Plants are exposed to a variety of environmental stresses, ranging from insects and phytopathogens known as biotic stressors, to edaphic stressors including drought and salinity - clustered under the group of abiotic stresses. Facing these pernicious risks, plants have adopted several strategies to survive in stressful environments. With contemporary advances in technology and scientific research, it is possible to insert a specific gene or trait into a plant in order to confer salt tolerance. For example, a thiol methyltransferase enzyme in cabbage converts Cl¯ and other halide ions into their corresponding methyl halides, which are released directly into the air. Cloning the TMT1 gene and functionally expressing this gene into tobacco plants conferred salt tolerance on these plants. Although increased salt tolerance is a favourable and beneficial trait for plant productivity, the emission of methyl halides into the atmosphere can be noxious for the environment. Indeed, methyl halides are some of the factors contributing to climate change, widely believed to be the foremost environmental problem of the twenty-first century. Climate change is affecting all forms of life on earth and its impacts are often severe and irreversible. For that reason, it has been placed at the forefront of the international political agenda. The present study focused on two main physiological traits of stress resistance in tobacco plants which have been genetically engineered with the cabbage TMT1 gene: The production of methyl halides, particularly methyl chloride, as a way to confer salt tolerance; and synthesis of the stress hormone, ethylene. Both pathways share a common metabolite, S-adenosyl-L-methionine (SAM), for the synthesis of the final products. SAM, derived from the amino acid methionine (Met), is a universal methyl group donor. It plays essential roles in plant metabolism, by acting as a precursor for ethylene, polyamines, and vitamin B1 synthesis, and as a source of atmospheric dimethylsulphides. Therefore, it is important that the plant maintains the SAM pool at a level sufficient to serve all the different metabolic pathways. The present work set out to determine whether addition of another SAM-dependent pathway through TMT insertion in tobacco plants would negatively affect ethylene synthesis by lessening the amount of SAM available for ethylene biosynthesis. Detailed experimental studies were conducted, including in vitro and in vivo experiments, to examine the potential effect of TMT gene insertion on SAM availability for ethylene synthesis in tobacco plants. Three series of in vitro tests, differing by the number of leaf discs used, the final headspace volume in each flask, the incubation period in the different solutions and the time of introducing salt solutions, were carried out. Data obtained from two series of in vitro experiments revealed a decrease in ethylene emission when salt solutions were added at the beginning of the experiment and when leaves where incubated overnight in the presence of 0.1 M NaBr, coupled with the production of methyl halides, whereas the other series of in vitro tests as well as the in vivo results showed no alteration in ethylene accumulation because of TMT insertion when tobacco leaves were exposed to salt treatments. According to the results presented in this study, the amounts of available SAM in transformed tobacco are likely sufficient to serve both ethylene and methyl halides biosynthetic pathways. Besides, in vivo results indicate that inserting the TMT1 gene that improves salt stress resistance in tobacco should not dramatically alter ethylene synthesis, and therefore, would be unlikely to affect any physiological trait associated with ethylene production if this gene is used to engineer salt tolerance in high-value crops. Although TMT insertion does not alter ethylene emission in transgenic plants and tends to be an efficient tool to confer salt tolerance in halo-intolerant crops, its environmental cost is of great concern and, therefore, should be taken into consideration to mitigate the amounts of methyl halides emitted into the atmosphere because of this insertion.

A new analytical technique to measure the chemical composition distribution (CCD) of polyolefins, crystallization elution fractionation (CEF), was introduced in 2006 during the First International Conference on Polyolefin Characterization. CEF is a faster and higher resolution alternative to the previous polyolefin CCD analytical techniques such as temperature rising elution fractionation (TREF) and crystallization elution fractionation (CRYSTAF) (Monrabal et al., 2007). Crystallization elution fractionation is a liquid chromatography technique used to determine the CCD of polyolefins by combining a new separation procedure, dynamic crystallization, and TREF. In a typical CEF experiment, a polymer solution is loaded in the CEF column at high temperature, the polymer is allowed to crystallize by lowering the solution temperature, and then the precipitated polymer is eluted by a solvent flowing through the column as the temperature is raised. CEF needs to be calibrated to provide quantitative CCD results. A CEF calibration curve consists of a mathematical relationship between elution temperature determined by CEF and comonomer fraction in the copolymer that could be estimated by Fourier transform infrared spectroscopy (FTIR) and carbon-13 nuclear magnetic resonance (13C NMR). Different comonomer types in ethylene/α-olefin copolymers will have distinct calibration curves. The main objective of this thesis is to obtain CEF calibration curves for several different ethylene/α-olefin copolymers and to investigate which factors influence these calibration curves. A series of homogeneous ethylene/α-olefin copolymers (1-hexene, 1-octene and 1-dodecene) with different comonomer fractions were synthesized under controlled conditions to create CEF calibration standards. Their average chemical compositions were determined by 13C NMR and FTIR and then used to establish CEF calibration curves relating elution temperature and comonomer molar fraction in the copolymer.

