Le travail présenté dans ce mémoire est une contribution à l’étude prospective des effetsprovoqués par des éléments traces métalliques (Zn, Cd et Pb) sur des suspensions cellulaires detomate (Solanum lycopersicum, L.). L’objectif principal de l’investigation est de démontrerl’implication de la paroi dans la réaction de défense des cellules contre le stress métallique à l’instarde celles qu’elles sont capables de développer contre les agressions biotiques.Le premier chapitre a consisté à caractériser des paramètres quantitatifs (croissance, hydratation) etqualitatifs (viabilité, réactivité enzymatique) pour mettre en évidence les effets généralement nocifscausés par l’introduction des éléments traces métalliques (ETM) dans les milieux de culture aumoment de la phase exponentielle de croissance. Outre la diminution de la croissance (arrêt et mortcellulaire), l’état physiologique des cellules, apprécié par leur perte de turgescence, témoigne de lacapacité de tolérance des cellules de tomate vis-à-vis du Zn, par rapport aux deux autres ETM.Le second chapitre a permis de montrer que les cellules de tomate se sont défendues contreles agressions métalliques en augmentant leur biomasse pariétale, notamment en présence de zinc.En outre, la paroi apparaît dans tous les cas comme le principal compartiment de séquestration desETM en excès. La comparaison entre les trois espèces métalliques montre que les parois des cellulesde tomate retiennent mieux le cadmium que le zinc et le plomb.Le troisième chapitre, consacré à l’étude de la composition osidique des parois dans unchamp expérimental réduit aux plus faibles doses de zinc, a fourni des données inédites,notamment à propos des pectines extraites ou non par les procédés employés (CDTA, EPGase). Lesrésultats (quantités et caractéristiques des extraits pectiques) ont été discutés en fonction destraitements subis par les cellules mais également avec le souci de trouver des explications à larétention du zinc dans la paroi et un schéma de structure hypothétique de la paroi a été proposé.En définitive, ce travail répond à la question posée initialement et apparaît comme unepréparation à caractère académique d’un projet environnemental d’utilisation des végétaux pour laphytoremédiation. / The aim of this work was to evaluate the effects of heavy metals (Zn, Cd, Pb) on tomato(Solanum lycopersicum, L.) suspension-cultured cells. The main objective was to demonstrate thattomato cells subjected to metal stress react by modifying their cell walls as they can do in responseof a pathogen attack.In the first chapter, cell parameters were characterized with both quantitative(growth, water content) and qualitative (viability, enzymatic activities) aspects to highlightdeleterious effects of heavy metal (HM) when added in the culture medium during exponential cellgrowth. In addition to growth reducing (growth break, turgor pressure loss and cell death), tomatocells have showed higher tolerance capacity to Zn compared to Cd and Pb.The second chapter demonstrated that tomato cells were able to protect themselvesagainst HM stress by increasing their cell wall biomass and also the HM amount retained by cellwall polymers. Cell walls appeared to assume important roles in HM accumulation (Cd>Zn>Pb)and could therefore limit their influx into the cells. Our results also suggested that HM fixation bycell walls was not only due to an increase in cell wall biomass but also to an improvement of itsbinding capacity.The last chapter, devoted to study the osidic composition of tomato primary cell walls forthe lowest Zn doses, has provided original data particularly about pectins. Results have beendiscussed in order to understand the binding capacity of cell walls in function of Zn treatments.Then, an hypothetical structure of tomato cell wall of cultured cells has been proposed.Finally, this work has answered to the initial question and has constituted a preparativestudy for next phytoremediation projects.

