Usage of Flavinium Salts as Catalysts of Oxidation Reactions Summary This diploma thesis deals with use of flavinium salts as a catalysts of oxidation reactions. 3,7,8,10-tetramethylisoalloxazin 25, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate 16 and 5-ethyl-1,3-dimethylalloxazinium perchlorate 26 had been prepared. Salts 16, 26 and other previously prepared phlavinium salt 28 were tested as potential catalysts for the oxidation of phenylboronic acids to the corresponding phenols, and especially for the use of oxygen as the oxidizing agent. The best solvent systems were found through testing and followed possible influence of the substituent on the phenyl ring of boronic acid was investigated. This initial screening can be used as a basis for further and more detailed testing of catalytic efficiency of flavinium salts and to study the oxidation mechanism.

The exposure of plants to high salt concentrations causes accumulation of sodium ions. This leads to the inability of the plants to uptake water, a disturbance of ion homeostasis, a decrease in photosynthesis and oxidative stress. As a result of the salt stress, the availability of NADPH decreases. The adaptation to the concentrations of salt depends on plant's ability to compensate for the decreased availability of NADPH, which can be further used in antioxidative cycles and the synthesis of antioxidative compounds and osmoprotectants. In this work, the reduction of relative water content, a decrease in the Rubisco enzyme activity, an increase of Hsp70 in the leaves and an increase in the accumulation of sodium ions was shown in cucumber plants (Cucumis sativa L. convar. Jogger F1) exposed to salt stress (100 mM NaCl). As a consequence of salt stress, an increase in the activity of NADPH providing enzymes was found. Particularly on the second and third day of salt stress, an increase in the activity (up to 270 %) of: NADP-isocitrate dehydrogenase, glucose-6-phosphate dehydrogenase, NADP-malic enzyme, non-phosphorylating glyceraldehyde-3-phosphate dehydrogenase in leaves was detected. The activity of less abundant NADP-dehydrogenases (glucose 1-dehydrogenase, gluconate 2-dehydrogenase, galactose...

The thesis deals with moisture transport in porous medium of quartz sandstone. Capillary water and its movement is crucial for processes such as salt and frost weathering, growth of organisms and development of honeycombs and tafone. However, moisture transport is still not well described. I focused particularly on two new methods applied to sandstone investigation. In the laboratory I studied moisture transport in sandstone samples by means of repeated injection of uranine solution. I observed the evolution of evaporation front based on the changes in solution concentration indicated by difference in color of uranine solution. Additionally I investigated moisture content in the shallow subsurface of sandstone outcrops in the field using suction pressure and moisture content measurements by microtensiometers and TDR in three locations in the Bohemian Cretaceous Basin. Uranine proved to be an excellent tracer for visualization of the evaporation front geometry and its evolution in time. The results suggest that moisture transport is considerably affected by the presence of biofilms which are hydrophobic and retain moisture transport to surface. In addition, the values of suction pressure measured in honeycombs and a tafone are in agreement with the salt weathering model proposed by Huinink et al. (2004).

Master of Science / Food Science Institute / Elizabeth Boyle / Intrinsic factors impact Listeria monocytogenes growth in ready-to-eat poultry products. Sliced deli turkey was formulated with in-going concentrations of 1.5% NaCl or 0.75% NaCl/0.75% KCl, 0 ppm or 200 ppm NaNO[subscript]2, and using 10% or 45% pump for a total of 8 treatments. Turkey roasts were sliced and inoculated with a 5-strain L. monocytogenes cocktail or peptone water (control), vacuum packaged, and stored at 4[degree]C. Treatments were sampled on days 0, 7, 14, 21, 28, 42, 63, and 91 of storage to determine L. monocytogenes mean log growth and aerobic plate count (APC). The pH, water activity, residual nitrite concentration, and percent fat, moisture, protein, and sodium were measured using control treatments on each sampling day. There was a nitrite by day and a percent pump by day interaction (P<0.05) for L. monocytogenes and APC populations. Listeria monocytogenes populations in treatments containing 200 ppm NaNO[subscript]2 were 0.70 to 2.39 log CFU/cm[superscript]2 lower compared with products formulated with 0 ppm NaNO[subscript]2. Using 10% pump reduced L. monocytogenes populations by 0.62 to 1.50 log CFU/cm[superscript]2 on days 7 to 28 and at day 63 compared with 45% pump treatments. Incorporating 1.5% NaCl or 0.75% NaCl/0.75% KCl into formulations did not affect (P>0.05) L. monocytogenes populations during storage. On days 7 through 91, APC populations were 0.76 to 2.96 log CFU/cm[superscript]2 lower with inclusion of 200 ppm NaNO[subscript]2 compared to 0 ppm NaNO[subscript]2. There was a treatment by day interaction (P<0.05) for L. monocytogenes populations and APC. The initial inoculum level of L. monocytogenes averaged 2.21 log CFU/cm[superscript]2 and was similar (P>0.05) for all treatments on day 0. Listeria monocytogenes populations increased (P<0.05) from day 0 to 14 by 1.30 to 5.04 log CFU/cm[superscript]2. Overall, L. monocytogenes populations increased during storage and by day 91 L. monocytogenes populations were similar regardless of NaNO[subscript]2 level used except for treatments formulated with 0.75% NaCl/0.75% KCl and 10% pump. Listeria monocytogenes and APC populations were influenced by nitrite concentration and percent pump, while inclusion of NaCl or NaCl/KCl did not affect L. monocytogenes growth during refrigerated storage in vacuum packed sliced deli turkey.

