Le traitement des effluents aqueux issus des usines de retraitement de La Hague est un enjeu important pour l'environnement. Ces effluents sont contaminés par des substances organiques et des éléments possédant une radioactivité résiduelle. Ce travail porte donc sur le développement et l'optimisation du procédé de dépollution avec pour objectifs d'exempter l'effluent de toute pollution et de former un déchet final compatible avec les matrices de conditionnement classiques dans le milieu nucléaire. Le procédé de séparation se décompose en deux étapes : l'étape de solubilisation de la pollution dans des micelles de tensioactifs et l'étape de précipitation d'une phase minérale par transition sol-gel.Dans la cadre de la thèse, seule la pollution due aux radionucléides a été étudiée. Lors de la première étape, la stratégie a consisté à utiliser des molécules complexantes capable d'interagir avec les ions et de former des complexes préférentiellement solubles dans le cœur des micelles de tensioactifs. Par la suite, la deuxième étape a consisté à ajouter un précurseur de silice qui après hydrolyse et polycondensation permet d'agréger les micelles contenant les complexes entre elles et de former une phase silice qui précipite de façon in-situ. L'objectif de dépollution de l'effluent a été atteint et le déchet final formé est une poudre de silice contenant les micelles et la pollution qui après calcination est compatible avec les matrices de conditionnement telles que le verre ou le ciment. Différentes études ont permis de définir un système de référence pour lequel le procédé de séparation est optimal. Ce système comprend un tensioactif non-ionique (P123), un ion simulant les radionucléides (néodyme), une molécule complexante (HDEHP) et un précurseur de silice (TEOS). Ainsi, ce système a fait l'objet d'études approfondies pour élargir le champ d'action du procédé de séparation et pour comprendre les mécanismes en jeu lors de la complexation des ions et de la solubilisation micellaire, puis lors de la formation de la poudre de silice avec des techniques de diffusion, d'imagerie, de spectrométrie et d'analyses de surface.En conclusion, le procédé alternatif de dépollution développé dans cette thèse a permis d'atteindre les objectifs de dépollution et d'expliquer les différents mécanismes qui régissent chaque étape du procédé.Mots-clés : Tensioactifs, Lanthanides, Ligands organophosphorés, Procédé sol-gel, Diffusion des neutrons, wet-STEM / Treatment of aqueous outflows by complexation in micellar media and precipitation with sol-gel processAbstract Being able to deal with aqueous outflows from treatment sites in the Hague is a major environmental issue. These outflows are contaminated with organic substances and elements with residual radioactivity.This work deals with the development and optimization of the process of depolluting, and we aim at removing all pollution from the outflow, and produce a final waste compatible with traditional conditioning matrices in the nuclear area. The separation process consists of two steps: dissolving the pollution in the surfactants micelles, and precipitating a mineral phase via sol-gel transition. Within this thesis, only pollution originating from radionuclides is studied. During the first step, our strategy is to use complexing molecules able to interact with ions and to form mainly solvable complexes at the core of surfactant micelles. Thereafter, the second step consisted to add silica precursor which, after hydrolyse and polycondensation, makes it possible to aggregate those micelles that contain complexes together, and to form a silica phase which precipitates in an in-situ fashion.The goal to depollute the outflow was achieved, and the final waste thus produced is a silica powder that contains the micelles and the pollution which, after calcination, is compatible with conditioning matrices such as glass or concrete. A reference system for which the separation process is optimal was defined throughout various studies. This system contains a non-ionic surfactant (P123), an ion that surrogates radionucleides (neodymium), a complexing agent (HDEHP) and a silica precursor (TEOS). Hence, this system was further studied in order to broaden the application scope of the separation process, as well as to understand the mechanisms involved, during the complexation of the ions and the micellar solubilization and during the formation of the silica powder. This study was performed using diffusion, imaging and spectrometry techniques.To conclude, the alternative depolluting process developed as part of this thesis allowed to achieve the depolluting goals and to explain the different mechanisms that govern each step of the process.Keywords: Surfactants, Lanthanides, Organophosphorous ligands, Sol-gel process, Neutrons scattering, wet-STEM

[pt] A injeção de água é o método de recuperação secundário mais utilizado no mundo. Mesmo em situações em que esse método não é o mais adequado, a facilidade de implantação e os menores custos comparativos impõem esse método como a opção selecionada. Em campos de óleo pesado, a razão de mobilidade desfavorável e as heterogeneidades de reservatório precipitam a formação de digitações viscosas e altos valores de saturação residual de óleo, levando a baixos fatores finais de recuperação. Os poços produtores desses campos produzem com altas frações de água muito rapidamente. O tratamento da água produzida é o principal custo operacional desses campos. O uso de emulsões diluídas de óleo em água foi avaliado como método de controle de mobilidade. Foi desenvolvido um extenso programa experimental em sandpacks de areia de sílica e plugs de arenito (Berea e Bentheimer) de forma a comparar as recuperações finais de óleo, perfis de pressão de injeção e razões água-óleo acumuladas nos casos de injeção de água, injeção de surfactantes e macroemulsões. Todos os meios porosos ensaiados foram saturados com petróleo cru originário da Bacia de Campos (20 graus API). Um estudo paramétrico foi feito de forma a identificar a influência da vazão de injeção, distribuição de tamanhos de gotas de óleo emulsionadas, concentração de óleo e permeabilidade no desempenho das emulsões injetadas. O programa foi complementado com um ensaio 3D (arenito Castlegate na configuração um quarto de five-spot) onde o fluido injetado foi