Frente ao aumento populacional e consequente incremento na demanda por alimentos, é importante estabelecer um melhor aproveitamento da área de cultivo, objetivando a colheita de produtos agrícolas em maior quantidade e de melhor qualidade. O aumento da concentração de micronutrientes nos produtos colhidos, especialmente de zinco é um desafio crescente para a agricultura, com possibilidade de trazer benefícios à saúde humana e à produtividade da cultura. Nesse sentido, a aplicação foliar de zinco realizada periodicamente, à partir da antese floral, é uma técnica capaz de incrementar o teor do micronutriente nas sementes e biofortificar os grãos de feijão e trigo, causando melhoria de aspectos agronômicos (crescimento vegetativo e produtividade da cultura) de plantas provenientes dessas sementes, além de resultar proveitos para a saúde humana daqueles que se alimentam de produtos biofortificados, e ainda com potencial para produzir grãos e sementes como produtos de maior valor comercial no mercado, valendo-se de inovação tecnológica. Porém, atualmente pouco se conhece sobre os diversos aspectos desta técnica. Assim sendo, objetivou-se: (i) elucidar o efeito da aplicação foliar de zinco, à partir da antese floral, como método para incrementar o teor do micronutriente nos grãos de feijão (Phaseolus vulgaris L.) e de trigo (Triticum aestivum L.), em substrato com teor adequado do micronutriente (ii) utilização de diferentes fontes de zinco aplicadas via foliar visando estabelecer a melhor fonte para o aumento do teor do micronutriente no grão de feijoeiro e (iii) determinação das doses de zinco mais adequadas a serem aplicadas através de pulverização foliar visando o aumento do teor do nutriente no grão de plantas de feijão e de trigo. Com base nos resultados obtidos, concluiu-se que (i) a aplicação foliar de zinco realizada periodicamente, à partir da antese floral é capaz de aumentar o teor do micronutriente em grãos de feijão e de trigo; (ii) a fonte mais viável para o enriquecimento de grãos de feijão é o sulfato de zinco; (iii) e todas as doses testadas (125, 250, 375 e 500 g Zn ha-1) aplicadas via foliar na forma de sulfato de zinco foram efetivas para o enriquecimento de grãos de feijão e de trigo, em relação ao controle (0 g Zn ha-1). / In view of the population increase and consequent growth of food demand, it is important to establish a better utilization of the cultivation area, aiming the harvest of agricultural products in greater quantity and of better quality. The increased concentration of micronutrients in products harvested, especially zinc, is a growing challenge for agriculture, with potential to bring benefits to human health and crop productivity. In this matter, the foliar zinc application performed periodically starting at floral anthesis is a technique capable of increasing the micronutrient content in the seeds and biofortifying grains of common bean and wheat, causing agronomic aspects improvement (vegetative growth and crop productivity) of plants derived from these seeds, in addition to bringing benefits to human health of those who feed on biofortified products, and still with potential to produce grains and seeds as products of greater commercial value in the market, being a technological innovation. However, currently little is known about the aspects that circumvent this technique. The objective of this study was: (i) elucidate the effect of foliar application of zinc, starting at floral anthesis, as a method to increase the micronutrient content of common bean (Phaseolus vulgaris L.) and wheat (Triticum aestivum L.) (ii) the use of different sources of zinc applied in a foliar way, in order to establish the best source for increasing the micronutrient content in common bean grains, and (iii) the determination of the most suitable zinc doses, applied by foliar spraying to increase the nutrient content of common bean and wheat plants. Based on the results obtained, it was concluded that (i) the periodic application of zinc foliar application starting at floral anthesis is capable of increasing the micronutrient content in common bean and wheat grains; (ii) the most viable source for the enrichment of bean grains is zinc sulphate; (iii) and all the doses tested (125, 250, 375 and 500 g Zn ha-1) applied via foliar in the form of zinc sulfate were effective for the enrichment of common bean and wheat grains, in relation to the control (0g Zn ha-1).

HudBay Minerals (formerly the Hudson Bay Mining and Smelting Co., Limited) has operated a Zn and Cu processing facility in Flin Flon, MB since the 1930’s. Located in the Boreal Shield, the area surrounding the mine complex has been severely impacted by both natural (forest fires) and the anthropogenic disturbance, which has adversely affected recovery of the local forest ecosystem. Zinc is one of the most prevalent smelter-derived metals in the soils and has been identified as a key factor limiting natural revegetation of the landscape. Because metal toxicity is related more to speciation than to total concentration, Zn speciation in soils from the impacted landscape was characterized using X-ray absorption fine structure, X-ray fluorescence mapping and µ-X-ray absorption near edge structure. Beginning with speciation at a micro-scale and transitioning to bulk speciation was able to determine Zn speciation and link it to two distinct landform characteristics: (1) soils stabilized by metal tolerant grass species—in which secondary adsorption species of Zn (i.e., sorbed to Mn and Si oxides, and as outer-sphere adsorbed Zn) were found to be more abundant; and (2) eroded, sparsely vegetated soils in mid to upper slope positions that were dominated almost entirely by smelter derived Zn minerals, specifically Franklinite (ZnFe2O4). The long-term effect of liming on pH and Zn speciation was examined using field sites limed by a community led organization over a ten year period. Upon liming to a pH of 4 to 4.5, the eroded, sparsely vegetated soils where found to form a Zn-Al-Hydroxy Interlayer Material (HIM) co-precipitate, reducing the phytotoxicity of both Zn and Al and allowed for boreal forest vegetation to recovery quickly in these areas. The grass stabilized soils experienced a steady pH increase, as compared to a sporadic pH increase in the heavily eroded soils, as the buffering capacity was overcome allowing for a transition between multiple adsorption species based upon the point of zero charge of reactive soil elements. Ultimately reaching a near neutral pH after ten years, this allowed for the formation of stable Zn-Al-layered double hydroxide (LDH) soil precipitates and significantly reduced concentrations of plant available Zn.