A series of pyrene end-labeled monodisperse poly(ethylene oxide)s (PEO(X)-Py2 where X represents the number average molecular weight (Mn) of the PEOs and equals 2, 5, 10 and 16.5 K) and one pyrene mono-labeled PEO (PEO(2K)-Py1) were synthesized and characterized in solution using fluorescence. First, the end-to-end cyclization (EEC) of PEO(X)-Py2 was investigated in seven organic solvents with viscosities (η) ranging from 0.32 to 1.92 mPa•s. The classical Birks scheme was used to globally fit the pyrene monomer and excimer fluorescence decays. The fraction of pyrenes that did not form excimer (ffree) was found to increase with increasing η and Mn. This result was contrary to the assumptions made by Birks’ scheme. To account for this, ffree was assumed to represent the fraction of PEO chains other than the monolabeled polymer impurities that cannot accomplish EEC. A fluorescence blob model (FBM) was applied to handle this assumption in the process of excimer formation for the PEO(X)-Py2 samples in solution. The radius of a blob, Rblob, in organic solvents was determined according to the results retrieved from the FBM. To quantitatively account for the existence of pyrene impurity in pyrene-labeled macromolecules, known amounts of PEO(2K)-Py1 were added into a PEO(2K)-Py2 solution and the fluorescence decays were fitted globally according to the Birks scheme and “model free” (MF) analysis to verify the validation of the MF analysis. The MF analysis was then applied to determine the amounts of 1-pyrenebutyric acid (PyBA) that had been added to a solution of pyrene end-labeled fourth generation dendritic hybrid (Py16-G4-PS). The results demonstrated that the contribution from unwanted fluorescent species could be isolated and quantitatively accounted for by fitting the fluorescence decays of the pyrene monomer and excimer globally with the MF analysis. Since the PEO(X)-Py2 samples form hydrophobic pyrene aggregates in aqueous solution, a sequential model (SM) was proposed to characterize the pyrene excimer formation of PEO(X)-Py2 in water at different polymer concentration (CP). The capture distance over which the pyrenyl end-groups experience hydrophobic forces in water was determined by assuming that the end-to-end distances of the PEO(X)-Py2 samples adopt a Gaussian distribution and that the fraction of pyrenes that are aggregated (fE0) determined by the sequential model corresponds to the fraction of PEO(X)-Py2 chains whose end-to-end distance is smaller than the hydrophobic capture distance. Since a surfactant can interact with a hydrophobically modified water-soluble polymer in aqueous solution, the interactions taking place between PEO(X)-Py2 and sodium dodecyl sulfate (SDS) were investigated at a low PEO(X)-Py2 concentration. The pyrene monomer and excimer fluorescence decays of the PEO(X)-Py2 and SDS solutions were acquired at various SDS concentrations and globally fitted according to the MF analysis to retrieve the parameters that described the kinetics of pyrene excimer formation. At high SDS concentrations above the critical micelle concentration (CMC), the pyrene end-groups of the short-chain samples (PEO(2K)-Py2 and PEO(5K)-Py2) were incorporated inside the same micelle and excimer was formed intramolecularly, while most pyrene groups of the long-chain samples (PEO(10K)-Py2 and PEO(16.5K)-Py2) were isolated into different micelles. Lastly, both the rheological properties and fluorescence behavior of a pyrene-labeled hydrophobically-modified alkali-swellable emulsion (Py-HASE) polymer in basic aqueous solution with SDS were studied. Furthermore, a joint experimental setup that combined a rheometer and a steady-state fluorometer was applied to investigate at the molecular level the effect that a shearing force had on the polymeric network. However, despite the dramatic decrease in solution viscosity with increasing shear rate, no change in the fluorescence spectra was detected, suggesting that changes in the polymeric network that affected the balance of intra- versus intermolecular pyrene associations did not impact the process of excimer formation. Together the experiments described in this thesis represent the broadest set of examples found in the scientific literature where information on the dynamics and level of association of pyrene-labeled polymers has been retrieved through the quantitative analysis of the fluorescence decays acquired with pyrene-labeled polymers in solution.

