Since the 18th-century scientists are studying diatoms, fascinated by their beauty and diversity. Their nano- and micropatterned biosilica cell walls are outstanding examples of biologically controlled mineral formation. Although the knowledge about diatom cell wall formation increased over the last 60 years, the process is still far away from being completely understood. Diatom cell walls exhibit highly interesting material properties, making them appealing to material scientists. Due to those properties, diatom cell walls are on the brink of becoming powerful tools in nanotechnology. However, the production of tailored silica structures for nanotechnology requires a much better understanding of the processes and components involved in cell wall morphogenesis. Recent studies set the focus on insoluble organic matrices as important parts of this process, suggesting that they act as templates in silica morphogenesis. Therefore, in this study, the occurrence of insoluble organic matrices and their possible silica precipitation activity was analyzed in the three diatom species T. pseudonana, T. oceanica and C. cryptica. For all three species girdle band and valve derived insoluble organic matrices could be identified. The extracted insoluble organic matrices exhibited structural features present in the corresponding biosilica cell walls. The highest similarities were found in the valve derived matrices of C. cryptica. Accessibility studies showed that the biosilica associated insoluble organic matrices of T. pseudonana were only partially accessible, arguing for an entrapment of insoluble organic matrices in the silica, rather than an attachment to the surface of the cell wall. All examined insoluble organic matrices of the three species exhibited intrinsic silica precipitation activity. The most intriguing structures were formed by the insoluble organic matrices of C. cryptica, yielding a porous silica pattern. The addition of biosilica derived soluble components or long-chain polyamines promoted this process and moreover lead to the reconstitution of biosilica-like hierarchical silica pore patterns. The generated silica structures were templated by the underlying structure of the insoluble organic matrix. The result presented in this thesis make this the first study reporting the in vitro generation of diatom biosilica-like hierarchical silica pore patterns using all natural cell wall components. It supports the hypothesis of microplates acting as templates for biosilica morphogenesis and introduces an interesting experimental setup for silica-based in vitro studies on the mechanism of pore formation in diatoms.

Made available in DSpace on 2017-07-25T19:30:47Z (GMT). No. of bitstreams: 1 Silvano Harkatin.pdf: 1558277 bytes, checksum: 5f4533a401fd66edf359180bcca181b9 (MD5) Previous issue date: 2014-11-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Integrated systems of agricultural production (ISAP), when well managed, can result in environmental benefits, including the optimization of the use of phosphorus (P) for food production. Brazilian soils are presented naturally low in P, and practices aimed at efficient use of this nutrient can result in economic and environmental benefits to society. The objectives of this study were: (i) measure the quantitative yield of annual ryegrass (Lolium multiflorum Lam) and soybean (Glycine max (L.) Merrill); (ii) to evaluate the accumulation of P (annual ryegrass and soybean); (iii) investigate the changes in the attributes of soil fertility (pH and available-P); (iv) to assess the yield of dry matter available for grazing (DMA); (v) yield of crude protein (YCP); and (vi) concentrations of neutral detergent fiber (NDF), acid detergent fiber (ADF), crude protein (CP) and P in ryegrass in ISAP undergo sources (triple superphosphate - TSP, reactive phosphate - RP Arad and magnesium thermophosphate - MTP) and P levels (0, 60, 120 and 180 kg ha-1 P2O5 total). The experiment was installed in April / 2009 at farm Capon do Cipo, in the municipality of Castro (PR). The experimental design was a randomized complete block in incomplete factorial (3x3 + 1). After 48 months of study, soil samples from the 0-5, 5-10, 10-15 and 15-20 cm were collected to determine the concentrations of available P by two methods (Mehlich-1 – M-1 and ion exchange resin - IER) to assess the availability of P for the soybean