A proposta deste trabalho é a produção de matrizes de nanotubos de dióxido de titânio seguindo os métodos de anodização eletroquímica de titânio estabelecidos da literatura. O objetivo central é a compreensão aprofundada das etapas do processo de crescimento dos nanotubos de TiO2, para posterior otimização de sua síntese visando as diferentes aplicações. Com este propósito foram realizados sistematicamente os seguintes estudos: das diferentes fases de crescimento dos nanotubos de TiO2, do efeito dos diferentes parâmetros de anodização na morfologia dos nanotubos e da reprodutibilidade dos processos. Visando as diferentes aplicações foram estudados métodos para obtenção de membranas autossustentadas e remoção de nanoresíduos. O método de camada sacrificial de fotoresiste positivo apresentou melhor resultado para remoção de nanoresíduos do topo dos nanotubos de TiO2 do que as demais técnicas. Por último, os arranjos obtidos com esta método foram aplicados na fabricação dos sensores de pH. / This work proposes the production of titania nanotubes arrays following the electrochemical anodization methods of a titanium sheet established in the literature. The main goal is a deep comprehension of the different TiO2 nanotubes growth stages for further optimization aiming the diverse applications. In this way the following systematic studies were performed: of the initial growth stages, of the effect of each anodization parameter on the nanotubes morphology and of the process reproducibility. In addition, methods for the production of self-sustained membranes as well as for obtaining a nanotube array surface free of nanoremnants were studied aiming the different applications. Positive photoresist bases sacrificial layer method presented a better result to eliminate nano-remnants on top of TiO2 nanotubes than other techniques. Finally, the nanotubes arrays obtained with this method were utilized for pH sensors fabrication.

Because of its high specific strength, durability, and biocompatibility, titanium is a widely used material for orthopedic implants. However, its insufficient binding with the surrounding bone tissue regularly leads to stress shielding, bone resorption and implant loosening. A promising solution to improve adhesion is to modify the implant surface chemistry and topography by coating it with a protein-eluting polyelectrolyte complex. Bone morphogenetic protein 2 (BMP-2), a potent osteoconductive growth factor, was adsorbed onto the surface of anodized titanium, and polyelectrolyte multilayer (PEM) coatings prepared from solutions of poly-L-histidine (PLH) and poly(methacrylic acid) (PMAA) were built on top of the BMP-2. The effect of solution pH during the deposition process was investigated. High levels of BMP-2 released over several months were achieved. Approximately 2 μg/cm² of BMP-2 were initially adsorbed on the anodized titanium and a pH-dependent release behavior was observed, with more stable coatings assembled at pH = 6-7. Three different diffusion regimes could be determined from the release profiles: an initial burst release, a sustained release regime and a depletion regime. Mass adsorption monitoring using quartz crystal microbalance with dissipation monitoring (QCM-D) showed that PLH was adsorbed in greater quantities than PMAA, and that more mass was adsorbed per bilayer as the number of bilayers grew. Moreover, the pH of the water used during the rinsing step significantly impacted the composition of the multilayer. Atomic force microscopy (AFM) and contact angle analysis (CAA) were used to determine the topography and surface energy of the PEMs. No visible change was observed in surface morphology as the assembly pH was varied, whereas the surface energy decreased for samples prepared at more basic pH. These variations indicate that the influence of the initial BMP-2 layer can be felt throughout the PEM and impact its surface structure.

