Planar two-dimensional (2-D) nanostructured indium oxide (InOx) and one-dimensional (1-D) tin oxide (SnO2) semiconductor metal-oxide layers have been utilised for gas sensing applications. Novel layered Surface Acoustic Wave (SAW) based sensors were developed consisting of InOx/SiOxNy/36°YXLiTaO3, InOx/SiNx/SiO2/36°YXLiTaO3 and InOx/SiNx/36°YXLiTaO3 The 1 µm intermediate layers of silicon oxynitride (SiOxNy), silicon nitride (SiNx) and SiO2/SiNx matrix were deposited on lithium tantalate (36°YXLiTaO3) substrates by r.f. magnetron sputtering, electron-beam evaporation and plasma enhanced chemical vapour deposition (PECVD) techniques, respectively. As a gas sensitive layer, a 100 nm thin layer of InOx was deposited on the intermediate layers by r.f. magnetron sputtering. The targeted gases were ozone (O3) and hydrogen (H2). An intermediate layer has multiple functions: protective role for the interdigital transducers' electrodes as well as an isolating effect from InOx sensing layer, thereby improving the sensor performance. The developed SAW sensors' exhibited high response magnitudes with repeatable, reversible and stable responses towards O3 and H2. They are capable of sensing concentrations as low as 20 parts-per-billion for O3 and 600 parts-per-million for H2. Additionally a conductometric type novel sensing structure of SnO2/36°YX LiTaO3 was also developed by depositing a thin layer of SnO2 nanorods by PECVD. The gas sensing performance exhibited repeatable, reversible, stable responses towards NO2 and CO. The surface morphology, crystalline structure and preferred orientation of the deposited layers were investigated by Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). A polycrystalline, oxygen deficient non-stoichiometric InOx with grain sizes of 20-40 nm was revealed. The 1-D nanostructures were characterised by Transmission Electron Microscopy (TEM) showing nanorods with needle-like shape , diameters of 10-20 nm a t the top and 30-40 nm at the base as well as a preferential growth orientation of [ ] on the LiTaO3 substrate. The developed sensors are promising for O3, H2 and CO sensing.

<p>One-step photoinitiated free radical carbonylation was employed for the rapid (5–7 min) labelling of aliphatic carboxylic acids, esters, and amides with a short-lived positron emitter ¹¹C (t_½ = 20.3 min) at the carbonyl position. The labelled compounds were synthesized from alkyl iodides (0.05–0.1 mmol), [¹¹C]carbon monoxide, and appropriate nucleophiles. Decay-corrected radiochemical yields were up to 74%; conversion of [¹¹C]carbon monoxide reached 85–90%; specific radioactivity was 158–192 GBq/mmol. The labelled compounds were identified and characterized using HPLC, LC-MS, and ¹H and ¹³C NMR. The effects of solvents, additives, photoirradiation, temperature, and reaction time were studied and discussed.</p><p>[<i>carbonyl-</i>¹¹C]Amides were synthesized using amines in 1–2 equiv. to iodides, exploiting solvent effects to control reactivity. [<i>carboxyl-</i>¹¹C]Acids were synthesized using water as a nucleophile, in binary and ternary aqueous solvent mixtures; the addition of TBAOH or KOH was necessary to obtain high radiochemical yields. [<i>carbonyl-</i>¹¹C]Esters were synthesized using primary and secondary alcohols, <i>tert-</i>butanol, and phenol. Bases were KOH, BuLi, LiHDMS.</p><p>The effects of photosensitizers were studied and exploited to accelerate the labelling of carboxylic acids and esters resulting in 75–85% decay-corrected radiochemical yields under mild conditions without the use of bases.</p><p>A mild procedure for the ¹¹C-carboxylation of alkyl iodides using DMSO as an oxygen nucleophile was developed. This method is expected to be suitable in the macroscale synthesis of carboxylic acids using isotopically unmodified carbon monoxide.</p><p>Radical carbonylation was applied to improve the synthesis of an extensively used PET tracer, [<i>carbonyl</i>-¹¹C]WAY-100635. The tracer was synthesized in one step, whereas a common approach via Grignard reagents requires three steps.</p><p>In addition, several (¹³C)compounds were synthesised using the described methods.</p><p>Free radical carbonylation may be used for the ¹¹C-carbonylation of alkyl iodides, whereas transition-metal carbonylation – of aryl halides and triflates. Thus, the two carbonylation methods are complementary with respect to the scope of synthetic targets.</p>