crop (2012/13). Similar yields were observed among the evaluated sources (TSP, RP and MTP) at 48 months of experimental evaluation; However, higher accumulation of P were observed for the most soluble sources. The determination of P by the extractors (M-1 and IER) overestimated the concentrations of P in the soil in condition of application of RP. But best fixes between soil P and crop attributes were higher for extraction by IER in 0-20 cm layer. Lower concentrations of NDF in annual ryegrass were verified by applying MTP, without, however, presenting the highest concentrations of P. / Sistemas integrados de produção agropecuário (SIPAs), quando bem manejados, podem resultar em benefícios para o ambiente, inclusive, otimização de uso do fósforo (P) para produção de alimentos. Os solos brasileiros apresentam-se naturalmente pobre em P, e as práticas que visam eficiência de uso deste nutriente podem resultar em benefícios econômicos e ambientais para a sociedade. Os objetivos deste trabalho foram: (i) mensurar o rendimento quantitativo do azevém anual (Lolium multiflorum Lam) e da cultura da soja (Glycine max (L.) Merrill); (ii) avaliar o acúmulo de P (azevém anual e soja); (iii) averiguar as alterações nos atributos de fertilidade do solo (pH e P-disponível); (iv) avaliar o rendimento de massa seca disponível por pastejo (MSP); (v) rendimento de proteína bruta (RPB); e as (vi) concentrações de fibra insolúvel em detergente neutro (FDN), fibra insolúvel em detergente ácido (FDA), proteína bruta (PB) e P no azevém anual, em SIPA submetido a fontes (superfosfato triplo – SFT, fosfato natural reativo – FNR Arad e termofosfato magnesiano – TFM) e doses de P (0, 60, 120 e 180 kg ha-1 de P2O5 total). O experimento foi instalado em abril/2009 na Fazenda Capão do Cipó, no município de Castro (PR). O delineamento experimental empregado foi o de blocos completos casualizados em esquema fatorial incompleto (3x3+1). Aos 48 meses de estudo, foram coletadas amostras de solo das camadas de 0-5, 5-10, 10-15 e 15-20 cm, para determinação das concentrações de P disponível por dois métodos (Mehlich-1 – M-1 e resina trocadora de íons – RTI) para avaliação da disponibilidade de P para a cultura da soja (2012/13). Foram verificados rendimentos similares entre as fontes avaliadas (SFT, FNR e TFM) aos 48 meses de avaliação experimental; todavia, maiores acúmulos de P foram verificados para as fontes mais solúveis. A determinação de P pelos extratores (M-1 e RTI) superestimou as concentrações de P no solo em condição de aplicação de FNR. Porém, melhores correlações entre o P solo e os atributos das culturas foram maiores para a extração por RTI na camada 0-20 cm. Foram verificadas menores concentrações de FDN na pastagem de azevém anual mediante a aplicação de TFM, sem, no entanto, apresentar as maiores concentrações de P.

Les nanoparticules supportées sur un support solide permettent de catalyser un grand nombre de réactions. Dans ce travail, nous nous sommes intéressé à la préparation du matériau, puis à son utilisation dans une réaction de catalyse. Le support utilisé est un polymère poreux insoluble de structure microcellulaire appelé polyHIPE, obtenu par la polymérisation d'une émulsion inverse concentrée. La partie réactive est apportée par la génération in situ de nanoparticules de palladium. Nous avons synthétisé une large gamme de matériaux hybrides palladium/polyHIPEs, puis nous les avons caractérisé par diverses techniques comme le MEB, le MET, l'XPS ou la spectroscopie infrarouge. Nous avons contrôlé la taille moyenne et l'état de dispersion des particules grâce au choix des conditions et/ou par une fonctionnalisation adéquate des supports. Nous avons choisi, pour tester l'efficacité en catalyse, de comparer nos supports sur la catalyse d'une réaction de couplage de type Suzuki-Miyaura. Nous avons mis en évidence une forte dépendance de l'activité avec la force de stabilisation des particules, ainsi qu'avec la chimie de surface des nanoparticules. Certains des catalyseurs préparés proposent une bonne activité par rapport aux catalyseurs commerciaux et même, dans un cas, par rapport à un catalyseur homogène. Deux études préliminaires proposent également des améliorations potentielles du support, pour la manipulation des catalyseurs (préparation sous forme de billes) ou leur utilisation dans des conditions de haute température (carbonisation).

