Cette thèse s’inscrit dans le cadre de synthèses de matériaux innovants contenant des entités cationiques que sont le guanidinium et l’ammonium. Ces entités cationiques confèrent des propriétés intéressantes et fonctionnelles pour chacun des systèmes ioniques suivants : tensio-actifs, liquides ioniques et ionosilices. A cet effet, nous avons procédé à l’étude de deux familles de composés : les sels de guanidiniums et les ionosilices. Pour les sels de guanidiniums, nous avons étudié la formation et les propriétés d’auto-assemblage de tensio-actifs en utilisant différentes techniques de mesures (conductivité, tension de surface et calorimétrie). Ce remarquable synthon moléculaire qu’est le guanidinium a été aussi mis en avant comme liquide ionique pour l’extraction du méthyl orange, du diclofenac et du chromate. Quant aux ionosilices, bien qu’ils présentent aussi des propriétés intéressantes pour l’extraction ionique et l’adsorption de principes actifs, leur mise en forme reste cependant un paramètre clef pour cibler leur application. En effet, la mise en forme des ionosilices en nanoparticules permet l’extension des applications dans le domaine de la nanomedecine. Ainsi, durant cette thèse, des nanoparticules avec des sous-structures ioniques ammoniums sont synthétisées pour la première fois et utilisées comme nano-vecteur pour le relarguage d’un anti-inflammatoire (diclofenac). Par ailleurs, dans le but d’une extraction ionique en flux continu, des matériaux contenant des fonctions ioniques sous forme de monolithe ont été synthétisés à partir de précurseur ammonium par voie sol gel. Ainsi cette thèse nous a permis de trouver les éléments théoriques, illustratifs et expérimentaux des différentes facettes de la formation de matières à base d’unités cationiques aux propriétés remarquables que sont les sels de guanidiniums et les sels d’ammoniums. / This dissertation deals with innovative synthetic materials bearing cationic entities that are guanidinium and ammonium. These cationic entities give interesting and functional properties for each ionic system studied: surfactant, ionic liquid and ionosilica. For this purpose, we investigated two families groups composed of: guanidiniums salts and ionosilica. Regarding guanidiniums salts, we studied the formation and self-assembly behavior of guanidinium surfactants using different measurement techniques (conductivity, surface tension and calorimetry). This remarkable molecular synthon that represents guanidinium was also highlighted as an ionic liquid for the extraction of methyl orange, diclofenac and chromate. As for ionosilicas, although they also have advantageous properties for ion extraction and adsorption of the active ingredients, however their shaping remains a key parameter for targeting their application. In fact, the design of ionosilica material as nanoparticle allows applications extension in the field of nanomedicine. So during this thesis, nanoparticles containing ammonium substructures were synthesized for the first time and used as a nano-vector to deliver an anti-inflammatory drug (diclofenac). Furthermore, with the aim of ionic extraction in continuous flow, materials containing ionic functions as monolith were synthesized from ammonium precursor via sol gel route. This thesis allowed us to find the theoretical, experimental and illustrative elements of the different aspects of materials formation based on cationic entities with remarkable properties that are guanidiniums and ammonium salts.