Neste trabalho foi estudado o comportamento químico e geoquímico dos íons cobre, chumbo, níquel e zinco em área impactada por efluente industrial. Foram também consideradas uma área de montante não impactada que possibilitou a caracterização de background e outras duas áreas de jusante que possibilitaram a verificação da extensão da contaminação. Em cada área foram coletadas amostras de solo da Zona Não Saturada, Franja Capilar e Zona Saturada. Amostras de água subterrânea também foram coletadas, nos períodos chuvosos e de seca. O solo é composto essencialmente por Quartzo e Caulinita. Os resultados das análises granulométricas das amostras estudadas indicam textura predominantemente areia siltica e silte arenoso, já as análises químicas apontam para quantidades quase nulas de matéria orgânica, baixo CTC e ?pH negativo. A água subterrânea apresenta características ácidas, sendo que a Área Fonte apresenta pH médio inferior a 4. Nas áreas de Montante e Jusantes os valores médios de pH são respectivamente 6,7 e 5,7. Os resultados do estudo demonstraram que os altos teores de íons metálicos observados na Área Fonte podem estar associados por adsorção e oclusão junto às partículas de solo na forma de oxi-hidróxidos de Fe, Al e Mn. As altas concentrações da solução, principalmente de íons cobre, causaram saturação dos sítios de adsorção da caulinita ali presente, explicando as altas concentrações de íons também em água subterrânea. As baixas concentrações catiônicas observadas nas águas subterrâneas à Jusante possivelmente estão relacionadas aos fenômenos de dispersão, resultando na diluição da solução por variação na velocidade de percolação, bem como no transporte de contaminante de zonas mais concentradas para menos concentradas, caracterizado pela difusão. Fenômenos de adsorção e precipitação também contribuem para as baixas concentrações nas áreas de jusante, onde o pH se apresenta mais alto e as soluções mais diluídas. Assim como o sistema DPE e a barreira hidráulica, através do fenômeno de advecção. / The chemical and geochemical behavior of copper, lead, nickel and zinc was studied in an impacted area. It was also considered a not affected area located up gradient and one down-gradient to evaluate the extent of contamination. In each area soil samples were collected from the unsaturated zone and capillary fringe and saturated zone. Groundwater samples were also collected, in rainy periods and drought. The soil consists mainly of quartz and kaolinite. Soil texture analysis indicate texture predominantly sand-loam and silt-loam. Chemical analyses do not show a significant amount of organic matter, low CEC and DpH negative. Groundwater has acidic characteristics; source area has an average pH of less than 4. In the areas up gradient and down-gradient the mean values of pH are respectively 6.7 and 5.7. Results demonstrate that the high metallic ions levels observed in the source area may be associated by adsorption and occlusion with the soil particles in the form of oxy- hydroxides of Fe , Al and Mn. High ion metals concentrations observed in the source area, mainly copper ion, caused saturation of the adsorption sites, elucidating the elevated ion concentrations in groundwater. The low cationic concentrations observed in down-gradient groundwater can be linked to the dispersion phenomenon, resulting in dilution by variation in speed, as well as transport of contaminant from more concentrated to less concentrated zones, characterized by molecular diffusion . Adsorption and precipitation phenomena are expected to be in place at down gradient areas, where pH is higher and solutions more diluted. Finally, it is understood that the DPE system and the hydraulic barrier have also contributed through advection phenomenon to reduce concentrations in groundwater.

Etude expérimentale et modélisation, en fonction du pH et de la concentration en NaCl, du système ternaire U(VI)-NaCl-H2O à T = 155°C et pression de vapeur saturante. Une étude expérimentale sur la solubilité de l'U(VI) dans des saumures de NaCl (0.5 – 6 M) en fonction du pH (3-13) a été réalisée à T = 155°C et pression de vapeur saturante. Les résultats obtenus ont montré que la phase solide initiale UO3 se transforme en de multiples phases solides d'uranates de sodium de formule générale Na2xUyO(x+3y) hydratés dont le rapport molaire Na/U croit avec l'accroissement du pH et de la concentration de NaCl. La solubilité de l'U(VI) est directement gouvernée par trois paramètres physico-chimiques : le pH, le ligand Cl- et le cation Na+. Les deux premiers favorisent fortement la solubilité de l'U(VI) sous forme de complexes d'U(VI) avec les ligands OH- et Cl- à pH = 4. A la différence des deux premiers