Dietary fibers can interfere in the bioavailability of mineral elements both negatively and positively. This has been the subject of several researches because there is a great interest in essential minerals; also, some studies have been done regarding toxic elements such as cadmium (Cd). Environmental contamination with Cd and its consequent interference in the food chain can cause serious problems in humans and animals affecting several organs in general, and this can become even worse when exposure takes place during growth. Fiber-rich supplements are employed by people that have low levels of fiber in the diet. On the other hand, multimixtures (MMs) are low-cost food supplements with different compositions that are used to improve the nutritional conditions of children. These supplements are normally rich in fibers and mineral elements. The objective of this study was to evaluate the effect of MMs and other food products rich in dietary fibers on the absorption of mineral elements and on Cd absorption, accumulation, and toxicity in growing rats. Three independent experiments were conducted. In the first experiment, MMs, used as supplements at a 5% proportion in diets, increased apparent absolute absorption of phosphorus, magnesium and manganese, proportionally to its level of dietary fiber, but did not interfere in calcium or copper absorption. This suggests that these supplements can be a source of some minerals in the diet, and similar proportions to those employed in this study did not diminish calcium and copper absorption. In the second experiment, one MM, rich in fibers and essential minerals did not diminish either Cd accumulation or toxicity when this metal was employed at 25 mg/kg in the diet, but MM diminished Cd accumulation in the kidneys when it was employed at 5 mg/kg in the diet. This latter Cd level is similar to human exposure in some contaminated areas, which suggests that MM may contribute to diminish Cd toxicity in polluted areas. In the third experiment, when flaxseed and bran wheat were compared to purified cellulose, it was observed that flaxseed, which has a higher proportion of soluble fiber, increased Cd accumulation in the liver and kidneys of growing rats in comparison to the other two fiber sources, which have basically insoluble fiber. These results indicate that foods with a higher proportion of soluble fiber can increase Cd body retention, suggesting that one should be careful when ingesting these foods in Cd contaminated areas. Flaxseed and bran wheat, used as sources of dietary fiber for rats exposed do Cd, decreased apparent absorption of Ca and P and increased apparent absorption of Mg in comparison to purified cellulose, which might be attributed to an interaction of Cd and phytate present in these fiber sources. Results of the present study show that MMs can be source of some essential mineral, besides reducing renal Cd accumulation, after exposure to low Cd doses. It was also observed that different sources of fiber may differentially affect the retention of toxic metals like Cd, and one should be careful when using foodstuffs rich in soluble fiber, like flaxseed, which can increase Cd retention. / As fibras alimentares (FA) podem interferir na biodisponibilidade de elementos minerais tanto negativa quanto positivamente. Este tem sido um assunto de diversas pesquisas e grande interesse em relação aos minerais essenciais e alguns estudos também têm sido feitos em relação aos elementos tóxicos como o cádmio (Cd). A contaminação ambiental com Cd e sua conseqüente entrada na cadeia alimentar pode levar a graves problemas no homem e nos animais em geral, afetando vários órgãos, o que pode ser mais grave quando a exposição se dá durante a fase de crescimento. Suplementos ricos em fibra são utilizados por parte da população em face da falta deste constituinte em suas dietas. Por outro lado, as multimisturas (MMs) são suplementos alimentares de composição variável e baixo custo, utilizados para melhorar o estado nutricional de crianças, sendo que estes suplementos são normalmente ricos em fibra e também em elementos minerais. O objetivo deste trabalho foi avaliar o efeito de MMs e outros produtos alimentícios ricos em FA sobre a absorção de elementos minerais e sobre a absorção, acumulação e toxicidade do Cd, em ratos em crescimento. Foram conduzidos três experimentos independentes. No primeiro experimento as multimisturas, usadas como suplementos na proporção de 5% da dieta, aumentaram a absorção absoluta aparente de fósforo, magnésio