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Les métallo-β-lactamases sont des enzymes qui confèrent aux bactéries qui les synthétisent une résistance aux antibiotiques. La classe B représente les β-lactamases, dans lesquelles le site actif contenant un ou deux atomes de Zn favoriserait l'hydrolyse des antibiotiques. La dégradation des antibiotiques par les enzymes bactériennes est un mécanisme majeur de résistance. L’objectif de ce travail de thèse est de mettre en œuvre des outils de modélisation fondés sur des méthodes de mécanique quantique en vue de déterminer les structures de métallo-β-lactamases avec des inihibiteurs, étape nécessaire pour comprendre ultérieurement quels sont les mécanismes de réaction favorisant la dégradation d’un inhibiteur par des métallo-β-lactamases et fournir des informations qui serviront à mieux interpréter les phénomènes biologiques.Nous avons tout d’abord déterminé les géométries et la stabilité de complexes de coordinations métalliques de systèmes modèles contenant du Zn, comme dans les sites métalliques des métallo-β-lactamases, ou du Cu, complexés à des histidines coordonnées par les Nπ ou Nτ, afin de voir s’il y a une préférence géométrique pour l’une ou l’autre des deux coordinations et voir l’influence de ces différentes coordinations possibles sur les paramètres géométriques au niveau du site métallique. Enfin la présence d’eau et l’influence du solvant aqueux a été étudiée. Grâce à ces méthodes de chimie quantique fondées sur la théorie de la fonctionnelle de la densité, nous avons montré comment ces méthodes permettent d’avoir des informations structurales sur la symétrie adoptée par les centres métalliques, du Zn2+ et du Cu2+. Cette étude structurale nous a permis de mettre en évidence des différences structurales entre ces deux ions métalliques et de déterminer les spectres vibrationnels. Ces investigations nous ont permis de mettre en évidence la nature des liaisons métal-ligand grâce à des approches topologiques. Nous avons montré que ces études préliminaires nous ont permis de choisir la meilleure méthode de calculs DFT pour étudier des centres à zinc dans des structures de β-lactamases.Pour compléter l’étude de structures de métallo-β-lactamases, nous avons déterminé la structure de l’enzyme native L1 (β-lactamase) qui a permis de reproduire les paramètres géométriques des structures expérimentales de L1. Nous avons montré que l’approche combinant des études quantiques et classiques (QM/MM) permet de reproduire avec une très bonne confiance les paramètres structuraux de sites actifs de l’enzyme L1.Enfin, nous avons déterminé les structures de certains sites actifs de la famille B3 des Métallo-β lactamases (Enzyme L1) pour comparer les affinités de différentes familles d’inhibiteurs synthétisées à l’IBM de Montpellier (Institut des Biomolécules de Montpellier) et prédire la structure possible de L1 avec différents inhibiteurs par des méthodes QM/MM pour voir si cette stratégie pourra être appliquée à d’autres inhibiteurs pour des métallo-β-lactamases. / Metallo-β-lactamases are enzymes that give the bacteria that synthesize them antibiotic resistance. B Class represents the beta-lactamases, wherein one or two Zn atom(s) promote(s) β-lactams (antibiotics) hydrolysis. The major resistance mechanism is the degradation of the β-lactams by bacterial enzymes called β-lactamases. One major approach to overcome this resistance deals with combination therapy in which a β-lactam drug is given along with a β-lactamase inhibitor, which protects the former from inactivation. The objective of this thesis is to implement modeling tools based on quantum mechanical methods to determine metallo-β-lactamase structures with inhibitors, a step necessary to understand at a later stage the mechanisms of response to the degradation of the inhibitor by β-lactamases and to provide information that will serve to better interpret biological phenomena.We have first determined the geometries and the stability of metal coordination complexes of model systems containing Zn, as in the metallo-β-lactamase metal sites, or Cu, complexed to histidines coordinated by Nπ or Nτ, in order to see if there is a geometric preference for one or the other of the two coordination’s and to see the influence of these different possible coordination’s on the geometrical parameters at the metallic site. Finally, the presence of water and the influence of the aqueous solvent were studied. Using these methods of quantum chemistry based on the density functional theory, we have shown how these methods provide structural information on the symmetry adopted by the metallic centers of Zn2 + and Cu2 +. This structural study allows us to demonstrate