In this study, the effect of a donor ligand on the stabilization of a carbonyl pyrazine tungsten complex was studied. The pentacarbonylpyrazinetungsten(0) complex could be formed from the photolysis of hexacarbonyltungsten(0) in the presence of pyrazine and could be isolated as crystalline solid. However, the complex was found to be unstable in solution, being converted to a bimetallic complex, (CO)5W(pyz)W(CO)5 and free pyrazine molecule. Two complexes exist in solution at equilibrium. The equilibrium constant could be determined by 1H-NMR spectroscopy and found to be 0.0396 at 25&deg / C. To test whether the introduction of a second pyrazine ligand might provide stability for the carbonyl-pyrazine-tungsten complex, W(CO)4(pyz)2 was attempted to be synthesized. The cis-W(CO)4(pyz)2 complex could be generated from the thermal substitution reaction of cis-W(CO)4(piperidine)2 with excess pyrazine in dichloromethane. However, this complex could not be isolated because of the lack of stability. The complex could only be identified by IR spectroscopy in solution. To stabilize the pentacarbonylpyrazinetungsten(0) complex, trimethylphosphite was introduced to the complex as a donor ligand. For this purpose, cis-W(CO)4[P(OCH3)3](thf), photogenerated from W(CO)5[P(OCH3)3] in tetrahydrofuran (thf), was reacted with pyrazine. The replacement of tetrahydrofuran with pyrazine (pyz) yielded cis-W(CO)4[P(OCH3)3](pyz). The complex could be isolated from the reaction solution and characterized by means of IR, 1H-, 13C-, 31P-NMR, and Mass spectroscopies. The introduction of P(OCH3)3 has proved that a donor ligand will strengthen the metal-pyrazine bond and thus stabilizes the complex. As a result of this stabilization, the complex could be isolated as the first example of tungsten pyrazine complexes that contain a donor ligand.

Pentacarbonylacryloylferrocenetungsten(0) complex was synthesized photochemically from hexacarbonyltungsten(0) and acryloyferrocene (acfc). UV irradiation of W(CO)6 in the presence of acryloylferrocene at 10 oC for 4 hours in n-hexane solution generates the W(CO)5(&amp / #61544 / 2-acfc) complex as the sole monosubstitution product of the photolysis, as monitored by FT-IR spectroscopy. The product complex could be isolated from the reaction solution and characterized by IR, Raman, 1H-NMR, 13C-NMR spectroscopies, mass spectrometry and elemental analysis. The complex was found to be unstable in solution and to decompose to the parent W(CO)6 complex and free acryloylferrocene molecule. The instability of the complex makes its isolation as analytically pure substance difficult. In order to stabilize the tungsten-olefin bond, trimethylphosphite was introduced as a donor ligand into the molecule. Thus, a complex containing a donor ligand in addition to the olefinic ligand was prepared starting with W(CO)6, trimethylphosphite, and acryloylferrocene. UV irradiation of W(CO)5[P(OMe)3] with acryloylferrocene in n-hexane solution at room temperature generates W(CO)4[P(OMe)3](&amp / #61544 / 2-acfc), which was isolated from the reaction solution and characterized by IR, 1H-NMR, 13C-NMR spectroscopies and mass spectrometry. The complex was found to have a cis arrangement of four CO groups in the pseudo-octahedral geometry. However, the cis-W(CO)4[P(OMe)3](&amp / #61544 / 2-acfc) complex was found to be less stable than W(CO)5(&amp / #61544 / 2-acfc).

Today, ceramic, polymer, and composite nanofibers are among the most charming materials for nanotechnology. Because of their small characteristic dimension, high surface area, and microstructural features, they provide unique mechanical, optical, electronic, magnetic, and chemical properties for an extensive variety of materials applications. Electrospinning provides an effective way of the nanofiber production in a nanometer scale. This technique utilizes a high voltage DC to create a strong electric field and a certain charge density in a viscous solution contained in a pipette. As a result, fibers with diameters ranging from the micrometer to nanometer are formed from this charged solution. This study deals with, the fabrication of alumina borosilicate ceramic nanofibers using electrospinning technique. Alumina borosilicates contain important components having intriguing characteristics for many applications and have been widely studied with different compositions. In this study, alumina borosilicate/PVA solution was prepared using the conventional sol-gel method. Polyvinyl alcohol (PVA) was added into this solution to increase the viscosity for electrospinning. After the alumina borosilicate/PVA solution was electrospun into fibers, high temperature sintering was carried to obtain ceramic alumina borosilicate fibers. The products were characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform-infrared spectroscopy (FT-IR), and thermogravimetric/differential thermal analysis (TG-DTA) techniques.