e manganês, proporcionalmente ao seu teor de fibra alimentar, não chegando a interferir na absorção de cálcio e cobre, o que sugere que estes suplementos podem ser fonte de alguns minerais na dieta e, em proporções semelhantes àquela utilizada neste estudo, não reduziriam a absorção de cálcio ou cobre. Num segundo estudo, uma MM, rica em fibra e em minerais essenciais, não reduziu a acumulação nem a toxicidade do Cd quando este foi utilizado na dose de 25 mg/kg de dieta, mas reduziu a acumulação renal do metal quando este foi utilizado na dose de 5 mg/kg de dieta, a qual é compatível com a exposição humana em algumas áreas contaminadas, sugerindo que a multimistura poderia contribuir para reduzir a toxicidade do Cd em zonas de contaminação ainda inevitável. No terceiro experimento, em que se comparou a linhaça e o farelo de trigo com a celulose purificada, observou-se que a linhaça, que contêm maior proporção de fibra solúvel, aumentou a quantidade de Cd retido no fígado e rins dos ratos em crescimento em comparação com as outras duas fontes, que contêm predominantemente fibra insolúvel. Estes resultados indicam que alimentos com maior proporção de fibra solúvel podem aumentar a deposição corporal de Cd, sugerindo que deve haver cuidado na ingestão dos mesmos em regiões contaminadas com Cd. A linhaça e o farelo de trigo, usados como fonte de fibra alimentar para os ratos expostos ao Cd, reduziram a absorção aparente do cálcio e do fósforo e aumentaram a absorção aparente de magnésio em comparação com a celulose, o que poderia ser atribuído a uma interação do Cd com o fitato presente naquelas fontes de fibra. Os resultados deste trabalho mostram que as MMs podem ser fonte de alguns minerais essenciais, além de reduzir a acumulação renal de cádmio, após exposição a baixas doses deste metal. Também observou-se que diferentes fontes de fibra podem interferir de forma diversa na retenção de minerais tóxicos como o Cd, devendo-se ter cuidado com fontes ricas em fibras solúveis, como a linhaça, que podem aumentar a retenção do metal.

Raw seeds of sixteen common bean (Phaseolus vulgaris L.) cultivars were evaluated along two consecutive harvests (2001/2002 and 2002/2003) concerning their physicochemical characteristics, as well as the effect of cooking and storage conditions on starch and dietary fiber contents. Serum lipids and blood glucose levels were also evaluated in normolipidemic-normoglycemic rats witch were fed diets containing bean cultivars with different soluble fiber/total fiber ratios (SF/TF): Pérola diet (0.11), Diamante Negro diet (0.19) and Iraí diet (0.26); control group was fed a standard diet (with insoluble fiber). Except for dry matter, moisture, and total dietary fiber, cultivars kept their chemical characteristics between harvests. Regarding similarity among macronutrient levels (crude protein-CP, total dietary fiber, insoluble dietary fiber, soluble dietary fiber-SF, digestible starch-DS, and resistant starch-RS) seeds from harvests 2001/2002 and 2002/2003 were categorized into four different groups; the same was done for micronutrients (Fe, Zn, Mn, Cu, Ca, Mg, and P), and four groups were also identified. Guateian 6662 and Rio Tibagi were considered the cultivars with the best nutritional profile (highest levels of CP, SF, DS, Fe, and Zn). Storage under refrigerated or freezing conditions did not change fiber content of cooked beans, but decreased their DS content and increased RS content, mainly in seeds with low RS levels before cooking. Concerning biological response, rats fed bean diets experienced lower values for serum cholesterol (P<0.05) and lower glycemic indexes (P<0.05). It was also observed a similar weight gain among groups, however animals fed bean based diets showed lower fat retention (P<0.05). The effects of bean diets on experimental groups were more remarkable in animals fed Iraí diet (SF/TF: 0.26). / Foram analisadas as características físico-químicas de sementes cruas de dezesseis cultivares de feijão comum (Phaseolus vulgaris L.), ao longo de duas safras consecutivas (2001/2002 e 2002/2003), bem como os teores de amido e fibra alimentar nas sementes após cozimento e estocagem. Avaliaram-se, também, os lipídeos séricos e a glicose sanguínea de ratos normolipidêmicos e normoglicêmicos, alimentados com dietas contendo cultivares de feijão com diferentes relações fibra solúvel/fibra total (FS/FT): dieta Pérola (0,11), dieta Diamante Negro (0,19) e dieta Iraí (0,26); o grupo controle recebeu dieta padrão (com fibra