Submitted by Biblioteca da Faculdade de Farmácia (bff@ndc.uff.br) on 2017-03-23T19:00:13Z No. of bitstreams: 1 Peçanha, Bruna Rachel de Britto [Dissertação, 2012].pdf: 3907379 bytes, checksum: f2acabc3c1c39363b86f0d651d6b5936 (MD5) / Made available in DSpace on 2017-03-23T19:00:13Z (GMT). No. of bitstreams: 1 Peçanha, Bruna Rachel de Britto [Dissertação, 2012].pdf: 3907379 bytes, checksum: f2acabc3c1c39363b86f0d651d6b5936 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Polímeros de impressão molecular (MIPs) foram sintetizados e aplicados como adsorventes na técnica de extração em fase sólida (EFS). O método de polimerização por precipitação foi utilizado para a síntese dos polímeros, devido à simplicidade de preparo, altos rendimentos e obtenção de partículas mais uniformes, devido a não trituração do polímero. O MIP foi sintetizado com ácido metacrílico (MAA) como monômero funcional, trimetacrilato de trimetilolpropano (TRIM) e dimetacrilato de etilenoglicol (EDMA) como agentes de reticulação e o cloridrato de amilorida (AMI) foi escolhido como molécula-molde. Diferentes proporções de MAA, TRIM, EDMA, volume e tipo de solvente foram utilizadas para ajuste das condições ideais de síntese. Os MIP foram avaliados quanto à capacidade de adsorção comparando-se a polímeros sintetizados na ausência da molécula-molde (NIP, polímeros não impressos). O solvente de elevada polaridade empregado na síntese (THF:MeOH:H2O) permitiu o emprego da técnica para moléculas polares como AMI. O controle no volume de solvente permitiu a obtenção de partículas maiores, de modo que a EFS foi realizada em condições usuais, o que confere um potencial para aplicação dessa técnica de polimerização na preparação de adsorventes para EFS. O polímero que apresentou maior capacidade adsortiva no ensaio realizado em tampão citrato-acetato pH 6,5 foi o MIP/NIP 12 (AMI:MAA:TRIM 1:8:10), com uma taxa média de adsorção de 83 e 88% para NIP e MIP, respectivamente. A adsorção foi elevada devido a interação iônica entre MAA e AMI promovida pelo controle de pH, porém foi não específica. O polímero MIP/NIP 12 foi aplicado como adsorvente na EFS, onde a recuperação de AMI foi avaliada nos resíduos de carregamento e eluição com solventes. O carregamento com tampão citrato-acetato pH 6,5 foi o ideal, favorecendo a interação iônica do polímero com o analito. A eluição total de AMI do cartucho somente ocorre após lavagem com o solvente na presença de ácido, que protona os grupos carboxila do polímero, rompendo assim a interação iônica com o analito / Molecularly imprinted polymers (MIPs) were synthesized and applied as adsorbents in solid-phase extraction technique (SPE). The polymers have been synthesized by precipitation polymerization method because of its simplicity, high yields and good control of final size and shape of particles. MIP was synthesized using methacrylic acid (MAA) as functional monomer, trimethylolpropane trimethacrylate (TRIM) and ethyleneglycol dimethacrylate (EDMA) as cross-linker and amiloride hydrochloride (AMI) was chosen as template. Different ratios of MAA, TRIM and EDMA, volume and type of solvent were used to adjust the optimal synthesis conditions. The MIP were tested for adsorption capacity compared to the polymers synthesized in the absence of template molecule (NIP, non-imprinted polymers). The polar solvent mixture used (THF:MeOH:H2O) allowed the synthesis of MIP of polar molecules as AMI. The solvent volume control afforded the larger particles so the SPE was performed in the usual conditions, giving a potential application for this polymerization technique in the preparation of adsorbents for SPE. The polymers with higher adsorption capacity at the test performed in citrateacetate buffer pH 6,5 was MIP/NIP 12 (AMI:MAA:TRIM 1:8:10) with adsorption rate of 83 and 88% for NIP and MIP, respectively. The recognition of MIP was due to ionic interaction between MAA and AMI promoted by pH control, but was not specific. The polymer MIP/NIP 12 was used as a solid-phase extraction sorbent and the recoveries of AMI was evaluated using different loading and elution conditions. The loading with buffer citrate-acetate pH 6,5 was optimal, due to ionic interaction of the polymer with the analyte. Total elution of AMI bound to the polymers only occurs after washing with a acid-containing solvent, because of protonation of the carboxyl groups of the polymer and disrupting the ionic interaction with the analyte

No description available.