The reaction of potassiumtetrachloroplatinate with 2-aminothiophenol, yielded a dark blue solid product. This work is about the characterization of this dark blue solid and the investigation of its binding interaction to DNA and enzyme activity. The blue solid product or the &ldquo / blue complex&rdquo / (as we called it in this work) is soluble in acetone, acetonitrile and DMSO yielding a blue solution. It is stable in solution and has a very strong absorption band at 724 nm. The product is paramagnetic and displays one kind of platinum in XPS (platinum binding energies were obtained at 71.1 and 74.6 eV, respectively). The elemental (C, H, N, S, Pt) analysis indicated that the platinum to ligand (2- aminothiophenolate) mole ratio is 1:2. The interpretation of the data collected from elemental analysis and ESR, XPS, NMR, CV measurements leads to conclude that the blue complex prepared in this work is a new platinum blues. This is the first example of platinum blues, in which the bridging ligand is a nitrogen and sulfur donor one. The proposed structure can be visualized as a dimer of binuclear head-tohead isomer of the green product, with C2h symmetry. The band at 724 nm is assigned to an allowed electronic transition from a metal-5dz orbitals based MO to metal-6pz orbitals based MO in tetranuclear core. In order to determine the binding mode of the blue complex to ct-DNA, electronic absorption spectroscopy is employed and hyperchromism about 17.5 percent is observed, which indicates a weak binding of the blue complex to DNA, such as electrostatic interaction of metal ions or H-bonding through the hydroxyl group of the complex. Voltammetric titration carried out in solution suggested the preferential stabilization of Pt(III) to Pt(II) on binding to DNA. The blue complex inhibits the GSTs activity between 45-200 micromolar, in sheep liver GST enzyme. The GST enzymes causes drug resistance, therefore inhibition of this enzyme suggests that this complex can be used in combined chemotherapy.

ABSTRACT AXIAL LIGAND SUBSTITUTION REACTION KINETICS OF PYRIMIDINE-2-THIONATO BRIDGED BINUCLEAR PLATINUM(III) COMPLEXES G&ouml / y, Aytun&ccedil / M. S. Department of Chemistry Supervisor: Prof. Dr. H&uuml / seyin iS&ccedil / i Co-supervisor: Assoc. Prof.Dr. Seniz &Ouml / zalp Yaman September 2007, 89 pages The kinetics of the ligand substitution reactions, which is represented by the equation, [Pt2(C4H3N2S)4X2] + 2Y- Pt2(C4H3N2S)4Y2 + 2X- where X- = Cl-, Br-, I- and Y- = Cl-, Br-, I- are studied in acetonitrile in the presence of excess Y- ion concentrations, under constant ionic strength. All reactions are reversible. The rate of the above reaction is dependent on binuclear complex and entering ligand concentrations. Thus general rate equation can be written as Rate = k [Y-]a[Pt2(C4H3N2S)4X2]b The reaction rates are first order with respect to the substrate complex (b=1). The experimentally determined values of the order of the reaction with repect to entering ligand, &ldquo / a&rdquo / , are 0.96&plusmn / 0.057 (X=I-, Y=Cl-), -0.49&plusmn / 0.037 (X=Cl-, Y=I-), 0.28&plusmn / 0.023 (X=I-, Y=Br-), 0.48&plusmn / 0.044 (X=Br-, Y=I-), 0.53&plusmn / 0.042 (X=Br-, Y=Cl-), and -0.21&plusmn / 0.014 (X=Cl-, Y=Br-). The rate constants are 12.1&plusmn / 2.05 M-1s-1 (X=I-, Y=Cl-), (5.7&plusmn / 1.6)x10-3 M1/2s-1 (X=Cl-, Y=I-), 0.3&plusmn / 0.27 M-0.3s-1 (X=I-, Y=Br-), 0.53&plusmn / 0.11 M-1/2s-1 (X=Br-, Y=I-), 1.74&plusmn / 0.16 M-1/2s-1 (X=Br-, Y=Cl-), and 1.71&plusmn / 0.37x10-2 M0.2s-1 (X=Cl-, Y=Br-). To obtain information about the energetics of the reactions, the temperature dependence of the rate constants is determined and the activation parameters &amp / #916 / H* and &amp / #916 / S* are calculated. The values &amp / #916 / S* are negative and, in the range of -81 and -236 J K-1 mol-1. These results support an associative-interchange, Ia, mechanism. All data obtained in this work are used to propose a mechanism which will be consistent with the experimentally determined rate law.

