In recent years, a number of high profile accidental fires have occurred in several road and rail tunnels throughout the world. Many of these fires grew rapidly to catastrophic size and claimed many lives. The processes involved in the rapid growth and extremely severe of these fires are not adequately understood as yet. The introduction to this thesis reviews a number of these accidental fires and describes much of the previous experimental research which has brought about the current understanding of tunnel fire behaviour. A detailed review of the relevant parts of elementary fire dynamics is also presented. This thesis addresses two main questions: 1. What is the influence of longitudinal ventilation on fire size in tunnels? and 2. What is the influence of tunnel geometry on fire size? The answers to both these questions are determined using a probabilistic method called Bayes Theorem. This provides a method of answering the above two questions using the handful of experimental data which are available. It is found that the heat release rate (HRR) of a heavy goods vehicle (HGV) fire may be greatly increased in magnitude by longitudinal ventilation, for example by about a factor of 5 with a longitudinal ventilation velocity of 3ms-1. It is also found that longitudinal ventilation may cause a significant increase in the HRR of large pool fires, but may cause a decrease in the HRR of small pool fires and car fires. An equation is derived to predict the influence of tunnel geometry on HRR. It is found that HRR varies principally with the width of the tunnel and the width of the fire object. The HRR of a fire in a tunnel my be increased up to four times due to the geometry of the tunnel.

L'objet de ce travail repose sur la recherche, le développement de nouveaux composés antibactériens, devant, selon le concept initial, interagir avec la paroi bactérienne. Ces derniers sont de nature polycationique, intégrant sur une structure calixarènique tridimensionnelle ou aromatique plan, des fonctions guanidiniums en nombre variable. Certains ont été développés en tant que prodrogues hydrosolubles, capables de libérer in vivo un principe actif (acide nalidixique). Le chapitre I porte sur introduction, l'étude bibliographique des calixarènes et leurs applications en biologie. Dans chapitre II, nous présentons les résultats (synthèse et caractérisation) obtenus pour les parents partiellement substitués du tétra-para-(guanidinoéthyl)calix[4]arène. Le but de ces synthèses est d'appréhender le rôle, l'importance du nombre et le positionnement des fonctions guanidines sur le calixarène. Nous abordons au chapitre III, les différentes étapes de synthèse, de caractérisation et l'évaluation par CLHP de nouvelles prodrogues hydrosolubles. Le comportement de prodrogue potentiel est ainsi démontré pour l'un d'entre eux. Dans le quatrième chapitre sont décrites les synthèses et caractérisations de nouvelles structures poly-ioniques, intégrant un motif central de type benzène, porteur d'un nombre variable de motifs latéraux para-(guanidinoéthyl)phényléther, et conçues comme une alternative aux calixarènes précédemment développés. Le chapitre V est dédié aux résultats des évaluations biologiques de l'ensemble de ces composés. Nous montrons que plusieurs des dérivés préparés, prodrogues ou non, présentent une activité anti-bactérienne très intéressante / The main objective of this work is based on the search and the development of new antibacterial compounds able to interact with a bacterial wall. The proposed compounds are of polycationic nature, elaborated on calixarene structure or an aromatic platform and containing guanidinium functions in various number and position. Some of them were developed as water-soluble prodrugs of the quinolone: nalidixic acid. The chapter I talk about introduction and a bibliographical study on calixarenes and their applications in biology. The chapter II presents the results obtained for the synthesis, the characterization of the partially substituted analogues of the tétra-para (guanidinoéthyl) calix[4]arene. The objective of this part is to understand the role and the importance of the number and the positioning of the guanidines functions on the calixarene core. In chapter III, are presented the various steps leading to the synthesis, the characterization and the evaluation by HPLC ways of new water-soluble prodrugs. The work is centered on a set of ionic derivatives of calix[4]arenes carriers of nalidixic acid. The prodrug behavior was demonstrated for one of them. The chapter IV presents the syntheses and characterizations of star-like poly-ionic structures are described, based on a benzene core, including a variable number of para (guanidinoéthyl) phényléther subunits. The chapter V is dedicated to the results of the biological evaluations of all the structure synthetized. For some compounds, viability and cellular toxicity were evaluated on eukaryotic cells. We show that many of the new prepared derivatives, prodrugs or not, present very interesting anti-bacterial activities