dopado com Iodeto de Potássio para permitir melhor visualização da modificação de saturações de óleo e água com um tomógrafo de raios X. Os resultados obtidos indicaram ganhos na produção de óleo e redução da razão água-óleo acumulada. A possibilidade de preparar as emulsões óleo-água a serem injetadas a partir da água produzida pelo próprio campo traz um grande ganho ambiental ao se reduzir o descarte superficial de água oleosa. O efluente se transforma em um recurso. / [en] Water injection is the most used secondary recovery method in the world. This option is generally chosen even in situations where it is not the most efficient alternative to recover the oil due to its comparative simple implementation and lower operational costs. In heavy oilfields, the unfavorable mobility ratio between injection and displaced fluids in addition to reservoir heterogeneities cause water fingering phenomenon, high residual oil saturation and consequently poor final oil recoveries. Producer wells start to produce high water cuts very soon. Produced water treatment for surface disposal is the main operational cost in these oilfields. The use of diluted oil-in-water macroemulsions was evaluated as a mobility control method for these cases. An extensive experimental program was performed using silica sandpacks and sandstone plugs (Berea and Bentheimer) in order to evaluate final oil recovery factors, cumulative water-oil ratio and pressure behavior, comparing water injection, surfactant solution injection and oil-in-water injection. All porous media were saturated with crude oil from Campos Basin (20 degrees API). A parametric study was performed to identify the effect of injection rate, oil droplets size distributions, emulsion oil concentration and permeability level in emulsion injection performance. The experimental program was completed by an X-Ray computerized tomography monitored experiment in a Castlegate sandstone block (1/4 five-spot configuration). This block was submitted to an alternate water/emulsion/water injection. All injection fluids were doped with Potassium Iodide in order to better visualize oil and water saturations changes during this experiment. The results obtained have indicated final oil recovery improvement and cumulative water/oil reduction. The possibility, after some treatment, to prepare diluted oil-in-water emulsions using produced water from the oilfield brings the additional environmental benefit to emulsion injection. It would be a way to convert an effluent in a resource with clear environmental advantages.

La tension interfaciale est une grandeur physico-chimique d'intérêt pour de nombreuses industries et notamment l'industrie pétrolière. Cette grandeur est l'un des paramètres qui permet d'optimiser le rendement d'un puits de pétrole. La difficulté liée à sa mesure dans les conditions réservoirs a amené à étudier les systèmes eau/tensioactif/huile par simulation moléculaire. Ce travail a permis de montrer que la Dynamique Particulaire Dissipative (DPD) était un outil adapté pour l’étude de systèmes eau/tensioactif/huile sous différents aspects, de la caractérisation de la structure des interfaces au calcul de la tension interfaciale. Cette thèse a permis la démonstration de l’influence non-négligeable de la variation des paramètres de la force harmonique, l’amplitude K et la distance d’équilibre r0 , sur le calcul de la tension interfaciale et sur la structure des interfaces à forte concentration en tensioactif. En effet, la structure des tensioactifs aux interfaces est le résultat d’une balance subtile entre les forces intra et inter moléculaire. L’étude d’une population modèle de tensioactifs non chargés a permis de montrer que la DPD reproduit bien l'évolution de la tension interfaciale en fonction de la concentration en tensioactif en solution et en fonction du coefficient de partage de tensioactifs modèles non chargés. Une méthodologie est proposée pour caractériser les systèmes contenant des interfaces et où la tension interfaciale est calculée.Des travaux prospectifs ont permis de montrer que la DPD permettait d'étudier des phénomènes liés à la tension interfaciale comme le mûrissement d'Ostwald dans les émulsions d'huile dans l'eau. Ces derniers travaux ouvrent la voie à l’étude d’autres systèmes d’intérêt pour le milieu pétrolier comme le décollement de gouttes de pétroles adsorbées sur des parois ou l’étude d’émulsions pétrolières. / The interfacial tension is a physical-chemical property that numerous industrial areas have an interest of especially the petroleum industry. This property is one of the many which helps to optimize production wells' rate of return. Measuring that property in reservoir's conditions (high pressure and temperature) is highly difficult and led to study water/surfactant/oil systems using molecular modeling. The difficulty to measure that specific physical-chemical property linked to the pressure and temperature conditions in the reservoirs led the scientists to study water/surfactant/oil systems using molecular modeling. This thesis establishes that the Dissipative Particle Dynamics (DPD) is able to study water/surfactant/oil systems. The study of the effect of the variation of the harmonic force's parameters, namely the force constant K and the equilibrium distance r0, demonstrated that their variation can heavily influence the interfacial tension computation. Actually, a subtle balance exists between the intra and inter-molecular interactions, which influences the local structure of the surfactants at the oil-water interface, modifies the interfacial tension and influences the interface stability. It was demonstrated that DPD reproduces the variation of interfacial tension with the bulk surfactant concentration and the effect of the variation of hydrophobicity of models of un-charged surfactants on interfacial tension by mean of their coefficient partition. We established a method to properly study systems containing interfaces where interfacial tension is computed. Prospective work showed that DPD was a good tool to study microscopic phenomenon which can be observed macroscopically like the Ostwald ripening in oil in water emulsions. This is a first step before studying others systems of interest for the petroleum industry such as oil/water emulsion or the adsorption of oil droplets on rock wall.