Made available in DSpace on 2014-06-11T19:29:42Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-08-20Bitstream added on 2014-06-13T20:39:15Z : No. of bitstreams: 1 marques_ls_me_ilha.pdf: 598207 bytes, checksum: 01faa04755519bb4bedc4f6984a8d39f (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O abacaxizeiro é classificado como uma cultura exigente em fertilidade do solo, sendo o N o nutriente mais importante para o desenvolvimento da planta e aumento do tamanho e massa dos frutos. O objetivo deste trabalho foi avaliar quantitativamente e qualitativamente os frutos de abacaxi cv. Smooth Cayenne na região noroeste do estado de São Paulo, utilizando fontes e doses de N, aplicado antes e após a indução do florescimento, em solo corrigido quanto ao teor de potássio. O trabalho foi conduzido na Fazenda Água Limpa, no município de Guaraçaí-SP, em um solo Latossolo Vermelho-Amarelo. As mudas foram plantadas em sulcos na superfície do solo, no dia 17/03/2009, com espaçamento de 1,10m entrelinhas, 0,40m entre fileiras e 0,40m entre plantas, com densidade aproximada de 33.000 plantas ha-1, sendo cada parcela composta por quatro fileiras duplas com 56 plantas/parcela no total. A indução floral foi realizada em duas épocas, em virtude da pouca porcentagem de plantas induzidas na primeira, ou seja, nos dias 21/02/2009 e 05/05/2009, com as respectivas colheitas dos frutos realizada nos dias 12/09/2009 (203 dias após a indução) e 27/11/2009 (206 dias após a indução). As avaliações realizadas foram duas análises nutricionais da folha “D”, uma antes e outra após a indução floral, e duas análises dos frutos, devido à realização de duas colheitas. O delineamento experimental adotado foi o de blocos ao caso com quatro repetições, em esquema fatorial 3x5 (para 1ª análise foliar sem efeito de época) e 2x3x4 (para a 2ª análise da folha e as duas análises dos frutos), sendo composto por duas épocas de aplicação de N: toda a dose aplicada no dia 06/10/2008 (antes da indução floral) ou toda no dia 12/06/2009 (após a indução floral), 3 fontes de N, sulfato de amônio, uréia e nitrato de amônio, e quatro doses de N (7,5; 15; 22,5 e 30 g planta-1)... / Pineapple plant is demanding in fertility of soil, and N is the most important nutrient for the development of plant and increase of size and mass of fruits. The objective of this work was to evaluate quantity and quality of fruits of pineapple cv. Smooth cayenne in the northwest area of São Paulo State, using sources and doses of N, applied before and after the flowering induction, in soil fertilized with potassium. The work was conducted at Água Limpa farm, in Guaraçaí-SP, in a Red-yellow Latosol. The seedlings were planted in furrows at soil surface, in 03/17/2009, with spacing of 1.10m between double lines, 0.40m between single lines and 0.40m among plants, with approximate density of 33,000 plants ha-1, being each plot composed of four double lines with 56 plants/plot in the total. The flowering induction was accomplished in two times, due to little percentage of plants induced in the first time, in other words, in 02/21/2009 and 05/05/2009, with the respective crops of the fruits accomplished in 09/12/2009 (203 days after the induction) and 11/27/2009 (206 days after the induction). The evaluations were: two nutritional analyses in D leaf, one before and other after the flowering induction, and two analyses of fruits, due to the accomplishment of two crops. A randomized block design with four repetitions in a factorial scheme 3x5 (for 1st leaf analysis without time effect) and 2x3x4 (for 2nd leaf analysis and two fruit analyses), being composed by two times of N application: the total dose accomplished in 10/06/2008 (before the floral induction) or total dose in 06/12/2009 (after the floral induction), 3 sources of N, ammonium sulfate, urea and ammonium nitrate, and four N doses (7.5; 15; 22.5 and 30 g plant-1) was used. Ammonium sulfate provided higher leaf N and S content as applied on pineapple plant before or after the floral induction. For the fruits harvested ... (Complete abstract click electronic access below)

New possibilities of nutrients removal by additions of magnesium compounds were studied in primary treatment and supernatant of side stream in wastewater treatment. The precipitation product from this method is magnesium ammonium phosphate (MAP) socalled struvite. High efficiencies on NH4-N and PO4-P removals have been demonstrated up to over 90 % respectively in side stream from dewatering of digested sludge. In order to find out the nutrient removal efficiency in raw wastewater and the feasibility of MAP recycling in wastewater treatment, the postulations of combining MAP and nitrification-denitrification process, and MAP and partial nitritation-anmmox process were carried out by experimental works in the laboratory at Land and Water Resources Department, KTH. It was found that 92-97 % of PO4-P and 57 % of NH4-N were removed from raw wastewater by Mg2+ addition at pH10 to pH10.5. The research work revealed that recycling of MAP by nitrification-denitrification and partial nitritation-anmmox processes may be a feasibly process combination. In MAP and nitrification -denitrification process, the released ammonium was mostly oxidized to nitrate in nitrification phase and ready for denitrification. Based on presented results on MAP and partial nitritation-anmmox process, it was found that the released ammonium was consumed by anammox bacteria.

