Magnetite (Fe3O4) thin films were prepared by a sol-gel process in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Xerogel films were obtained by drying the coated films at 110 &deg / C. The films were sintered between 300 &deg / C and 450 &deg / C in order to observe the phases existing in the films at different temperatures. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. DTA analysis showed that, sintering temperature should be selected between 291 &deg / C and 350 &deg / C in order to produce magnetite thin films. Prepared magnetite thin films were characterized by XRD, SEM, AFM, TEM, VSM and UV-Vis spectrometer. In-plane grazing angle diffraction studies showed that magnetite phase was present upon sintering the films at 300 &deg / C. From the SEM studies, it was shown that films with defect free surfaces were obtained and by cross section studies, thickness of the films was found as ~10-200 nm. AFM images showed that no cracks or any other defects on the film surface were present. TEM results proved the existence of single phase magnetite in the produced films. UV-Vis spectrum results showed that transmittance of the films increases with decreasing sintering temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900-1100 nm. Magnetic properties of magnetite thin films were also examined by VSM (Vibrating Sample Magnetometer) and ferromagnetic behaviour was shown using VSM data.

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.

Sol-gel processing routes for encapsulation of double stranded DNA in solid porous silica hosts have been established. The encapsulation was carried out in two steps: hydrolysis of a silica-forming alkoxide-based sol was followed by condensation/gelation to a solid form upon addition of a buffer solution containing DNA molecules. The effects of gelation chemistry and DNA amount on chemical and microstructural properties of resultant silica matrices and on DNA encapsulation efficiency were investigated. The analytical characterization was performed by UV-vis spectroscopy, 29Si nuclear magnetic resonance spectroscopy and by nitrogen adsorption studies. It was demonstrated that DNA incorporation had a pH-dependent catalytic effect on gelation kinetics and promoted silica network completion. In addition, the scale of porosity and the average pore size of the resultant silica increased with gelation pH and also with DNA-buffer solution in the starting sol-gel formulation. The chemistry-derived pore size variation controls the DNA encapsulation efficiency in the silica matrices and the DNA holding capacity strongly depends on the scale of the porosity attained. The selective adsorption of ethidium bromide- a DNA-intercalative reagent molecule- on DNA-silica gels confirmed that the DNA molecules remained entrapped within the silica host in their native state without any deterioration. Besides pure silica, amine-functionalized hybrid silica hosts were also formed by sol-gel. The hybrid gels were found not to be suitable for DNA encapsulation, as these matrices dissolve in aqueous environment due to incomplete silica network formation. The DNA-doped silica hosts may provide promising matrices for development of biosensors, bioreactors and bioassay platforms.

Titanium dioxide (TiO2), a semiconductor, has been used in many areas like heterogeneous photocatalysis. In the present study, the effect of hydrothermal treatment conditions and the use of carbon nanotubes on the photocatalytic activity of sol-gel synthesized titanium dioxide were examined. The anatase particles were transformed into layered trititanate particles with either nanotube or nanoplate structure by hydrothermal treatment under the alkaline conditions. Post hydrothermal treatment under neutral conditions was also applied and mesoporous particles were transformed into nanostructured, highly crystalline and ordered anatase particles. Photocatalytic activities of hydrothermally treated samples were determined against Escherichia coli under solar irradiation. Results showed that hydrothermal treatment under alkaline conditions improved the photocatalytic activity. However, although being highly crystalline, after post treatment, a limited activity was obtained because of dehydration of active (101) face of anatase. Nevertheless, TiO2&amp / #8217 / s initial inactivation constant rose from 0.6 to 2.9 hr-1 after regeneration of active sites in aqueous medium under solar irradiation. In order to enhance the surface area and improve activity, multi-walled carbon nanotubes were utilized during the synthesis of TiO2. The effect of calcination conditions and presence of sodium, iron and cobalt on the photocatalytic activity were also studied. For these samples, photocatalytic activities were tested with methylene blue solution under UV irradiation. It was observed that the utilization of CNTs enhanced both the surface area and the activity. Compositions with highest CNT content had better activities for their ability to delay charge recombination. While pure TiO2&amp / #8216 / s initial decomposition constant was 0.8 hr-1, with sodium doping the best value of 1.9 hr-1 was achieved.