L’idée directrice de ce travail de thèse était d’introduire au sein de mésophases lipidiques des molécules de β-cyclodextrine (βCD) amphiphiles obtenue par bio-estérification afin d’obtenir des nano-assemblages plurimoléculaires et multi-compartimentés combinant trois fonctions essentielles pour le transport ou la vectorisation de molécules thérapeutiques : (i) la capacité d’incorporer une substance d’intérêt par formation de complexe d’inclusion avec la cyclodextrine ; (ii) être biocompatibles et aptes à passer facilement les barrières biologiques ; (iii) pouvoir co-incorporer une seconde substance d’intérêt, hydrophile ou hydrophobe, dont l’action biologique soit différente de celle assurée par la première substance. L’ensemble des travaux ont porté sur le dérivé βCD-C10 polysubstitué en face secondaire par des chaînes hydrocarbonées en C10 avec un degré moyen de substitution de 7,5. L’association de ce dérivé avec trois catégories de lipides a été envisagée : des tensioactifs micellaires non-ioniques (Brij 98, Polysorbate 80, n-dodécyl-β-D-maltoside), un lipide lyotrope non lamellaire formant des mésophases de type cubique bicontinue (monooléine), un phospholipide s’auto-organisant en bicouches propices à l’obtention de vésicules (dimyristoyl phosphatidylcholine). Selon une démarche principalement physico-chimique, différentes techniques ont été mises en œuvre pour caractériser les systèmes mixtes lipide/βCD-C10 aux échelles moléculaire et supramoléculaire : diffusion-diffraction des rayons X, calorimétrie différentielle, spectrophotométrie d’absorption UV-visible, spectroscopie de fluorescence, diffusion de la lumière statique (turbidimétrie) ou quasi-élastique, microscopie optique et microscopie électronique par cryo-transmission. L’ensemble des résultats démontrent que le dérivé βCD-C10 forme spontanément ou selon un protocole très simple, des assemblages plurimoléculaires mixtes avec les trois catégories de lipides, assemblages dont la topologie dépend de la structure chimique du lipide et du taux de cyclodextrine amphiphile incorporé (tubules, vésicules uni- ou oligolamellaires, cubosomes). Ces assemblages sont stables et capables d’incorporer une substance hôte hydrophobe, notamment les vésicules mixtes tensioactif non-ionique/ βCD-C10 et les cubosomes mixtes monooléine/P80/ βCD-C10. / The key idea of this Ph.D. thesis is to introduce amphiphilic β-cyclodextrin molecules (βCD), obtained by bio-transesterification, within lipid mesophases in order to obtain multi-compartment plurimolecular nano-assemblies, which combine three essential functions for transport or delivery of therapeutic molecules: (i) capacity to incorporate a substance of interest through formation of inclusion complexes with the modified cyclodextrin; (i) biocompatibility and ability to easily pass the biological barriers; and (iii) possibility for co-encapsulation of a second substance of interest, a hydrophilic or a hydrophobic one, whose biological action is different from that provided by the first substance. The performed Ph. D. work focused on the β-cyclodextrin derivative βCD-C10 with an average degree of substitution of 7.5 of the secondary face of the macrocycle by hydrocarbon chains C10. The association of this derivative with three classes of amphiphiles was studied: (i) nonionic micellar surfactants (Brij 98, Polysorbate 80, n-dodecyl β-D-maltoside), (ii) a lyotropic nonlamellar lipid forming bicontinuous cubic mesophases (monoolein), and (iii) a phospholipid (dimyristoyl phosphatidylcholine), which self-ssembles into bilayer membranes permitting the production of vesicles.The employed physical-chemical approach involved different techniques for characterization of the mixed βCD-C10/lipid systems at molecular and supramolecular levels: cryo-transmission electron microscopy, X-ray diffraction, differential scanning calorimetry, UV-visible absorption spectroscopy, fluorescence spectroscopy, turbidimetry, and quasi-elastic light scattering.The obtained results indicated that the βCD-C10 derivative forms spontaneously (or via a very simple preparation protocol) plurimolecular mixed nano-assemblies with the three types of lipids. The topologies of the resulting nano-assemblies essentially depend on the chemical structures of the lipids and the degree of incorporation of the amphiphilic cyclodextrin (tubules, unilamellar or oligolamellar vesicles, and cubosomes). These assemblies, namely the mixed vesicles of nonionic surfactant/βCD-C10 and the cubosomes of mixed monoolein/P80/βCD-C10 compositions, are stable and capable of incorporation of hydrophobic guest substances.

