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An electrochemical cell consisting of a flow-through yttria-stabilized zirconia (YSZ) sensor and a flow-through Ag/AgCl reference electrode has been employed to measure pH of high-temperature acidic sulphate solutions relevant to the pressure acid leaching (PAL) of nickel laterites. In a previous study, this cell was used to measure pH of H2SO4, Al2(SO4)3-H2SO4 and MgSO4-Al2(SO4)3-H2SO4 solutions at 250oC. In this work, the solutions range in complexity from the binary MgSO4-H2SO4, NiSO4-H2SO4, and Al2(SO4)3-H2SO4, through the ternary MgSO4-Al2(SO4)3-H2SO4 and NiSO4-Al2(SO4)3-H2SO4, to the PAL process solutions, whereas the temperature ranges from 200oC to 250oC. The measured and theoretical pH values typically agree within less than 0.1 pH unit and 0.2 pH units in synthetic solutions and PAL solutions, respectively. This is an improvement over the results of the previous study in synthetic solutions, which show differences between theory and experiment as high as 0.4 pH units. The conversion of measured potentials into pH values is based on the new mixed-solvent electrolyte (MSE) speciation model of the OLI Systems software calibrated independently based on solubility measurements. Both Henderson’s equation and the exact definition of the diffusion potential were employed in treating the obtained experimental data. Experimental pH values calculated using the diffusion potentials evaluated by either approach are essentially the same. This finding suggests that Henderson’s equation, which is based on readily available limiting ionic mobilities, can be effectively used. Lithium chloride is found to be a suitable alternative to sodium chloride as the reference electrode solution for the measurement of pH of aluminium-containing solutions, because it did not induce precipitation of aluminium as an alunite-type compound. The experimental results indicate that the high-temperature behaviour of Ni, Co and Mn sulphates can be satisfactorily approximated with that of MgSO4. The experimental findings also support the postulation that acid should be added to a PAL process so that the solution pH is around 1 at the leach temperature, regardless of the feed composition. The cell can be used for hydrometallurgical process research and development on a laboratory scale with very satisfactory performance, provided that a well-behaved YSZ sensor is available.

Class of 2009 Abstract / OBJECTIVES: The primary objective of this experiment was to characterize the pH stability range of 20% Pluronic lecithin organogel (PLO). We intended to determine the viscosity at varying pHs. We prepared six samples of 20% PLO. METHODS: An initial rheological reading of each sample was recorded by a dynamic stress rheometer. Each sample was titrated drop-wise with citric acid or KOH in 0.5 pH increments. When the desired pH was obtained, a 0.5 mL sample was analyzed with a dynamic stress rheometer, RS-200, using Rheos software. RESULTS: Since PLO is a non-Newtonian substance, viscosity changed relative to shear stress and we were not able to examine a correlation of pH with viscosity. Instead we inputted the data into Microsoft Excel® and plotted a shear stress versus viscosity curve for each sample to identify trends. CONCLUSIONS: We were unable to achieve our primary objective of determining the viscosity characterization of 20% PLO at varying pHs due to the non-Newtonian nature of the material. Subjectively, we determined the viscosity of 20% PLO is not substantially affected by pH. Other factors such as temperature, excess liquid, and surfactant ability may influence viscosity and need to be examined in the future.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Memoria para obtener el título de Química / Chile es uno de los diez mayores productores de vino en el mundo y el cuarto exportador a nivel global, alcanzando una producción de más de mil millones de litros en el año 2016. Para la elaboración de vinos de calidad, existen diversas variables de importancia tales como la temperatura de producción, los niveles de exposición al oxígeno, el pH, el contenido de compuestos fenólicos, metales, entre otros. De hecho, el vino (particularmente el vino tinto) es un producto reconocido por su alta concentración de compuestos fenólicos y capacidad antioxidante (CA), los que se vinculan no solo a determinadas propiedades fisico-químicas y sensoriales, si no que a los potenciales efectos beneficiosos sobre la salud derivados de su consumo moderado. En este trabajo, se realizó un