A Pulse Detonation Engine (PDE) is a propulsion device that takes advantage of the pressure rise inherent to the efficient burning of fuel-air mixtures via detonations. Detonation initiation is a critical process that occurs in the cycle of a PDE. A practical method of detonation initiation is Deflagration-to-Detonation Transition (DDT), which describes the transition of a subsonic deflagration, created using low initiation energies, to a supersonic detonation. This thesis presents the effects of obstacle spacing, blockage ratio, DDT section length, and airflow on DDT behavior in hydrogen-air and ethylene-air mixtures for a repeating PDE. These experiments were performed on a 2 diameter, 40 long, continuous-flow PDE located at the General Electric Global Research Center in Niskayuna, New York. A fundamental study of experiments performed on a modular orifice plate DDT geometry revealed that all three factors tested (obstacle blockage ratio, length of DDT section, and spacing between obstacles) have a statistically significant effect on flame acceleration. All of the interactions between the factors, except for the interaction of the blockage ratio with the spacing between obstacles, were also significant. To better capture the non-linearity of the DDT process, further studies were performed using a clear detonation chamber and a high-speed digital camera to track the flame chemiluminescence as it progressed through the PDE. Results show that the presence of excess obstacles, past what is minimally required to transition the flame to detonation, hinders the length and time to transition to detonation. Other key findings show that increasing the mass flow-rate of air through the PDE significantly reduces the run-up time of DDT, while having minimal effect on run-up distance. These experimental results provided validation runs for computational studies. In some cases as little as 20% difference was seen. The minimum DDT length for 0.15 lb/s hydrogen-air studies was 8 L/D from the spark location, while for ethylene it was 16 L/D. It was also observed that increasing the airflow rate through the tube from 0.1 to 0.3 lbs/sec decreased the time required for DDT by 26%, from 3.9 ms to 2.9 ms.

The physical and catalytic properties of silica supported platinum or rhodium model catalysts are studied under both ultra high vacuum (UHV) and elevated pressure reaction conditions (>1torr). Platinum or rhodium nanoparticles are vapor deposited onto a SiO2/Mo(112) surface and characterized using various surface analytical methods. CO chemisorption is utilized as a surface probe to estimate the concentration of various sites on the nanoparticles through thermal desorption spectroscopy (TDS) and infrared reflection absorption spectroscopy (IRAS) along with microscopy techniques to estimate particle size. The results are compared with hard sphere models of face centered cubic metals described as truncated cubo-octahedron. Results demonstrate the excellent agreement between chemisorption and hard sphere models in estimating the concentration of undercoordinated atoms on the nanoparticle surface. Surfaces are then subjected to high pressure reaction conditions to test the efficacy of utilizing the rate of a chemical reaction to obtain structural information about the surface. The surfaces are translated in-situ to a high pressure reaction cell where both structure insensitive and sensitive reactions are performed. Structure insensitive reactions (e.g. CO oxidation) allow a method to calculate the total active area on a per atom basis for silica supported platinum and rhodium model catalysts under reaction conditions. While structure sensitive reactions allow an estimate of the types of reaction sites, such as step sites (≤C7) under reaction conditions (e.g. n-heptane dehydrocyclization). High pressure structure sensitive reactions (e.g. ethylene hydroformylation) are also shown to drastically alter the morphology of the surface by dispersing nanoparticles leading to inhibition of catalytic pathways. Moreover, the relationships between high index single crystals, oxide supported nanoparticles, and high surface area technical catalysts are established. Overall, the results demonstrate the utility of model catalysts in understanding the structure-activity relationships in heterogeneous catalytic reactions and the usefulness of high pressure reactions as an analytical probe of surface morphology.

Utilization of natural gas in remote locations necessitates on-site conversion of methane into liquid fuels or high value products. The first step in forming high value products is the production of ethylene and acetylene. Non-thermal plasmas, due to their unique nonequilibrium characteristics, offer advantages over traditional methods of methane reforming. Different kinds of non-thermal plasmas are being investigated for methane reforming. Parameters of these processes like flow rate, discharge size, temperature and other variables determine efficiency of conversion. An efficient process is identified by a high yield and low specific energy of production for the desired product. A study of previous work reveals that higher energy density systems are more efficient for methane conversion to higher hydrocarbons as compared to low energy density systems. Some of the best results were found to be in the regime of warm discharges. Thermal equilibrium studies indicate that higher yields of ethylene are possible with an optimal control of reaction kinetics and fast quenching. With this idea, two different glow discharge reactor systems are designed and constructed for investigation of methane reforming. A counter flow micro plasma discharge system was used to investigate the trends of methane reforming products and the control parameters were optimized to get best possible ethylene yields while minimizing its specific energy. Later a magnetic glow discharge system is used and better results are obtained. Energy costs lower than thermal equilibrium calculations were achieved with magnetic glow discharge systems for both ethylene and acetylene. Yields are obtained from measurements of product concentrations using gas chromatography and power measurements are done using oscilloscope. Energy balance and mass balances are performed for product measurement accuracy and carbon deposition calculations. Carbon deposition is minimized through control of the temperature and residence time conditions in magnetic glow discharges. Ethylene production is observed to have lower specific energies at higher powers and lower flow rates in both reactors. An ethylene selectivity of 40 percent is achieved at an energy cost of 458MJ/Kg and an input energy cost of 5 MJ/Kg of methane.

