Composite liners are used in landfills to isolate solid waste from the local environment. The combination of a high-density polyethylene (HDPE) geomembrane and compacted clay liner (CCL) is commonly used worldwide. In the Ontario region, bentonite sand mixtures (BSMs) and the local clay i.e. Leda clay, can be considered as appropriate CCL materials. However, the interface failure between smooth HDPE and CCL is a critical issue for landfill safety. The shear stress behavior and strength parameters at the interface between the HDPE and CCL can be affected by many factors, such as temperature and chemicals. The temperature difference between winter and summer in the Ontario region is approximately 50°C, which causes a freeze-thaw (F-T) phenomenon in local landfills. Leachate and heat are generated during the solid waste stabilization process. Landfill leachate usually contains a high concentration of cations, which can carry heat, thus affecting the landfill liner properties. As a result, the interface shear stress behavior and strength parameters are affected by the aforementioned conditions. In this thesis, a series of experiments were conducted on the shear stress behavior at the interface of Leda clay / HDPE and bentonite sand mixture (BSM) / HDPE. In order to understand the influence of the F-T phenomenon, the samples were tested by varying the number of F-T cycles. Meanwhile, in order to understand the combined influence of cations and heat, the samples were saturated with different solutions, i.e. distilled water, potassium chloride and calcium chloride solutions. Then they were cured in an oven with different temperatures and room temperature, respectively. All of the laboratorial shear tests have been performed by using a direct shear machine. Results show that the BSM /HDPE and Leda clay/ HDPE interfaces are both influenced by the F-T cycles. The BSM/HDPE interface shear of the samples between 0 and 5 F-T cycles has more obvious differences, while the friction angle of compacted Leda clay/HDPE exhibits distinct reduction in the first 3 cycles, after which, the difference becomes hard to differentiate. The results also indicate that both high temperature and high concentration of cations from leachate can slight reduce the interface shear stress of BSM/HDPE. However, the combined influence of thermal-chemical conditions is not much more obvious compared to the effects of a single thermal or chemical condition. The BSM materials, which were saturated with different solutions, are also tested by using X-ray diffraction to examine the mineral changes in the BSM. The calcium and potassium cations convert sodium-bentonite into calcium-rich bentonite and illite/semectie mixtures, respectively. Nevertheless, the changess of clay part caused by the combined effect of heat and leachate have limited influence on the BSM/HDPE interface shear behavior.

Foram utilizadas 8 vacas Holandesas em lactação, distribuídas em um quadrado latino (4x4), replicado, conduzidos durante o verão, por um período de 72 dias. O objetivo desse trabalho foi estudar quatro níveis de dietas catiônicas, sobre a IMS, produção, composição e propriedades físico-químicas do leite, pH urinário, temperatura corporal e parâmetros ácido-base do sangue, em vacas após o pico de lactação. Para a manipulação do BCAD, foram adicionadas diferentes concentrações de bicarbonato de sódio nas dietas, obtendo-se os seguintes tratamentos: +150, +250, +400 e +500mEq/kg MS. A temperatura corporal das vacas não foi afetada pelo balanço cátion-aniônico da dieta. O bicarbonato, o pH, o CO2 total e a pCO2 do sangue aumentaram linearmente com o aumento do BCAD. A concentração de cálcio no sangue apresentou resposta quadrática, com maior valor para o menor BCAD. As concentrações de sódio e potássio do sangue não foram modificadas significativamente pelo BCAD e a concentração de cloro diminuiu linearmente com o aumento do BCAD. O aumento do BCAD resultou em aumento da ingestão de matéria seca e produção de leite. Não houve diferença significativa para as variáveis: porcentagem de gordura, densidade e índice crioscópico, do leite. O pH do leite aumentou linearmente e a acidez apresentou resposta cúbica, com o aumento do BCAD. Conclui-se que a manipulação do BCAD afeta o equilíbrio ácido-base das vacas, mesmo dentro de variação positiva. Devido ao aumento da IMS e da produção de leite, verificou-se efeito benéfico do uso de dietas catiônicas, para vacas após o pico de lactação. / Eight lactating Holsteins cows were distributed in 4 x 4 replicated Latin square, during the summer, for a period of 72 days. The objective of this research was to study the effect of four cationic diets levels, on the dry matter intake, milk production, composition, and physico-chemical parameters, urinary pH, body temperature and blood acid-base parameters, in cows, after the lactation peak. For DCAB manipulation were added different concentrations of sodium bicarbonate in the diets and the following treatments were obtainned: +150, +250, +400 e +500mEq/kg DM. The cows body temperature was not affected by dietary cation-anion balance. Blood bicarbonate, pH, total CO2 and pCO2 increased linearly with the increase of dietary CAB. Calcium concentration in the blood decreased quadratically with dietary CAB increased. Sodium and potassium concentration in the blood were not modified significantly with the DCAB and concentration of chloride decreased linearly with increase of DCAB. Increasing BCAD resulted in higher DM intake and milk yield. The diets did not affect milk fat percentage, density and crioscopic index. Milk pH increased linearly and acidity decreased cubically with the increase of dietary CAB. It was concluded that DCAB manipulation affected the acid-base status of cows, even inside of positive variation. Due to the increase of DM intake and milk yield, it was verified a beneficial effect of the cationic diets for cows after the lactation peak.

