Uma das caracterÃsticas fisiolÃgicas mais importantes das halÃfitas pertencentes ao gÃnero Atriplex à a enorme habilidade de acumular solutos orgÃnicos e inorgÃnicos com o intuito de se ajustar osmoticamente em condiÃÃes de elevada salinidade e deficiÃncia hÃdrica. Contudo estudos compreensivos sobre a contribuiÃÃo relativa desses solutos inorgÃnicos e orgÃnicos no ajustamento osmÃtico de folhas dessas halÃfitas ainda sÃo poucos explorados na literatura. Esse trabalho pretende pela primeira vez na literatura fazer um estudo detalhado, da participaÃÃo e da contribuiÃÃo relativa da maioria dos solutos orgÃnicos e inorgÃnicos no potencial osmÃtico de folhas de Atriplex nummularia, submetidas a concentraÃÃes crescentes de NaCl, ciclos sucessivos de seca e ao polietileno glicol (PEG). Para responder as questÃes acima mencionadas foram conduzidos trÃs grandes experimentos seqÃenciais. No primeiro experimento, mudas de Atriplex nummularia com quatro meses de idade, foram cultivadas em vasos de argila contendo como substrato areia, sendo irrigadas a cada dois dias com soluÃÃo contendo concentraÃÃes crescentes de NaCl (0, 100, 200, 300 e 400 mmol L-1) durante 120 dias. O experimento foi realizado em condiÃÃes de casa de vegetaÃÃo. No segundo experimento, mudas de A. nummularia, com idade de 18 meses foram transplantadas para recipientes de polietileno contendo 5.0 kg de vermiculita, em condiÃÃes de casa de vegetaÃÃo, onde foram submetidas aos seguintes tratamentos (Controle; seca; NaCl + seca; NaCl) por trÃs ciclos sucessivos de seca-reidrataÃÃo (3 semanas) seguido de uma recuperaÃÃo no final do Ãltimo ciclo (apÃs 48 h). No terceiro experimento, plÃntulas de A.nummularia, com idade de dois meses foram transplantadas para cultivo hidropÃnico em vasos plÃsticos com capacidade para 0,8 em sala de crescimento sob condiÃÃes controladas onde sofrerÃo um prÃ-condicionamento com ou sem NaCl por duas semanas. ApÃs foram submetidas aos seguintes tratamentos (controle; PEG; NaCl; NaCl + PEG). Em conclusÃo, os resultados da presente investigaÃÃo demonstram que as plantas de Atriplex nummularia foram capazes de manter o seu crescimento mesmo em condiÃÃes de alta salinidade, principalmente pela capacidade de manutenÃÃo de seu status hÃdrico. Os resultados tambÃm sugerem que a GB à o maior soluto orgÃnico envolvido com o ajustamento osmÃtico (AO) do citoplasma e que sua acumulaÃÃo parece ser uma resposta adaptativa ao estresse provocado pelo NaCl. Em adiÃÃo, o Ãons salinos Na+ e Cl- contribuÃram para a maioria do AO das folhas submetidas ao NaCl. O impacto relativo do K+ sobre o AO das folhas foi reduzido consideravelmente com o aumento da dose externa de NaCl. Os resultados evidenciam tambÃm que o prÃ-condicionamento com NaCl influenciou positivamente no crescimento de Atriplex nummularia, em condiÃÃes de seca, evidenciado pelo maior acÃmulo de massa seca e melhor status hÃdrico das folhas. Dentre os solutos inorgÃnicos analisados, o Na+ e o Cl- foram os que mais contribuÃram para a osmorregulaÃÃo das folhas em condiÃÃes de deficiÃncia hÃdrica. Enquanto, GB foi o soluto orgÃnico mostrou o maior percentual de contribuiÃÃo para o potencial osmÃtico. Entretanto os resultados mostraram que o prÃ-condicionamento das plÃntulas de Atriplex nummularia com NaCl nÃo foram capazes de atenuar os efeitos induzidos pelo PEG.