Suite aux grands changements politiques, économiques et sociaux que l’Occident a connus depuis plus d’un siècle, de nombreux problèmes ont émergé, de nouveaux défis ont été lancés et plusieurs approches et solutions ont été avancées. L’avènement de la démocratie, un exploit humain inestimable, a plus ou moins règlementé la pluralité idéologique, pour permettre un exercice politique organisé. Aujourd’hui, dans le nouvel ordre mondial, c’est la pluralité morale et religieuse qui a besoin d’être gérée; un défi pour les institutions démocratiques et pour la société civile, afin de réaliser un mieux vivre-ensemble dans le dialogue, la compréhension et le compromis. Or, beaucoup de travail est encore à faire : dans un premier temps, à l’intérieur de chaque tradition religieuse; dans un deuxième temps, entre les différentes traditions; et dans un troisième temps, entre ces traditions et la modernité. Le ‘dogmatisme’ est au cœur de ces débats, qu’il soit d’ordre traditionnel ou moderne, il entrave la raison dans son processus de libération et d’émancipation. La problématique de ce mémoire concerne la gestion de la pluralité morale et religieuse en Occident. Dans ce travail, nous allons essayer de démontrer comment la libération du dogmatisme en général et la libération du ‘dogmatisme’ musulman, en particulier, peuvent contribuer à la réalisation d’un mieux vivre-ensemble en Occident. Pour ce faire, nous analyserons les projets de deux penseurs musulmans contemporains : Muhammad Arkoun et Tariq Ramadan. Notre recherche va essentiellement se pencher sur leurs attitudes vis-à-vis de la tradition et de la modernité, car, nous pensons que l’enjeu du ‘dogmatisme’ est lié aux rapports des musulmans à leur tradition et à la modernité. Selon nos deux penseurs, la libération du ‘dogmatisme’ musulman n’est possible qu’à condition de pouvoir changer à la fois notre rapport à la tradition et à la modernité. Arkoun pense que ce changement doit suivre le modèle de la libération occidentale, au moyen d’une critique subversive de la tradition islamique. Cependant, Ramadan opte pour une réforme radicale de la pensée islamique qui vise une critique globale de la tradition, mais, qui épargne les fondements de la foi : le ‘sacré’. / Following the major political, economic and social changes that occurred in the West for over a century, many problems have emerged, new challenges have surfaced, and several approaches and solutions have been proposed. The advent of democracy, an invaluable human achievement, more or less regulated ideological plurality, and allowed the evolution of an organized political exercise. Today, in the new world order, it is the moral and religious diversity that need to be managed. The challenge remains for democratic institutions and civil society to create a better harmonious community through dialogue, understanding and compromise. However, much work is still to be done : first, within each religious tradition, second, between different traditions and third, between tradition and modernity. Dogmatism is at the heart of these debates. An order, whether traditional or modern hampers objectives reasoning in the process of liberation and emancipation. The issue of this paper concerns the management of the moral and religious plurality in the West. In this work, we will try to demonstrate how the relinquishing of ‘dogmatism’ in general and the relinquishing of Muslim ‘dogmatism’ in particular, can contribute to the achievement of a harmonious in a pluralistic West. This will be achieved by shedding light on the projects of two contemporary Muslim thinkers : Muhammad Arkoun and Tariq Ramadan. Our research is mainly to reflect on their attitudes towards tradition versus modernity, as we believe that the issue of dogmatism is linked to Muslims’ attitude towards tradition and modernity. According to these two thinkers, the release of muslims’ ‘dogmatism’ is only possible by changing both our relationship to tradition and modernity. Arkoun thinks this change should follow the model of Western release through a subversive critique of the Islamic tradition. However, Ramadan opts for a radical reform of Islamic thought through a comprehensive critique of the tradition, in order to save the foundation of faith : The ‘sacred’.