structural differences between these two metal ions and to determine the vibrational spectra. These investigations were able to demonstrate the nature of the metal-ligand bonds through topological approaches. We have shown that these preliminary studies have conducted us to choose the best method of DFT calculations for studying zinc centers in β-lactamase structures.To complete the study of metallo-β-lactamase structures, we have determined the structure of the native enzyme L1 (β-lactamase) which permitted to reproduce the geometric parameters of the experimental structures of L1. We have shown that the combination of quantum and classical approaches (QM/MM) allows to reproduce with very good confidence the structural parameters of the L1 enzyme active sites.Finally, we have determined the structures of certain active sites in the B3 family of Metallo-β lactamases (Enzyme L1) to compare the affinities of different families synthesized at IBM in Montpellier (Institute of Biomolecules of Montpellier) and to predict the possible structure of L1 with different inhibitors by QM / MM methods to see if this strategy can be applied to other inhibitors for metallo-β-lactamases.

Submitted by Maria Suzana Diniz (msuzanad@hotmail.com) on 2015-11-12T13:09:59Z No. of bitstreams: 1 Arquivototal.pdf: 4725274 bytes, checksum: 00ba23047c493bdc8d085328b0239721 (MD5) / Made available in DSpace on 2015-11-12T13:10:01Z (GMT). No. of bitstreams: 1 Arquivototal.pdf: 4725274 bytes, checksum: 00ba23047c493bdc8d085328b0239721 (MD5) Previous issue date: 2015-01-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The squeeze casting process is a casting process in which the cast metal in the liquid state is solidified under pressure in a metal mold closed off by a punch. In general components manufactured by squeeze casting have fine grained, high surface finish and almost free of porosity, may be the same of different sizes and shapes, the mechanical properties are enhanced significantly in comparison with the traditional method of casting and, in addition, parts manufactured by squeeze casting possess superior weldability and are able to heat treatment, and finally compared to the common casting parts manufactured by squeeze casting are formed in one operation with a lower energy consumption. The objective of this study is to analyze the influence of pressure as well as the zinc content of the alloys in the secondary dendrite spacing, the hardness and tensile strength limit, and correlate the microstructures with the mechanical properties and process parameters. For this purpose we used the mass compositions Al-Zn 1% Al-Zn 3% and Al-Zn 5% solidified with the squeeze casting process using the pressure 50 MPa, 100 MPa and 150 MPa, and the pressing time of 5 seconds. It is observed that the increase in pressure causes a reduction in dendrite spacing until 100 MPa, pressure variations from this point up to 150 MPa causes a increase in the secondary dendrite spacing, was also observed that the Vickers hardness and the tensile strength limit have a relationship with the secondary dendrite spacing. / O processo squeeze casting é um processo de fundição, no qual o metal vazado no estado liquido, é solidificado sob pressão dentro de um molde metálico fechado por um punção. Em geral componentes fabricadas por squeeze casting possuem granulação fina, excelente acabamento de superfície e quase livre de porosidade, os mesmo podem ser de diferentes tamanhos e formatos, as propriedades mecânicas são aumentadas significantemente, em comparação ao método tradicional de fundição e, além disso, peças fabricadas por squeeze casting possuem soldabilidade superior e são aptas a tratamentos térmicos, e finalmente em comparação com a fundição comum peças fabricadas por squeeze casting são formadas em uma só operação com um menor consumo de energia. O objetivo deste trabalho é analisar a influencia da pressão assim como do teor de zinco das ligas no espaçamento dendrítico secundário, na microdureza e no limite de resistência à tração, e correlacionar as microestruturas com as propriedades mecânicas e com os parâmetros de processo. Para tal foram utilizadas as composições Al-1%Zn , Al-3%Zn e Al-5%Zn em massa, solidificadas com o processo squeeze casting usando as pressões 0 MPa, 50 MPa, 100 MPa e 150 MPa, com o tempo de prensagem de 5 segundos. Observa-se que o aumento da pressão causa uma diminuição no espaçamento dendrítico até a pressão 100MPa, a partir deste ponto variações até 150 MPa causam aumento no espaçamento dendrítico secundário, observou-se também que a microdureza vickers assim como o limite de resistência à tração apresentam uma relação com o espaçamento dendrítico secundário.