In this work , metal functional polymers, namely Cr-PS-b-P2VP, Co-PS-b-P2VP, Au-PS-b-P2VP, Fe-PS-b-P2VP and Mo-PS-b-P2VP were prepared by thermal reaction of hexacarbonylchromium, Cr(CO)6, octacarbonyldicobalt,Co2(CO)8, hydrogentetrachloroaurate(III), H(AuCl4).4H2O, trichloroiron(III), FeCl3.6H2O, molybdenum(VI)oxide, MoO3 and PS-b-P2VP. TEM images indicated formation of AuIII, Cr and Co nanoparticles. On the other hand, crystalline structures were detected for Fe-PS-b-P2VP and Mo-PS-b-P2VP. Samples involving nanoparticles were further characterized by FTIR, UV-Vis and direct pyrolysis mass spectroscopy techniques. FTIR analysis indicated dissapearance of characteristic carbonyl peaks of Cr(CO)6 and Co2(CO)8 for Cr-PS-b-P2VP and Co-PS-b-P2VP samples. The appearance of a peak at about 467 cm-1 supported the formation of metal-nitrogen bond. Pyrolysis mass spectrometry analysis showed an increase in the thermal stability of P2VP chains involving coordinated pyridine units. The thermal stability of these chains increased in the order Co&lt / Cr &lt / Au3+ indicating stronger coordination in the same order.

Zeolites are microporous hydrated aluminosilicate crystals containing alkali and/or alkali earth metal cations in their frameworks. Due to their molecular size pores, they can separate molecules according to their size and shape. Zeolites are mostly used in ion exchange, adsorption processes and catalytic applications. The hydrophilic/hydrophobic character of zeolites also makes them favorable materials for adsorption based separations. Recently the potential of zeolite/ceramic composite membranes have been shown in the separation of liquid and gas mixtures. Self-supported zeolite membranes with asymmetric structure can be an alternative to the composite zeolite membranes. Because asymmetric structure may eliminate the problems originated from the differences in thermal expansion coefficients of zeolites and ceramics. In this study tubular zeolite A membranes were prepared on binderless zeolite A supports. The supports were perepared by hydrothermal conversion of amorphous aluminosilicate tubes into zeolite A. The amorphous aluminosilicate powder, which was obtained by filtering the homogenous hydrogel with a composition of 2.5Na2O:1Al2O3:1.7SiO2:150H2O, was mixed with an organic binder (HEC-Hydroxyethyl Cellulose) and water to obtain the paste. The paste was then extruded through a home-made extruder into bars and tubes. These extrudates were dried at room temperature for 24 hours, calcined at 600oC for 2 hours to remove organic binder and finally synthesized at 80oC for 72 hours in hydrothermal conditions to convert amorphous aluminosilicate to zeolite. The effect of composition of the synthesis solution on the crystallinity and morphology of zeolite A tubes and bars were investigated. The crystallization field of zeolite A bars has been established and shown on a ternary phase diagram. Tubes were mechanically stable, typically had a crystallinity over 90% and a macroporosity of 35%. The tubes were composed of highly intergrown crystals of zeolite A. The average particle size was 3.5 &micro / m. The asymmetric membranes were synthesized by growing zeolite A films on binderless zeolite A supports with a geometry of disk, bar and tube. Continuous zeolite A films can only be obtained when the supports were saturated with water prior to synthesis. The film thicknesses were approximately 5 &micro / m on disks and approximately 10 &micro / m on tubes. A method was proposed to prepare self-supported tubular zeolite A membranes in this study.