One-step photoinitiated free radical carbonylation was employed for the rapid (5–7 min) labelling of aliphatic carboxylic acids, esters, and amides with a short-lived positron emitter 11C (t½ = 20.3 min) at the carbonyl position. The labelled compounds were synthesized from alkyl iodides (0.05–0.1 mmol), [11C]carbon monoxide, and appropriate nucleophiles. Decay-corrected radiochemical yields were up to 74%; conversion of [11C]carbon monoxide reached 85–90%; specific radioactivity was 158–192 GBq/mmol. The labelled compounds were identified and characterized using HPLC, LC-MS, and 1H and 13C NMR. The effects of solvents, additives, photoirradiation, temperature, and reaction time were studied and discussed. [carbonyl-11C]Amides were synthesized using amines in 1–2 equiv. to iodides, exploiting solvent effects to control reactivity. [carboxyl-11C]Acids were synthesized using water as a nucleophile, in binary and ternary aqueous solvent mixtures; the addition of TBAOH or KOH was necessary to obtain high radiochemical yields. [carbonyl-11C]Esters were synthesized using primary and secondary alcohols, tert-butanol, and phenol. Bases were KOH, BuLi, LiHDMS. The effects of photosensitizers were studied and exploited to accelerate the labelling of carboxylic acids and esters resulting in 75–85% decay-corrected radiochemical yields under mild conditions without the use of bases. A mild procedure for the 11C-carboxylation of alkyl iodides using DMSO as an oxygen nucleophile was developed. This method is expected to be suitable in the macroscale synthesis of carboxylic acids using isotopically unmodified carbon monoxide. Radical carbonylation was applied to improve the synthesis of an extensively used PET tracer, [carbonyl-11C]WAY-100635. The tracer was synthesized in one step, whereas a common approach via Grignard reagents requires three steps. In addition, several (13C)compounds were synthesised using the described methods. Free radical carbonylation may be used for the 11C-carbonylation of alkyl iodides, whereas transition-metal carbonylation – of aryl halides and triflates. Thus, the two carbonylation methods are complementary with respect to the scope of synthetic targets.

ABSTRACT SYNTHESIS AND CHARACTERIZATION OF ETHANOL ELECTRO-OXIDATION CATALYSIS Demir-Kivrak, Hilal Ph.D., Department of Chemical Engineering Supervisor : Prof. Dr. Deniz &Uuml / ner Co-supervisor : Dr. Sadig Kuliyev October 2010, 196 pages In this study, the role of defects, the role of Sn in relation to defects, and the role of oxide phase of tin in ethanol electro-oxidation reaction were investigated. Firstly, adsorption calorimetry measurements were conducted on monometallic (1%Pt, 2%Pt, and 5%Pt) and bi-metallic (5% Pt-Sn) &gamma / -Al2O3 supported Pt catalysts. It was observed that while saturation coverage values decreased, intermediate heats remained same for Pt-Sn catalysts by the increasing amount of tin. The effect of particle size was investigated on Pt/C (pH=5), Pt/C (pH=11) catalysts at different scan rates. At high scan rates (quite above diffusion limitations), current per site activities were nearly the same for 20% Pt/C (E-Tek), Pt/C (pH=11), and Pt/C (pH=5) catalysts, which explained as electro-oxidation reaction takes place at the defects sites. Furthermore, the effect of support on ethanol electro-oxidation was investigated on CNT supported Pt catalyst. Results indicate that only the metal v dispersions improved ethanol electro-oxidation reaction and support did not have any effect on ethanol electro-oxidation reaction. Results on the 20% Pt-Sn/C (15:1 to 1:1 Pt: Sn atomic ratios) and 20% Pt-SnO2/C (6:1 and 1:1) catalysts indicated that ethanol electro-oxidation activity increased by increasing tin amount. For 20% Pt-Sn/C catalysts, Pt-Sn (6:1)/C indicated best activity. On the other hand, 20% Pt-SnO2 (6:1)/C catalyst was better than Pt-Sn (6:1)/C in terms of ethanol electro-oxidation activity due to the fact that there was low contact between Pt and tin oxide particles.