Nitrogen is often a limiting factor for plant growth due to its heterogenous distribution in the soil and to seasonal and diurnal changes in growth rates. In most soils, NH4+ and NO3 – are the predominant sources of inorganic nitrogen that are available for plant nutrition. In this context, plants have evolved mechanisms that enable them to optimize nitrogen acquisition, which include transporters specialized in the uptake of nitrogen and susceptible to a regulation that responds to nitrogen limiting or excess conditions. Although the average NH4+ concentrations of soils are generally 100 to 1000 times lower than those of NO3 – (Marschner, 1995), most plants preferentially take up NH4+ when both forms are present because unlike NO3– / NH4+ has not to be reduced prior to assimilation and thus requires less energy for assimilation (Bloom et al., 1992). Apart from high uptake rates in roots, high intracellular ammonium concentrations also result from quantitatively important internal breakdown of amino acids (Feng et al., 1998), and originates in high quantities during photorespiration (Mattson et al., 1997, Pearson et al., 1998). Thus, NH4+ is a key component of nitrogen metabolism for all plants and can accumulate to varying concentrations in all compartments of the cell, including the cytosol, the vacuole and in the apoplast (Wells and Miller, 2000; Nielsen and Schjoerring, 1998). Two related families of ammonium transporters (AMT1 and AMT2), containing six genes which encode transporter proteins that are specific for ammonium had been identified prior to this thesis and some genes had partially been characterised in Arabidopsis (Gazzarrini et al., 1999; Sohlenkamp et al. 2002; Kaiser et al., 2002). However, these studies were not sufficient to assign physiological functions to the individual transporters and AMT1.4 and AMT1.5 had not been studied prior to this thesis. Given this background, it was considered desirable to acquire a deeper knowledge of the physiological functions of the six Arabidopsis ammonium transporters. To this end, tissue specific expression profiles of the individual wildtype AtAMT genes were performed by quantitative real time PCR (qRT-PCR) and promoter-GUS expression. Modern approaches such as the use of T-DNA insertional mutants and RNAi hairpin constructs were employed to reduce the expression levels of AMT genes. Transcript levels were determined, and physiological, biochemical and developmental analysis such as growth tests on different media and 14C-MA and NH4+ uptake studies with the isolated insertional mutants and RNAi lines were performed to deepen the knowledge of the individual functions of the six AMTs in Arabidopsis. In addition, double mutants of the insertional mutants were created to investigate the extent in which homologous genes could compensate for lost transporter functions. The results described in this thesis show that the six AtAMT genes display a high degree of specifity in their tissue specific expression and are likely to play complementary roles in ammonium uptake into roots, in shoots, and in flowers. AtAMT1.1 is likely to be a ‘work horse’ for cellular ammonium transport and reassimilation. A major role is probably the recapture of photorespiratory NH3/NH4+ escaping from the cytosol. In roots, it is likely to transport NH4+ from the apoplast into cortical cells. AtAMT1.3 and AtAMT1.5 appear to be specialised in the acquisition of external NH4+ from the soil. Furthermore, AtAMT1.5 plays an additional role in the reassimilation of NH3/NH4+ released during the breakdown of storage proteins in the cotyledons of germinating seedlings. It was difficult to distinguish a specialisation between the transporters AtAMt1.2 and AtAMt1.1, however the root and flower specific expression patterns are different and indicate alternative functions of both. AtAMT1.4 has a very distinct expression which is restricted to the vascular bundels of leaves and to pollen only, where it