Zirconium tungstate (ZrW2O8) is a ceramic that shows large isotropic negative thermal expansion over a wide range of temperature. This unique property makes it an interesting candidate for applications where thermal expansion mismatch between components constitutes a problem. ZrW2O8 is typically produced by solid-state reaction between zirconium oxide and tungsten oxide at 1200oC. In some studies, ZrW2O8 precursors have been produced from relatively expensive zirconium and tungsten sources. While the origin of negative thermal expansion has been the main focus in the majority of publications, production of particles with controlled size, distribution and morphology has not been studied extensively. Electrospinning is a simple technique for producing micron/nano sized fibers from polymer solutions. The method can also be used for producing ceramic or polymer/ceramic composite fibers by electrospinning of a mixture of ceramic precursors or ceramic nanoparticles with suitable polymers. Ceramic precursors could be synthesized either by sol-gel or chemical precipitation routes before mixing them with polymer solutions and a final burnout step would be needed, in case the fiber is desired to be composed of the ceramic phase. Electrospinning technique has not been employed to the production of ZrW2O8 ceramic fibers. In this study a novel precursor for ZrW2O8 from relatively cheaper and abundant starting chemicals, namely zirconium acetate and tungstic acid were used. Experimental details of development of the precursor are presented with a discussion on the effects of solution parameters on the phase purity of the fired product. Besides the solution parameters investigated (i.e. solubility of tungstic acid, adjustment of the stoichiometry, final pH of the solution, ageing time), evolution of the heat treatment protocol was used in the production of phase pure ZrW2O8. Second, the suitability of the developed precursor for producing ZrW2O8 in fiber form was investigated. Preliminary studies involved the adjustment of the viscosity of precursor solution for electrospinning with poly (vinyl alcohol) (PVA). Optimum PVA concentration leading to bead-free nanofiber mats and a method to increase the fiber production rate were reported. The characterization of the products was achieved by SEM and XRD.

Lithium tetraborate (Li2B4O7) has aroused interest of scientists since 1960s by the courtesy of the thermoluminescence (TL) property it possesses. Over and above, it found widespread use in surface acoustic wave apparatuses, in sensor sector and in laser technology due to its non linear optical characteristics. For the uses in thermoluminescence dosimetry lithium tetraborate is activated by addition of a variety of metals as dopants. This study comprises the synthesis of lithium tetraborate by two methods (high temperature solid state synthesis and water/solution assisted synthesis) as well as doping and characterization of the material. Lithium tetraborate is readily commercially available in TL dosimetry / hence, the main aim is to specify practical production conditions to pioneer domestic production. In high temperature synthesis, the initial heating was performed at 400oC for 3 hours. Then the samples were heated at 750oC for two hours, intermittently mixed to enhance diffusion and exposed to the same temperature for another two hours. In water/solution assisted synthesis, stoichiometric quantities of reactants were mixed in water by heating and agitating in order to achieve homogenous mixing and good dispersion of the material. The remnant of water was removed from the system by 3 hours initial heating at 150oC. The synthesis stage is followed by doping step where the metals Cu, Ag and In in different proportions were doped in lithium tetraborate by solid state and solution assisted synthesis techniques. Powder X-ray diffraction method was employed for the characterization of the material. The thermal properties of doped and un-doped materials were studied by DTA (Differential Thermal Analyses). Besides, FT-IR (Fourier Transform Infra red) spectrometry analyses were performed in order to detect differences in the bond structure caused by doping The XRD patterns obtained showed that lithium tetraborate production was successful by both high temperature solid state synthesis and solution assisted synthesis Moreover, it was inferred from the XRD results that addition of dopants did not have a sound effect on the crystal structure. Furthermore, the DTA results displayed that addition of different dopants to the structure of lithium tetraborate did not cause any noticeable difference. The extensive TL measurements showed that the TL response of the material produced is affected by production and doping methods.

In this study, differences in glow curves of Mn doped LTB powder samples synthesized with solid and wet synthesis methods and doped by using solid and wet doping techniques were investigated. Firstly, LTB was synthesized by using wet synthesis method which mainly comprises dissolution of reactants in water as solvent. Second way to produce LTB which was used in this study was solid synthesis method. In solid synthesis method, reactants were mixed in powder form. In the second part of the study, LTB produced by two different methods were doped with Mn and additionally Ag, Mg or P by using two different doping techniques. In order to see structural differences between differently synthesized and differently doped LTB samples which contained different amount of dopant powder X-Ray Diffraction (XRD) method was employed. Besides, FTIR (Fourier Transform Infrared) spectroscopy analyses were performed in order to detect differences in the bond structure caused by doping. Additionally, Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) was used to determine the actual amount of dopant in LTB. Also morphological structures of samples were compared by using Scanning Electron Microscopy (SEM). Thermoluminescence measurements were performed with (TLD) Thermoluminescence Dosimeter equipment. XRD and FTIR analysis showed that syntheses of products were done in well success. Addition of dopants did not cause any changes in structural or bonding properties of LTB. It was possible to observe that, synthesis and doping methods and dopant concentration effect the thermoluminescence glow curves of doped LTB.