The objective of this study was to investigate the role of organic cation transporters (OCTs) in the uptake of hydrophilic drugs into the olfactory bulb and subsequently to the brain. Two OCT2 substrates, amantadine and cimetidine were used as model drugs for this purpose. Bovine nasal explants (olfactory and respiratory tissue) were used as an in vitro model for preliminary screening to identify the role of transporters involved in the uptake of drug across these tissues. It was observed from both PCR and immunohistochemistry that OCTs, OCT2, OCTN1 and OCTN2 were present in the bovine respiratory and olfactory mucosa. Transport studies of amantadine in the presence and absence of OCT2 and OCTN2 inhibitors indicated that both these transporters play a role in the transport of amantadine across the bovine respiratory mucosa, whereas transport across the olfactory mucosa was predominantly via OCT2. This was followed by in vivo studies in rats where the blood, striatum and olfactory bulb concentrations of amantadine were determined following intranasal and intra-arterial administration. Shortly after nasal administration, the olfactory bulb concentrations exceeded the concentrations in the striatum suggesting the olfactory pathway to be the major route of uptake. Co-administration of the drug with an OCT2 inhibitor intranasally showed statistically significant reductions in the brain uptake of amantadine. A synergistic inhibitory effect on amantadine uptake was observed with the combined inhibition OCT2 and OCTN2. Additionally, the CNS exposure of these drugs following intranasal administration in the presence and absence of the OCT inhibitors was evaluated using the ratio of the free drug concentrations in the brain compared to plasma. While the plasma concentration profiles were similar both in the presence and absence of inhibition, the free drug ratios were highest when no inhibitor was included. Additionally similiar in vivo studies were also carried out for a second model drug, cimetidine, where cimetidine uptake into the rat brain was found to be significantly reduced in the presence of the OCT2 inhibitor, pentamidine. This demonstrates that there was a greater CNS exposure to each drug when OCT transporters were active, confirming their role in their direct CNS distribution from the nasal cavity to the brain. The results of this study suggest that OCT substrates might be good candidates for the delivery to the brain via the olfactory route.

>Magister Scientiae - MSc / In this thesis, we construct the ultrafilter space of a topological space using ultrafilters as points, study some of its properties and describe a method of generating compactifications through the ultrafilter space. As part of investigating some properties of the ultrafilter space, we show that the ultrafilter space forms a monad in the category of topological spaces. Furthermore, we show that rendering the ultrafilter space suitably separated results in a generation of separated compactifications which coincide with some well-known compactifications. When the ultrafilter space is rendered T0 or sober, the resulting compactifications is a stable Compactifications. Rendering the ultrafilter space T2 or Tychono results in the Stone_ Cechcompactification

Thesis advisor: Shih-Yuan Liu / Described herein are two projects on the application and effects of BN/CC isosterism on indole-containing compounds. In the first chapter, the synthetic route to an unnatural boron and nitrogen-containing analogue of tryptophan (BN-tryptophan) via late-stage functionalization of BN-indole is disclosed and its spectroscopic properties are reported with respect to the natural amino acid, tryptophan. The incorporation of BN-tryptophan into proteins expressed in E. coli using selective pressure incorporation, a residue specific method of unnatural amino acid incorporation, is then reported and its reactivity and fluorescence in the proteins characterized. In the second chapter, the synthesis of a BN-indole-containing aromatic scaffold is reported and the cation-π binding ability characterized by nuclear magnetic resonance (NMR) monitored titrations is disclosed. The resulting chemical shifts were analyzed using a non-linear curve fitting procedure and the extracted association constants (Ka’s) compared with the natural indole scaffold. Computations were also performed to support the titration results. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