This thesis is focused on the determination of platinum in samples of road dust and soil by atomic absorption spectrometry. The theoretical part describes the basic physical and chemical properties of platinum, platinum function in automotive converters and its behavior in the environment. In the experimental section summarizes the methods used to decompositions samples, concentration of the analyte and the main results of the measurements.

The concept of integrated sensors in the Biotage® Extrahera™ system to perform live-monitoring of pressure inside SPE-columns is investigated. A test-rig containing the components necessary to simulate the pressure-cycle in the system is constructed and a printed-circuit board assembly is designed and implemented into its 24-column format. Liquid samples with varying viscosity are then synthesized using water and glycerol, which are used in a simplified 2-step SPE-process during which the pressure inside the columns is logged. The results obtained showed that the concept is viable and methods for clog detection as well as state assessment are discussed. However, it was established that the solution needs further testing involving complete SPE-processes with real samples before any detailed algorithms can be presented. A pre-study is finally done regarding solutions for minimizing the design to allow for implementation into the system's more spatially restricted 96-column format.

This diploma thesis is based on the current issue of the presence of pharmaceuticals in various components of the environment. Concerning the contamination by residues of pharmaceuticals the most affected environment is the aquatic environment where these substances leaks especially from wastewater treatment plants, which eliminate them during the cleaning process only partially. This work is focused on the selected group of pharmaceuticals, non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, caffeine, naproxen, ketoprofen, diclofenac) in waste water. For analysis purposes two types of sampling were used and compared: the conventional spot sampling of wastewater and the sampling using passive samplers POCIS. The sampling took place at the inflow and outflow of the wastewater treatment plant in Brno Modřice. The solid phase extraction (SPE) using Oasis HLB columns was used as the extraction method. Extracted sample was derivatized then. Derivatization agents were: MSTFA (N-methyl-N-(trimethylsilyl)trifluoroacetamid) and BSTFA (N, O-bis(trimethylsilyl) trifluoroacetamid). The final analysis was performed using gas chromatography with mass spectrometric detection Time-of-Flight (GC/TOF-MS).

This research explored in-vitro and in-vivo performance of three salbutamol metered dose inhalers (MDIs): Ventolin Evohaler (Evo), Airomir (Airo) and Salamol. In the in-vitro studies, critical quality attributes of the MDI using an Andersen cascade impactor (ACI) were examined and included measurement of fine particle dose (FPD) and total delivered dose (TDD). Bioequivalence studies were conducted in humans using the urinary pharmacokinetic method. Post-inhalation urinary excretion of salbutamol in the first 0.5 hour (lung deposition, USAL0.5) and over 24 hours (total systemic bioavailability, USAL24) were compared to determine the bioequivalence of the MDIs. The spacers recommended for use with these inhalers were also studied, and charcoal block studies were performed to assess the extent of USAL0.5. The three MDIs had FPD (μg) of 78, 91 and 89, respectively; the latter pair was equivalent. Their USAL0.5 (6, 7 & 7 μg) was however not bioequivalent. These MDIs delivered equivalent dose (177, 174 & 180 μg) which reflected on their USAL24 (101, 84 & 97 μg). Nevertheless, USAL24 was inequivalent between Evo and Airo. The FPD of Evo with Volumatic (VOL), AeroChamber Plus (AERO) and Able spacer was 78, 68 and 74 μg, respectively. The AERO treatment method was not equivalent to the MDI while VOL and Able were equivalent between them. Spacer USAL0.5 (16, 15 & 14 μg) was not bioequivalent to the MDI but to each other. The spacer in-vitro TDD (95, 85 & 92 μg) was inequivalent to the MDI treatment method. In contrast, their USAL24 was bioequivalent (97, 85 & 90 μg). The FPD of Airomir with AERO (95 μg) was in-vitro equivalent while USAL0.5 (15 μg) of this treatment method was bio-inequivalent to the MDI alone. On the contrary, the TDD (110 μg) and USAL24 (84 μg) of AERO were respectively in-vitro inequivalent and bioequivalent to the MDI alone. The FPD (μg) of Salamol MDI alone and with VOL (84) and AERO (86) as well as between the spacers was equivalent. However, the USAL0.5 of the MDI was not bioequivalent to spacers (20 and 18 μg) despite being equivalent between the spacers. In contrast, the respective TDD (103 and 95 μg) of spacer treatment