Made available in DSpace on 2014-12-17T14:07:10Z (GMT). No. of bitstreams: 1 CarinaGMMB_TESE.pdf: 4060316 bytes, checksum: 4ffd1d674b7bda144d5cd732432d8bfb (MD5) Previous issue date: 2012-12-14 / One of the major challenges faced nowadays by oil companies is the exploration of pre-salt basins. Thick salt layers were formed in remote ages as a consequence of the evaporation of sea water containing high concentrations of NaCl and KCl. Deep reservoirs can be found below salt formations that prevent the outflow of oil, thus improving the success in oil prospection. The slurries used in the cement operations of salt layers must be adequate to the properties of those specific formations. At the same time, their resulting properties are highly affected by the contamination of salt in the fresh state. It is t herefore important to address the effects of the presence of salt in the cement slurries in order to assure that the well sheath is able to fulfill its main role to provide zonal isolation and mechanical stability. In this scenario, the objective of the present thesis work was to evaluate the effect of the presence of NaCl and KCl premixed with cement and 40% silica flour on the behavior of cement slurries. Their effect in the presence of CO2 was also investigated. The rheological behavior of slurries containing NaCl and KCl was evaluated along with their mechanical strength. Thermal and microstructural tests were also carried out. The results revealed that the presence of NaCl and KCl affected the pozzolanic activity of silica flour, reducing the strength of the hardened slurries containing salt. Friedel?s salt was formed as a result of the bonding between free Cl- and tricalcium aluminate. The presence of CO2 also contributed to the degradation of the slurries as a result of a process of carbonation/bicarbonataion / Atualmente, um dos grandes desafios para as empresas petrol?feras ? a explora??o de petr?leo em bacias dominadas por estruturas salinas, mais conhecidas por zonas evapor?ticas. A camada de sal ? formada pela evapora??o da ?gua do mar, cuja composi??o qu?mica inclui altas concentra??es de cloreto de s?dio (NaCl). Reservat?rios profundos s?o encontrados abaixo de espessas camadas de sal que vedam o fluxo de ?leo para fora da rocha, aprisionando hidrocarbonetos e aumentando, assim, a probabilidade de sucesso na prospec??o de ?leo e g?s. Atendendo ?s condi??es de po?o, s?o utilizadas pastas de cimento do tipo Portland para isolar, promover resist?ncia mec?nica ao po?o e impedir a intercomunica??o zonal das forma??es rochosas produtoras. Deste modo, as pastas de cimento devem atender ? natureza dos sais, pois estes se encontram na natureza com distintas caracter?sticas. Assim, este trabalho teve como objetivo avaliar o comportamento da adi??o de sais NaCl e KCl em sistemas de pastas de cimento contendo 40% de s?lica flour e avaliar o comportamento dessas pastas frente a presen?a de CO2. As propriedades foram avaliadas atrav?s de ensaios de reologia, resist?ncia ? compress?o pelo m?todo ultrass?nico (UCA) e resist?ncia mec?nica pelo m?todo destrutivo, bem como com o uso de t?cnicas de caracteriza??o t?rmica (TG/DTG), difra??o de raios X (DRX), microscopia eletr?nica de varredura (MEV) e an?lise de EDS em microanalisadores de sonda eletr?nica (EPMA). Os resultados mostraram que a presen?a do NaCl e KCl, interferem na atividade pozol?nica da s?lica, reduzindo a resist?ncia das pastas quando adicionado altas concentra??es dos sais. Essa interfer?ncia foi comprovada devido a forma??o do sal de Friedel, resultado da liga??o dos cloretos livres ao aluminato tric?lcico, incorporado ?s fases s?lidas do cimento hidratado. Para o estudo da influ?ncia de meios ricos em CO2 em pastas de cimento, foi observada a degrada??o das pastas atrav?s do processo de carbonata??o seguido da bicarbonata??o, resultando na perda da resist?ncia mec?nica