A laboratory test program was conducted to determine the moisture-suction relationships of geosynthetic clay liners (GCLs). Moisture-suction relationships were determined by combining suction data from pressure plate tests, contact filter paper tests, and relative humidity tests, then fitting water retention curves (WRCs) to the data. WRCs were determined for wetting processes and drying processes in terms of gravimetric moisture content and volumetric moisture content. The effects of GCL type, hydration solution, wet-dry cycles, and temperature on the moisture-suction relationships were analyzed. The three GCLs of the test program consisted of configurations of woven and nonwoven geotextiles reinforced with needlepunched fibers. A geofilm was adhesively bonded to the nonwoven side of one of the GCL products. The hydration solution tests involved hydrating GCLs with deionized water, tap water, 0.1 M CaCl2, or soil water from a landfill cover test plot for a 30-day conditioning period prior to testing. Cyclic wet-dry tests were conducted on the GCL specimens subjected to 20 wet-dry cycles from 50% to 0% gravimetric moisture content prior to testing. Temperature tests were conducted at 2°C, 20°C, and 40°C. GCL type affected moisture-suction relationships. The GCLs with an adhesively-bonded geofilm exhibited lower air-entry suction and higher residual suction than GCLs without a geofilm. The degree of needlepunched fiber pullout during hydration contributed to hysteresis between wetting WRCs and drying WRCs. Hysteresis was high for suction values below air-entry suction and was low for suction values greater than air-entry suction. Cation exchange reduced the water retention capacity for all three GCL types. The saturated gravimetric moisture contents were reduced from approximately 140% to 70% for wetting WRCs and 210% to 90% for drying WRCs for GCLs hydrated in deionized water compared to CaCl2 solution. Hysteresis of the nonwoven product decreased from 71%, to 62%, to 28% with respect to deionized water, tap water, and CaCl2 solution. Hysteresis of the woven product exposed to soil water was 24% and 0%, in terms of saturated gravimetric moisture content and saturated volumetric moisture content, respectively. The swell index, Atterberg Limits, mole fraction of bound sodium, and scanning electron microscopy images that were determined of bentonite from the conditioned GCLs indicated that changes in water retention capacity corresponded with cation exchange. Wet-dry cycles and temperature affected the moisture-suction behavior for GCLs. Wet-dry cycles reduced hysteresis and increased the swelling capacity of GCL specimens. Microscopy images indicated that wet-dry cycles caused weak orientation of the clay particles. Increasing temperature resulted in a small decrease in water retention capacity. Results of the test program provided a means for predicting unsaturated behavior for GCLs.

Protein folding studies have provided important insights about the key role of non-covalent interactions in protein structure and conformational stability. Some of these interactions include salt bridges, cation-π, and anion-Ï€ interactions. Understanding these interactions is crucial to developing methods for predicting protein secondary, tertiary, quaternary structure from primary sequence and understanding protein-protein interactions and protein-ligand interactions. Several studies have described how the interaction between two amino acid side chains have a substantial effect on protein structure and conformational stability. This is under the assumption that the interaction between the two amino acids is independent of surrounding interactions. We are interested in understanding how salt bridges, cation-π, and anion-π interactions affect each other when they are in close proximity. Chapter 1 is a brief introduction on noncovalent interactions and noncovalent interaction cooperativity. Chapter 2 describes the progress we have made measuring the cooperativity between noncovalent interactions involving cations, anions and aromatic amino acids in a coiled-coil alpha helix model protein. Chapter 3 describes cooperativity between cation, anion, and nonaromatic hydrophobic amino acids in the context of a coiled-coil alpha helix. In chapter 4 we describe a strong anion-π interaction in a reverse turn that stabilizes a beta sheet model protein. In chapter 5 we measure the interaction between a cysteine linked maleimide and two lysines in a helix and show that it is a general strategy to stabilize helical structure.

No description available.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23598号 / 理博第4760号 / 新制||理||1682(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 若宮 淳志, 教授 倉田 博基 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethoxysilane with PTA in acidic media. The obtained material had high BET surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its XRD patterns were absent. This proved the embedding of PTA on a sub-molecular level. The material demonstrated high adsorption capacity of Cs. Unexpectedly, porosity of the adsorbent increased after substitution of most protons by cesium cations. Cation exchange also favored agglomeration of the material particles. Kinetic studies showed that the adsorption data correlates strongly with the pseudo-second order model. The adsorbent had two types of adsorption sites: heteropolyacid anions and silanol groups. However, adsorption on silanol groups was very sensitive to the temperature. At the increased temperature, the nature of adsorption fit the Langmuir model extremely well. The obtained results can be used in the development of an effective adsorbent for clean-up of water contaminated by radioactive cesium-137.