insolúvel). Exceto pelos teores de matéria seca, umidade e fibra alimentar total, as cultivares estudadas mantiveram suas características físico-químicas constantes ao longo das safras. Conforme a similaridade nos teores de macronutrientes (proteína bruta-PB, fibra alimentar total, fibra alimentar insolúvel, fibra alimentar solúvel-FS, amido disponível-AD e amido resistente-AR) as sementes das safras 2001/2002 e 2002/2003 foram categorizadas em quatro grupos distintos; da mesma forma, em relação aos micronutrientes (Fe, Zn, Mn, Cu, Ca, Mg e P), quatro grupos puderam ser identificados. As cultivares Guateian 6662 e Rio Tibagi apresentaram o melhor perfil nutricional (maiores teores de PB, FS, AD, Fe e Zn). A armazenagem sob refrigeração e o congelamento não determinaram alterações nos teores de fibra dos grãos cozidos, mas redução do AD e aumento do AR, principalmente naqueles com AR mais baixo antes do cozimento. Em relação à resposta biológica, os ratos alimentados com dietas contendo feijão apresentaram valores para colesterol sérico e índice glicêmico menores que os do grupo controle (p<0,05). Foi observado, também, que apesar do ganho de peso dos animais ter sido semelhante entre os grupos, os ratos alimentados com as dietas contendo feijão apresentaram menor retenção de gordura corporal (p<0,05). Os efeitos das dietas sobre os animais experimentais foram mais expressivos no grupo alimentado com a dieta Iraí (FS/FT: 0,26).

L'amélioration de la dissolution des médicaments peu solubles présente de nombreux défis.Dans cette thèse, un procédé d'extrusion-sphéronisation a été étudié en profondeur pour améliorer la dissolubilité du médicament avec une formulation de nano-émulsion. Le but du travail de thèse est de décrire les propriétés et les procédés de fabrication de minigranules permettant d'augmenter la solubilité des principes actifs peu solubles dans l'eau et donc d‘améliorer leur biodisponibilité lors de l'administration par voie orale, pour deux modèles de molécules différentes qui sont l‘acide folique (vitamine peu soluble dans l'eau) et le kétoprofène (anti-inflammatoire non stéroïdien qui présente une solubilité limitée dans les fluides gastriques à cause de son pKa (classe II dans le système de classification biopharmaceutique – BCS, ayant une action anti-inflammatoire, antalgique et antipyrétique). Cette étude décrit la préparation par extrusion-sphéronisation, caractérisation et étude de dissolution in vitro d'acide folique et de pastilles de kétoprofène revêtues de Acryl-EZE®, Advantia® Performance dans un minicoatère à lit fluidisé. Les résultats des essais ont montré la faisabilité de la préparation de pastilles enrobées entériques contenant un AINS et que, en revêtant le système multiparticulaire avec Acryl-EZE® 93A92545 et Advantia® Performance190024HA49 à un gain pondéral de 17,5%, 12,0%, respectivement, du médicament à partir des pastilles peuvent être obtenus. Les résultats des essais de dissolution ont indiqué que dans un milieu acide, le revêtement de film a entraîné un retard dans la libération du médicament, alors qu'aucun retard n'a été observé dans un milieu tampon à pH 6,8. / Improvement in dissolution of poorly soluble drugs has many challenges.In this thesis, an extrusion-spheronization process was thoroughly studied forimproving dissolubility of drug with nano-emulsion formulation.The aim of the thesis work is to describe the properties and manufacturing processes ofpellets to increase the solubility of poorly soluble active ingredients in water and thus improvetheir bioavailability when administered orally: folic acid (water-insoluble vitamin) andketoprofen (Non-steroidal anti-inflammatory, having anti-inflammatory, analgesic andantipyretic action, class II in the Biopharmaceutical Classification System).This study describes the preparation by extrusion-spheronization, characterisation andin vitro dissolution study of folic acid and ketoprofen pellets. Ketoprofen pellets coated withAcryl-EZE®, Advantia® Performance in a fluid-bed minicoater. The results of the tests showedthe feasibility of the preparation of enteric-coated pellets containing a NSAID and that bycoating the multiparticulate system with either 17.5% Acryl-EZE® 93A92545 or with 12%Advantia® Performance 190024HA49 weight gain, an enteric release of the drug from thepellets can be obtained. The results of dissolution testing indicated that in acidic media, entericfilm coating resulted in a delay in the release of the drug, while no delay was observed in pH6.8 buffer media.