is likely to be involved in the loading of NH4+ into the cells.The AtAMT2.1 expression pattern is confined to vascular bundels and meristematic active tissues in leaves where ammonium concentrations can reach very high levels. Additionally, the Vmax of AtAMT2 increases with increasing external pH, contrasting to AtAMT1.1. Thus, AtAMT2.1 it might be specialised in ammonium transport in ammonium rich environments, where the functions of other transporters are limited, enabling cells to take up NH4+ over a wide range of concentrations. The root hair expression ascribes an additional role in NH3/NH4+ acquisition where it possibly serves as a transporter that is able to acquire ammonium from basic soils where other transporters become less effective.RNAi lines showing a reduction in AtAMT gene mRNA levels and NH4+ transport kinetics, grew slower and flowering time was delayed. This indicates that NH4+ is a crucial and limiting factor for plant growth. / Ammonium stellt die von Pflanzen bevorzugte Aufnahmeform anorganischen Stickstoffes dar. Neben dem natürlichen Vorkommen im Boden, wird Ammonium während des Aminosäurestoffwechsels und der Photorespiration innerhalb des Pflanzenkörpers freigesetzt. Um Ammonium aus diesen Quellen zu assimlieren und zwischen den einzelnen Zellen zu transportieren hat die dikotyle Samenpflanze Arabidosis thaliana sechs veschiedene Ammoniumtransporter (AMT) evolviert. Zur Charakterisierung der spezifischen Funktionen der AMts wurden Expressionsprofile der jeweiligen Gene innerhalb der Wurzeln, des Sprosses und der Blüten unter verschiedenen Nährstoffbedingungen mittels quantitativer real-time PCR (qRT-PCT) und Promotor-GUS Expression erstellt. Weiter wurde die Fähigkeit zur spezifischen Regulation der einzelnen Transportergene in Abhängikeit des Stickstoffbedarfes der Pflanze analysiert. Zur Reduktion der mRNA Level der AMTs wurden RNA-Interferenz (RNAi) Mutanten erzeugt und um den Effekt des Verlustes einzelner AMTs zu studieren wurden T-DNA Insertionsmutanten dieser Gene isoliert. Von den mutanten Linien wurden die Transkriptionsraten durch qRT-PCR bestimmt und die NH4+ Transportleistungen durch 14C-Methylammonium (14C-MA) und Ammonium-Aufnahme Experimente analysiert. Weiter wurden Wachstumsanalysen der Mutanten auf verschiedenen Nährmedien durchgeführt und ihre vegetative und generative Entwicklung charakterisiert. Von den isolierten T-DNA Insertionsmutanten wurden Doppelmutanten aller Kombinationen hergestellt und phänotypisch analysiert.Es zeigte sich, daß der an der Plasmamembran lokalisierte AtAMT1.1 in allen Organen in hohen Konzentrationen exprimiert wird und unter Stickstoffmangelbedingungen vermehrt gebildet wird. Vermutlich dient er der generellen Assimilation von internen Ammonium und dessen Transport vom Apoplasten in den Symplasten. AtAMT1.3 und AtAMT1.5 sind in den Wurzeln und hier besonders in den epidermalen Wurzelhaaren exprimiert, die unter anderem der Aufnahme externer Nährsalze dienen. Beide unterliegen starker Regulation durch den internen Stickstoffbedarf der Pflanze. Es ist zu vermuten, daß sie primär der Aufnahme von Ammonium aus dem Boden dienen. AtAMT1.2 wird überwiegend an den vaskulären Geweben und den Blattparenchymzellen exprimiert. Überlappende Expressionsmuster mit AtAMT1.1 machen es schwierig eine spezifische Funktion zu identifizieren. AtAMT1.4 wird ausschließlich im männlichen Gametophyten exprimiert und dient hier vermutlich der Versorgung des Pollen mit Nährsalzen. AtAMT2 wird u.a. in den Wurzelhaaren exprimiert. Seine steigende Affinität zu Ammonium in basischem Milieu, umgekehrt zu AtAMT1.1, läßt vermuten, daß er der Pflanze die Ammoniumaufnahme bei steigendem pH ermöglicht. Im oberirdischen Sproß ist er überwiegend in Meristemen aktiv. Die in der Ammoniumaufnahme beeinträchtigten RNAi-Linien zeigten langsames Wachstum und blühten später als der Wildtyp. Es sind die ersten beschriebenen Ammoniumtransportermutanten, die einen solchen Phänotyp zeigen.