Doctor of Philosophy / Department of Chemical Engineering / Peter H. Pfromm / The expanded Renewable Fuel Standard (RFS2), established under the Energy Independence and Security Act (EISA) of 2007, mandates the production of 136.3 GL/year of renewable fuels in the U.S. in 2022: 56.8 GL/year of corn-ethanol, 60.6 GL/year of second generation biofuels such as cellulosic ethanol, and 18.9 GL/year of advanced biofuels such as biomass-based diesel. One of the several challenges when a biochemical conversion technique is used to produce bioethanol from corn and cellulosic feedstock is the high energy demand for recovering and purifying ethanol, which is mainly due to the low concentration of ethanol in the fermentation broth and the challenging water-ethanol vapor liquid equilibrium. Dilute ethanol from the fermentation broth can be separated and concentrated aided by salt extractive distillation to directly produce fuel ethanol leading to significant energy savings. Techniques other than highly energy intensive evaporative salt concentration/crystallization and solids drying for recovering salt, which is used to facilitate distillation, have rarely been considered. In this study, a novel combination of electrodialysis and spray drying was investigated to recover the salt. Salt extractive distillation – with salt recovery enabled by electrodialysis – was conceptually integrated in the fermentation broth-ethanol separation trains of corn and cellulosic ethanol facilities and investigated through process simulation with Aspen Plus® 2006.5 to reduce the recovery and purification energy demand of bioethanol. Experiments for the electrodialytic concentration of calcium chloride from high diluate concentrations, prevalent in the salt recovery process when calcium chloride is used as the salt separating agent in the salt extractive distillation of bioethanol, were carried out to determine the fundamental transport properties of an ion exchange membrane pair comprising commercially available membranes for implementation in the conceptual process designs. The maximum calcium chloride concentration achievable through electrodialytic concentration is 34.6 wt%, which is mainly limited by the water transport number. In case of corn-ethanol, retrofitted salt extractive distillation resulted in an energy demand reduction of about 20% and total annual cost savings on the order of MM$0.5 per year when compared with the state-of-the-art rectification/adsorption process for producing fuel ethanol from the beer column distillate. In case of cellulosic ethanol, salt extractive distillation with direct vapor recompression provided the highest energy savings of about 22% and total annual cost savings on the order of MM$2.4 per year when compared with the base case comprising conventional distillation and adsorption for recovering and purifying ethanol from the fermentation broth. Based on the conceptual process design studies, an overall maximum energy savings potential of 1.5*10[superscript]17 J or about 0.14 Quad (as natural gas higher heating value) per year could be estimated for the targeted 56.8 GL of corn-ethanol and 60.6 GL of cellulosic ethanol to be produced in the U.S in 2022 when salt extractive distillation enabled by electrodialysis is implemented in the fermentation broth-ethanol separation trains of the corn and cellulosic ethanol facilities.

Water is a simple molecule but is an essential part of life. One key aspect of the properties of water is the hydrophobic effect, and whilst there is an appreciation of this phenomenon at the macro-scale (raindrops falling off leaves) and the micro-scale (the structure of cellular systems), a complete understanding at the molecular level still eludes science. Addressing this issue, our studies involve synthetic supramolecular compounds that assemble in water via the hydrophobic effect. First of all, a novel water-soluble deep-cavity cavitand was synthesized. It possesses four endo methyl groups on top rim of the cavitand, eight water-solubilizing carboxylic acid groups coated on the cavitand exterior, and a relatively large hydrophobic interior. Compared to a previous well-studied water-soluble deep-cavity cavitand octa-acid (OA), this novel cavitand (TEMOA) possesses a non-monotonic assembly profile in the presence of a homologous series of straight-chain alkanes. Three supramolecular species were observed: 1:1, 2:2, and 2:2 and they are approximately isoenergetic. Second, we examined the guest-controlled self-sorting in assemblies. A mixture of OA and TEMOA formed hetero-capsular complex driven by the hydrophobic effect. The extent of homo- or hetero-dimerization is intimately tied to the size of the guest being encapsulated. TEMOA is less predisposed to dimerize than OA, thus TEMOA possesses the ability to form various self-assembled states, such as tetrameric and hexameric assemblies. Furthermore, we also discussed our observation of how external stimuli such as changing the nature or concentration of a co-solute salt influences a unique, unusual transition from one assembled state to another.