The primary objective of this research is to develop a mathematical framework that could be used to model or predict the rate of fluid absorption and release in fibrous sheets made up of solid or porous fibers. In the first step, a two-scale two-phase modeling methodology is developed for studying fluid release from saturated/unsaturated thin fibrous media made up of solid fibers when brought in contact with a moving solid surface. Our macroscale model is based on the Richards’ equation for two-phase fluid transport in porous media. The required constitutive relationships, capillary pressure and relative permeability as functions of the medium’s saturation, are obtained through microscale modeling. Here, a mass convection boundary condition is considered to model the fluid transport at the boundary in contact with the target surface. The mass convection coefficient plays a significant role in determining the release rate of fluid. Moreover the release rate depends on the properties of the fluid, fibrous sheet, the target surface as well as the speed of the relative motion, and remains to be determined experimentally. Obtaining functional relationships for relative permeability and capillary pressure is only possible through experimentation or expensive microscale simulations, and needs to be repeated for different media having different fiber diameters, thicknesses, or porosities. In this concern, we conducted series of 3-D microscale simulations in order to investigate the effect of the aforementioned parameters on the relative permeability and capillary pressure of fibrous porous sheets. The results of our parameter study are utilized to develop general expressions for kr(S) and Pc(S). Furthermore, these general expressions can be easily included in macroscale fluid transport equations to predict the rate of fluid release from partially saturated fibrous sheets in a time and cost-effective manner. Moreover, the ability of the model has been extended to simulate the radial spreading of liquids in thin fibrous sheets. By simulating different fibrous sheets with identical parameters but different in-plane fiber orientations has revealed that the rate of fluid spread increases with increasing the in-plane alignment of the fibers. Additionally, we have developed a semi-analytical modeling approach that can be used to predict the fluid absorption and release characteristics of multi-layered composite fabric made up of porous (swelling) and soild (non-swelling) fibrous sheets. The sheets capillary pressure and relative permeability are obtained via a combination of numerical simulations and experiment. In particular, the capillary pressure for swelling media is obtained via height rise experiments. The relative permeability expressions are obtained from the analytical expressions previously developed with the 3-D microscale simulations, which are also in agreement with experimental correlations from the literature. To extend the ability of the model, we have developed a diffusion-controlled boundary treatment to simulate fluid release from partially-saturated fabrics onto surfaces with different hydrophilicy. Using a custom made test rig, experimental data is obtained for the release of liquid from partially saturated PET and Rayon nonwoven sheets at different speeds, and on two different surfaces. It is demonstrated that the new semi-empirical model redeveloped in this work can predict the rate of fluid release from wet nonwoven sheets as a function of time.

L’optimisation de l’incorporation et de la libération de principes actifs dans les produits formulés constitue un des enjeux majeurs des industries pharmaceutiques et cosmétiques. L'objectif principal de notre étude est de proposer un modèle prédictif de la diffusion de petites sondes au sein des émulsions concentrées. Pour cela, il a fallu considérer à la fois la formulation d’émulsions concentrées stables et leur caractérisation rhéologique et structurelle ainsi que la prédiction des paramètres de transfert des sondes au sein des émulsions concentrées. On entend par paramètres de transfert, tous les paramètres permettant de caractériser les différents mécanismes de transfert de sondes dans les émulsions concentrées pris en compte dans notre système, à savoir le coefficient de diffusion dans les phases continue et dispersée, le coefficient de transfert à l’interface eau/huile, le coefficient de partage à l’équilibre de la sonde entre les deux phases de l’émulsion. Une nouvelle approche de caractérisation de la structure des émulsions concentrée a permis l’obtention des paramètres importants de structure (taille des gouttes et épaisseur du film de la phase continue). L’étude détaillée des mécanismes et processus diffusionnels est réalisée avec la prise en compte des résultats liés à la caractérisation structurelle du système d’étude. Ainsi, un modèle de diffusion fondé sur une approche phénoménologique est proposé pour prédire l'évolution des profils de concentration de la sonde dans les émulsions concentrées. Les cinétiques expérimentales de