methods were in-vitro inequivalent to the MDI alone albeit having bioequivalent USAL24 (86 and 87 μg). The variations in the in-vitro performance of the three MDIs are most likely due to differences in their formulations and designs. As the performance metrics of the MDI influence lung deposition, substituting one MDI with another can have clinical implications. Although the spacers reduced in-vitro TDD of the MDI to about half, their use increased lung deposition by over two folds, the magnitude of which varied with the MDI and spacer type. Despite significant decrease in dose delivery, the total systemic bioavailability with the spacers was similar to that with the MDI alone. This systemic bioequivalence is more likely due to greater USAL0.5 with the spacers. The results of the charcoal block studies reinforced this outcome. The present study is unique as it used a clinically relevant salbutamol MDI dose (two puffs), assessed results for equivalence and analysed ACI deposition data further as stage groups. The deposition on adjacent ACI stages were grouped together as coarse, fine and extra-fine particle masses to identify their more likely deposition sites in the human respiratory tract. Moreover, this thesis describes highly sensitive and novel HPLC and SPE methods, developed and validated to quantify salbutamol in urinary and aqueous matrices. As the clinical effects of MDIs are related to their lung deposition, the current work emphasizes the importance of spacer use. Nevertheless, differences in dose delivery between spacers may have clinical consequences. Hence, only the specific spacer recommended for use with the MDI should be used. / World Federation, Stanmore, London and Sadaat Welfare Foundation, Bradford, West Yorkshire

This Master thesis examines a phenomenon that occurs in the upper polar atmosphere, namely, Polar Mesospheric Winter Echoes, or PMWEs. PMWEs are radar echoes observed by Very High Frequency Mesosphere Stratosphere Troposphere (VHF MST) radar, from altitudes of 60 to 76 km at 7 to 15 UT, in the winter months from the middle of September to the beginning of May. The aforementioned specifications are the partial results of this thesis.PMWEs are generally understood to be caused by turbulence; however, radar data indicate some rare cases where PMWEs can be created with velocities exceeding the speed of sound, which is not possible with current turbulence theory. Kirkwood et al., 2006 and Belova, Kirkwood, and Sergienko, 2013 hypothesised that infrasound could generate the necessary conditions for PMWEs with velocities equal to or exceeding the speed of sound. Observations of PMWEs presented in this thesis have been carried out by the MST radar ESRAD, located at Esrange (67 56’N, 21 04’E) near Kiruna in northern Sweden. The radar operates at 52 MHz and has been performing continuous radar observations since Dec 1996. Observations of the infrasounds presented in this thesis were carried out by a microbarometer located close to Rymdcampus in Kiruna. Access to the data is restricted, but through university administration, this master’s thesis has been granted permission to use the data for the study of PMWEs. The instrument performed continuous infrasound measurements from the 24th of May 2016 and forward. This thesis will perform a full analysis of all radar data from the 17th of Dec 1996 until the 31st of Jan 2021 to assess the altitude interval, diurnal interval and yearly interval. The data given in the first section are a result of this work. Additionally, space weather parameters relation with the occurrence of PMWEs is analysed. Space weather parameters are very important for the chemistry and conditions present in the mesosphere. It is shown thatt here is a strong relation between solar wind and PMWE occurrence, decent relation with Kp index and no to weak relation with solar particle event (SPE). Correlating space weather and PMWEs in greater detail could be the subject of other studies. Last but most interesting, microbarometer data will be analysed for days where high-speed PMWEs are detected. Because of the rarity of these high-speed PMWEs, only seven total cases were found from 24 May 2016 onward, making the analysis of the infrasound measurements very limited, and no connection was found. However, it was found that days with high-speed PMWEs had an abnormally low amount of infrasound detections, further making analysis difficult but raising questions of why. This could mean that infrasound signals might be hindered from reaching the ground on days where we have high-speed PMWEs. No further conclusions can be made, as this indicates relation but not causation. Airborne infrasound instruments could be used to detect weaker infrasound signals due to being unaffected by wind disturbance at the ground.