paramètres, le cation Na+ inhibe la solubilité de l'uranium (VI) en le précipitant sous forme de multiples composés d'uranates de sodium très peu solubles. Les résultats de mesures de solubilité de l'U(VI) obtenues servent de base de données de référence pour calculer les variations de la concentration de chaque complexe soluble d'U(VI) en fonction de deux paramètres, pH et [Na], à l'aide d'une équation de type exponentielle d’un paraboloïde elliptique négatif. Un modèle empirique a également été mis au point, à partir des équations de Pitzer, afin de déterminer, de manière continue, les variations des divers paramètres physico-chimiques des ions solubles présents dans une saumure de NaCl en fonction de quatre paramètres : pH, [Na], T et P du milieu réactionnel. Ce modèle est valable jusqu’à [NaCl] = 6M, T = 300°C et P = 100 MPa. / An experimental study on the solubility of U(VI) in concentrated (0.5-6.0 M) NaCl solutions as a function of pH (3-13) has been realized at 155°C and saturation vapor pressure. The obtained results indicate that the initial solid phase UO3 initial solid phase is transformed into multiple solid phases of hydrated sodium uranates with general formula Na2xUyO(x+3y), the Na/U molar ratio of which increases with increasing pH and NaCl concentration. The solubility of U(VI) is directly dependant of three physico-chemical parameters : the pH, the Cl- ligand, and the Na+ cation. The first two parameters strongly favour the U(VI) solubility in the form of aqueous U(VI) complexes with the OH-and Cl- ligands at a pH = 4, while the Na+ cation inhibits the solubility of U(VI) as it precipitates into various low solubility sodium uranates. The results of solubility measurements obtained for U(VI) serve as a reference data base for the calculation of concentration variations of each soluble U(VI) complex as a function of two parameters, pH and [Na], with the use of a negative elliptic paraboloïd exponential. An empirical model has also been developed from the Pitzer equations in order to determine, in a continuous way, the variations of various physico-chemical parameters of the soluble ions present in the concentrated NaCl solutions as a function of four parameters: pH, [Na], T and P of the reaction medium. This model is valid up to [NaCl] = 6M, T = 300°C and P = 100 MPa.

O cádmio (Cd) é um metal pesado e dos mais abundantes elementos encontrados no ambiente. Existem evidências de sua relação coma osteopenia, osteoporose, e osteomalacia e fragilidade do tecido ósseo. Este estudo visa avaliar o efeito do pH da água de beber na gênese da alteração óssea provocada pela intoxicação por cádmio. Neste estudo, foram utilizados90 ratosWistar (Ratus Norvegicus albinus), adultos, machos,divididos em 6 grupos, aos quais foram administrados: A -solução de cloreto de Cd(400mg/L) com pH neutro (pH 7,0); B -solução de cloreto de Cd(400mg/L) com pH ácido (pH 5,0); C -solução de cloreto de Cd(400mg/L) com pH básico (pH 8,0). D -pH ácido (pH 5,0); E -pH básico (pH 8,0); F -pH neutro (pH 7,0). Nofêmur esquerdo de cada rato avaliou-se a densidade óssea, por meio do densitômetro de dupla emissão (DEXA), ensaiosbiomecânicos e escala de HU na tomografia computadorizada espiral.Os resultados demostram que a densidade óssea reduziunos grupos que receberam cádmio e no grupo sem administração de cádmio para o pH 5 ocorreu uma redução da densidade mineral óssea (DMO) e do conteúdo mineral ósseo (CMO). A rigidez biomecânica mostrou-se aumentada para o grupocom pH 5 sem cádmio. Como conclusão geral o cádmio reduziu a densidade óssea. / The cadmium (Cd) is a heavy metal, one of the most abundant elements found in the environment. There are evidences of its relationship in osteopenia, osteoporosis e osteomalacia and fragility of the bone tissue. This study aims to evaluatethe effect of the pH of the drinking water in the bonealteration origin caused by cadmium intoxication. This study envolved90 wistar rats (Ratus Norvegicus albinus), adults, males,divided in 6groups, were witch one receved: A -cadmium choride solution (400mg/L)withneutral ph (pH 7,0); B -cadmium choride solution(400mg/L) with acid ph (pH 5,0); C -cadmium choride solution(400mg/L)with basic ph(pH 8,0); D -with acid ph (pH 5,0); E -basic ph (pH 8,0); F -neutral pH (pH 7,0).Left femurs from each rat were evaluatedbybone density,DEXA,biomechanictest,HU scale from computerized tomography. The results shows that bone density became lower in the groups that received cadmium. In that wich received no cadmium with pH 5 ocurred an lower level of bone mineral density (BMO) andbone mineral content (BMC).The bone rigidity proved increased in the pH 5 with no cadmium. As a general conclusion, cadmium reduced the bone density.