libération des sondes sont comparables à celles simulées par le modèle sans paramètres ajustables. Cette comparaison montre une bonne adéquation entre le modèle de diffusion et l’expérience / In the field of controlled release technology for new drugs, models that can predict its delivery during application are important for device design. The main objective of this work is to develop a predictive model able to describe the drug delivery from highly concentrated water-in-oil emulsions. These systems consist of deformed droplets dispersed in a continuous film. Their structure’s characteristics make them favourable for their use as releasing devices. A combination of different transfer mechanisms has been implemented in a mathematical model in order to simulate release experiments under different operating conditions (volume fraction, oil/surfactant ratio). A sensitivity analysis has been performed to point out the most relevant parameters affecting the drug’s release: drug partition and diffusion coefficients. Partition coefficient of the drug for different surfactant concentrations has been obtained through a predictive thermodynamic model UNIFAC, and the diffusion coefficient using Chang and Wilke equations in addition to the Stefan- Maxwell development. An original and simple technique has been used to determine indirectly the mean droplet size of the concentrated emulsions, through measurements of continuous phase’s thickness by analysis of incoherent polarized steady light transport through emulsion samples. In a general view, the diffusion model proposed for small drug diffusion in concentrated emulsions, which was first proposed for diluted emulsions, predicts successfully the evolution of mandelic acid concentrations during release experiments undertaken in perfect sink conditions

L'analyse des phénomènes locaux comme les effets de bord libre et le délaminage dans les structures multicouches nécessite des théories fines qui donnent une bonne description de la réponse locale. Étant donné que les approches tridimensionnelles sont, en général, très coûteuses en temps de calcul et en mémoire, des approches bidimensionnelles de type layerwise sont souvent utilisées. Dans ce travail de doctorat, un modèle layerwise en contrainte, appelé LS1, est appliqué au problème du multi-délaminage dans les plaques stratifiées invariantes dans le sens longitudinal. L'invariance dans la direction de la longueur nous permet d'aborder le problème analytiquement. Dans un premier temps, nous proposons une méthode analytique pour l'analyse des plaques multicouches multi-délaminées soumises à la traction uniaxiale. La singularité des contraintes interlaminaires aux bords libres et l'initiation du délaminage en mode III sont étudiées. Un modèle raffiné, nommé LS1 raffiné, est proposé pour améliorer les approximations dans les zones de singularités telles que les bords libres et les pointes de fissure. Les résultats du modèle raffiné sont validés en les comparant avec ceux obtenus par éléments finis tridimensionnels. Dans un deuxième temps, l'approche analytique proposée est étendue à la flexion cylindrique des plaques multicouches. La propagation du délaminage en modes I et II est étudiée et les approximations du modèle LS1 sont validées. À la fin, nous généralisons la méthode analytique proposée afin de prendre en considération tous les chargements invariants dans le sens longitudinal. L'approche finale permet d'analyser les plaques multicouches rectangulaires soumises à des charges invariantes sur les faces supérieure et inférieure, les forces ou les déplacements imposés sur les bords latéraux ainsi que quatre types de chargement sur les extrémités longitudinales: traction uniaxiale, flexion hors plan, torsion et flexion dans le plan. La solution analytique du modèle LS1 est obtenue pour une plaque stratifiée soumise à tous les chargements mentionnés ci-dessus. L'approche est validée en comparant avec la méthode des éléments finis tridimensionnels pour plusieurs types de chargement / The analysis of local phenomena such as free-edge effects and delamination in multilayered structures requires the accurate theories which can provide a good description of the local response. Since the three-dimensional approaches are generally very expensive in computational time and memory, the layerwise two-dimensional approaches are widely used. In this Ph.D. thesis, a stress layerwise model, called LS1, is applied to the multi-delamination problem in longitudinally invariant multilayered plates. The invariance in the longitudinal direction allows us to solve the problem analytically. At first, we propose an analytical method for the analysis of multi-delaminated multilayered plates subjected to the uniaxial traction. The free-edge interlaminaire stress singularities and the mode III delamination onset are investigated. A refined model, called Refined LS1, is proposed in order to improve the approximations in singularity zones such as free edges and crack tips. The results of the refined model are validated by comparing them