Bemisia tabaci Gennadius (Hemiptera: Aleyrodidae) biotype B is a cosmopolitan, devastating insect pest due to their direct damages and transmission of plant viruses. Entomopathogenic fungi comprise the most diverse group of pathogens regulating arthropod pest populations in agroecosystems. Anamorphic fungal entomopathogens, including Beauveria bassiana, Isaria fumosorosea, and Lecanicillium spp., are among the main biocontrol agents of whitefly populations. Advances in research focusing on virulence, mass production, formulation, and storage stability of fungal propagules are imperative for the development of efficient mycopesticides toward whiteflies and other soft-bodied insects. Therefore, this study placed emphasis on screening for virulent fungal strains, enhancement of efficacy using nonionic surfactants in spray tank-mix, development of liquid culture conditions for rapid production and stabilization processes of single-yeast like cells known as blastospores. Firstly, we selected virulent strains of B. bassiana and I. fumosorosea displaying fastest speed of kill and inciting highest mortality levels of whitefly nymphs and adults along with their ability to produce high numbers of conidia on moistened parboiled rice. Secondly, insecticidal performance was enhanced by combining nonionic surfactants with spore suspensions rendering additive or synergistic effects. These surfactants also allowed reducing the volume application rate without altering fungal bioefficacy. Results from liquid fermentation studies using B. bassiana and I. fumosorosea revealed that appropriate amounts of inexpensive ingredients, such as cottonseed flour and glucose, are suitable for the rapid production of high yields of blastospores (3 days pre-culture and 2-3 days culture). The resultant blastospores of various strains survived well to desiccation and remained viable for more than one year under refrigeration. Moreover, these air-dried blastospores of both fungal species showed higher virulence against whitefly nymphs when compared with solid-substrate produced conidia. Optimized liquid culture production for B. bassiana blastospores was also achieved through the manipulation of oxygen rates and osmotic pressure in the liquid media. Furthermore, these blastospores produced in highly aerated and hyperosmotic liquid medium containing 140 g glucose L-1 were also more virulent to whitefly nymphs than those cells derived from low-osmotic medium amended with 40 g glucose L-1. These optimal conditions were also scaled up in 5-L bioreactor that yielded 1-2 × 1012 viable blastospores L-1 in 6 days at a cost of US$ 0.19 L-1. These blastospores were formulated with diatomaceous earth for air drying or for spray drying. Formulated blastospores of B. bassiana survived dehydration using both drying methods and showed improved shelf life when stored under vacuumpackaged at 4 °C rather than 28 °C. However, when these blastospores were actively packaged with dual action oxygen-moisture scavenging system, blastospores showed prolonged stability for up to 7 months at 28 °C and still remained virulent to whiteflies. Therefore, this low-cost production and stabilization method for the rapid production of shelf stable, virulent blastospores of B. bassiana and I. fumosorosea may expand the commercial use of mycopesticides for insect control in mainstream agriculture. / A mosca-branca, Bemisia tabaci Gennadius (Hemiptera: Aleyrodidae) biótipo B, é uma praga cosmopolita e devastadora devido aos prejuízos oriundos dos seus danos diretos e transmissão de vírus. Fungos entomopatogênicos compreendem um grupo diversificado, que desempenha ação importante na regulação de populações de praga em agroecossistemas. Fungos ascomicetos anamórficos, como Beauveria bassiana, Isaria fumosorosea e Lecanicillium spp., constituem relevantes agentes de biocontrole de moscas-brancas. Avanços na pesquisa focando virulência, produção massal, formulação e estabilização de propágulos fúngicos são fundamentais para o desenvolvimento de micopesticidas eficientes contra moscas-brancas e outros insetos. Desta forma, este trabalho objetivou selecionar isolados fúngicos virulentos à mosca-branca; aumentar a eficácia mediante uso de surfactants não-iônicos em suspensões conidiais; desenvolver meios de cultura para produção rápida e estável por fermentação líquida submersa de células leveduriformes conhecidas por blastosporos. Na primeira etapa, isolados virulentos de B. bassiana e I. fumosorosea foram selecionados pela rápida e elevada atividade inseticida a ninfas e adultos de mosca-branca, bem como alto rendimento de conídios em arroz parboilizado. A adição de surfactantes organosiliconados permitiu a redução do volume de calda aplicado com resultados aditivos ou sinérgicos de controle. Foi ainda verificado que altos rendimentos de blastosporos tanto de B. bassiana como I. fumosorosea foram obtidos em curto tempo de fermentação líquida (3 dias de précultivo e 2-3 dias de cultivo) usando nutrientes de baixo custo, como glucose e farelo de algodão. Esses blastosporos foram tolerantes à dessecação e mantiveram viabilidade por mais de um ano sob refrigeração (4 °C). Os blastosporos foram mais virulentos que conídios aéreos, o que coloca esta estrutura como a mais indicada como ingrediente ativo em bioinseticidas para moscas-brancas. Mediante manipulação nutricional e física do ambiente de fermentação, a produção de blastosporos de B. bassiana foi optimizada mediante aumento da aeração e pressão osmótica do meio líquido. Blastosporos produzidos em meio líquido altamente aerado e hiperosmótico (140 g glucose L-1) mostraram-se mais virulentos à mosca-branca em relação àqueles produzidos em meio hipo-osmótico (40 g glucose L-1). Esse processo foi reproduzido em escala piloto usando biorreator de 5 L resultando numa produção de 1-2 × 1012 blastosporos viáveis L-1 em apenas 3 dias a um custo de US$ 0,19 L-1. Blastosporos de B. bassiana formulados com terra de diatomáceas e secados em fluxo de ar contínuo, ou secados em spray dryer tiveram estabilidade extendida por até 8 meses a 4 °C e superior em relação a 28 °C. Durante empacotamento, o uso de sachês absorventes de oxigênio e umidade prolongou consideravelmente a viabilidade de blastosporos armazenados a 28 °C por até 7 meses sem afetar sua eficiência contra mosca-branca. Em suma, esses resultados demonstram a viabilidade técnica e econômica de produção de blastosporos virulentos de B. bassiana e I. fumosorosea, tolerantes à dessecação e estáveis durante armazenamento. Esta tecnologia é uma nova opção que pode contribuir para expansão comercial de bioinseticidas à base de fungos entomopatogênicos.