A proposta deste trabalho é a produção de matrizes de nanotubos de dióxido de titânio seguindo os métodos de anodização eletroquímica de titânio estabelecidos da literatura. O objetivo central é a compreensão aprofundada das etapas do processo de crescimento dos nanotubos de TiO2, para posterior otimização de sua síntese visando as diferentes aplicações. Com este propósito foram realizados sistematicamente os seguintes estudos: das diferentes fases de crescimento dos nanotubos de TiO2, do efeito dos diferentes parâmetros de anodização na morfologia dos nanotubos e da reprodutibilidade dos processos. Visando as diferentes aplicações foram estudados métodos para obtenção de membranas autossustentadas e remoção de nanoresíduos. O método de camada sacrificial de fotoresiste positivo apresentou melhor resultado para remoção de nanoresíduos do topo dos nanotubos de TiO2 do que as demais técnicas. Por último, os arranjos obtidos com esta método foram aplicados na fabricação dos sensores de pH. / This work proposes the production of titania nanotubes arrays following the electrochemical anodization methods of a titanium sheet established in the literature. The main goal is a deep comprehension of the different TiO2 nanotubes growth stages for further optimization aiming the diverse applications. In this way the following systematic studies were performed: of the initial growth stages, of the effect of each anodization parameter on the nanotubes morphology and of the process reproducibility. In addition, methods for the production of self-sustained membranes as well as for obtaining a nanotube array surface free of nanoremnants were studied aiming the different applications. Positive photoresist bases sacrificial layer method presented a better result to eliminate nano-remnants on top of TiO2 nanotubes than other techniques. Finally, the nanotubes arrays obtained with this method were utilized for pH sensors fabrication.

Wound treatment is a significant field in healthcare, but one with huge potential and need for advancement. Infection monitoring, in its current state, is a largely primitive affair, relying on visual and olfactory inspection to detect bacteria. As a result, early detection is impossible, and doctors and patients are forced to remove dressings to investigate the wound in a laborious, painful, and unsanitary process. When an infection is detected, the treatment is typically systemic administration of antibiotics. Systemic administration reduces the concentration of antibiotics that can be brought to bear on the infection because it interacts with the entire body and is dissipated by the time it reaches the wound and increases the risk of side effects or antibiotic resistance. Within this thesis, a smart, thread-based wound dressing is presented that addresses these issues by providing a pH-based early detection system accompanied by a topical, on-demand drug delivery system. The device has been tested in vitro and in vivo, on bacterial culture and on an animal model, and demonstrated effectiveness at detecting and eliminating bacteria, and at promoting wound healing. This smart wound dressing has the potential to improve treatment and outcomes for a wide variety of injuries, varying from burns to chronic wounds. / Graduate / 2020-10-10

Arsenic (As) is a toxic semi-metallic element found in groundwater, soils, and plants. Natural and anthropogenic sources contribute to the distribution of arsenic in the environment. Arsenic’s toxic and mobile behavior is associated with its speciation ability. There are two types of arsenic available to the environment, inorganic and organic arsenic. Of the two, inorganic arsenic is more toxic to humans and more mobile in the environment. Two inorganic compounds responsible for arsenic contamination are trivalent arsenite, As (III), and pentavalent arsenate, As (V). Trivalent arsenate is considered to be more soluble, toxic, and mobile than pentavalent arsenate. Arsenic’s absorptive properties in plant cells and ability to attach to minerals causing secondary contamination are due to environmental factors such as pH, redox potential, and solubility. The current maximum contaminant level for arsenic in water is 10 µg/L (or ppb). Research on arsenic involving high concentrations already present in groundwater (>300ppb) are compared either with crops irrigated with such water or a human indicator (such as; hair, nails, blood, or urine) in order to determine exposure limits. In this current research, relationships between the area in the studies and the contaminated media (water, soil, vegetation) were tested to determine if arsenic in water was correlated with arsenic concentrations present in soil and vegetation. Commercially obtained ITS Quick Rapid Arsenic Test Kits were used to measure arsenic concentrations for the media tested. A method for analysis of arsenic in vegetation was developed, with an estimated 80% recovery. The pH and conductivity were also taken for water and soil samples as a means of correlative comparison. The development of faster and portable methods for arsenic concentration may provide means for predicting the relationship between all contaminated media. The purpose of the study was to determine the correlation between arsenic water concentration and pH for water, soil, or vegetation and whether it plays an overall role in the amount of arsenic present. As a result, water and soil pH played a significant role in the presence of arsenic in the water and vegetation, respectively. A moderate negative correlation between arsenic in water and water pH was discovered to have a Spearman’s rho value of -0.708 with a p ≤ 0.05. In addition, a significant negative correlation between soil pH and arsenic in vegetation was also discovered to have a Spearman’s rho of -0.628 at a p ≤ 0.05. Even though, pH was significantly correlated with arsenic concentrations in different media, there is evidence that pH plays a role also in the amount of arsenic available in the soil and vegetation. Further studies are recommended.