La production microbienne de molécules d'intérêt pourrait être améliorée par des stratégies d'ingénierie du vivant. L'ingénierie enzymatique joue un rôle central dàns la conception d'organismes hôtes efficaces car l'efficacité de la voie dépend en premier lieu de l'efficacité des enzymes. Aujourd'hui, il est utile de savoir quelles conceptions d'enzymes synthétiques sont efficaces et quels paramètres doivent être testés pour les caractériser. La colocalisation spatiale d'enzymes à l'intérieur de la voie métabolique pourrait améliorer la production de la molécule d'intérêt finale en permettant une biotransformation rapide des intermédiaires de la voie de biosynthèse. Des protéines multidomaines regroupant plusieurs activités enzymatiques sont décrites dans la littérature. Ces travaux ont permis la création de fusions synthétiques d'enzymes caroténogéniques pour la production de bêta-carotène chez Saccharomyces cerevisiae. Différents types de fusions et de configurations enzymatiques ont été testés. L'étude a permis ia création d'une fusion enzymatique tripartite efficace produisant deux fois moins d'intermédiaires et deux fois plus de bêta-carotène. Les mesures précises de la concentration de chaque caroténoïde, associées à la quantification des enzymes, ont permis de caractériser l'efficacité de chaque enzyme synthétique. D'autres stratégies de colocalisation spatiale d'enzymes ont également été testées en utilisant des domaines d'interaction tels que la cohesinedockérine ou la protéine oligomériques CcmK2. Certaines enzymes caroténogéniques préservent leur fonctionnalité au sein de ces configurations. Des systèmes enzymatiques construites modifient le flux métabolique des caroténoïdes et produisent des caroténoïdes différents de ceux des enzymes naturelles. Un contrôle plus affiné des activités enzymatiques pourrait permettre un contrôle précis de la nature du caroténoïde final produit / Microbial production of molecules of interest can be improved by severa! engineering strategies. Enzymatic engineering has a central role in the conception of efficient host because pathway's efficiency depends in first place on the efficiency of the enzymes. Knowing which synthetic enzymes conceptions are efficient and knowing to characterize the best candidates are essential. Enzyme colocalisation inside metabolic pathway might improve the production of final molecule of interest by allowing rapid biotransformation of intermediates of the pathway. Multidomain proteins regrouping severa! enzymatic activities are described in the literature. This work has focused in part on the creation of synthetic fusion of sorne carotenogenic enzymes for the production of beta carotene in Saccharomyces cerevisiae. Different types of enzymatic fusions and configurations have been tested and. characterized. The study allowed the creation of an efficient tripartite enzyme. fusion which produces two times Jess intermediates and two times more beta carotene. Precise measurement of each caro teno id' s concentration coupled with quantification of enzymes allows the characterization of the efficiency of each synthetic enzyme. Other strategies for enzyme spatial co localisation have also been tested using domains of interaction like cohesin-dockerin or the oligomeric protein CcmK2. Sorne carotenogenic enzymes are still functional using those configurations. Sorne of the enzymatic systems modify the metabolic flow ofcarotenoids and produce carotenoids different from the natural systems. Sorne strategies have changed the metabolic flux of carotenoids inside the pathway. Interestingly, a fine control of activity of enzyme might allow a fine control of the nature of the final carotenoid

This study presents an analysis of the organic matter in meteorites, particularly carbonaceous chondrites (CCs), using advanced experimental techniques such as Two-step laser desorption laser ionization mass spectrometry (L2MS-oTOF) and Atmospheric Pressure Photoionization-Orbitrap (APPI-Orbitrap). The analysis focuses on the molecular complexity of both soluble (SOM) and insoluble (IOM) organic matter as well as the bulk rock and identifying and classifying different molecular families to understand the chemical composition of the meteorites. A new software tool, SpectraC, was developed to aid in analysing and comparing mass spectra from multiple meteorite samples simultaneously. The findings