Les revêtements galvanisés alliés sont produits par immersion à chaud d’une bande d'acier dans un bain de zinc fondu à environ 460 °C, saturé en fer et contenant de faibles quantités d'aluminium (de 0,1 à 0,135% poids), suivie d’un traitement thermique (jusqu'à des températures voisines de 500-530 °C pendant environ 10 s) afin de déclencher les réactions d'alliation entre le fer et le zinc. La microstructure finale de ce type de revêtement est composée d'une succession de couches stratifiées de phases Fe-Zn et ses propriétés d'usage sont directement liées à la distribution de ces phases dans le revêtement. Les paramètres process à appliquer sur ligne industrielle doivent donc être optimisés pour obtenir la microstructure de revêtement souhaitée avec des coûts minimaux. Le développement d'un tel revêtement passe par différentes réactions complexes : la formation de la couche d'inhibition, la rupture de cette couche, la consommation du zinc liquide et l'enrichissement en fer du revêtement solide. Les cinétiques de ces réactions doivent être étudiées et modélisées séparément afin de contrôler avec précision l'évolution du revêtement au cours du cycle thermique. Dans ce travail, les deux premières réactions ont été étudiées dans le cas des aciers IF Ti. La cinétique de formation de la couche d'inhibition est extrêmement rapide et n’a par conséquent pas été étudiée. L'attention a été portée sur la nature de cette couche et sur les mécanismes responsables de sa formation. Il a été démontré que la couche d'inhibition formée dans des bains classiques pour la production de ces revêtements est composée d'une première couche très mince de Fe2Al5Znx (20-30 nm) sur la surface de l’acier et d’une seconde couche plus épaisse de δ (FeZn7) (environ 200 nm) au-dessus. Lorsque l'acier est immergé dans le bain de zinc, la dissolution du premier dans le second conduit à une sursaturation en fer à l'interface solide / liquide. Une très fine couche de Fe2Al5Znx métastable germe alors sur la surface de l'acier favorisée par des relations préférentielles d’épitaxie avec la ferrite. Par la suite, une couche de δ germe sur la couche de Fe2Al5Znx ce qui permet à la microstructure finale de devenir thermodynamiquement stable. L'effet de la teneur en aluminium du bain sur la nature de la couche d'inhibition a également été étudié. Quand la teneur en aluminium du bain diminue, la couche de Fe2Al5Znx devient discontinue car cette phase devient plus métastable et sa germination sur la surface de l'acier moins probable. Cette étape d’inhibition n'est que transitoire et un traitement thermique prolongé conduira à la rupture de la couche d'inhibition et au développement des réactions Fe-Zn. Le mécanisme de rupture, contrôlé par la diffusion du zinc dans les joints de grains de l'acier, peut être expliqué à l'aide du diagramme de phase ternaire Al-Fe-Zn et résumé en deux étapes : la disparition de la couche de Fe2Al5Znx à l'interface couche d’inhibition / acier résultant de l’enrichissement de cette interface en zinc, et la germination de la phase Г (Fe3Zn10) aux joints de grains de l'acier lorsque la concentration en zinc y devient suffisante. C’est cette germination qui va provoquer localement la rupture de la couche d’inhibition. La cinétique de cette réaction dépend fortement de la composition chimique de l'acier IF Ti et de la teneur en aluminium du bain. D'une part, il apparaît que l'effet de la composition chimique de l'acier sur la cinétique de rupture d'inhibition est contrôlé par la compétition entre deux phénomènes opposés : la vitesse de diffusion du zinc dans les joints de grains de l'acier et la capacité de l'acier à y accumuler les atomes de zinc. D'autre part, la diminution de la teneur en aluminium du bain favorise la discontinuité de la couche de Fe2Al5Znx, ce qui accélère la rupture de la couche d'inhibition car le zinc est supposé diffuser plus rapidement dans δ que dans Fe2Al5Znx. / Hot-Dip GalvAnnealed (HDGA) coatings are produced by the immersion of the steel strip into an iron-saturated liquid zinc bath at around 460 °C containing small amounts of aluminium (from 0.1 to 0.135 wt.