In this retrospective cohort from 2002 through 2007, 104,003 singleton live births in Hillsborough County, Florida were analyzed to elucidate the relationship between feto-infant morbidity outcomes and prenatal exposure to six criteria air pollutants. This study is based on three linked databases: The Florida Hospital Discharge database; The vital statistics records of singleton live births; Air Pollution meteorological data from the Environmental Protection Agency. There are six common air pollutants, particulate matter 2.5 (PM2.5), particulate matter 10 (PM10), ground-level ozone (O3), carbon monoxide (CO), nitrogen (NOx), and lead (Pb). These pollutants are harmful to human health and the environment. The primary outcomes of interest were low birth weight (LBW), preterm births, and small for gestational age (SGA). The intent of this project is to address these issues of air pollution effects and the methodology surrounding the study of air pollution. Using modeling, exposure values of the six criteria air pollutants were assigned to mothers over their period of pregnancy. To address these methodological concerns, this study utilizes the structural equation modeling, quartile groupings with dose response, and trimester groupings to evaluate the relationship between air pollution and birth outcomes of pregnant residents. Using structural equation modeling a significant B value of 0.35 indicated that exposure to the six criteria pollutant in pregnancy may have a significant relationship to all five birth outcomes if they are broken down into latent variables. Quartile data demonstrated that NOx seemed to have most significant associations with all outcomes with a dose response for SGA. PM10 and PM2.5 had some association to LBW and VLBW at high levels. PM10 demonstrated significance in the higher doses for SGA. However, the only dose response relationship that was demonstrated for PM10 and PM2.5 was in VLBW. PM10 also demonstrated a dose response with very preterm. If sub-divided into trimester data, PM10 demonstrated a significant relationship between exposures in all trimesters and LBW, VLBW, and SGA. PM2.5 demonstrated a significant relationship between exposures in all trimesters and VLBW. CO demonstrated a significant relationship in the 2nd trimester for LBW as well as for SGA. Mothers and their babies are a vulnerable population who are more susceptible to lower levels of pollution. These air pollutants can possibly have long-term effect on their children. Implantation of laws and regulations, warning system, or more strict EPA standards may be needed to adequately control the cost to our society.

No description available.

The past decade has witnessed dramatic changes in the oil and gas industry with the drilling and production extending into progressively deeper waters and higher operating pressures, therefore making it essential to gain a better understanding of the behaviour of gas hydrate at high pressure conditions. New experimental 3-phase H−LW−V (Hydrate−Liquid Water−Vapour) equilibrium data for nitrogen and H−LW−V (Hydrate−Liquid Water−Vapour) and H−LW−LHC (Hydrate−Liquid Water−Liquid Hydrocarbon) data for ethane and propane simple clathrate hydrates were generated by a reliable fixed-volume, isochoric, step-heating technique. The accuracy and reliability of the experimental measurements are demonstrated by comparing measurements with reliable literature data from different researchers. Additional experimental data up to high pressure (200 MPa when available) for CH4, C2H6, C3H8, i-C4H10, N2, Ar, Kr, Xe, H2S, O2, CO and CO2 clathrates have been gathered from literature. The Valderrama modification of the Patel-Teja (VPT) equation of state combined with non-density-dependent (NDD) mixing rules is used to model the fluid phases with previously reported binary interaction parameters. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. Langmuir constants have been calculated by both Kihara potential as well as direct techniques. Model predictions are validated against independent experimental data and a good agreement between predictions and experimental data is observed, supporting the reliability of the developed model.

No description available.