análisis para evaluar la contribución relativa de diversos constituyentes del vino a la capacidad antioxidante. Las variables en estudio fueron: pH, hierro y concentración de ácido galico (AG) o catequina (CAT) o ácido cafeico (CAF) según correspondiera, y los resultados fueron analizados mediante un diseño Screening Factorial 23 con el objetivo de obtener la capacidad antioxidante por el método Ensayo de DPPH. Para cada solución modelo donde los compuestos fenólicos fueron AG y CAT, se observó que solo estos generaron una contribución significativa y positiva a la capacidad antioxidante, resultando no significativas las variables: pH, hierro y sus interacciones. En cambio, para la solución modelo conteniendo CAF se obtuvo que la concentración de Fe (III), fue la única variable significativa, con contribución positiva a la CA, probablemente debido a la formación de ácido caftárico, el cual podría coordinar al Fe (III). De acuerdo a estos últimos resultados, se realizó un cuarto experimento, donde se utilizó Fe (II) en vez de Fe (III), en las mismas condiciones del experimento anterior, y se obtuvo un resultado diferente: las variables pH, CAF y la interacción pH-Fe(II) resultaron significativas, la primera con contribución negativa y las dos restantes con contribución positiva. El pH podría afectar la cupla redox Fe(II)/Fe(III) y esto influir en la coordinación del ácido caftárico. Para comprobar el estudio anterior, se realizó otro experimento para evaluar la CA, pero en vino tinto real. Para este efecto, se utilizó un tratamiento con resina de intercambio catiónico para analizar un mismo vino a diferentes pH y concentración de hierro, de esta forma se obtuvo: un vino a pH 2,3 y ≈0 mg L-1 de hierro (Vino CR) y un vino a pH 3,4 y ≈1 mg L-1 de hierro (Vino SR). Mediante el método ORAC-FL, la CA inicial de ambos vinos disminuye en el tiempo, lo contrario se observó por el método DPPH, la CA aumentaba, probablemente por efecto de reacciones de copigmentación en el vino. Para estudiar el efecto del hierro se fortificó ambos vinos a una concentración de 5 mg L-1 de hierro (III), se obtuvo, inicialmente, que por ORAC-FL la capacidad antioxidante aumentó en comparación al vino sin dopar y, al transcurrir 21 dias ocurría lo mismo. Por DPPH la capacidad antioxidante de los vinos fortificados fue menor frente a los no fortificados y esto se mantuvo en el tiempo. Respecto al estudio del efecto de pH en el vino, los resultados demostraron que el pH no tenía mayor incidencia en la capacidad antioxidante por el método ORAC-FL, probablemente debido a que este implica el uso de buffer a pH 7,4. Mediante DPPH se observó un aumento de la CA para vinos SR y CR a medida que aumentaba el pH en el rango 3,0>pH>4,0 y, en el tiempo, sólo se observó un aumento de la CA en los vinos SR / Chile is one of the ten wine-producing countries in the world and the fourth of wineexporting countries, reaching a production of over a billion liters in 2016. In the production of quality wines there are many important variables such as oxigen exposure, pH, phenolic content, metals, among others. In fact, wine (red wine, particularly), is known for its high phenolic content and antioxidant capacity that are not just related to physicochemical and sensory properties but also to the potential beneficial effects on health derived from moderate consumption. In this research an analysis to evaluate the relative contribution of various constituents of the wine to the antioxidant capacity was performed. The variables under study were: pH, iron and gallic acid (AG) or catechin (CAT) or caffeic acid (CAF), and the results were analyzed through an Screening factorial 23 design with the goal to obtain the antioxidant capacity by DPPH. In the model wine solution with AG and CAT was observed that only these factors generated a significant and positive contribution to the antioxidant capacity resulting in non significant variables: pH, iron and their interactions. However, for the solution containing CAF, the Fe (III) concentration was the only significant variable, with a positive contribution to CA, probably due to the formation of caftaric acid, which could coordinate Fe (III). According to the latter results, a fourth experiment was performed, where Fe (II) was used instead of Fe (III), under the same conditions of the previous experiment, and a different result was obtained: pH, CAF and the pH-Fe (II) interaction were significant, the first with negative contribution and the remaining two with a positive contribution. The pH could affect the Fe (II) / Fe (III) redox couple and this may influence the caftaric acid coordination. To verify the previous study, another experiment was conducted to evaluate CA, but now in real red wine. For this purpose, a cation exchange resin treatment was used to obtain the same red wine at different pH and iron concentration: CR Wine (pH 2.3, ≈0 mg L-1 iron), SR Wine (pH 3,4; ≈1 mg L-1 iron). By ORAC-FL method, the initial CA of both wines decreased over time, on the other hand by the DPPH method was observed, the CA increased, possibly due to co-pigmentation reactions in wine. To study the iron effect, both wines were fortified at a concentration of 5 mg L-1 of iron (III). Initially by ORAC-FL it was found that the antioxidant capacity increased compared to non-fortified wine, after 21 days the same result was obtained. By DPPH method the antioxidant capacity of fortified wines was lower compared to nonfortified wines and this was maintained over time too. Regarding the pH study effect in wine, the results showed that the pH had no higher incidence in the antioxidant capacity by the ORAC-FL, probably because this method involves the use of buffer at pH 7.4. DPPH increased the antioxidant capacity for SR and CR wines as the pH increased in the range 3.0> pH> 4.0 and, over time, only an increase in AC was observed in SR wines

This thesis reports the design and development of novel voltammetric pH sensors for buffered, low-buffered and unbuffered media. pH sensors in stagnant and hydrodynamic environments were designed and developed for performing measurements using square wave voltammetry. Chapter 1 introduces the motivation of this project, the current development of electrochemical sensors, and the basic theory and techniques of electrochemistry concerned within the thesis. The existing development of carbon-based electrochemical sensors and the application of screen-printing technology in sensor fabrication are highlighted. Chapter 2 introduces the screen-printing technology and the fundamental methods of numerical simulation. In addition, reagents, equipment and software packages used in the thesis are listed in this chapter. In Chapter 3, a novel design of quinone derivative-based pH probes is presented for the application in stagnant weakly buffered media (< 1mM), based on previous studies of quinone compounds in buffered media. The results from the weakly buffered system is consistent with the results in buffered systems. To further extend the application of this design in unbuffered media, a numerical model of a pH-sensitive redox particle immobilised on an electrode was developed, which predicted that the accumulation of hydrogen ions near the electrode is the possible limiting factor for the performance of this design in unbuffered media. To develop a pH-monitoring technology for unbuffered media, Chapter 4 reports on the design, fabrication and testing of different electropolymerised-phenol derivative modified electrodes, which overcome the limitation of hydrogen ions accumulation. The results revealed that 2-(methylthio)phenol graphite resin electrodes have high accuracy (ca. 1% error) in unbuffered media, benchmarked by a commercial glass pH meter. This is the first detailed study on the v application of the economical and scalable technology in pH sensing in unbuffered environment. Chapter 5 presents a unique design of electrochemical pH sensors, free from the need to use a glass reference electrode. This design integrates a pH indicator and an internal reference electrode. Different designs of ferrocene screen-printed electrodes were tested as the internal reference electrode. The nafion-coated ferrocene screen-printed electrode showed stable peak potential in a wide pH range (pH 1 - 12) with good durability (stable in 500+ cycles of test). It was then cross connected with an alizarin electrode, forming the pH sensor free from a glass reference electrode. Chapter 6 describes novel designs of hydrodynamic pH sensors. The design of a microfluidic pH sensor modified by poly-sodium salicylate was firstly demonstrated. The sensor showed a Nernstian response in a wide pH range and, in hydrodynamic conditions, provided improved accuracy in unbuffered media compared to the stagnant state. For more convenient measurements, a novel rocking disc electrode was studied for pH sensing, modified with alizarin and poly-salicylic acid as pH indicators. The electrodes modified by both chemicals showed a Nernstian response in buffered media and the highest accuracy in unbuffered media was reached at 50 rpm.