with those obtained by a three-dimensional finite element model. Afterwards, the proposed analytical approach is extended to the cylindrical bending of the multilayered plates. The propagation of delamination in modes I and II is studied and the approximations of the LS1 model are validated. At last, we generalize the proposed analytical method to take into account all invariant loads in the longitudinal direction. The final approach allows us to analyze the rectangular multilayered plates subjected to invariant loads on the top and bottom surfaces, imposed displacements or forces at the lateral edges, and also four types of loading at the longitudinal ends: uniaxial traction, out-of-plane bending, torsion and in-plane bending. The analytical solution of the LS1 model is obtained for a laminated plate subjected to all the loads mentioned above. The approach is validated by comparison with the three-dimensional finite element method for various types of loading

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / The research work in this thesis aims at investigating the basic physic-chemical properties of magnetic and metal nanoparticles (NPs) for biomedical applications such as magnetic hyperthermia and controlled drug release. Magneto-plasmonic properties of magnetic NPs are important to evaluate potential applications of these materials. Magnetic property can be used to control, monitor and deliver the particles using a magnetic field while plasmonic property allows the tracking of the position of the particles, but aggregation of NPs could pose a problem. Here, the aggregation of NPs is investigated via the Faraday rotation of gold coated Fe[subscript]2O[subscript]3 NPs in alternating magnetic fields. In addition, the Faraday rotation of the particles is measured in pulsed magnetic fields, which can generate stronger magnetic fields than traditional inductive heaters used in the previous experiments. In the second project, the formation of protein-NPs complexes is investigated for hyperthermia treatment. The interactions between gold and iron-platinum NPs with octameric mycobacterial porin A from Mycobacterium smegmatis (MspA) and MspA[superscript])cys protein molecules are examined to assemble a stable, geometrically suitable and amphiphilic proteins-NPs complex. Magnetic NPs show promising heating effects in magnetic hyperthermia to eliminate cancer cells selectively in the presence of alternating magnetic field. As a part of investigation, the heating capacity of a variety of magnetic NPs and the effects of solvent viscosity are investigated to obtain insight into the heating mechanism of these particles. Finally, the controlled drug release of magnetic NPs loaded liposomes by pulsed magnetic field is investigated. The preliminary data indicate about 5-10% release of drug after the application of 2 Tesla magnetic pulses. The preliminary experiments will serve as the initial stage of investigation for more effective magnetic hyperthermia treatment with the help of short magnetic pulses.

Sugarcane is one of the crops with the highest extraction of macronutrients from the soil, both in cane-plant and ratoon crops, being critical its reposition by means of fertilizers. In the Brazilian sugarcane agrosystem, the supply of elements, such as, potassium (K), calcium (Ca), magnesium (Mg) and sulfur (S) is commonly performed by fertilizers, like potassium chloride, and soil amendments, such as, lime and phosphogypsum, producing high costs by sole application. In this context, the study aimed to determine the potential of polyhalite as a multi-nutrient source of K, Ca, Mg and S and its effects on yield and quality of sugarcane. In order to reach this objective, the study was divided into three stages: i) field evaluation in low K soil comparing doses of POLY with the combined application of KCl and GYP to evaluate yield, quality, soil chemical parameters, straw and stalk macronutrient content in two sugarcane varieties. ii) elemental, mineralogical and release characterization of the polyhalite (POLY) and potassium chloride (KCl) by the use of micro X-ray fluorescence spectrometry (µXRF) and X-ray diffraction spectrometry; and (iii) evaluation under glasshouse conditions to evaluate the residual effect of the application of POLY dosages contrasted to the application of KCl, GYP and kieserite (KIE) in the leaf macronutrients content, and biomass production in an Oxisol with a low level of K. Based on the field experiment, the application of calcium (Ca), magnesium (Mg), sulfur (S) and mainly potassium (K), irrespective the source applied, affected positively the yield in sugarcane. Related to the dosage, application of 105 kg K2O ha-1, which corresponds to farmer\'s recommended dosage, promoted the highest stalk yields for both varieties, CV7870 and RB867515. This dosage keeps the adequate nutritional status of sugarcane ratoon and enhance the K content in stalk, promoting the accumulation of sucrose in this plant organ. In relation to the soil parameters, for the variety RB867515, after