of the study reveal the complex chemical composition of meteorites, with condensed aromatics dominating most samples, and highlight the importance of using multiple techniques for a more complete understanding of the sample’s contents. This research lays the foundation for future work in astrochemistry, including the development of a state-of-the-art analytical tool and further exploration of the organic matter in meteorites. / Cette étude présente une analyse de la matière organique dans les météorites, en particulier les chondrites carbonées (CC), en utilisant des techniques expérimentales avancées telles que la spectrométrie de masse à ionisation laser par désorption en deux étapes (L2MS-oTOF) et l’ionisation photochimique à pression atmosphérique-Orbitrap  (APPI-Orbitrap). L’analyse se concentre sur la complexité moléculaire de la matière organique soluble (SOM) et insoluble (IOM) ainsi que sur la roche globale, et identifie et classe différentes familles moléculaires pour comprendre la composition chimique des météorites. Un nouvel outil logiciel, SpectraC, a été développé pour aider à analyser et comparer les spectres de masse de plusieurs échantillons de météorites simultanément. Les résultats de l’étude révèlent la composition chimique complexe des météorites, avec une domination des aromatiques condensés dans la plupart des échantillons, et mettent en évidence l’importance d’utiliser plusieurs techniques pour une compréhension plus complète du contenu des échantillons. Cette recherche pose les bases des travaux futurs en astrochimie, y compris le développement d’outils analytiques de pointe et l’exploration plus poussée de la matière organique dans les météorites.

Made available in DSpace on 2017-07-25T19:29:56Z (GMT). No. of bitstreams: 1 Shivelly Los Galetto.pdf: 1282228 bytes, checksum: 7b526c0d4cf80dfb8b2da93aafdd7187 (MD5) Previous issue date: 2013-02-20 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / Crop-livestock integration (CLI) is a practice that, when properly managed and associated with no-tillage (NT), has been improving a soil quality. However, most of soils in Brazil have a low level of phosphorus (P). Thus, the development of strategies to increase phosphorus use efficiency has been crucial for sustainable agribusiness in an agronomic and economic viewpoint. The objectives of this study were to evaluate the accumulation of P and yields of corn, soybean, black oat and ryegrass fertilized with sources and levels of P2O5 in CLI under NT and to evaluate the bioavailability of P for maize, extracted by the methods Melich-1 (M1), ion exchange resin (IER) and modified Morgan (MM), after 36 months of experimentation. The experiment was established in April 2009, in the municipality of Castro-PR in a Dystric Cambisol and the experimental design was an incomplete factorial (3x3+1), with four replications. The treatments consisted in surface (total area) application of levels (0, 60, 120 and 180 kg ha-1 yr-1 P2O5) during sowing of winter forage (black oat or annual ryegrass) in the form of triple superphosphate (TSP), reactive rock phosphate (RRP) and magnesium termophosphate (MTP). The dry matter yields for black oat (2009 and 2011) and ryegrass (2010), grain yield for maize (2009/10 and 2011/12) and soybean (2010/11), and P accumulation were evaluated in these crops. In 36 months of study, soil samples were collected from the layers 0-5, 5-10, 10-15 and 15-20 cm, to determine the concentrations of available P by different methods extractants (M1, IER and MM) and to assess the availability of P for maize (2011/12). The use of TSP, during sowing of black oat occasioned the highest yield of dry matter (DM) and P accumulation in DM (P-DM) in this crop. However, for the maize crop, the treatments did not affect grain yield (GY) and P accumulation in plant (P-Ac) at the first year of use. The treatments did not affect the yield of DM annual ryegrass and GY of soybean, in the second year of assessment. However, there was a greater accumulation of P-DM in the annual ryegrass, when applying MTP. For soybeans, the P-Ac was higher in the treatments with early application of TSP and MTP. The application of MTP during sowing of black oat occasioned the highest yield of DM and P-DM in this crop. The GY and P-Ac were higher in maize, occasioned by the use TFM, in the third year of study. Concentrations of available P in soil after 