Nous avons observé une augmentation ‘’transient’’du taux de cristallisation interfacique de l’a-Si lorsqu’on réimplante du Si à proximité de l’interface amorphe/cristal. Après amorphisation et traitement thermique à 650°C pendant 5s de la couche a-Si crée par implantation ionique, une partie a été réimplantée. Les défauts produits par auto-réimplantation à 0.7MeV se trouvent à (302±9) nm de l’interface initiale. Cela nous a permis d’étudier d’avantage la variation initiale de la vitesse SPE (Épitaxie en phase solide). Avec des recuit identiques de 4h à 500°C, nous avons déterminé les positions successives des interfaces et en déduit les taux de cristallisation SPE. La cristallisation débute à l’interface et continue graduellement vers la surface. Après le premier recuit, (252±11) nm s’est recristallisé dans la zone réimplantée soit un avancement SPE de 1.26x10^18at./cm2. Cette valeur est environ 1.50 fois plus importante que celle dans l’état relaxé. Nous suggérons que la présence de défauts à proximité de l’interface a stimulé la vitesse initiale. Avec le nombre de recuit, l’écart entre les vitesses diminue, les deux régions se cristallisent presque à la même vitesse. Les mesures Raman prises avant le SPE et après chaque recuit ont permis de quantifier l’état de relaxation de l’a-Si et le transfert de l’état dé-relaxé à relaxé. / We observed a ‘’transient’’ increase of planar crystallization rate of a-Si when one reimplanted Si near the interface amorphous / crystal. After amorphization and heat treatment at 650°C for 5s, one part has been re-implanted. The defects produced at 0.7 MeV by self-re-implantation are located at (302±9) nm of the initial interface. This allows us to better study the initial variation of SPE speed (solid phase epitaxy). With recrystallisation anneals at 500±4°C for 4h, we have determined the successive positions of the interfaces and have deduced the SPE recrystallization rate. Crystallization began at the interface and continues gradually to the surface. After the first annealing, (252±11)nm was recrystallized in the re-implanted state. That means 1.26x10^18at./cm2 SPE enhancement. This value is approximately 1.50 times greater than that in the relaxed state. We suggest that the presence of defects near the interface stimulate the speed. Raman measurements taken after each annealing allowed us to know the transfer of the un-relaxed state to the relaxed state. After the number of anneals treatments, both areas progress almost at the same speed / Dans ce travail nous avons étudié le phénomène de diffusion du cuivre et de l’argent dans a-Si en présence de l’hydrogène à la température de la pièce et de recuit. Une couche amorphe de 0.9μm d’épaisseur a été produite par implantation de 28Si+ à 500 keV sur le c-Si (100). Après celle-ci, on procède à l’implantation du Cu et de l’Ag. Un traitement thermique a produit une distribution uniforme des impuretés dans la couche amorphe et la relaxation de défauts substantiels. Certains défauts dans a-Si sont de type lacune peuvent agir comme des pièges pour la mobilité du Cu et de l’Ag. L’hydrogène implanté après traitement thermique sert à dé-piéger les impuretés métalliques dans certaines conditions. Nous n’avons détecté aucune diffusion à la température de la pièce au bout d’un an, par contre un an après à la température de recuit (1h à 450°C) on observe la diffusion de ces métaux. Ce qui impliquerait qu’à la température de la pièce, même si l’hydrogène a dé-piégé les métaux mais ces derniers n’ont pas pu franchir une barrière d’énergie nécessaire pour migrer dans le réseau. / In this work we studied the diffusion phenomenon of copper and silver in a-Si in the presence of hydrogen at room temperature and annealing temperature. The 0.9 μm -thick a-Si layers were formed by ion implantation 28Si + at 500 keV on c-Si (100). After this Cu ions and Ag ions were implanted at 90keV.The heat treatment produces a uniform distribution of impurities in the amorphous layer and the relaxation of substantial defects. Vacancies defects in a-Si can act as traps for the mobility of Cu and Ag. Hydrogen implanted is used to de-trap metal impurities such as Cu and Ag. However we did not detect any diffusion at room temperature during 1 year, but after one year at the annealing temperature (450°C for 1h) we observe the distribution of these metals. Implying that the room at temperature, although the hydrogen de-trapping metals but they could not crossed an energy barrier required to migrate in the network.