%, normally) and its subsequent heating (up to temperatures around 500-530 °C for about 10 s, typically) in order to trigger the alloying reactions between iron and zinc. The final microstructure of this kind of coatings is composed of a sequence of stratified Fe-Zn phase layers and its in-use properties are directly related to the phase distribution within the coating. The process parameters to be performed in industrial lines must therefore be optimized in order to obtain a successful coating microstructure with the minimum costs. The development of such a coating passes through different and complex reactions: the inhibition layer formation, the inhibition layer breakdown, the liquid zinc consumption and the iron enrichment of the solid coating. The kinetics accounting for these reactions must be studied and modelled separately in order to accurately control the evolution of the coating along the heat treatment performed in the industrial line. In the present work, the two first reactions were investigated in the case of Ti IF steel grades. The kinetics of the inhibition layer formation is extremely fast and has therefore not been investigated in detail. Concerning this reaction, the focus was given to the nature of this inhibition layer and to the mechanisms accounting for its formation. It has been found that the inhibition layer formed in typical baths for galvannealed coatings production is composed of a very thin layer of the Fe2Al5Znx phase (20-30 nm) on the steel surface and a thicker layer of the δ (FeZn7) phase (around 200 nm) on its top. As the steel strip enters the zinc bath, iron dissolution from the former into the latter leads to an iron supersaturation at the solid / liquid interface. As a result, a very thin layer of metastable Fe2Al5Znx nucleates on the steel surface favoured by preferential epitaxial relationships with ferrite. Subsequently, δ nucleates on the Fe2Al5Znx layer allowing the final microstructure of the inhibition layer to become thermodynamically stable. The effect of the bath aluminium content on the nature of this inhibiting structure has also been studied. As the bath aluminium content is lowered, the Fe2Al5Znx layer becomes discontinuous: the lower the bath aluminium content is, the higher the metastability of Fe2Al5Znx is and the less probable its nucleation on the steel surface is. The inhibition state is only transient and continued heat treatment will lead to the inhibition layer breakdown and the development of the further Fe-Zn alloying reactions. The breakdown mechanism, controlled by the diffusion of zinc towards the steel grain boundaries, can be explained using the Al-Fe-Zn ternary phase diagram and summarized in two steps: the disappearance of the Fe2Al5Znx layer at the inhibition layer / steel interface as a result of the enrichment of this interface in zinc, and the local nucleation of the Г (Fe3Zn10) phase at the steel grain boundaries, breaking the inhibition layer off, when the zinc concentration at these locations becomes high enough. The kinetics accounting for this reaction strongly depends on the Ti IF steel chemical composition and the bath aluminium content. On the one hand, it has been found that the effect of the steel chemical composition on the inhibition layer breakdown kinetics would be ruled by the competition between two opposite phenomena: the rate of zinc diffusion at the steel grain boundaries and the ability of the steel to accumulate the zinc atoms at these locations On the other hand, decreasing the bath aluminium content favours the discontinuity of Fe2Al5Znx, which accelerates the inhibition layer breakdown as zinc is expected to diffuse faster through δ than through Fe2Al5Znx.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Carried out an experiment under field conditions, in Russas, CE, in order to evaluate the response of papaya (Carica papaya L.) to phosphorus and zinc fertilization under irrigation for one year of cultivation. The experiment was a NEOSSOLO QUARTZARÃNICO, using a randomized block design in a factorial design with five doses of P2O5 (105, 157.5, 210, 315 and 420 kg / ha) and five Zn (0, 3.12, 6.24, 12.48 and 18.72 kilograms / ha), with four replications, totaling 25 treatments and 100 plots. The variables were: P and Zn in soil from 0 to 20 and 20 to 40 cm depth, content of P and Zn in the leaf (petiole), plant height, girth and productivity. The nutrient content in soil and leaf, plant height and stem diameter were evaluated after six months of planting. Productivity was assessed on the first