INTRODUÇÃO: A Síndrome do Desconforto Respiratório (SDR) é uma das principais causas de morbi-mortalidade no período neonatal, acometendo predominantemente os recém-nascidos prematuros, devido a uma está deficiência de surfactante pulmonar. O Instituto Butantan desenvolveu um surfactante de origem porcina com objetivo de torná-lo disponível a todo Sistema Único de Saúde. O objetivo deste estudo foi avaliar, em um modelo experimental de SDR (coelho), a estabilidade do Surfactante Butantan (SB) um ano após sua produção e armazenamento a 2 a 8ºC.. MÉTODOS: 94 coelhos prematuros foram randomizados em dois grupos de tratamento: grupo Butantan e grupo Curosurf (controle), e foram analisados em seis momentos de avaliação: momento zero (imediatamente após a retirada do refrigerador ao final de 1 ano de armazenamento), momento 1 (24 horas após ter sido mantido a 24ºC), momento 2 (após 30 dias de armazenamento a 20º C), momento 3 (após 60 dias de armazenamento a 20º C), momento 4 (após 90 dias de armazenamento a 20º C) e momento 5 (após 180 dias de armazenamento a 20º C). Após receberem o surfactante, os animais foram ventilados por 15 minutos para avaliação da pressão ventilatória e complacência pulmonar dinâmica e curva pressão-volume pulmonar, seguindo-se à avaliação histopatológica dos pulmões. RESULTADOS: A eficácia do SB foi semelhante à do Curosurf, um ano após a sua produção e armazenamento a 2 a 8ºC. Neste momento de avaliação, não houve diferença estatisticamente significante entre os grupos de estudo quanto a: pressão ventilatória, complacência pulmonar dinâmica e curva pressão-volume pulmonar. Ao longo dos seis meses de armazenamento inadequado do SB, demonstrou-se a redução de sua eficácia durante a fase expiratória da curva pressão-volume pulmonar. No entanto, a análise histopatológica, demonstrou não haver diferença significante entre os dois grupos de estudo em nenhum dos momentos de avaliação. CONCLUSÕES: As propriedades bioquímicas do SB foram preservadas após um ano de sua produção e armazenamento em refrigeração de 2 a 8ºC. Condições inadequadas de armazenamento resultam em alterações das propriedades bioquímicas do SB e, conseqüentemente, de sua função, o que foi demonstrado por parâmetros de mecânica ventilatória, mas não pela análise histopatológica dos pulmões / INTRODUCTION: Respiratory Distress Syndrome (RDS) is one of the major causes of death among premature newborns, and its development results from surfactant deficiency. The Butantan Institute has recently produced a porcine-derived surfactant preparation in order to make it available nationwide for RDS treatment in the near future. The aim of this study was to evaluate, in an animal model of surfactant deficiency (premature rabbits), the stability of the Butantan Surfactant (SB) one year after its production and storage in the refrigerator, at 2 to 8ºC. METHODS: 94 premature newborn rabbits were randomized into two treatment groups: SB or Curosurf®(control surfactant), and were assessed in six different time-points: time-point zero (immediately after removal of surfactant from the refrigerator after one year of storage); time-point 1 (after 24h of storage at 24ºC), time-point 2 (after 30 days of storage at 20ºC), time-point 3 (after 60 days of storage at 20ºC), time-point 4 (after 90 days of storage at 20ºC) and time-point 5 (after 180 days of storage at 20ºC). The animals were artificially ventilated for 15 minutes for lung mechanics assessment (ventilatory pressure, dynamic lung compliance and pressure-lung volume curve), followed by removal of the lungs for histopathologic analysis. RESULTS: After one year of its production and storage at 2 to 8ºC, SB was as efficient as Curosurf. At this time-point, The Butantan Surfactant showed no significant differences with Curosurf® regarding the ventilatory pressure, dynamic lung compliance and pressure-lung volume curve. Throughout the six month period of warming, SB showed a decreasing efficiency, as revealed by the expiratory phase of the pressure-lung volume curve. However, the histopathologic analysis revealed no significant differences between the two groups, in any of the study time-points. CONCLUSIONS: The Butantan Surfactant preserved its biochemical properties one year after its production and storage at 2 to 8ºC. On the other hand, adverse storing conditions can lead to alterations in the SB biochemical properties that result in deterioration of its function, which was demonstrated in this study by changes in lung mechanics, but not in the histopathologic analysis

Formulações a base de dispersões oleosas de conídios aéreos de fungos entomopatogênicos apresentam diversas vantagens em comparação à aplicação de produtos não formulados; entretanto, a complexidade e a falta de compreensão dos fatores que influenciam a persistência desse tipo de formulação fazem com que ainda seja pouco utilizada. O efeito de diferentes níveis de secagem de conídios, tipo de óleo, métodos de extração, estabilidade de blastosporos, compatibilidade de surfactantes e adição de aditivos foram avaliados para o desenvolvimento de micopesticidas formulados em óleo. Os melhores resultados obtidos com os conídios em óleo foram avaliados quanto à proteção conferida à radiação UV e a eficiência das formulações na mortalidade de Tenebrio molitor. Zeolita foi a argila mais eficiente na manutenção da viabilidade de blastosporos de M. anisopliae e B. bassiana, e apesar de resultados promissores a estabilidade desses propágulos foi muito inferior a de conídios aéreos. Vinte surfactantes foram avaliados quanto a inocuidade aos conídios, em dois ensaios, culminando com a seleção dos quatro mais compatíveis, dois deles E5 e E7, avaliados nos experimentos posteriores demonstraram bom potencial para compor a formulação como agentes emulsionantes. Dois aditivos foram avaliados na formulação e respostas distintas foram observadas. O A1 foi altamente incompatível, enquanto diferentes concentrações de A2 (1, 3 e 5%) incrementaram a sobrevivência dos conídios em até sete vezes. As vantagens da presença do A2 ficaram evidentes também em combinações de óleo com os quatro emulsionantes