In this study, 20/80 (weight %) Poly(ethylene terephthalate) (PET) /High Density Polyethylene (HDPE) Microfibrillar Reinforced Composites (MFC) were prepared by using high density polyethylene (HDPE) as the matrix material, poly(ethylene terephthalate) (PET) as the reinforcing component. Ethylene n-butyl acrylate-glycidyl methacrylate (E-nBA-GMA) and ethylene methyl acrylate (E-MA) as the compatibilizers in 1, 5, and 10 wt. %. The objective of this study is to produce MFCs based on PET and HDPE via extrusion-drawing-injection method and to characterize as extruded, as drawn and injection molded materials in terms of morphologies, and mechanical and thermal properties. In addition, the effect of compatibilizer type and content on properties of PET-HDPE composites was studied. For comparison purposes, conventional PET-HDPE composites with and without compatibilizer were prepared. Also, the effect of screw speed and drawing speed on the morphologies and mechanical and thermal properties were investigated. The effect of low and high injection temperature molding on morphologies were also observed. SEM analyses showed that, extruded blends became oriented after drawing. The fibrillar structure was preserved after injection molding. High injection molding temperature destroyed the structure of PET microfibers. In addition, it was also observed that the adhesion between HDPE and PET improved with the addition of the compatibilizers. Tensile strength and tensile modulus values of PET/HDPE MFCs increased with increasing drawing speed. Increasing the screw speed resulted in a slight decrease in tensile strength values. Addition of the compatibilizers to the system decreased tensile strength and tensile modulus values. Results of impact tests designated that the impact strength of the materials with and without MFC structure increased with the increasing amounts of E-nBAGMA. DSC analyses pointed out that, melting temperatures of HDPE and PET phase did not change significantly with increasing drawing speed or with the addition of the compatibilizer. As the drawing speed increased from 2.7 m/min to 6.2 m/min, degree of crystallinity of the drawn samples of the PET phase increased.

The variation in properties of Polypropylene (PP) / Ethylene Vinyl Acetate (EVA) blends upon EVA content, temperature, and light stability were followed by using tensile testing, impact testing, and differential scanning calorimetry (DSC). Young&rsquo / s modulus of the blends decreased with increasing drawing temperature and EVA content. The stress at break values of the blends slightly increased with EVA whereas decreased with drawing temperature. The percent strain at break values of the blends were found to increase abruptly by increasing EVA content and drawing temperature. These changes in the mechanical properties are the indication of compatibility. The impact tests were performed only at 0&deg / C, 25&deg / C and the impact strength increased with the temperature and EVA content, but none of the samples were broken at higher testing temperatures. The effect of stabilizer was very obvious because stabilizer-free samples failed after 400 hours whereas, the samples with stabilizer resisted up to 750 hours. Elongation values of the samples decreased because of increasing brittleness by UV irradiation. We also observed chain stiffening effect by crosslinking in all samples upon UV irradiation. Thermal analysis of the blends of the drawn samples showed an increasing trend of crsytallinity with increasing drawing temperature. Increasing drawing temperature made polymer chains more flexible because of the increasing chain mobility. These flexible chains were then oriented in one direction during tensile testing and therefore uniaxial crystallization occurred. The morphology of impact and tensile tests samples were also analyzed by scanning electron microscope (SEM). The fibrillation of pure PP is higher than the fibrillation of the blends.