Poröse Materialien zeichnen sich durch hohe spezifische Oberflächen bzw. hohe spezifische Porenvolumina aus. Dies macht sie zu geeigneten Kandidaten für die Gasspeicherung, Stofftrennung und die heterogene Katalyse, die Hauptanwendungsgebiete poröser Materialien. Um poröse Materialien hinsichtlich der eben genannten Anwendungsfelder zu optimieren ist es von entscheidender Bedeutung, sie hinsichtlich ihrer jeweiligen Anwendung maßzuschneidern. Eine Klasse hochporöser Materialien, bei der das Maßschneidern der Poren möglich ist, ist die der metallorganischen Gerüstverbindungen [engl. Metal-Organic Frameworks (MOFs)]. MOFs zeichnen sich durch einen modularen Aufbau aus, der ein systematisches Design der Poren erlaubt. Auch poröse Polymere können durch Funktionalisierung der entsprechenden Monomere hinsichtlich verschiedener Anwendungsgebiete gezielt synthetisiert werden. Ein Ziel dieser Arbeit war die Integration des Metalls Rhodium als knotenbildendes Element in ein MOF. Dazu wurde Rhodium(II)-acetat, welches bereits das Schaufelradmotiv enthält, mit den trifunktionellen Carbonsäuren Trimesinsäure und 4,4´,4´´ Benzen-1,3,5-triyl-tribenzoesäure zu den MOFs DUT 82 und DUT 83 umgesetzt. Das Schaufelradmotiv als sekundäre Baueinheit in DUT-82 konnte durch röntgenabsorptionspektroskopische Untersuchungen nachgewiesen werden. Nach überkritischem Trocknen gefolgt von thermischer Aktivierung zeigten DUT-82 und DUT-83 eine permanente Porosität mit spezifischen BET-Oberflächen von bis zu 1150 m2g-1. Weiterhin konnte für DUT-82 eine sehr hohe Affinität zu Kohlenmonoxid, die selten für MOFs beobachtet wird, nachgewiesen werden. Berechnungen der Adsorptionsenthalpie ergaben bei niedrigen Beladungen einen Wert von ungefähr 50 kJmol-1, was für eine Chemisorption von Kohlenmonoxid an DUT-82 bei niedrigen Drücken spricht. Weiterhin zeigten katalytische Untersuchungen, dass sich DUT-82 als heterogener Hydrierkatalysator eignet. In einer Modellreaktion konnte Styrol erfolgreich zu Ethylbenzen umgesetzt werden. In einem weiteren Teil der Arbeit sollte ein MOF synthetisiert werden, das Stabilität und eine hohe Kapazität für Schwefelwasserstoff miteinander vereint. Eine Klasse bereits bekannter MOFs mit hoher Stabilität basiert auf dem [Zr6O4(OH)4]12+-Cluster. Durch Kombination des [Zr6O4(OH)4]12+-Clusters mit Bipyridindicarboxylat konnte das MOF UiO-67(bipy) hergestellt werden, welches isostrukturell zu UiO 67 ist. Untersuchungen an UiO 67(bipy) zeigten, dass das unbeladene Netzwerk keinen Schwefelwasserstoff adsorbiert. Die Bipyridinfunktionalität wurde anschließend für die permanente Integration weiterer Metallzentren (Metall = Cu, Ni, Co) genutzt. Dazu wurde UiO-67(bipy) zu wässrigen oder ethanolischen Metallsalzlösungen gegeben und es kam zur Adsorption der Metallsalze aus der Flüssigphase. Durch die postsynthetische Integration der Metallsalze konnte die Adsorptionskapazität der resultierenden Metallsalz@UiO-67(bipy)-Materialien für Schwefelwasserstoff bis auf 8 Gew.% gesteigert werden. Neben Adsorption und Katalyse ist die Sensorik ein weiteres Anwendungsfeld von MOFs. Eine organische Einheit, die sich als sensitive Komponente für eine Integration in ein MOF anbietet, ist Dihydro-1,2,4,5-tetrazin, das zu 1,2,4,5-Tetrazin oxidiert werden kann. Das bemerkenswerte Merkmal dieser Reaktion ist der radikale Farbwechsel von Gelb nach Pink. Nach erfolgreicher Synthese der Dihydro-1,2,4,5-tetrazindicarbonsäure sollte sie durch Kombination mit dem [Zr6O4(OH)4]12+-Cluster zu einem UiO-66 analogen Netzwerk in ein stabiles Netzwerk integriert werden. Da die direkte Syntheseroute eines UiO-66 analogen Netzwerks nicht zum Erfolg führte, wurde die mildere Variante des Linkeraustauschs gewählt. Über diese Route konnte das Dihydro-1,2,4,5-tetrazindicarboxylat erfolgreich partiell in das UiO-66 Netzwerk integriert werden. Anschließende Untersuchungen zeigten, dass die in das Netzwerk eingebaute Dihydro-1,2,4,5-tetrazin-Einheit sowohl in der Flüssig- als auch in der Gasphase erfolgreich oxidiert werden kann, was durch UV/vis-Messungen belegt werden konnte. Eine weitere Klasse poröser Materialien, die hervorragende chemische Stabilität aufweist, ist die der konjugierten Triazin-Netzwerke. Sie entstehen durch Cyclotrimerisierung multifunktioneller Nitrile. Durch geschickte Wahl der Monomere ist eine Funktionalisierung der Triazin-Netzwerke möglich. Um ein chirales Triazin-Netzwerk zu synthetisieren, wurde Spirobiindan erfolgreich mit Nitrilgruppen funktionalisiert. Die Umsetzung des Monomers in einer Zinkchlorid-Schmelze führte zu porösen Polymeren mit spezifischen BET-Oberflächen von bis zu 1180 m2g 1. Dabei konnte die Porengrößenverteilung des Triazin-Netzwerkes durch Variation des Verhältnisses von Zinkchlorid zu Monomer gezielt eingestellt werden. Die Polymersynthese erfolgte mit einer racemischen Mischung des Monomers und führte somit zu einem achiralen Polymer. Erste Untersuchungen zeigten, dass eine Trennung des racemisch vorliegenden Monomers mittels Hochleistungsflüssigchromatographie möglich ist. Die Imidazoliumgruppe ist eine weitere Baueinheit, die in Triazin-Polymere integriert werden sollte, da sie leicht in ein N-Heterocyclisches Carben überführt werden kann. N-Neterocyclische Carbene können direkt als Katalysator bzw. als Ligand für eine Vielzahl von Metallen zur Generierung eines Katalysators genutzt werden. Über mehrstufige Synthesen konnten zwei nitrilfunktionalisierte Imidazoliumsalze hergestellt werden. Die anschließende Cyclotrimerisierung führte zu porösen Polymeren mit spezifischen BET-Oberflächen von bis zu 680 m2g-1. Erste katalytische Untersuchungen zum Einsatz dieser Triazin-Netzwerke in Umpolungsreaktionen von Zimtaldehyd mit 2,2,2 Trifluoracetophenon zeigten jedoch lediglich einen geringen Umsatz zum gewünschten Produkt.