Le domaine de l'agriculture produit une part importante des gaz à effet de serre (GES) au Canada (8%) soit 8% des 747 Mt eq. CO[indice inférieur 2] émis chaque année. L'industrie porcine, un secteur clé de l'industrie agroalimentaire est en forte croissance au Canada depuis le milieu des années 80. L'entreposage du lisier préalablement séparé compte pour la plus grande partie du méthane (CH[indice inférieur 4]) émis, un GES au pouvoir de réchauffement global 25 fois celui du dioxyde de carbone (CO[indice inférieur 2]). Pour traiter le CH[indice inférieur 4], la biofiltration a déjà fait ses preuves pour le traitement des émissions de CH[indice inférieur 4] provenant des lieux d'enfouissement sanitaires (LES) et des mines. Ce procédé peut être également appliqué au CH[indice inférieur 4] issu de l'industrie porcine. Lors de la biofiltration du CH[indice inférieur 4], plusieurs facteurs clé peuvent améliorer la performance du système de traitement biologique comme, par exemple, la température, le pH, la nature du milieu filtrant, le taux d'humidité du lit et les nutriments. En particulier, l'apport en nutriments est un facteur déterminant pour la croissance et le maintien des microorganismes traitant le CH[indice inférieur 4]. Plusieurs nutriments doivent être fournis pour assurer le bon fonctionnement d'un biofiltre : carbone, oxygène, azote, phosphore, potassium et autres. D'un autre côté, certaines substances peuvent inhiber l'oxydation du CH[indice inférieur 4] dans un biofiltre et influencer la flore microbienne : un inhibiteur ayant fait l'objet de nombreuses études sur des supports de terre est l'ammonium (NH[indice inférieur 4][indice supérieur +]). Les expériences en laboratoire devaient déterminer l'impact du NH[indice inférieur 4][indice supérieur +] dans la solution nutritive contenant du nitrate sur un biofiltre rempli d'un garnissage inorganique traitant le CH[indice inférieur 4]. Dans les conditions expérimentales considérées (Débit d'air : 0,18 m[indice supérieur 3] h[indice supérieur -1] ; Concentration de CH[indice inférieur 4] à l'entrée : 3000 ppmv ; Débit de solution nutritive : 1,5 L j[indice supérieur -1]), l'ajout de NH[indice inférieur 4][indice supérieur +] dans la solution nutritive a eu un impact sur la performance du biofiltre, faisant diminuer la conversion du CH[indice inférieur 4] de 70 à 13% entre 0,05 et 0,5 gN-NH[indice inférieur 4][indice supérieur +] L[indice supérieur -1]. Les résultats de cette étude ont aussi démontré que l'augmentation progressive du NH[indice inférieur 4][indice supérieur +] réduit l'effet inhibiteur de celui-ci sur la performance du biofiltre.

