hmpy) and 2-(2-hydroxyethyl)pyridine (2-hepy), namely trans-[Pd(2-hmpy)2(sac)2]·H2O (1), trans-[Pt(2-hmpy)2(sac)2]·3H2O (2), trans-[Pd(2-hepy)2(sac)2] (3) and trans-[Pt(2-hepy)2(sac)2] (4), have been synthesized and characterized by elemental analysis, UV-vis, IR and NMR. Single crystal X-ray analysis reveals that the metal(II) ions in each complex are coordinated by two sac and two 2-hmpy or 2-hepy ligands with a trans arrangement. Anticancer effects of 1-4 were tested against four different cancer cell lines (A549 and PC3 for lung cancer, C6 for glioblastoma, and Hep3B for liver cancer). Cytotoxicity was first screened by the MTT assay and the results were further confirmed by the ATP assay. The mode of cell death was determined by both histological and biochemical methods. Among the metal complexes, complex 2 resulted in relatively stronger anti-growth effect in a dose-dependent manner (3.13-200μM), compared to the others, by inducing apoptosis.