Giant molecular clouds (GMCs), out of which stars form, are complex, dynamic systems, which both influence and are shaped by the process of star formation. In this dissertation, I examine three different facets of the dynamical motions within GMCs. Collapse modes in different dimensional objects. Molecular clouds contain lower dimensional substructures, such as filaments and sheets. The collapse properties of finite filaments and sheets differ from those of spherical objects as well as infinite sheets and filaments. I examine the importance of local collapse modes of small central perturbations, relative to global collapse modes, in different dimensional objects to elucidate whether strong perturbations are required for molecular clouds to fragment to form stars. I also calculate the dependence of the global collapse timescale upon the aspect ratio of sheets and filaments. I find that lower dimensional objects are more readily fragmented, and that for a constant density, lower dimensional objects and clouds with larger aspect ratios collapse more slowly. An edge-driven collapse mode also exists in sheets and filaments and is most important in elongated filaments. The failure to consider the geometry of a gas cloud is shown to lead to an overestimation of the star formation rate by up to an order of magnitude. Molecular tracers of turbulent energy dissipation. Molecular clouds contain supersonic turbulence that simulations predict will decay rapidly via shocks. I use shock models to predict which species emit the majority of the turbulent energy dissipated in shocks and find that carbon monoxide, CO, is primarily responsible for radiating away this energy. By combining these shock models with estimates for the turbulent energy dissipation rate of molecular clouds, I predict the expected shock spectra of CO from molecular clouds. I compare the results of these shock models to predictions for the emission from the unshocked gas in GMCs and show that mid-to-high rotational transitions of CO (e.g., J = 8 to 7), should be dominated by shocked gas emission and should trace the turbulent energy being dissipated in molecular clouds. Orion-Eridanus superbubble. The nearby Orion star forming region has created a large bubble of hot plasma in the local interstellar medium referred to as the Orion-Eridanus superbubble. This bubble is unusual in that it is highly elongated, is believed to be oriented roughly parallel to the galactic plane, and contains bright filamentary features on the Eridanus side. I fit models for a wind driven bubble in an exponential atmosphere to the Orion-Eridanus superbubble and show that the elongation of the bubble cannot be explained by such a model in which the scale height of the galactic disk is the typical value of 150 pc. Either a much smaller scale height must be adopted or some additional physics must be added to the model. I also show that the Eridanus filaments cannot be equilibrium objects ionized by the Orion star forming region. / Graduate / 0606 / andyrpon@gmail.com