Tetramethyl ammonium manganese trichloride ([CH3)4N][Mn(II)Cl3]) known as TMMC, has been one of the most interesting systems in experimental magnetism due to its highly one-dimensional magnetic Heisenberg behaviour. The focus of this research programme was to study its magnetic and structural properties as a function of pressure. TMMC crystals were prepared by slow evaporation technique at room temperature; however it quickly became apparent that the material is only weakly magnetic and requires a pressure cell with a very low background. This discovery lead to the programme of instrumentation development for studies of weakly magnetic materials and gave a dualistic nature to the project. The first pressure cell developed was a piston-cylinder type cell for magnetic susceptibility measurements in a Magnetic Properties Measurement System (MPMS®) based on Superconducting Quantum Interference Device (SQUID) technology from Quantum Design, USA. It has been carefully designed in order to reduce the magnetic background. One way in which this has been achieved was through making the pressure cell symmetric with respect to the sample in order to provide an integrable response in the SQUID magnetometer. The cell was made of beryllium copper alloy which has a low background even at low temperature. The use of a multi-layered cylinder with the interference fit method has resulted in the increased strength of the cell and allowed larger sample volume. The use of Lamé equation and finite element method to calculate the change of the cell diameter or cell length as a function of internal pressure enables us to eradicate the need of superconductive manometer. The cell has been successfully tested up to a maximum pressure of 10 kbar. Further development of the cell has resulted in development of an electrical plug for in situ pressure measurement inside the pressure cell. This has been achieved by means of a manganin pressure sensor calibrated to provide pressure reading at any given temperature. For structural studies, a diamond anvil cell (DAC) was designed to conduct singlecrystal X-ray diffraction measurements at low temperature. The design was based on the well-known Merrill-Bassett DAC and on the design of the miniature DAC which has been developed for use within He-3 system in the Physical Properties Measurement System (PPMS®), Quantum Design. The cell has been tested down to liquid nitrogen temperatures with a cryostream cooling system and has shown a significant improvement compared to the standard pressure cells. The frost formation on the surface of the cell has slowed down significantly compared to the tests on the Merrill-Bassett cell, which led to a better quality diffraction pattern from the sample inside the cell. This result has been achieved due to the high thermal conductivity of the materials used in the construction and the minimisation of the DAC, which was effectively built around the Boehler-Almax diamond anvils. With the help of some of the high-pressure instruments mentioned above, highpressure properties of TMMC have been studied in this project. The structuremagnetism relationship was established from the results of magnetic and structural measurements under pressure. The magnetic susceptibility data helped to establish the change of the intrachain antiferromagnetic coupling constant as a function of pressure, while X-ray structures of TMMC were refined from ambient pressure to 17 kbar using a synchrotron X-ray diffraction technique. The structure of TMMC at room temperature was confirmed to be hexagonal. However, indirect evidence of the hexagonal-monoclinic structural phase transition was observed at above 17 kbar and room temperature. The combination of the magnetic and structural data has helped to establish that the interaction between high spin d5 metal orbitals (Mn(II)) in facesharing octahedral has a contribution from both direct exchange and superexchange interactions. The power-law relationship developed by Bloch was also observed in this system.

No description available.

Call number: LD2668 .T4 1957 M87 / Master of Science

As atividades humanas vêm aumentando dramaticamente a quantidade de nitrogênio inorgânico liberado nos ecossistemas, seja através da aplicação de fertilizantes na agricultura, da descarga de dejetos humanos e de seus rebanhos, ou da queima de combustíveis fósseis. Os excessos de nitrogênio são eventualmente transportados para corpos d´água, onde podem, na forma de nitrato, nitrito e amônio, atingir concentrações tóxicas para organismos aquáticos. Nesta pesquisa tive dois objetivos principais. O primeiro foi testar em laboratório a toxicidade relativa dos íons nitrato, nitrito e amônio, e a variação interespecífica na sensibilidade a esses íons, em larvas de cinco espécies de anuros (Rhinella ornata, Hypsiboas faber, Hypsiboas pardalis, Physalaemus cuvieri e Physalaemus olfersii ). Para isso utilizei bioensaios seguindo protocolos internacionalmente padronizados para testes de ecotoxicidade com organismos aquáticos, e que portanto permitem máximas reprodutibilidade e comparabilidade de resultados entre compostos, espécies, e laboratórios. No entanto, estes bioensaios carecem de realismo uma vez que simulam um cenário de exposição aguda a altas concentrações de contaminantes quando na natureza o cenário de exposição