Fast depletion of oil reserves necessitates the development of novel alternative motor vehicle fuels. Global warming problems also initiated new research to develop new fuels creating less CO2 emission. Nowadays, dimethyl ether (DME) and diethyl ether (DEE) are considered as important alternative clean energy sources. These valuable ethers are produced by the dehydration reaction of methanol and ethanol, respectively, in the presence of acidic catalysts. Besides DEE, ethylene which is very important in petrochemical industry, can also be produced by ethanol dehydration reaction. In the first part of this study, the catalytic activity of tungstophosphoric acid (TPA), silicotungstic acid (STA) and molybdophosphoric acid (MPA), which are well-known heteropolyacids were tested in ethanol dehydration reaction. The activities of other solid acid catalysts, such as Nafion and mesoporous aluminosilicate, were also tested in the dehydration reaction of ethanol. In the case of DME production by dehydration of methanol, activities of STA, TPA and aluminosilicate catalysts were tested. Among the heteropolyacid catalysts, STA showed the highest activity in both ethanol and methanol dehydration reactions. With an increase of temperature from 180oC to 250oC, Ethylene selectivities increased while DEE selectivities decreased. Ethylene yield values over 0.70 were obtained at 250oC. The presence of water in the feed stream caused some reduction in the activity of TPA catalyst. Very high DME yields were obtained using mesoporous aluminosilicate catalyst at about 450oC. The surface area of heteropolyacids are very low and they are soluble in polar solvents such as water and alcohols. Considering these drawbacks of heteropolyacid catalysts, novel mesoporous STA based high surface area catalysts were synthesized following a hydrothermal synthesis route. These novel catalysts were highly stable and they did not dissolve in polar solvents. The catalysts containing W/Si ratios of 0.19 (STA62(550)) and 0.34 (STA82(550)) have BJH surface area values of 481 m2/g and 210 m2/g, respectively, with pore size distributions ranging in between 2-15 nm. These catalysts were characterized by XRD, EDS, SEM, TGA, DTA, DSC, FTIR and Nitrogen Adsorption techniques and their activities were tested in ethanol dehydration reaction. Calcination temperature of the catalysts was shown to be a very important parameter for the activities of these catalysts. Considering the partial decomposition and proton lost of the catalysts over 375oC, they are calcined at 350oC and 550oC before testing them in ethanol dehydration reaction. The catalysts calcined at 350oC showed much higher activity at temperature as low as 180oC. However, the catalysts calcined at 550oC showed activity over 280oC. Ethylene yield values approaching to 0.90 were obtained at about 350oC with catalysts calcined at 350oC. DEE yield past through a maximum with an increase in temperature indicating its decomposition to Ethylene at higher temperatures. However, at lower temperatures (&lt / 300oC) Ethylene and DEE were concluded to be formed through parallel routes. Formation of some acetaldehyde at lower temperatures indicated a possible reaction path through acetaldehyde in the formation of DEE. DRIFTS results also proved the presence of ethoxy, acetate and ethyl like species in addition to adsorbed ethanol molecules on the catalyst surface and gave additional information related to the mechanism.

ABSTRACT DESIGN, SYNTHESIS AND ELECTROPOLYMERIZATION OF A NEW CHEMILUMINESCENT TERTHIENYL SYSTEM Atilgan, Nurdan M.Sc. Department of Chemistry Supervisor: Prof. Dr. Ahmet M. &Ouml / nal Co-Supervisor: Assist. Prof. Dr. Atilla Cihaner September 2008, 57 pages A novel monomer, possessing chemiluminescence properties, 5,7-di-ethylenedioxythiophen-2-yl-2,3-dihydro-thieno[3,4-d]pyridazine-1,4-dione (ETE-Lum) was synthesized. Chemiluminescence properties of ETE-Lum were investigated in alkaline water solution in the presence of H2O2 and this reaction was catalyzed by Fe+3 ion and blood. This study submits a new opportunity to investigate forensic and analytical application instead of 5-amino-2,3-dihydro-1,4-phthalazine-dione (luminol). Response of other metalic cations was also investigated under the same reaction conditions. Electrochemical properties of ETE-Lum were studied in 0.1 M acetonitrile/tetrabutylammonium perchlorate solvent system containing BF3-Et2O and also in neat BF3-Et2O solution. In addition, the corresponding polymer film of ETE-Lum (PETE-Lum) was synthesized successfully via repetitive cycling by cyclic voltammetry and its electrochemical properties were investigated in a monomer-free electrolyte solution. Spectroelectrochemical behavior of the polymer film on indium tin oxide working electrode was also investigated by recording the electronic absorption spectra, in-situ, in monomer-free electrolyte solution at different potentials. Furthermore, spectroelectrochemical studies revealed that PETE-Lum had an electronic band gap of 1.66 eV. The results of electrochemical and electroluminesence measurements indicated that chemiluminecent unit of monomer was protected during polymerization. In addition, PETE-Lum film was found to be electrochemiluminescence active, maintaining its activitiy over 1000 cycles.