O uso de composto de lixo (CL) e de lodo de esgoto (LE) na agricultura é uma alternativa viável para a melhor disposição destes resíduos urbanos em solos. Estudos de longo prazo podem melhorar o entendimento da dinâmica e as modificações que estes materiais ocasionam no solo e na resposta de plantas. O objetivo desse estudo foi avaliar os efeitos residuais (aplicações entre 2002 e 2006) e imediatos (reaplicação em 2015, após pousio) dos resíduos CL e LE, em dois solos [Latossolo Vermelho distroférrico (LVd) e um Argissolo Vermelho distrófico (PVd)], quanto às modificações em atributos químicos do solo, elementos-traços (ET) e resposta de plantas de aveia (Avena sativa) e milho (Zea mays). O experimento consta de colunas de solo, com aplicação de duas doses dos resíduos, CL e LE, com base no suprimento de nitrogênio, sendo a maior repetida e enriquecida com ET (Cd, Cu, Ni, Pb e Zn), além de tratamentos com adubação mineral e testemunha. Quanto aos efeitos residuais, na camada de 0-20 cm de ambos os solos, os resíduos promoveram maiores teores de C orgânico e P disponível e valores de CTC, porém o CL resultou em maiores valores de pH do solo. Com exceção do Cu, os teores de ET no solo diminuíram com o tempo. A produção de matéria seca de aveia diminuiu expressivamente após o longo período de pousio, possivelmente pela limitação em N. Os tratamentos com LE enriquecido com ET resultaram em maior acúmulo destes elementos na parte aérea da aveia. Após a reaplicação dos resíduos, o LE resultou em maior produção de matéria seca e maior acúmulo de macronutrientes (N, P, Ca e Mg) pelas plantas de milho em comparação ao CL. Os tratamentos com CL e LE enriquecidos determinaram nas plantas teores de ETS não essenciais considerados fitotóxicos. / The use of urban solid waste compost (SWC) and sewage sludge (SS) in agriculture is a viable alternative for better disposal of these urban residues in soils. Long-term studies may improve the understanding of the dynamic and changes caused by these materials in soils and plant responses. The aim of this study was to evaluate residual effects (applications from 2002 to 2006) and immediate effects (application in 2015, after a fallow time) of SWC and SS residues in two soils [Typic Haplorthox (LVd) and Arenic Paleudult (PVd)], regarding soil chemical attributes and trace elements (ET) and oat (Avena sativa) and corn (Zea mays) plant responses. The experiment is carried out in soil columns with application of two doses of both SWC and SS and also with the major dose enriched with ET (Cd, Cu, Ni, Pb and Zn), besides mineral fertilization and control treatments. Residue doses were established according N supply. Regarding residual effects in the 0-20 cm layer of both soils SWC and SS materials improved organic C and available P contents and CEC values, but soil pH was higher for SWC treatments. Except for Cu, soil ET contents decreases with time. Oat dry matter production was very small after the fallow time possibly due to low residual N supply. Treatments enriched with ET resulted in higher contents of these elements in oat shoots. After residue reapplication SS caused higher corn dry matter production and macronutrient (N, P, Ca and Mg) contents than SWC. Non-essential metal in levels possibly toxic for corn plants resulted from treatments with SWC and SS enriched with ET.

Un changement de pH peut induire une modification des propriétés chimiques et physiques des molécules, par exemple leur interaction avec la lumière. La modélisation de tels phénomènes est complexe en raison de l’ensemble statistique des états de protonation microscopiques et de la nature quantique de la propriété étudiée. Dans cette thèse, nous présentons un protocole de calcul qui associe une méthode capable d'échantillonner à la fois ces micro-états et les changements structuraux à un pH donné, et un cadre traitant la partie pertinente de la macromolécule avec des traitements avancés de mécanique quantique et le reste du système avec la mécanique moléculaire classique. Nous rapportons également la validation de ce protocole sur le relativement petit peptide M et son application à la rhodopsine sensorielle d'Anabaena, une protéine microbienne. Nous avons pu révéler quels sont les acides aminés titrables responsables du spectre d'absorption dépendant du pH de cette biomolécule / A change in the pH can modify the chemical and physical properties of molecules such as the way they interact with light. Modeling such phenomena is complex, because of the statistical ensemble of microscopic protonation states and of the very quantum nature of the property of interest. In this thesis, we present a computational protocol which merges a method capable of sampling at the same time these microstates and the structural changes at a given pH, and a framework treating the relevant portion of the macromolecule with advanced quantum mechanics treatments and the rest of the system with classical molecular mechanics. We also report the validation of this protocol on the relatively small peptide M and its application to the anabaena sensory rhodopsin, a microbial protein. We have revealed which are the titratable amino-acids responsible for the pH-dependent absorption spectrum of this biomolecule