The aim of this study was to investigate the viability of patterning by immobilization, photocatalytic removal, and re-immobilization steps of the enzyme on photocatalytically active thin films for biosensor fabrication purposes. For this aim, TiO2-SiO2-Au sol-gel colloids were synthesized and deposited on glass substrates as thin films by dip coating. Cysteamine linker was assembled on gold nanoparticles to functionalize thin films with amine groups for immobilization of model enzyme invertase. Effect of immobilization temperature, enzyme concentration of the immobilization solution and immobilization period on invertase immobilization were investigated. The immobilized invertase activity was found independent from the immobilization temperature in the range tested (4oC-room temperature). The optimum enzyme concentration and period for immobilization was determined as 10&micro / g/ml and 12 hours respectively. The resulting invertase immobilized thin films showed high storage stability retaining more that 50% of their initial activity after 9 weeks of storage. Photocatalytic enzyme removal and re-immobilization studies were carried out by irradiating the invertase immobilized thin films with blacklight. Upon 30 minutes of irradiation, immobilized invertase was completely and irreversibly inactivated. Initial immobilized invertase activity (before the irradiation) was attained when invertase was re-immobilized on thin films that were irradiated for 5 hours. Thus it was inferred that with sufficient exposure, enzymes can be completely removed from the surfaces which makes the re-immobilization possible. The possibility of enzyme removal with photocatalytic activity and re-immobilization can pave the way to new patterning techniques to produce multi-enzyme electrode arrays.

The aim of this study was to immobilize the redox enzyme laccase over TiO2-SiO2-Au thin film coated ITO glass substrates in order to prepare electrochemically active surfaces for biosensor applications. Colloidal TiO2-SiO2-Au solution was synthesized by sol-gel route and thin film was deposited onto the substrates by dipcoating method. The cysteamine was utilized as a linker for immobilization of enzyme covalently through gold active sites. Preliminary studies were conducted by using invertase as model enzyme and Pyrex glasses as substrates. The effect of immobilization parameters such as immobilization temperature, concentration of enzyme deposition solution, immobilization time for laccase were examined. Leakage studies were conducted and storage stability of immobilized laccase was determined. Highest laccase activity was achieved when immobilization was performed with 50 &micro / g/ml solution at 4&deg / C for 2 hours. Laccase activity decreased after 4 hours of impregnation in enzyme solution. Laccase leakage was observed in the first usage of substrates and 55% activity decrease was determined in the subsequent use which might be attributed to the presence of uncovalently adsorbed enzyme on the fresh samples. In air and in buffer storage stabilities were also tested. It was found that the activity of samples almost vanished after 6 days regardless of storage conditions. Both enzymes had more activity on ITO substrate.

The aim of this study is to produce maghemite nanoparticles by using different production methods. To achieve this purpose Sol-Gel Processing and Microwave Synthesis methods were employed. Suitable characterization techniques like XRD, TEM, BET, and VSM were performed to control the properties of the synthesized particles whether they are suitable for certain applications. In the sol-gel part of the study two different routes were employed to obtain maghemite nanoparticles. In the first route TEOS (tetraethoxysilane) was used as the precursor. Approximate particle sizes of these samples lie between 12.0-23.4 nm. From the magnetization measurements saturation magnetization (Ms) values are obtained between 4-12 emu/g. In the second route of the sol-gel method ethylene glycol and diethylene glycol were used as starting materials. Ms value was found as 28 emu/g for the ethylene glycol sample as the highest magnetization value due to having the highest amount of maghemite phase. The superparamagnetic behavior observed in these samples was tried to explain by curve fitting. Langevin and tangent hyperbolic functions were used to fit the magnetization curves. From the XRD study particle sizes of these samples lie in the 4.0-48.5 nm range and these results are consistent with the size distributions obtained from the TEM study. In the last part of the study microwave method was used to produce maghemite nanoparticles. Most of the samples contain maghemite and hematite phases together and particle sizes were between 3-30 nm. Ms values of these microwave samples were lower than that of the sol-gel samples with a value about 3.0 emu/g. Keywords: Maghemite, nanoparticle, superparamagnetism, sol-gel, microwave