Une consommation élevée de sel a été associée à beaucoup de maladies et à un risque accru de décès. Plusieurs mécanismes sous-jacents, y compris le stress oxydatif, ont été étudiés. Mais la salinité dans l'intestin et l'altération possiblement associée de son microbiote, récemment identifiées comme un symbiote critique de la santé et de la maladie, n'ont pas encore été explorées chez l'homme. En testant 1334 prélèvements de selles, nous avons montré qu'une salinité élevée était associée à une diminution de la diversité globale et à l'émergence de populations microbiennes halophiles dans l'intestin. La salinité fécale était associée au régime alimentaire salé et à l'obésité, conformément aux données épidémiologiques. Aucun procaryote halophile n’a été cultivé en dessous d'un seuil de salinité fécale de 1,5 %. Au-delà de ce seuil, nous avons découvert une diversité inattendue de microbiote halophile humain dont la richesse était corrélée avec les concentrations de sel; 64 espèces différentes ont été isolées, dont 21 nouvelles espèces et 43 espèces connues dans l'environnement mais non chez les humains. Trois procaryotes extrêmement halophiles ont été isolés, dont deux Archaea appartenant au genre Haloferax, avec une nouvelle espèce Haloferax massiliensis, et un nouveau genre bactérien, Halophilibacterium massiliense. D'autres études devraient spécifier les facteurs qui conduisent à la salinité intestinale et préciser si les altérations de microbiota intestinal associées à des niveaux élevés de sel peuvent être liées à des causes humaines / High salt intake has been linked with many diseases and an increased risk of death. Several underlying mechanisms, including oxidative stress, have been investigated, but salinity in human gut and the possible associated alteration of its microbiota recently identified as a critical symbiote of health and disease, have not yet been investigated in humans. Here, by testing 1,334 stools, we have shown that high salinity is associated with a decrease in overall diversity but the emergence of halophilic microbial populations in the intestine. Fecal salinity was associated with saline diet and obesity, according to epidemiological data. No halophilic prokaryote can be grown below a fecal salinity threshold of 1.5%. Beyond this threshold, we discovered an unexpected diversity of human cultured halophilic microbiota whose richness was correlated with salt concentrations; 64 different species were isolated, including 21 new unknown species and 43 known species in the environment but not in humans. Three extremely halophilic prokaryotes were isolated, including two Archaea belonging to the genus Haloferax, with a new species Haloferax massiliensis, and a new bacterial genus, Halophilibacteriums massiliense. Further studies should specify the factors driving gut salinity, and clarify if the gut microbiota alterations associated with high salt levels could be causally related to human diseas

Moringa (Moringa oleifera Lam.) belongs to the Moringaceae family and has several uses for family farms, mainly in water purification. However, there is little knowledge about the behavior of their seeds under stress conditions, which occurs under soils in northeastern region. The objective of this study was determine the Imbibition curve, and evaluate the water restriction, salinity, and pre-soaking of seeds in order to evaluate the initial development of Moringa oleifera. For the Imbibition curve, the weight of seeds was determined at every 4 hours. For water restriction induction were used different osmotic potentials (0, -0.1, -0.3, -0.4 and -0.6 MPa) obtained through the use of solutions of polyethylene glycol (PEG - 6000). For salinity tests there were used the solutions of sodium chloride at 5 concentrations (0, 25, 50, 100, 200 and 250 mol.m-3). For pre-soaking was employed two seed batches, using a non storage seeds and other batch with three-months storage at cold chamber. The pre-soaking seeds with distilled water were evaluated to assess the overcoming stress. For each treatment, was used a completely randomized design with four