tende a ser crônico e prolongado a baixas concentrações. Além disso, bioensaios usam mortalidade como principal variável de resposta, quando também efeitos subletais podem influenciar a persistência de populações ao modular o sucesso dos indivíduos. Por isso, meu segundo objetivo foi testar em laboratório se concentrações relativamente baixas e ecologicamente relevantes de nitrato, nitrito e amônio podem afetar a sobrevivência, o crescimento, o desenvolvimento e o comportamento das larvas de R. ornata, P. cuvieri e H. faber. Demonstrei através dos bioensaios de exposição aguda que nitrato, a forma mais abundante na natureza, é de baixa toxicidade quando comparada a nitrito e amônio. Demonstrei também que há significativa variação interespecífica na sensibilidade ao nitrogênio inorgânico, e que o ranqueamento de sensibilidade das espécies ao nitrato e ao nitrito foram similares, possivelmente por conta de mecanismos comuns de ação tóxica. Através de experimentos de exposição crônica demonstrei que concentrações relativamente baixas de nitrogênio inorgânico podem causar efeitos letais e subletais às larvas de anuros se houver exposição prolongada. O nitrato causou redução no desenvolvimento larval de P. cuvieri e o amônio na sobrevivência e nas taxas de atividade nos girinos de H. faber. A exposição crônica ao nitrito também reduziu significativamente a sobrevivência das três espécies testadas, o crescimento de H. faber e as taxas de atividade de R. ornata. Contudo, é improvável que as concentrações de nitrito que manipulei em laboratório sejam comuns na natureza, especialmente em condições aeróbicas. Esta pesquisa, além de fornecer importantes informações sobre os possíveis efeitos da poluição por nitrogênio em larvas de anuros, contribui para o avanço da ecotoxicologia no Brasil ao estabelecer as bases para o emprego de espécies nativas de anfíbios como sistema-modelo experimental. Estudos futuros que almejem avaliar o risco ambiental da contaminação por nitrogênio deverão por um lado monitorar concentrações em hábitats naturais e por outro avaliar as consequências das interações sinérgicas entre nitrogênio inorgânico e outros estressores físicos, químicos ou biológicos para larvas de anfíbios. / Human activities dramatically increased the amount of inorganic nitrogen released in ecosystems through the application of fertilizers in agriculture, the generation of human and livestock waste, and the combustion of fossil fuels. This nitrogen eventually reaches water bodies where it can, in the form of nitrate, nitrite and ammonium, be toxic to aquatic organisms. In this study I had two main objectives. The first was to test the relative toxicity of nitrate, nitrite and ammonium, and the interspecific variation in sensitivity to these ions, in tadpoles of five anuran species (Rhinella ornata, Hypsiboas faber, Hypsiboas pardalis, Physalaemus cuvieri and Physalaemus olfersii ). This objective was accomplished by laboratory bioassays following internationally standardized protocols for ecotoxicity tests with aquatic organisms, therefore allowing maximum reproducibility and comparability of results among compounds, species and laboratories. However, these bioassays lack realism for simulating a scenario of acute exposure to high concentrations of contaminants, while exposure in nature tends to be chronic and prolonged at low concentrations. Furthermore, bioassays use mortality as the main response variable, whereas sublethal effects may also influence the persistence of populations by modulating individual success. My second objective was therefore to test in the laboratory if low and environmentally relevant concentrations of nitrate, nitrite and ammonium affect survival, growth, development and behavior of R. ornata, P. cuvieri and H. faber larvae. Through acute exposure bioassays I demonstrated that nitrate, the most abundant N form in nature, has low toxicity when compared to nitrite and ammonium. I also demonstrated that there is significant interspecific variation in the sensitivity to inorganic nitrogen, and that the ranking of species sensitivity to nitrate and nitrite were similar, possibly due to common mechanisms of toxic action. Through chronic exposure I demonstrated that relatively low concentrations of inorganic nitrogen can cause lethal and sublethal effects on anuran larvae if there is extended exposure. Nitrate decreased developmental rate in P. cuvieri and ammonia decreased survival and activity rates in H. faber tadpoles. Chronic exposure to nitrite also significantly reduced survival of all three species tested, growth of H. faber and activity rates of R. ornata. However, it is unlikely that the concentrations of nitrite manipulated in the laboratory are common in nature, especially in aerobic conditions. This is the first study to document deleterious effects of nitrogen pollution to Brazilian amphibian species, and contributes to the development of ecotoxicology in Brazil by establishing the basis for the employment of native amphibians as model experimental system. Future studies that aim to assess the environmental risk of nitrogen contamination should monitor concentrations in natural habitats and evaluate the effects of synergistic interactions between inorganic nitrogen and other physical, chemical or biological stressors to amphibian larvae.