Acid-base disturbances have serious clinical consequences and are particularly critical in patients whose cardiopulmonary function is compromised. Cellular transport of NH3 and NH4+ has important physiological significance in the regulation of acid-base balance. In the kidney, production and excretion of NH3/NH4+ is critical for net acid excretion. Recently, two non-erythroid glycoproteins (Rhbg and Rhcg) belonging to the Rh family were suggested to be involved in NH3/NH4+ transport. Thus far, the functional properties of these membrane proteins as transport mechanisms are not resolved. In this study, we expressed Rh proteins in Xenopus oocytes and demonstrated that they transport both NH4+ and NH3. As such, the Rh transporters are unique in being able to transport both the ionic and the neutral gaseous components of ammonia. Previous studies have shown that DIDS, a stilbene derivative known to inhibit anion exchangers, was shown to inhibit CO2 transport by AQP1. This led us to hypothesize that DIDS might also inhibit transport of other gases such as NH3 by Rh proteins. We therefore conducted the present study to test the effects of DIDS on NH4+ and NH3 transport by Rh glycoproteins. To do so we used ion-selective microelectrodes and two-electrode voltage clamp to measure changes in surface pH (pHs) and whole cell currents (I) induced by NH3/NH4+ and methyl ammonium (MA/MA+) with or without DIDS. All experiments were conducted in Xenopus oocytes expressing Rhbg. Rhbg was expressed by injecting the oocytes with cRNA of the cloned genes. Control oocytes were injected with H2O. Our results indicate that in oocytes expressing Rhbg, exposure to 5mM NH4Cl (NH3/NH4+) caused a decrease in surface pH (pHs) and an inward current. The decrease in pHs is caused by NH3 influx whereas the inward current is due to electrogenic NH4+ influx. In the presence of DIDS, exposure to 5mM NH4Cl caused a significantly smaller decrease in pHs and current. The %inhibition of pHs and ΔI were 33% and 49%, respectively (P<0.05). Similarly, exposing oocytes expressing Rhbg to 5mM MA/MA+ (a substitute to NH3/NH4+) caused a decrease in pHs and an inward current. In the presence of DIDS, the MA/MA+ induced changes in pHs and current were also inhibited (37% and 63%, respectively; P<0.05). DIDS had no effect on NH3/NH4+ transport in H2O-injected oocytes (not expressing Rhbg). In summary, our data support the following conclusions: 1) RhAG and Rhbg transport both the ionic NH4+ and the neutral NH3 species. 2) Transport of NH4+ is electrogenic. 3) RhAG and Rhbg expression both enhance MA transport, an electroneutral component. 4) Like Rhbg, RhAG also transports MA+, an electrogenic component. The charged MA+ seems to be a direct substrate for RhAG whose transport likely resembles that of NH4 +. 5) Rhcg is likely to be a predominantly NH3 transporter. 6) RhAG and Rhbg are unlikely to be NH4 +/H+ exchangers. Regarding the effect of DIDS, our data also indicate that 1) DIDS partially inhibits the transport of NH3 and MA by Rhbg without affecting endogenous NH3 and MA transport. 2) DIDS also inhibits the electrogenic transport of NH4 + and MA+ by Rhbg. 3) DIDS is the only inhibitor shown to block both gas (NH3) and ionic (NH4 +) transport by Rhbg. / acase@tulane.edu

Localized pH changes have been suggested to occur in the brain during normal function. However, a lack of methods for non-invasively measuring pH with high spatial and temporal resolution limits current knowledge of brain pH dynamics. Here I report that a magnetic resonance imaging (MRI) strategy named T1 relaxation in the rotating frame (T1ρ) is sufficiently sensitive to detect widespread pH changes in the mouse and human brain evoked by systemically manipulating carbon dioxide (CO2) or bicarbonate (HCO3). Moreover, T1ρ detected changes suggesting a localized acidosis in the human visual cortex induced by a flashing checkerboard. Lactate measurements and pH-sensitive 31P spectroscopy at the same site also suggest a localized