replications. For germination the seeds were placed in germination chamber, type BOD at 25ºC and continuous light and evaluated every 48 hours. For all tests (except for imbibitions curve) was evaluated the percentage, the speed germination index, time and average of speed germination, length and dry matter of root, hypocotyls and the whole seedling. The moringa seed needs 0.2 grams of water in a period of 128 hours to germinate. The germination of M. oleifera is possible under water restriction until -0.3 MPa, above this level is critical for germination and seedling development. The water pre-soaking with moringa seeds for 24 hours is effective for promoting lower pperiod to begin the germination. Vigor and germination of moringa seeds are inversely proportional to salt concentration, being affected when they are submitted to levels equal to or higher than 100 mol.m-3. Seeds water pre-soaking for 24 hours is effective to promote the reduction of the time necessary to initiate of the seeds germination, for seeds with / A moringa (Moringa oleifera Lam.), pertence à família Moringaceae e apresenta diversos usos para agricultura familiar nordestina, principalmente na purificação de água. No entanto, pouco se conhece sobre o comportamento de suas sementes em condições de estresse, que ocorrem em alguns solos da região nordeste. Assim, o objetivo deste trabalho foi realizar curva de embebição e avaliar o efeito do estresse hídrico e salino, e da pré-embebição de sementes na geminação de moringa. Para determinar a curva de embebição, foi monitorado o peso da semente em intervalos regulares de quatro horas. Para a simulação do estresse hídrico foram utilizadas diferentes soluções de polietilenoglicol (PEG 6000) a 0, -0,1; -0,3; -0,4 e - 0,6 MPa. Para o estresse salino, foram empregadas soluções de cloreto de sódio nas concentrações de 0, 25, 50, 100, 200 e 250 Mol.m-3. Para os processos de préembebição foram usadas dois lotes diferentes, sendo o primeiro de sementes recém colhidas e o segundo com sementes armazenadas por três meses. Além disso, testou-se a pré-embebição em sementes para superação do estresse salino. Para cada teste, foram empregadas quatro repetições de 25 sementes, em delineamento inteiramente casualizado. As sementes foram postas em câmera de germinação tipo BOD à 25ºC e luz contínua, sendo as avaliações realizadas a cada 48 horas. Para todos os testes (salvo a curva de embebição) avaliou-se a porcentagem, índice de velocidade, tempo médio e velocidade de germinação, tamanho e massa seca radicular, do hipocótilo e das plântulas inteiras. A semente de moringa necessita de 0,2 g de água em um período de 128 horas para germinar. Sob condições de restrição hídrica a germinação de sementes de moringa é possível em situações de -0,3 MPa, sendo níveis superiores a este, críticos para a germinação e formação de plântulas. O vigor e a germinação das sementes, bem como os eventos pós-germinativos da moringa é inversamente proporcional a concentração salina, sendo estas afetadas a níveis iguais ou superiores a 100 Mol.m-3. A pré-embebição de sementes de moringa em água por 24 horas é eficiente para promover a redução no tempo de início da germinação em sementes sob condições ou não de estresse salino.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Guanilina (GN), uroguanilina (UGN) e a enterotoxina termo-estÃvel da Escherichia coli (STa) fazem parte de uma nova famÃlia de peptÃdeos que ativam a formaÃÃo de cGMP. A ingestÃo de sal na dieta induz a secreÃÃo de GN e UGN no lÃmen intestinal, inibindo a reabsorÃÃo de sÃdio e induzindo a secreÃÃo de Cl-, HCO3- e Ãgua. Simultaneamente, esses hormÃnios estimulam a excreÃÃo renal de eletrÃlitos atravÃs da induÃÃo de natriurese, caliurese e diurese. Esse mecanismo altamente integrado permite a manutenÃÃo do sÃdio corporal, atravÃs da eliminaÃÃo desse excesso de sÃdio pela urina. Entretanto, essa regulaÃÃo fisiolÃgica entre o intestino e o rim na tem sido muito bem estudada. O objetivo desse