six months of production (1 st year of cultivation). Aside from stem diameter, all other variables were influenced by the levels of P2O5 and Zn, with interaction between the two nutrients in their effect on plant height, concentration of P and Zn in the soil, P concentration in leaves and productivity. The plant height increased linearly with increasing fertilizer with phosphorus and zinc. Phosphorus decreased availability of soil Zn, but did not influence the levels of Zn in the plant. Since the Zn influenced the content of P in the soil and the leaf. The highest yield was related to doses of 293 kg / ha P2O5 and 9.83 kg / ha of Zn. / Realizou-se um experimento em condiÃÃes de campo, em Russas, CE, com o objetivo de avaliar a resposta do mamoeiro sob irrigaÃÃo (Carica Papaya L.) à adubaÃÃo com fÃsforo e zinco, durante um ano de cultivo em solo NEOSSOLO QUARTZARÃNICO. O delineamento experimental utilizado foi o de blocos ao acaso, em um esquema fatorial 5 x 5 (105; 157,5; 210; 315; e 420 kg de P2O5/ha) e (0; 3,12; 6,24; 12,48 e 18,72 kg de Zn/ha), com quatro repetiÃÃes. As variÃveis avaliadas foram: conteÃdos de P e Zn no solo nas camadas de 0 a 20 e 20 a 40 cm de profundidade, teor de P e Zn na folha (pecÃolo), altura da planta, circunferÃncia do caule e produtividade. Os teores dos nutrientes no solo e na folha, altura de planta e diÃmetro do caule foram avaliados apÃs seis meses do plantio. A produtividade avaliada foi referente aos seis primeiros meses de produÃÃo (1 ano de cultivo). Com exceÃÃo do diÃmetro do caule, todas as outras variÃveis foram influenciadas P (P2O5) e Zn, havendo interaÃÃo entre os dois nutrientes no seu efeito sobre a altura da planta, concentraÃÃo de P e Zn no solo, teor de P na folha e produtividade. A altura da planta aumentou linearmente com o incremento da adubaÃÃo com fÃsforo e zinco. O fÃsforo diminuiu a disponibilidade de Zn no solo, porÃm nÃo influenciou os teores de Zn na planta. Jà o Zn influenciou os conteÃdos de P tanto no solo como na folha. A mÃxima produtividade foi relacionada Ãs doses de 293 kg/ha de P (P2O5) e 9,83 kg/ha de Zn.

Frente ao aumento populacional e consequente incremento na demanda por alimentos, é importante estabelecer um melhor aproveitamento da área de cultivo, objetivando a colheita de produtos agrícolas em maior quantidade e de melhor qualidade. O aumento da concentração de micronutrientes nos produtos colhidos, especialmente de zinco é um desafio crescente para a agricultura, com possibilidade de trazer benefícios à saúde humana e à produtividade da cultura. Nesse sentido, a aplicação foliar de zinco realizada periodicamente, à partir da antese floral, é uma técnica capaz de incrementar o teor do micronutriente nas sementes e biofortificar os grãos de feijão e trigo, causando melhoria de aspectos agronômicos (crescimento vegetativo e produtividade da cultura) de plantas provenientes dessas sementes, além de resultar proveitos para a saúde humana daqueles que se alimentam de produtos biofortificados, e ainda com potencial para produzir grãos e sementes como produtos de maior valor comercial no mercado, valendo-se de inovação tecnológica. Porém, atualmente pouco se conhece sobre os diversos aspectos desta técnica. Assim sendo, objetivou-se: (i) elucidar o efeito da aplicação foliar de zinco, à partir da antese floral, como método para incrementar o teor do micronutriente nos grãos de feijão (Phaseolus vulgaris L.) e de trigo (Triticum aestivum L.), em substrato com teor adequado do micronutriente (ii) utilização de diferentes fontes de zinco aplicadas via foliar visando estabelecer a melhor fonte para o aumento do teor do micronutriente no grão de feijoeiro e (iii) determinação das doses de zinco mais adequadas a serem aplicadas através de pulverização foliar visando o aumento do teor do nutriente no grão de plantas de feijão e de trigo. Com base nos resultados obtidos, concluiu-se que (i) a aplicação foliar de zinco realizada periodicamente, à partir da antese floral é capaz de aumentar o teor do micronutriente em grãos de feijão e de trigo; (ii) a fonte mais viável para o enriquecimento de grãos de feijão é o sulfato de zinco; (iii) e todas as doses testadas (125, 250, 375 e 500 g Zn ha-1) aplicadas via foliar na forma de sulfato de zinco foram efetivas para o enriquecimento de grãos de feijão e de trigo, em