acidosis. Consistent with the established role for pH in blood flow recruitment, T1ρ correlated with blood oxygenation level dependent contrast (BOLD), although T1ρ was directly sensitive to blood oxygen content. These observations provide the strongest evidence thus far for localized pH fluctuations in the human brain during normal function. Furthermore, they suggest a novel functional imaging strategy based on pH that is independent of traditional fMRI contrast mechanisms. Possible sources of acidosis include local metabolism, which is likely to correlate with the degree of stimulation and the associated changes in local neural activity. Therefore, we hypothesized that T1ρ and pH changes would increase with increasing stimulation frequency. To test this hypothesis, we used a full-field visual flashing checkerboard and varied the frequency between 1, 4, and 7Hz. The response was imaged with T1ρ, BOLD, and 31P spectroscopy. Supporting our hypothesis, we found that increasing stimulation frequency increased responses measured by all three imaging modalities. The activation area detected by T1ρ overlapped to a large degree with that detected by BOLD, although the T1ρ response area was significantly smaller. 31P spectroscopy detected a greater acidosis with the higher stimulation frequencies. These observations suggest that, similar to the BOLD response, the magnitude of the T1ρ and pH response depends on stimulation frequency and is thus likely to be activity-dependent. Brain acidosis is the end product of energy metabolism. Metabolically active cells lower local pH, the detection of which could help pinpoint regions activated by sensory stimuli, emotion, or cognitive task. fMRI mostly relies on BOLD changes in the venous system while arterial spin labeling (ASL) enables changes in tissue perfusion resulting from local cerebral blood flow (CBF) changes. BOLD contrast can be significantly distant from the actual site of neuronal activity because it relies on changes of the local magnetic field within veins. The venous contribution results in a loss of spatial specificity and spatial resolution of the BOLD response. In addition, the hemodynamic response to brief periods of neural activity is delayed. However, ASL contrast originates predominantly from tissue and capillaries. Even though functional signal changes detected by ASL have superior spatial and temporal resolution as compared to BOLD contrast, ASL contrast still suffers from poor temporal resolution due to delays in the hemodynamic response resulting from neurovascular coupling. Therefore, the ability to measure pH dynamics may provide a more localized and direct measure of brain activity. We hypothesized that pH-sensitive T1ρ response in the visual cortex will temporally precede the hemodynamic response measured by functional imaging including BOLD and ASL contrast since local acidosis evoked by neural activity may drive the hemodynamic response. To test this hypothesis, dynamic imaging was performed using T1ρ, BOLD, and ASL while viewing a phase-encoded expanding ring stimulus which induces travelling waves of neural activity in the visual cortex. We calculated the phase maps for the eccentricity across their occipital cortices for each of functional signal and compared the T1ρ temporal resolution with the hemodynamic response. This study suggests that T1ρ signal has a higher temporal resolution as compared to the hemodynamic response. This is further evidence that the T1ρ signal is not sensitive to blood oxygenation or other blood factors that might alter T1ρ. In conclusion, T1ρ imaging has the potential to provide a new functional imaging marker that may be more specific to the area of brain activity. Therefore, it is possible that by non-invasively detecting pH dynamics in the human brain, T1ρ MRI could offer a novel, more direct approach to map brain function. A number of psychiatric and neurological disorders could potentially benefit from the ability to study dynamic pH changes.