selecionados. As dispersões oleosas proporcionaram sobrevivência até sete vezes superior para conídios expostos a radiação UV em relação a conídios não formulados e dois experimentos comprovaram que as formulações oleosas testadas foram mais eficientes no controle de insetos, com reduções de até 2,3 vezes no tempo de sobrevivência de insetos. Os 12 bioensaios com mais de 20.000 leituras de viabilidade descritos neste trabalho permitiram um melhor entendimento dos fatores críticos que afetam a vida de prateleira de conídios, e indicam procedimentos que podem ser utilizados para melhorar a estabilidade de micopesticidas formulados em óleo. / Oil-based formulations of aerial conidia of entomopatogenic fungi have several advantages compared to the use of unformulated products; however, the complexity and lack of understanding of the factors that influence the persistence of this type of formulation make it still not widely used. The effect of different levels of drying conidia, oil type, extraction methods, blastospores stability, compatibility of surfactants and addition of additives were evaluated for the development of a mycopesticide oil formulation. The best results obtained with aerial conidia were evaluated regarding the protection against UV radiation and the efficacy of the formulations to control Tenebrio molitor. Zeolita was the most compatible clay in maintaining the viability of blastospores of M. anisopliae and B. bassiana, and despite promising results in the stability, the shelf life of these propagules was much lower than aerial conidia. Twenty surfactants were evaluated for safety to conidia in two trials resulting in the selection of the four most compatible, two of them E5 and E8, were evaluated in subsequent experiments demonstrating good potential as emulsifiers in oil-based formulations. Two additives were evaluated in the formulation and distinct responses were observed. A1 was highly toxic to the fungi, while different concentrations of A2 increased the survival of the conidia up to seven times. The advantages of A2 were evident also in combinations of oil with the four selected emulsifiers. Oil-based formulation provided survival up to seven times higher for conidia exposed to simulated UV radiation compared to unformulated conidia, and two experiments showed that oil formulations were more efficient in the insect control, with reductions of up to 2.3 times on the survival time of insects. Twelve bioassays and over 20.000 viability readings described in this work, allowed a better understanding of the critical factors that affect the shelf-life of conidia, and indicate methods that can be used to improve the stability of mycopesticides in oil-based formulations.

Die geordneten mesoporösen Silikamaterialien SBA-15 und MCM-41 zeichnen sich durch lange zylindrische Poren aus, die auf einem 2D-hexagonalen Gitter arrangiert sind. Auf Grund dieser Eigenschaften finden sie vielfach Anwendung in der Industrie, bieten jedoch auch die Möglichkeit Sorptionsvorgänge und die dadurch induzierten Verformungen auf der Nanometerebene zu untersuchen. Dazu werden im ersten Teil dieser Arbeit Kleinwinkelröntgenstreuungsdaten mit Hilfe eines Formfaktormodells angefittet, um die Adsorption von Fluid in den Poren in Abhängigkeit vom Dampfdruck nachvollziehen zu können. Basierend auf diesen Ergebnissen wird ein Gittermodell eingeführt, welches die Vorgänge während der Sorption mit Hilfe heuristischer Füllmechanismen reproduziert und im Abgleich mit experimentellen Daten Auskunft über die Verteilung der Porosität auf Mikro- und Mesoporen in SBA-15 gibt. Weiterhin wird der Einfluss der begrenzten Geometrie auf die Selbstassemblierung von Tensiden in SBA-15 untersucht. Hierzu werden Neutronenstreudaten durch die Kombination eines Formfaktormodells für die Bragg-Streuung und des Teubner-Strey-Modells für die diffuse Streuung modelliert und interpretiert. Der zweite Teil der Arbeit beschäftigt sich mit den elastischen Verformungen der mesoporösen Materialien durch die Fluidsorption. Dazu wird eine Molekulardynamik-Simulation eines Lennard-Jones-Fluids in einer Schlitzpore vorgestellt, um den Ursprung dieser Verformungen auf der mikroskopischen Ebene zu untersuchen. Diese Ergebnisse fließen anschließend in ein makroskopisches Modell eines ganzen Kristalliten des mesoporösen Materials ein, wodurch ein einfaches Multiskalenmodell entsteht. Die makroskopische Ebene wird dabei durch eine Finite-Elemente-Simulation beschrieben, die im Abgleich mit experimentellen Daten weitere Aussagen über die elastischen Eigenschaften des Materials erlaubt. / The ordered mesoporous silica materials SBA-15 and MCM-41 consist of long cylindrical pores arranged on a 2D-hexagonal lattice. Due to these features, they are used for a range of industrial applications but provide also a possibility to study sorption processes and sorption-induced deformations on the nanoscale. In the first part of this work small-angle X-ray scattering data are fitted with a form factor model in order to examine fluid adsorption in the pores. Based on these results a lattice model is introduced which reproduces the sorption process using heuristic filling mechanisms and clarifies how the porosity of SBA-15 is composed out of micro- and mesopores. Furthermore, the influence of the confined geometry on the self-assembly of surfactants in SBA-15 is studied. For this, neutron scattering data are modeled and interpreted by the combination of a form factor model for the Bragg scattering and the Teubner-Strey model for the diffuse scattering. The second part of this work focuses on the elastic deformations caused by fluid sorption in the mesoporous materials. A Molecular Dynamics simulation of a Lennard-Jones fluid in a slit-pore is presented in order to reveal the origin of these deformations on the microscopic scale. These results are subsequently implemented into a macroscopic model of whole crystallite, thereby creating a simple multi-scale model. The macroscopic scale is modeled with a Finite Elements simulation, which by comparison with experimental data delivers further insights into the elastic properties of the material.