Carbon dioxide (CO2) inhalation lowers brain pH and induces anxiety, fear, and panic responses in humans. In mice, CO2 produces freezing and avoidance behavior that has been suggested to depend on the amygdala. However, a recent study in humans with bilateral amygdala lesions revealed that CO2 can trigger fear and panic even in the absence of amygdalae, suggesting and important role for extra-amygdalar brain structures. Because the bed nucleus of the stria terminalis (BNST) contributes to fear- and anxiety-related behaviors and expresses acid sensing ion channel-1A (ASIC1A), we hypothesized that the BNST plays an important role in CO2-evoked fear-related behaviors in mice. We found that BNST lesions decreased both CO2-evoked freezing and CO2-conditioned place avoidance. In addition, we found that CO2 inhalation caused BNST acidosis, and that acidosis was sufficient to depolarize BNST neurons and induce freezing behavior; both responses depended on ASIC1A. Finally, disrupting Asic1a specifically in the BNST reduced CO2-evoked freezing whereas viral vector mediated expression of ASIC1A in the BNST of Asic1a-/- and Asic1a+/+ mice increased CO2-evoked freezing. Together, these findings identify the BNST as an extra-amygdalar fear circuit structure important in CO2-evoked fear-related behavior. Genetic disruption of the acid-sensing ion channel-1A (ASIC1A) in mice results in deficits in several fear- and anxiety-related behaviors. These deficits have been largely attributed to the loss of ASIC1A in neurons. However, recent studies have identified ASIC1A in several types of non-neuronal cells, including glia. To test the hypothesis that it is the loss of ASIC1A in neurons that results in the behavioral deficits seen in Asic1a-/- mice, we generated SynCre+Asic1aloxP/loxP mice, in which ASIC1A is disrupted specifically in neurons. To validate these mice, we confirmed by PCR that the Asic1a floxed allele was disrupted in brain, but not tail DNA. We further detected a reduction in ASIC1A protein in the SynCre+Asic1aloxP/loxP mice by western blotting and ASIC1A immunohistochemsitry. Further characterization of cre expression with a Rosa26 cre reporter mouse revealed that cre expression did not occur in all neurons, but verified that cre expression was neuron-specific. This neuron-specific knockout of ASIC1A led to behavioral deficits in several models of fear and anxiety, including cued and context fear conditioning, predator odor-evoked freezing and CO2-evoked freezing. Together, these findings suggest that it is ASIC1A in neurons that mediates these fear- and anxiety-related behaviors. Trimethylthiazoline (TMT), a predator odor isolated from fox feces, elicits freezing and avoidance responses in rodents. This TMT-evoked freezing behavior depends on the bed nucleus of the stria terminalis (BNST), a brain region thought to contribute to anxiety in both humans and mice. Because the acid-sensing ion channel-1A (ASIC1A) is robustly expressed in the BNST and has been previously implicated in TMT-evoked freezing, we hypothesized that the BNST might be a site of ASIC1A action in the TMT-evoked freezing response. Consistent with previous studies, we found that TMT-evoked freezing depended both on the olfactory bulb and on ASIC1A. Viral-mediated disruption of ASIC1A in the BNST reduced TMT-evoked freezing, whereas, viral mediated expression of ASIC1A in the BNST of Asic1a-/- mice increased TMT-evoked freezing. We further observed that TMT exposure induces a modest acidosis, likely due to TMT-induced respiratory suppression. However, this respiratory suppression was not unique to odors that evoke freezing, suggesting that it does not drive the TMT-evoked freezing response. Together, these findings suggest that the BNST is a key site of ASIC1A action in TMT-evoked freezing. Regulation of cerebral blood flow (CBF) is critical to insure that the brain has adequate resources to maintain normal function. One of the strongest regulators of CBF is carbon dioxide (CO2). CO2 and acidosis are thought to induce vasodilation and increase CBF by initiating nitric oxide (NO) synthesis, though the mechanism by which this occurs is unknown. Recent unpublished studies have suggested that the acid-sensing ion channel-1A (ASIC1A) plays a role in hypercapnia-induced vasodilation. Therefore, we hypothesized that CO2-induced NO production would depend on ASIC1A. We found that CO2 induced robust NO production in Asic1a+/+ but not Asic1a-/- mice. To test the role of neuronal ASIC1A in CO2-induced NO production, we generated SynCre+Asic1aloxP/loxP mice, in which ASIC1A is disrupted specifically in neurons. We found that CO2 did not induce significant NO production in the SynCre+Asic1aloxP/loxP mice, suggesting that it is ASIC1A in neurons that mediates this response. Together, these studies suggest that ASIC1A may mediate neurovascular coupling and regulate CBF.