A ocorrência de fármacos residuais no meio ambiente pode levar a efeitos adversos, tanto em organismos aquáticos como em terrestres. Os fármacos, tanto humanos como de uso veterinário, são absorvidos pelo organismo e estão sujeitos a reações metabólicas e, uma quantidade significativa dessas substâncias, tanto a original como seus metabólitos, são excretadas. Por não serem facilmente biodegradáveis, terem propriedades farmacológicas danosas quando administrados indevidamente, através de água contaminada, é crescente a preocupação com o destino destes fármacos residuais, principalmente com relação à avaliação de risco ambiental. A ocorrência destes resíduos, principalmente em águas superficiais e sistemas de abastecimento, vem sendo objeto de estudos em diversos países, principalmente na Europa. Por isso, a detecção, a eliminação e a investigação do destino destes compostos estrógenos em ecossistemas aquáticos têm tido prioridade na química ambiental. Estes produtos são encontrados nos corpos d\'água em baixas concentrações, de \'mü\'g L-1 a \'eta\'g L-1 e, mesmo assim, podem afetar os organismos por meio da bioacumulação. Estudos toxicológicos relacionados a efeitos crônicos em organismos expostos, são escassos. O objetivo do projeto foi adaptar e validar a metodologia analítica, e monitorar a presença de resíduos de hormônios nas águas dos Rios Corumbataí e Piracicaba e amostras de água de abastecimento da cidade de Piracicaba, SP, Brasil. Foram coletadas amostras de água bruta dos Rios Piracicaba e Corumbataí e água de abastecimento residencial da cidade de Piracicaba, SP, no período de novembro de 2007 a abril de 2009. Dentre os hormônios estudados estão o 17\'alfa\'-etinilestradiol (17\'alfa\'-EE2), 17\'beta\'-estradiol (17\'beta\'-E2) e estriol (E3). O método foi baseado na extração em fase sólida (SPE) e cromatografia líquida de alta eficiência (HPLC-DAD) / The occurrence of drug residues in the environment may lead to adverse effects, both on land and aquatic organisms. The drugs, for human and veterinary use, are absorbed by the organism and are subjected to metabolic reactions and a significant amount of these substances, both the original and its metabolites are excreted. By being not easily biodegradable and by having harmful pharmacological properties when administered through contaminated water, there is a growing concern about the fate of these residual drugs, especially in respect to the assessment of environmental risks. The occurrence of these residues, especially in surface Waters and water supplies has been the subject of studies in several countries, mainly in Europe. Therefore, detection, investigation and disposal of the fate of these estrogens compounds in aquatic ecosystems have a high priority in the field of environmental chemistry. These products are found in water bodies in low concentrations, from \'mü\'g L-1 a \'eta\'g L-1 and can still affect the organisms due to bioaccumulation. Toxicological studies related to chronic effects in the exposed organisms are scarce. The goals of this project was to adapt and validate the analytical methodology, and monitor the presence of hormone residues in the Waters of the Corumbataí and Piracicaba rivers and samples of water supply from the city of Piracicaba, SP, Brazil. We collected samples of raw water from the rivers of Piracicaba and Corumbataí and residential water supply from the city of Piracicaba in the period November 2007 to April 2009. Among the hormones studied are the 17\'alfa\'-ethinylestradiol (17\'alfa\'-EE2), 17\'beta\'-estradiol (17\'beta\'-E2) and estriol (E3). The method is based on solid phase extraction (SPE) and high performance liquid chromatography (HPLC-DAD)

