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Thesis (M.S.)--West Virginia University, 2010. / Title from document title page. Document formatted into pages; contains ix, 52 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 49-51).

Thesis (Ph. D.)--Johns Hopkins University, 1928. / Biography.

Techn. Universiẗat, Diss., 2001--Berlin.

This thesis examines the reactions of hydrocarbons exposed to chlorosulfonic acid in order to establish the reaction rate and associated molecular structure of each compound.

L’apport d’oxygène joue un rôle prépondérant dans le développement d’un incendie en milieu confiné. La quantité d’oxygène disponible pour la combustion va dépendre de son appauvrissement dû au feu mais aussi de l’apport d’air par le système de ventilation et / ou les ouvertures. Une baisse du niveau d’oxygène du mélange oxydant va conduire à une diminution du flux de chaleur provenant de la flamme vers la surface du combustible, ce qui, en retour, va entraîner une diminution du débit de pyrolyse. La présente étude expérimentale a un double objectif : comprendre les effets d’une atmosphère appauvrie en oxygène sur la combustion de matériaux solides et liquides et fournir des données nécessaires à la validation des outils de simulation numérique d’un incendie. Les essais expérimentaux ont été menés dans le calorimètre à atmosphère contrôlée CADUCEE de l’IRSN. Le poly méthacrylate de méthyle (PMMA) et l’heptane ont été utilisés comme combustibles, et pour chacun d’eux, différentes tailles de foyer ont été considérées. Les données collectées dans cette étude ont été comparées avec celles de la littérature pour divers matériaux et différentes échelles, révélant un bon accord. En supposant l’équilibre chimique, le calcul de la richesse du milieu réactionnel, à partir de la concentration de CO2 dans les fumées extraites, donne une richesse proche de l’unité, ce qui révèle une combustion incomplète faiblement réductrice. En fait, la flamme, et donc le débit de pyrolyse, s’adaptent à la concentration d’oxygène dans le mélange oxydant pour rester proche de la stœchiométrie. / Oxygen supply has a leading role in fire growth in confined spaces. The oxygen quantity available for combustion depends on the oxygen consumption by the fire and on the air supply from the mechanical ventilation system or openings. A decrease of oxygen concentration of the oxidant flow will lead to a decrease of the heat flux feedback from the flame to the fuel surface, which in turn will lead to a decrease in mass loss rate. The present experimental study has a dual objective: understand the effects of an under-oxygenated atmosphere on the combustion of solids and liquids and collect data for model validation. The Controlled Atmosphere Device for Unburnt and Carbon Emission Evaluation (CADUCEE) of IRSN has been used to conduct experiments at oxygen concentrations ranging from the limiting oxygen concentration for extinction to 21%vol. Fuels used are polymethylmethacrylate (PMMA) and heptane at different scales. A good agreement with literature data for various fuels and scales is found. Assuming chemical equilibrium, it is also found that the global equivalence ratio, deduced from the concentration of CO2 in the extracted gases, is close to unity, which reveals a weakly reductive incomplete combustion. This suggests that the flame, and thus the mass loss rate, adapt themselves to the available concentration of oxygen in the oxidant flow, to stay close to stoichiometry.

Methane-air, ethane-air, and n-heptane-air over-ventilated co-flow laminar diffusion flames were studied up to pressures of 2.03, 1.52, and 0.51 MPa, respectively, to determine the effect of pressure on flame shape, soot concentration, and temperature. A spectral soot emission optical diagnostic method was used to obtain the spatially resolved soot formation and temperature data. In all cases, soot formation was enhanced by pressure, but the pressure sensitivity decreased as pressure was increased. The maximum fuel carbon conversion to soot, ηmax, was approximated by a power law dependence with the pressure exponent of 0.92 between 0.51 and 1.01 MPa, and 0.68 between 1.01 and 2.03 MPa with ηmax=9.5% at 2.03 MPa for methane-air flames. For ethane-air flames, the pressure exponent was 1.57 between 0.20 and 0.51 MPa, 1.08 between 0.51 and 1.01 MPa, and 0.58 between 1.01 and 1.52 MPa where ηmax=23% at 1.52 MPa. For nitrogen-diluted n-heptane-air flames, ηmax=6.5% at 0.51 MPa.

Methane-air, ethane-air, and n-heptane-air over-ventilated co-flow laminar diffusion flames were studied up to pressures of 2.03, 1.52, and 0.51 MPa, respectively, to determine the effect of pressure on flame shape, soot concentration, and temperature. A spectral soot emission optical diagnostic method was used to obtain the spatially resolved soot formation and temperature data. In all cases, soot formation was enhanced by pressure, but the pressure sensitivity decreased as pressure was increased. The maximum fuel carbon conversion to soot, ηmax, was approximated by a power law dependence with the pressure exponent of 0.92 between 0.51 and 1.01 MPa, and 0.68 between 1.01 and 2.03 MPa with ηmax=9.5% at 2.03 MPa for methane-air flames. For ethane-air flames, the pressure exponent was 1.57 between 0.20 and 0.51 MPa, 1.08 between 0.51 and 1.01 MPa, and 0.58 between 1.01 and 1.52 MPa where ηmax=23% at 1.52 MPa. For nitrogen-diluted n-heptane-air flames, ηmax=6.5% at 0.51 MPa.

Chemical modifications of oligonucleotides provide an important tool to understand how the natural substrate works as well as how to improve their biochemical and biological properties as potential therapeutics and diagnostics. Our carba-LNA (2',4'-carba-bridged Locked Nucleic Acid) modified oligo-DNA or -RNA have been found to be useful to modulate oligo-RNA and -DNA activity. This thesis is based on four papers: Paper I (J. Org. Chem. 2010, 75, 7112-7128) deals with the synthesis of 2',4'-propylene-bridged (Carba-ENA) thymidine and its analogues. These carba-ENA nucleosides have been subsequently incorporated into 15mer antisense oligodeoxynucleotides (AON), and their affinity toward complementary mRNA and DNA, as well as their nuclease resistance and RNase H recruitment capability have been investigated in comparison with those of the native and ENA counterparts. Paper II (J. Org. Chem. 2012, 77, 6855–6872) illustrates the synthesis of dimethylbicyclo[2.2.1]heptane and a diastereomeric mixture of oxabicyclo[2.2.1]heptanes by the free-radical ring-closure reaction approach. The role of steric factors for different chair- and the boat-like transition states was evaluated involving the 5-exo radical ring closure reaction to a tethered olefin. Paper III (J. Org. Chem. 2012, 77, 9747-9755) shows an unusual strain releasing reaction of 1-mesyloxy-8,7-dimethylbicyclo[2.2.1]heptane by a base-promoted substitution at the chiral C3 followed by spontaneous concerted ring opening involving the most strained C2-C3-C4 bonds (with bond angle 94°) and the C2 bridgehead leading to anti-endo elimination of the C1-mesyloxy group by the conjugate base of adenine or thymine to give two diastereomeric C3'(S) and C3'(R) derivatives of 1-thyminyl and 9-adeninyl cyclohexene, and a mechanistic rational has been formulated. Paper IV (J. Org. Chem. 2014, 79, 7266−7276) focuses on the diastereospecific synthesis of E/Z bicyclo[2.2.1]heptane-7- and oxabicyclo[2.2.1]heptane-8-oximes and their corresponding C-nitroso derivatives. The comparative kinetic and thermodynamic studies of the conversions of the C-nitroso side products to the required oximes have been delineated leading to the synthesis of desmethyl sugar derivatives.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1964. / Typescript. Includes abstract, computer source code, and vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 328-337).