cultivation, most of the nutrient concentration remained in soil were not significant compared to control, suggesting that as much fertilizer is applied this variety will uptake and export. In contrast, the variety CV7870 showed higher remained values for soil Ca, Mg and S in the treatments compared to the control after cultivation, indicating a residual effect, irrespective the treatment. Based on the laboratory results, KCl granule in the moisture low-K sandy Oxisol has rapidly promoted dissolution of nutrients and then released Cl- and K+, being susceptible for leaching, whereas POLY granule performed as a slow-release fertilizer due to its low solubility compared to KCl, enhancing residual effect over time. The results of the glasshouse showed that DM yield and nutrient uptake were more correlated to high K dosages applied (42 and 63 mg kg-1) and K sources containing Ca and S in the formulation (POLY, KCl+GYP+KIE and ½KCl ½POLY), for both cane-plant and ratoon. However, when these sources were provided at the lowest dosage (21 mg kg-1) it was observed superior agronomic efficiency for all added nutrients, indicating that a combination of KCl and POLY can be used more efficiently as K source for sugarcane. Taking together, both experiments, in the field and in the greenhouse, showed that polyhalite is suitable to supply K, Ca, Mg and S at the farmer\'s dosage recommendation. Furthermore, the blend of 50% polyhalite and 50% KCl could be adopted for farmers minimizing plant nutrient losses with a more balanced nutrition. / A cana-de-açúcar é uma das culturas com maior extração de macronutrientes do solo, tanto em cana-planta quanto em soca, sendo fundamental sua reposição por meio de fertilizantes. O fornecimento de elementos como potássio (K), cálcio (Ca), magnésio (Mg) e enxofre (S) para cana-de-açúcar é comumente realizado por fertilizantes, como o cloreto de potássio, e condicionadores do solo, como calcário e gesso agrícola, gerando altos custos por cada aplicação. Neste contexto, o estudo teve como objetivo determinar o potencial de polialita (POLY) como fonte multi-nutriente de K, Ca, Mg e S e seus efeitos na produtividade e qualidade da cana-de-açúcar. Para isso, o estudo foi dividido em três etapas: i) avaliação em campo usando solo com baixo nível de K comparando doses de POLY com a aplicação combinada de KCl e gesso agrícola (GYP) para avaliar rendimento, qualidade, parâmetros químicos do solo, teor de macronutrientes de palha e colmo em duas variedades de cana-de-açúcar, CV7870 e RB867515. ii) caracterização elementar, mineralógica e de liberação do polihalita (POLY) e cloreto de potássio (KCl) pelo uso de espectrometria de micro fluorescência de raios X (µXRF) e espectrometria de difração de raios-X; e (iii) avaliação em condições de casa de vegetação do efeito residual da aplicação de dosagens de POLY em contraste com a aplicação conjunta de KCl, GYP e kieserite (KIE) no teor de macronutrientes foliares, e produção de biomassa. Com base no experimento de campo, a aplicação de Ca, Mg, S e principalmente K, independentemente da fonte aplicada, afetou positivamente o rendimento em cana-de-açúcar. Em relação à dosagem, a aplicação de 105 kg K2O ha-1, que corresponde à dosagem recomendada, promoveu os maiores rendimentos de colmos para ambas as variedades, CV7870 e RB867515. Essa dosagem mantém o estado nutricional adequado da cana-soca e aumenta o teor de K no colmo, promovendo o acúmulo de sacarose na planta. Em relação aos parâmetros do solo, para a variedade RB867515, após o cultivo, a maior parte da concentração de nutrientes remanescente no solo não teve efeito significativo em relação ao controle, sugerindo que, quanto mais fertilizante for aplicado, essa variedade será capaz de absorver e exportar. Em contrapartida, a variedade CV7870 apresentou maiores valores remanescentes de Ca, Mg e S no solo em relação ao controle após o cultivo, indicando um efeito residual, independentemente do tratamento. Com base nos resultados laboratoriais, o grânulo de KCl em solo úmido com baixo teor de K promoveu rapidamente a dissolução dos nutrientes e liberou Cl- e K+, sendo mais suscetível à lixiviação, enquanto que o grânulo POLY apresentou baixa solubilidade em comparação ao KCl, aumentando o efeito residual ao longo do tempo. Os resultados mostraram que a produção de biomassa e a absorção de nutrientes foram mais correlacionados às altas doses K (42 e 63 mg kg-1) e fontes de K contendo Ca e S na formulação (POLY, KCl + GYP + KIE e ½KCl ½POLY), tanto para cana-planta quanto para soca. Entretanto, quando essas fontes foram fornecidas na dose mais baixa (21 mg kg-1), foi observada eficiência agronômica superior para todos os nutrientes adicionados, indicando que uma combinação de KCl e POLY seria mais eficiente como fonte de K para cana-de-açúcar. Numa avaliação geral, a polihalita foi adequada para fornecer K, Ca, Mg e S na dose recomendada de 105 kg K2O ha-1. Assim mesmo, a mistura de 50% de polihalita e 50% de KCl pode ser adotada para os agricultores reduzindo as perdas nutricionais para planta.