Wong, Wing Yan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 76-79). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgments --- p.iii / Abstract --- p.iv / Abbreviations and Acronyms --- p.vii / Publications Originated from the Work of this Thesis --- p.ix / Chapter Part I: --- "Self-Assemblyy Stability Quantification, Controlled Molecular Switching, and Sensing Properties of an Anthracene-Containing Dynamic [2]Rotaxane" / Chapter Chapter 1 - --- Introduction / Chapter 1.1 --- Definition of Rotaxane --- p.2 / Chapter 1.2 --- Dynamic Covalent Chemistry in Rotaxane Synthesis --- p.5 / Chapter 1.3 --- Thermodynamic Template --- p.6 / Chapter 1.4 --- Molecular Sensing Properties in Rotaxane --- p.10 / Chapter 1.5 --- Examples --- p.13 / Chapter Chapter 2 - --- Anthracene-Containing Dynamic [2]Rotaxane / Chapter 2.1 --- Background --- p.17 / Chapter 2.2 --- Modification and Design of Dynamic [2]Rotaxane --- p.18 / Chapter 2.3 --- Self-Assembly of Rotaxane and Synthesis of Components --- p.19 / Chapter 2.4 --- Characterization / Chapter 2.4.1 --- 1H NMR Spectroscopy --- p.21 / Chapter 2.4.2 --- 13C NMR Spectroscopy --- p.23 / Chapter 2.4.3 --- Mass Spectrometry --- p.24 / Chapter 2.4.4 --- X-Ray Crystallography --- p.25 / Chapter 2.4.5 --- UV/Visible Absorption and Fluorescence Spectroscopies --- p.26 / Chapter 2.5 --- Effect of External Stimuli / Chapter 2.5.1 --- Addition of Water --- p.29 / Chapter 2.5.2 --- Addition of Acid --- p.33 / Chapter 2.5.3 --- Addition of Salts --- p.38 / Chapter 2.5.4 --- Addition of Amines --- p.40 / Chapter 2.6 --- Conclusions --- p.43 / Chapter Part II: --- Substituent Effect in Imine-Containing Molecular Tweezers / Chapter Chapter 3 - --- Molecular Tweezers / Chapter 3.1 --- Introduction --- p.46 / Chapter 3.2 --- Synthesis --- p.48 / Chapter 3.3 --- Characterization of Molecular Tweezers / Chapter 3.3.1 --- 1H NMR Spectroscopy --- p.49 / Chapter 3.3.2 --- Mass Spectrometry --- p.51 / Chapter 3.4 --- Characterization of Molecular Tweezers / Chapter 3.4.1 --- 1H NMR Spectroscopy --- p.51 / Chapter 3.4.2 --- X-Ray Crystallography --- p.59 / Chapter 3.4.3 --- Mass Spectrometry --- p.60 / Chapter 3.4.4 --- UV/Visible Absorption Spectroscopy --- p.61 / Chapter 3.5 --- Conclusions --- p.63 / Chapter Chapter 4 - --- Experimental Procedures / Chapter 4.1 --- General Information --- p.64 / Chapter 4.2 --- General Synthetic Procedures for Molecular Tweezers (34-40) --- p.65 / Chapter 4.3 --- Experimental Procedures --- p.65 / Chapter 4.4 --- Determination of Binding Constant K --- p.73 / References --- p.76 / Appendix / List of Spectra --- p.A-l / List of Crystal Data --- p.A-2