Propylene oxide (PO) is an important raw material for the chemical industry, which is produced commercially by the chlorohydrin process and hydroperoxide process. However the deficiencies in these processes have given rise to considerable interest in the development of a direct route to PO that does not produce by-products or coproducts. The development of novel, active and selective catalysts for gas phase oxidation of propylene using molecular oxygen were studied via testing a large number of catalysts by high-throughput screening method over combinatorially prepared different catalytic system in this study. v The promoted and un-promoted silver (Ag), copper (Cu), manganese (Mn) mono and bimetallic catalytic system over high and low surface area silica, alumina, titanium oxide and titanium-silicate supports were prepared by single step sol-gel method and by incipient wetness method. The study to determine the most effective catalyst and promoter in the epoxidation reaction with different reaction conditions, showed that potassium (K)- promoted Cu metal supported over high surface area silica favored the PO production at a high reaction temperature (350 &deg / C) and oxygen rich atmosphere (C3H6/O2=1.0). The catalyst showed high and low propylene oxide productivity was investigated by some of the characterization techniques. The highlydispersed copper particle over silica support was determined by XRD, TEM and XPS techniques. The only change between promoted and un-promoted catalyst was found out in the temperature dependence of propylene consumption and PO production rate. It was inferred that potassium (K) only neutralizes the acid sites of silica.

Metal coordinated polymer nanocomposites have gained great attention due to their superior characteristics. Polymethylmethacyrlate (PMMA) is the most commonly used polymer since it is easily processed. In this study, modified TiO2 nanoparticles prepared by insitu and exsitu methods were embedded into PMMA in order to improve its thermal stability and the effects of TiO2 nanoparticles on thermal characteristics of PMMA were investigated by direct pyrolysis mass spectrometry. The insitu method which is a sol gel method, TiO2/SiO2 nanoparticles were synthesized by mixing titanium(IV) tetraisopropoxide, TTIP, with silane coupling agent, 3-(3-methoxysilyl)methylmetacrylate, MSMA in absolute ethanol. In exsitu method, TiO2 powder was directly mixed with silane coupling reagent. TiO2/SiO2 nanoparticles were embedded into the PMMA by direct mixing resulting in exsitu and insitu TiO2/SiO2/PMMA nanocomposites. The synthesized TiO2/SiO2/PMMA nanocomposites were characterized by TEM, ATR-FT-IR and analyzed for the investigation of their reaction mechanism and thermal characteristics by pyrolysis mass spectroscopy. iv TEM images confirmed the formation of TiO2/SiO2 nanoparticles and TiO2/SiO2/PMMA nanocomposites and indicated that the average particle size of TiO2/SiO2 nanoparticles was around 6 nm whereas average particle size of SiO2/TiO2/PMMA nanocomposites were around 25 nm. The increase in the size of nanoparticles is associated with incorporation of TiO2/SiO2 nanoparticles into PMMA matrix. ATR-FTIR spectrum of 5% TiO2/SiO2/PMMA nanocomposites showed the formation of TiO2/SiO2 nanopartciles clearly. Pyrolysis mass spectrometry analysis revealed that incorporation of TiO2/SiO2 nano- particles into PMMA resulted in higher thermal stability only for low weight percentage insitu TiO2/SiO2/PMMA. At high weight percentages a decrease in thermal stability was detected. On the other hand, in case of exsitu TiO2/SiO2/PMMA, contrary to our expectations a decrease in thermal stability was detected. The decrease in thermal stability was attributed to evolution of methacrylic acid during thermal degradation of silane groups.

Indium tin oxide (ITO) thin films have been used as transparent electrodes in many technological applications such as display panels, solar cells, touch screens and electrochromic devices. Commercial grade ITO thin films are usually deposited by sputtering. Solution-based coating methods, such as sol-gel however, can be simple and economic alternative method for obtaining oxide films and also ITO. In this thesis, &ldquo / ITO sols&rdquo / and &ldquo / ITO nanoparticle-incorporated hybrid ITO coating sols&rdquo / were prepared using indium chloride (InCl3