MSc (Eng) dissertation - Faculty of Engineering and the Built Environment / Fertilizers are defined in the broadest sense as products that improve the levels of available plant nutrients or chemical and physical components that directly or indirectly enhance plant growth, yield and quality. The aim of this study was to produce slow controlled release fertilizers from oxidised coal. Two types of coals namely, Waterberg and Twistdraai (products, middlings) were utilised for the production of humic acids through slurry phase oxidation. The highest yields of humic acids were obtained in Waterberg and Twistdraai products samples. Subsequent to that, a nitrogen element was successfully inserted into the humic acid substrate. Humic acids are potential feedstock for modern manufacturing of organic fertilizers. The chemical substances regarded as hazardous to human consumption or those elements that negatively impact on the soil were significantly less detectable.

O complexo conhecido trans-[Ru(NO)(NH3)4(py)](BF4)3 foi sintetizado e caracterizado por cromatografia líquida de alta eficiência e espectroscopias de RMN de 1H, de absorção eletrônica e de infravermelho e RPE. O espectro de absorção de infravermelho do complexo apresenta o pico de estiramento de NO em 1931 cm-1 e o seu espectro de absorção eletrônica apresenta bandas em 237 nm (e = 5200 mol-1 L cm-1), 267 (e = 2300 mol-1 L cm-1), e 324 nm (e = 160 mol-1 L cm-1), concordantes com a literatura.O corante azul do Nilo (máx = 635 nm) sofre fotoquímica quando irradiado com luz de 577 nm, ao passo que os corantes rodamina-B (máx = 524 e 570 nm), fluoresceína sódica (máx = 437 nm) e tartrazina (máx = 438 nm) não. A fotólise do complexo em solução aquosa, pH ~3, com luz de 313 nm leva à liberação de NO. Soluções aquosas de trans-[Ru(NO)(NH3)4(py)](BF4)3 em pH 7,4 (tampão fosfato) na presença da forma monomérica dos corantes rodamina-B (lirr = 570 nm), fluoresceína sódica (lirr = 440 e 490 nm), tartrazina (lirr = 440 nm) e alaranjado de acridina (lirr = 440 nm) foram irradiadas com laser nas bandas de absorção máxima desses corantes. Para verificar se estava ocorrendo a liberação de NO pelo complexo através da sensibilização por corantes foram utilizados os capturadores de NO mioglobina e carboxy-PTIO. Os resultados indicam que não houve liberação de NO nesses casos, sugerindo que não ocorre transferência de energia de corantes para o complexo trans-[Ru(NO)(NH3)4(py)]3+, ao se irradiar na banda de absorbância máxima dos corantes, pelo mecanismo de Förster (transferência de energia a longa distância). Para que ocorra, a fotoquímica deve estar associada a uma transferência de energia do tipo Dexter, onde o corante é ligado diretamente ao complexo. / The known complex trans-[Ru(NO)(NH3)4(py)](BF4)3 was synthesized and characterized by high performance liquid chromatography, 1H NMR, EPR, and electronic and infrared absorption spectroscopies. The complex infrared absorption spectrum displays the NO stretching peak at 1931 cm-1 and its electronic absorption spectrum shows bands at 237 nm (e = 5200 mol-1 L cm-1), 267 (e = 2300 mol-1 L cm-1), and 324 nm (e = 160 mol-1 L cm-1), in agreement with reported values. The Nile blue dye (max = 635 nm) undergoes photochemistry by irradiation with 577 nm light, while rhodamine-B (max = 524 and 570 nm), sodium fluorescein (max = 437 nm) and tartrazine (max = 438 nm) do not. The photolysis of the complex in pH 3 aqueous solution with 313 nm light results in NO release. Aqueous solutions of trans-[Ru(NO)(NH3)4(py)](BF4)3 at pH 7,4 (BPS) in the presence of the monomeric forms of the rhodamina-B (lirr = 570 nm), sodium fluorescein (lirr = 440 e 490 nm), tartrazine (lirr = 440 nm), and acridine orange (lirr = 440 nm) dyes were irradiated at the their absorption maxima. In order to verify the NO release from the complex through sensitization by the dyes, the NO scavengers myoglobin and carboxy-PTIO were used. The results indicate that NO release does not occur under these circumstances, suggesting, thus, that there is no energy transfer from the dyes to the trans-[Ru(NO)(NH3)4(py)]3+ complex by irradiating at the dyes absorbance maxima bands by the Förster mechanism (long distance energy transfer). For the photochemistry to occur it should be associated to a Dexter type energy transfer, in which the sensitizer is directly attached to the complex.