36 months of study, had variations according to each extractor. The ion exchange resin extracted greater amounts of P, followed by the extractor M1 and MM. In the treatments that received application of TSP, the M1 and IER extractants has obtained similar efficiency when correlated with the maize’s attributes (DMY, GY, P-DM and P-Ex). IER was the most efficient extractor which correlated with the P-DM and P-Ex when were applied sources insoluble in water (RRP and MTP). The MM extractor was ineffective to predicting the bioavailability of P for the maize grown in a soil with high content of clay and Fe and Al oxides, which received the application of rates and sources of P in a CLI system under NT. / A integração lavoura-pecuária (ILP) tem sido uma prática que, quando bem manejada e associada ao sistema plantio direto (PD), aumenta a qualidade do solo. Todavia, a maioria dos solos brasileiros apresenta baixa fertilidade natural de fósforo (P). Desta forma, o desenvolvimento de estratégias que aumentem a eficiência de uso de fertilizantes fosfatados possibilita um agronegócio mais sustentável do ponto de vista agronômico e econômico. Os objetivos desse estudo foram avaliar o acúmulo de P e o rendimento das culturas de milho, soja, aveia preta e azevém anual adubados com fontes e doses de P2O5 na ILP em PD. Ainda, avaliar a biodisponibilidade de P para a cultura do milho, extraído pelos métodos de Melich-1 (M1), Resina trocadora de íons (RTI) e Morgan modificado (MM), após 36 meses de experimentação. O experimento foi instalado em abril/2009, no município de Castro-PR em um Cambissolo Háplico textura muito argilosa. Foi empregado delineamento em blocos ao acaso em esquema fatorial incompleto (3x3+1) com quatro repetições. Os tratamentos consistiram na aplicação superficial (em área total) de doses (0, 60, 120 e 180 kg ha-1 ano-1 de P2O5) por ocasião da semeadura da forrageira de inverno (aveia preta ou azevém anual), nas formas de superfosfato triplo (SFT), fosfato natural reativo (FNR) e termofosfato magnesiano (TFM). Foram avaliados os rendimentos de massa seca da aveia preta (2009 e 2011) e azevém anual (2010), de grãos de milho (2009/10 e 2011/12) e soja (2010/11), e o acúmulo de P nessas culturas. Aos 36 meses de estudo, foram coletadas amostras de solo das camadas de 0-5, 5-10, 10-15 e 15-20 cm, para determinação das concentrações de P disponível pelos diferentes métodos extratores (M1, RTI e MM) e, para avaliação da disponibilidade de P para a cultura do milho (2011/12). O uso de SFT, por ocasião da semeadura da aveia preta proporcionou maior rendimento de massa seca total (MST) e acúmulo de P na MST (P-MST) nesta cultura. No entanto, para a cultura do milho, os tratamentos não influenciaram o rendimento de grãos (RG) e acúmulo de P na parte área (P-Ac), no primeiro ano de uso. Os tratamentos não influenciaram o rendimento de MST do azevém anual e o RG de soja no segundo ano de avaliação. Porém, houve maior acúmulo de P-MST do azevém anual mediante aplicação de TFM e, para a soja, o P-Ac foi maior nos tratamentos com aplicação antecipada de SFT e TFM. A aplicação de TFM por ocasião da semeadura da aveia preta proporcionou maior rendimento de MST e P-MST nesta cultura, e também, maior RG e P-Ac no milho, no terceiro ano de estudo. A RTI extraiu maiores quantidades de P disponível, seguida do extrator de M1 e do MM. Nos tratamentos que receberam aplicação de SFT, os extratores de M1 e RTI obtiveram eficiência semelhante quando correlacionados com os atributos de RMS, RG, P-MS e P-Ex do milho. Para as fontes insolúveis em água (FNR e TFM), o P extraído pela RTI melhor se correlacionou com o P-MS e o P-Ex. A solução de MM foi ineficiente para prever a biodisponibilidade de P para o milho, cultivado em solo com alto teor de argila e óxidos de ferro e alumínio, que recebeu a aplicação de doses e fontes de P, em um sistema de ILP em PD.

The current study therefore aims to provide a comprehensive characterisation of weathered dry disposed ash cores, to reveal mobility patterns of chemical species as a function of depth and age of ash, with a view to assessing the potential environmental impacts. Fifty-nine samples were taken from 3 drilled cores obtained respectively from the 1 year, 8 year and 20-year-old sections of sequentially dumped, weathered, dry disposed ash in an ash dump site at Tutuka - a South African coal burning power station.