Há interesse mundial no desenvolvimento de pesquisas envolvendo produção e extração de colorantes naturais, devido a sérios problemas de segurança industrial associados ao uso de colorantes sintéticos. Este trabalho objetivou produzir colorantes naturais de Penicillium purpurogenum DPUA 1275 por cultivo submerso (em frascos agitados e em biorreator) e estudar a extração dos colorantes vermelhos. Para a produção, os estudos iniciais mostraram que 5 discos de micélio, sacarose e extrato de levedura como fontes de carbono e nitrogênio, respectivamente, e 336 horas de cultivo eram condições adequadas para a produção dos colorantes. Visando à otimização da produção, realizaram-se planejamentos fatoriais, com as variáveis independentes: tempo de cultivo; velocidade de agitação; pH; temperatura; concentração de sacarose e de extrato de levedura. As variáveis-respostas foram produção de colorantes amarelos, laranjas e vermelhos. Dos resultados obtidos, as variáveis mais significativas ao processo foram concentrações de extrato de levedura e de sacarose. A produção dos colorantes vermelhos foi otimizada, alcançando a produção de 2,97 UA490nm, nas condições 48,90 e 11,80 g/L de sacarose e extrato de levedura, respectivamente, 30°C, pH 4,5 150 rpm e 336 horas de cultivo. Nos experimentos em biorreator, o melhor resultado foi obtido na frequência de agitação de 500 rpm e na mudança do pH do meio para 8,0, após 96 horas de bioprocesso. Ademais, avaliou-se a estabilidade dos colorantes vermelhos presentes no meio fermentado em diferentes condições (pH, temperatura, sais, polímeros e tensoativos). Referente a pH e temperatura, os colorantes vermelhos mostraram-se mais estáveis nas condições alcalinas e a 70 °C. Tanto os sais (NaCl e Na2SO4) quanto os polímeros (PEG 1.000, 6.000 e 10.000 g/mol e NaPA 8.000 g/mol a 5 e 15%) e os tensoativos (Tween 20, CTAB e SDS) não causaram perda da cor nas condições avaliadas. Estudos de solubilidade e de coeficiente de partição octanol-água mostraram que os colorantes vermelhos apresentam solubilidade superior em solventes polares e característica mais hidrofílica. Nos estudos de extração, as técnicas avaliadas foram Sistemas Poliméricos de Duas Fases Aquosas (SPDFA) formados pelo sistema PEG/NaPA e Colloidal Gas Aphrons (CGA). Pela primeira técnica, os colorantes vermelhos migraram preferencialmente para a fase PEG. Os polímeros PEG 6.000 g/mol, na presença de NaCl 0,1 e 0,5 M, e PEG 10.000 g/mol, com Na2SO4 0,5M, se destacaram dentre as condições analisadas com coeficiente de partição (K) próximo a 13, em ambos os casos, e seletividade de proteínas (SeP) próximas a 3. Para a técnica de CGA, o CTAB proporcionou os melhores resultados, seguido do Tween 20. Porém, o valor de K foi inferior ao obtido com SPDFA, com um máximo de 5 (CTAB 2 mM/pH 9,0). Os resultados obtidos demonstram um novo produtor de colorantes naturais, as quais têm potencial de aplicação em diversos segmentos industriais. Ademais, os resultados obtidos mostraram a eficiência das técnicas utilizadas para extração dos colorantes vermelhos, com destaque para SPDFA, que apresentou maiores valores de K. / There is worldwide interest in developing research projects involving the production and extraction of natural colorants due to serious safety problems associated with industrial use of synthetic ones. The aim of this work was to investigate the production of natural colorants from Penicillium purpurogenum DPUA 1275 by submerged culture (rotatory shaker and bioreactor) besides studying the red colorants extraction. To the production step, initial studies showed that 5 agar mycelial discs, sucrose and yeast extract as carbon and nitrogen sources, respectively, and 336 hours of bioprocess promoted the best results. To optimize the colorants production a serie of factorial designs were performed. The independent variables studied were: fermentation time, agitation speed, pH, temperature, sucrose and yeast extract concentration under the responses production of yellow, orange and red colorants. From these results, the most significant variables for the process were sucrose and yeast extract concentration. The red colorants production was optimized achieving 2.97 UA490nm, in the following conditions: 48.90 and 11.80 g/L of sucrose and yeast extract, respectively, 30 °C, 4.5 pH, 150 rev min-1 and 336 hours of culture. In the experiments performed in bioreactor, the condition that promoted the best results was 500 rpm and pH adjusted for 8.0 after 96 hours of bioprocess. Furthermore, we evaluated the red colorants stability at different conditions (pH, temperature, salts, polymers and surfactants). Concerning to pH and temperature, the red colorants were more stable under basic conditions and 70 °C; not only the salts (NaCl and Na2SO4) but also the polymers (PEG 1000, 6000 and 10000 g/mol and NaPA 8000 g/mol) and the surfactants (Tween 20, CTAB and SDS) not promoted loss of color upon the conditions evaluated. Studies of red colorants solubility and octanol water coefficient showed that these compounds exhibit a higher solubility in polar solvents and present hydrophilic characteristics. Subsequently, the extraction of red colorant was evaluated through two extraction methods: Polymeric Systems Aqueous Two Phase (ATPS) composed by PEG and NaPA and Colloidal Gas Aphrons (CGA). For the first technique, the red colorant preferentially migrated to the PEG phase. The best results were obtained with PEG 6000 g/mol in the presence of 0.1 to 0.5 M NaCl and with PEG 10000 g/mol with 0.5 M Na2SO4. To both cases the partition coefficient (K) was close to 13 and the Selectivity in terms of proteins (SeP) was close to 3. For the CGA technique, CTAB gave the best results followed by Tween 20. However, the K values were lower than the ones obtained with ATPS with a maximum of 5 in the following condition: CTAB 2 mM/pH 9.0. For the SeP, the values obtained for both techniques were close. The results above show a new producer of natural colorants which have potential application in various industries. Moreover, the results show the efficiency of the techniques used to extract the red colorants, especially to ATPS that presented higher K values.