Accumulations of brackish groundwater exist across south Louisiana within the shallow, south-dipping Pleistocene to Upper Miocene Baton Rouge Aquifer System (BRAS). This research investigates the source of brackish groundwater through geochemical analysis of representative groundwater samples by comparing the following geochemical ratios along with other trace elements. Low Bromide (Br)/Chloride (Cl) and Potassium (K) /Cl ratios, high Sodium (Na) /Cl ratios, trace Magnesium (Mg) concentrations, and low Strontium (Sr) 87/Sr86 in brackish waters from the BRAS are inconsistent with in situ saline water from marine formation fluids of similar age. The ratios are consistent with in situ saline-water sources from Lower Miocene or Paleogene formation fluids from dissolved recrystallized halite. Deep formation fluids have interacted with Louann Salt diapirs underlying the BRAS area, dissolving halite, and are shown to have moved up fault planes and entered shallow aquifers to mix with the in situ groundwaters.

The western portion of the Mississippi/Atwater fold belt in the Gulf of Mexico contains what is known as The Green Knoll Salt Dome. The creation and growth of this salt diapir is punctuated by salt deposition, salt migration, sediment loading, and is linked to the “Frampton” fold belt. An indicator of these growth periods is exhibited in an angular unconformity (halo-kinetic sequence boundary) that flanks the diapir. This unconformity developed during the Miocene-Pliocene chronostratigraphic boundary. The “Redwood” (Green Canyon 1001) prospect was drilled after the discovery of middle Miocene sands containing hydrocarbons in the Mad Dog field (GC 826). The objective Miocene sand in the “Redwood” borehole was thin due to this angular unconformity causing the sand to pinch out. An evaluation of seismic and well log data provided by Bureau of Ocean Energy Management indicated that the unconformity might not provide the seal needed to trap hydrocarbons on the flank of the salt dome, or it did not allow enough sand to be deposited. A palinspastic structural restoration of the Green Knoll Salt Dome revealed that the growth of the Green Knoll and Frampton are connected. It is still possible that if a well were to be drilled further down dip from where The “Redwood” prospect was drilled, one may find a potential hydrocarbon reservoir.

The stratified flow of the lower Mississippi River due to density gradients is a well documented phenomenon. This stratification of fresh and saline water manifests itself as a heavier wedge of saline water that extends upriver and a buoyant fresh water plume extending into the Gulf of Mexico past the Southwest Pass jetties. The maximum absolute distance of saltwater intrusion observed anywhere in the world occurred on the Mississippi River in 1939 and 1940 when saltwater was observed approximately 225 km upstream from the mouth of Southwest Pass. The U. S. Army Corps of Engineers now prevents the wedge from migrating upstream by constructing a subaqueous barrier in the river channel. A curvilinear grid was constructed representative of the modern Mississippi River delta. Boundary conditions were developed for the drought year of 2012 and the grid was tested in order to evaluate the salinity intrusion and sediment transport abilities of the Cartesian Z-coordinate Delft3D code. The Z-model proved to have the ability to propagate the saline density current as observed in the prototype. The effect of salinity on fine sediment transport is evaluated by manipulation of the settling velocity through a cosine function provided in the model code. Manipulation of the fine sediment fall velocity through the cosine function was an effective means to simulate the re-circulation of flocculated sediments in the saline wedge turbidity maxima. In addition, the Z-model capably reproduced the fine sediment concentration profiles in a fully turbulent shear flow environment. With the ability to reproduce the seasonal saline density current and its effect on sedimentation within the turbidity maxima as well as sedimentation characteristics in a fully turbulent shear flow, a model capable of analyzing all of the major processes affecting fine sediment transport within the Mississippi River salt wedge estuary has been developed.

Beneath Keathley Canyon (KC) off the Southern Coast of Louisiana and Texas, allochthonous salt bodies have attained thicknesses of over 7620 m (25000 feet), providing excellent seals and migration pathways for hydrocarbons produced by post-rift sedimentary deposition. This study analyzes a small portion of the KC area, utilizing Petrel Seismic software and well information from the KC102 (Tiber) well. An intra-Miocene wedge, expressed beneath salt, may provide information about movement of allochthonous salt over Wilcox sands, sediment compaction, and hydrocarbon pathways. Progradational sedimentation is the driving force which leads to faulting in the early Miocene, allowing Jurassic salt to rise, spreading laterally and upwards towards the surface, scarring the sediments beneath it in glacier-like form. This intrusion helped to create the proper conditions for formation of a petroleum play system, maintain reservoir quality sands and temperatures, and create a four way closure in the Eocene for prospective well location.