relação ao controle (0 g Zn ha-1). / In view of the population increase and consequent growth of food demand, it is important to establish a better utilization of the cultivation area, aiming the harvest of agricultural products in greater quantity and of better quality. The increased concentration of micronutrients in products harvested, especially zinc, is a growing challenge for agriculture, with potential to bring benefits to human health and crop productivity. In this matter, the foliar zinc application performed periodically starting at floral anthesis is a technique capable of increasing the micronutrient content in the seeds and biofortifying grains of common bean and wheat, causing agronomic aspects improvement (vegetative growth and crop productivity) of plants derived from these seeds, in addition to bringing benefits to human health of those who feed on biofortified products, and still with potential to produce grains and seeds as products of greater commercial value in the market, being a technological innovation. However, currently little is known about the aspects that circumvent this technique. The objective of this study was: (i) elucidate the effect of foliar application of zinc, starting at floral anthesis, as a method to increase the micronutrient content of common bean (Phaseolus vulgaris L.) and wheat (Triticum aestivum L.) (ii) the use of different sources of zinc applied in a foliar way, in order to establish the best source for increasing the micronutrient content in common bean grains, and (iii) the determination of the most suitable zinc doses, applied by foliar spraying to increase the nutrient content of common bean and wheat plants. Based on the results obtained, it was concluded that (i) the periodic application of zinc foliar application starting at floral anthesis is capable of increasing the micronutrient content in common bean and wheat grains; (ii) the most viable source for the enrichment of bean grains is zinc sulphate; (iii) and all the doses tested (125, 250, 375 and 500 g Zn ha-1) applied via foliar in the form of zinc sulfate were effective for the enrichment of common bean and wheat grains, in relation to the control (0g Zn ha-1).

CdS is conventionally used as a buffer layer in Cu(In,Ga)Se2, CIGS, solar cells. The aim of this thesis is to substitute CdS with cadmium-free, more transparent and environmentally benign alternative buffer layers and to analyze how the material properties of alternative layers affect the solar cell performance. The alternative buffer layers have been deposited using Atomic Layer Deposition, ALD. A theoretical explanation for the success of CdS is that its conduction band, Ec, forms a small positive offset with that of CIGS. In one of the studies in this thesis the theory is tested experimentally by changing both the Ec position of the CIGS and of Zn(O,S) buffer layers through changing their gallium and sulfur contents respectively. Surprisingly, the top performing solar cells for all gallium contents have Zn(O,S) buffer layers with the same sulfur content and properties in spite of predicted unfavorable Ec offsets. An explanation is proposed based on observed non-homogenous composition in the buffer layer. This thesis also shows that the solar cell performance is strongly related to the resistivity of alternative buffer layers made of (Zn,Mg)O. A tentative explanation is that a high resistivity reduces the influence of shunt paths at the buffer layer/absorber interface. For devices in operation however, it seems beneficial to induce persistent photoconductivity, by light soaking, which can reduce the effective Ec barrier at the interface and thereby improve the fill factor of the solar cells. Zn-Sn-O is introduced as a new buffer layer in this thesis. The initial studies show that solar cells with Zn-Sn-O buffer layers have comparable performance to the CdS reference devices. While an intrinsic ZnO layer is required for a high reproducibility and performance of solar cells with CdS buffer layers it is shown in this thesis that it can be thinned if Zn(O,S) or omitted if (Zn,Mg)O buffer layers are used instead. As a result, a top conversion efficiency of 18.1 % was achieved with an (Zn,Mg)O buffer layer, a record for a cadmium and sulfur free CIGS solar cell. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 717