A ocorrência de fármacos residuais no meio ambiente pode levar a efeitos adversos, tanto em organismos aquáticos como em terrestres. Os fármacos, tanto humanos como de uso veterinário, são absorvidos pelo organismo e estão sujeitos a reações metabólicas e, uma quantidade significativa dessas substâncias, tanto a original como seus metabólitos, são excretadas. Por não serem facilmente biodegradáveis, terem propriedades farmacológicas danosas quando administrados indevidamente, através de água contaminada, é crescente a preocupação com o destino destes fármacos residuais, principalmente com relação à avaliação de risco ambiental. A ocorrência destes resíduos, principalmente em águas superficiais e sistemas de abastecimento, vem sendo objeto de estudos em diversos países, principalmente na Europa. Por isso, a detecção, a eliminação e a investigação do destino destes compostos estrógenos em ecossistemas aquáticos têm tido prioridade na química ambiental. Estes produtos são encontrados nos corpos d\'água em baixas concentrações, de \'mü\'g L-1 a \'eta\'g L-1 e, mesmo assim, podem afetar os organismos por meio da bioacumulação. Estudos toxicológicos relacionados a efeitos crônicos em organismos expostos, são escassos. O objetivo do projeto foi adaptar e validar a metodologia analítica, e monitorar a presença de resíduos de hormônios nas águas dos Rios Corumbataí e Piracicaba e amostras de água de abastecimento da cidade de Piracicaba, SP, Brasil. Foram coletadas amostras de água bruta dos Rios Piracicaba e Corumbataí e água de abastecimento residencial da cidade de Piracicaba, SP, no período de novembro de 2007 a abril de 2009. Dentre os hormônios estudados estão o 17\'alfa\'-etinilestradiol (17\'alfa\'-EE2), 17\'beta\'-estradiol (17\'beta\'-E2) e estriol (E3). O método foi baseado na extração em fase sólida (SPE) e cromatografia líquida de alta eficiência (HPLC-DAD) / The occurrence of drug residues in the environment may lead to adverse effects, both on land and aquatic organisms. The drugs, for human and veterinary use, are absorbed by the organism and are subjected to metabolic reactions and a significant amount of these substances, both the original and its metabolites are excreted. By being not easily biodegradable and by having harmful pharmacological properties when administered through contaminated water, there is a growing concern about the fate of these residual drugs, especially in respect to the assessment of environmental risks. The occurrence of these residues, especially in surface Waters and water supplies has been the subject of studies in several countries, mainly in Europe. Therefore, detection, investigation and disposal of the fate of these estrogens compounds in aquatic ecosystems have a high priority in the field of environmental chemistry. These products are found in water bodies in low concentrations, from \'mü\'g L-1 a \'eta\'g L-1 and can still affect the organisms due to bioaccumulation. Toxicological studies related to chronic effects in the exposed organisms are scarce. The goals of this project was to adapt and validate the analytical methodology, and monitor the presence of hormone residues in the Waters of the Corumbataí and Piracicaba rivers and samples of water supply from the city of Piracicaba, SP, Brazil. We collected samples of raw water from the rivers of Piracicaba and Corumbataí and residential water supply from the city of Piracicaba in the period November 2007 to April 2009. Among the hormones studied are the 17\'alfa\'-ethinylestradiol (17\'alfa\'-EE2), 17\'beta\'-estradiol (17\'beta\'-E2) and estriol (E3). The method is based on solid phase extraction (SPE) and high performance liquid chromatography (HPLC-DAD)