A eletrodeposição de gálio sobre cobre em meios de KOH 5,0 molL-1 e NaOH 5,0 molL-1 contendo 5,0 mmolL-1 de íons galato foi estudada na presença de surfatantes com cadeia de doze átomos de carbono. Foram estudados três surfatantes aniônicos - o dodecil sulfato de sódio (SDS), o dodecil benzeno sulfonato de sódio (SDBS) e o laurato de potássio (LK) - e um surfatante catiônico - o cloreto de dodecil amônio (DAC), em concentrações acima da c.m.c. Os estudos foram feitos sobre eletrodo de disco rotativo de cobre a 1000 rpm, empregando soluções alcalinas desaeradas e à temperatura de 25 ºC. Foram utilizadas como técnicas eletroquímicas a voltametria linear e a cronoamperometria. A análise da superfície, após a eletrodeposição, foi feita por microscopia eletrônica de varredura (MEV) e espectroscopia por dispersão de energia (EDS). Todos os anfifílicos estudados afetam a velocidade dos processos simultâneos de redução Ga(III)/Ga e H2O/H2. A ação inibidora ou catalítica, depende do potencial aplicado e da natureza do surfatante. Os surfatantes aniônicos inibem a reação H2O/H2 a baixas sobretensões catódicas. Em tais condições se admite que haja um número menor de moléculas de água adsorvidas por estarem os sítios do metal parcialmente ocupados pelas moléculas do anfifílico. A elevadas sobretensões catódicas a reação H2O/H2 é catalisada por estes anfifílicos, admitindo-se, nestas condições, que eles favoreçam a liberação do gás hidrogênio da superfície. O DAC, surfactante catiônico, inibe a reação H2O/H2 em toda a faixa de sobretensões catódicas estudada. Atribui-se a sua adsorção a uma interação eletrostática anfifílico-eletrodo, gerando um efeito inibidor maior à medida que o potencial se torna mais negativo. O SDBS inibe a eletrodeposição do gálio, mas confere ao depósito aspecto mais brilhante, a valores de potencial em que catalisa a reação H2O/H2. Soluções recém preparadas de SDS na presença de dodecanol (produto da hidrólise do anfifílico nestes meios), eleva os rendimentos de eletrodeposição do gálio de 12% para 18% a -1 ,35V (vs Hg/HgO). Neste mesmo potencial o DAC eleva os rendimentos do processo de forma comparável, embora iniba o mesmo na região de potencial em que a reação H2O/H2 é significativa. O LK inibe a eletrodeposição do gálio em todos os potenciais estudados, o que se atribui à formação de complexos com o íon Ga(III). Os ensaios por MEV e EDS confirmaram os rendimentos maiores de gálio na presença da mistura SDS-DOH. O depósito de gálio obtido a -1,55V (vs Hg/HgO) se dá sobre toda a superfície do cobre. A análise química radial mostrou que tanto na ausência de surfatantes quanto na presença da mistura SDS+DOH, a distribuição do gálio na superfície do disco de cobre, ainda que mostre decréscimo na bordas do eletrodo, é praticamente constante na maior parte da superfície. / Gallium electrodeposition on copper in 5.0 molL-1 KOH and 5.0 molL-1 NaOH solutions containing 5.0 mmolL-1 gallate ions, has been studied in the presence of twelve carbon atoms surfactants. Three anionic surfactants have been studied - sodium dodecyl sulfate (SDS), sodium dodecyl benzenosulfonate (SDBS) and potassium laurate (LK), and one cationic surfactant - dodecyl ammonium chloride (DAC) at concentrations above the c.m.c. The experiments have been made using rotating disk copper electrode (rotation frequency equal to 1000 rpm), using deaerated alkaline solutions at 25 ºC. Electrochemical techniques as linear voltammetry and chronoamperometry were used. Surface analysis after electrodeposition was made using scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS). All of the amphiphilics studied change the rate of the simultaneous cathodic Ga(III)/Ga and H2O/H2 processes. The inhibitive or catalytic reation depends on both the applied potencial and surfactant nature. Anionic surfactants inhibit the H2O/H2 reaction at lower overvoltages. It can be admitted under these conditions a lower number of adsorved water molecules due to the simultaneous adsorption of amphiphilic molecules. At higher cathodic overvoltages the H2O/H2 reaction is catalised by these surfactants. It can be admitted under these conditions that these molecules remove the hydrogen molecules from the electrode surface. DAC, a cationic surfactant, inhibits the reaction H2O/H2 on the entire range of cathodic overvoltages studied. Its adsorption can be attributed to the electrostatic interaction amphiphilic-electrode and in consequence, the inhibitive effect increases as the potencial attains more negative values. SDBS inhibits the gallium electrodeposition but the deposit is brighter with added SDBS. Recently prepared SDS solutions inhibits Ga(III)/Ga reaction. The presence of dodecanol (SDS hydrolise product in these media) increases the gallium electrodeposition yield from 12% to 18% at -1,35V/(Hg/HgO). At this same potencial DAC increases the yield of the process, similarly, but it inhibits the same reaction on the potencial range where the H2O/H2 reaction is significative. LK inhibits the gallium electrodeposition process on the entire range of potencials studied. This result can be attribuited to laurate gallium complex formation. SEM and EDS analyses have confirmed the best electrodeposition performance in the presence of SDS+DOH. The gallium deposits obtained at -1,55V/(Hg/HgO) spread on the entire copper surface. The radial chemical analysis has shown that either in the absence either in the presence of SDS+DOH mix gallium distribution is practically constant and uniform, except on the edge of the copper disk electrode.