trabalho à estudar as alteraÃÃes no metabolismo diÃrio e na funÃÃo renal de ratos submetidos a uma alta ingestÃo de cloreto de sÃdio. Os efeitos forma examinados usando ratos Wistar mantidos por 10 dias em gaiolas metabÃlicas. O grupo controle recebeu somente Ãgua destilada, enquanto que os grupos tratados receberam 1% e 2% de soluÃÃo de NaCl. Forma analisadas diariamente o volume urinÃrio, o peso corporal e o consumo de Ãgua e alimento. A funÃÃo renal foi avaliada atravÃs da perfusÃo de rim isolado de ratos apÃs dez dias de tratamento em gaiolas metabÃlicas, onde a perfusÃo foi realizada com soluÃÃo de Krebs-Henseleit modificada com 6g% de albumina bovina. Os dados foram comparados atravÃs de teste t de Student e ANOVA, com significÃncia p<0,05. O peso dos ratos tratados com 2% de NaCl apresentou uma reduÃÃo a partir do dia 8, em relaÃÃo ao controle, enquanto que 1% nÃo apresentou reduÃÃo significativa. O volume urinÃrio e o consumo de Ãgua apresentaram um aumento em ambos os tratamentos a partir do dia 2. O consumo de alimento ingerido nÃo apresentou grandes variaÃÃes entre os grupos. Em rim isolado de rato ambos os tratamentos aumentou a pressÃo de perfusÃo (PP). A resistÃncia vascular renal (RVR), o fluxo urinÃrio (FU), o ritmo de filtraÃÃo glomerular (RFG) e o clearance osmolar (Cosm) aumentou no grupo de 1% comparado ao controle, porÃm esses mesmos parÃmetros diminuÃram no grupo de 2%. Em relaÃÃo ao transporte de eletrÃlitos observa-se alteraÃÃo somente no grupo de 2%, onde reduziu o transporte de sÃdio (%TNa+, %pTNa+), potÃssio (%TK+, %pTK+) e cloreto (%TCl-, %pTCl-). Esses resultados sugerem que a alta ingestÃo de NaCl na dieta promove significativa alteraÃÃes no metabolismo diÃrio e na funÃÃo renal. / Guanylin (GN), uroguanylin (UGN), and the bacterial heat-stable enterotoxin (ST) peptides comprise a new family of cyclic guanosine 3â-5â monophosphate (cGMP)-regulating agonist. Ingestion of a salt meal induces secretion of GN and UGN into the intestinal lumen, where they inhibit Na+ absorption and induces Cl-, HCO3- , and water secretion. Simultaneously, these hormones stimulate renal electrolyte excretion by inducing natriuresis, kaliuresis, and diuresis. The highly integrated mechanism allows the organism to maintain sodium balance by eliminating excess NaCl in the urine. However, their physiological regulation within the kidney has not been studied. The aim of this study was showing changes on daily metabolism and renal function of rat under high sodium chloride ingestion. Its effects were examined using wistar rats maintained for ten days in metabolic cages. Control group received only water, two more groups received 1% and 2% solutions of sodium chlroride. We daily analyzed urinary volume, weigh, and food and water consume. The renal function was evaluated using isolated perfused kidneys, in which the kidneys were perfused after ten days in metabolic cages, only with Krebs-Henseleit solution containing 6g% of a previously dialysed bovine albumine serum. All data were analyzed by ANOVA and Student t-test with level of significance set at *p<0,05. Ratâs weights of 2% group decreased after eighth day, compared with control group, while 1% group did not show significative weight lost. Urinary volume and water consume increased, in both treatments, from second day. Food consume did not show significative among groups. In isolated kidney both treatments increase perfusion pressure (PP). The renal vascular resistence (RVR), urinary flow (UF), glomerular filtration rate (GFR) and the osmolar clearance (Cosm) increased in the 1% group compared with control group, however decreased in 2% NaCl group. Treatment with 2% NaCl decreased the sodium (%TNa+, %pTNa+), potassium (%TK+, %pTK+) and chloride (%TCl-, %pTCl-). These results suggest that a high salt ingestion on diet promote significative changes on daily metabolism and the renal function of rats.

Dans ce travail de thèse, nous avons étudié les interactions entre un polyoside anionique (pectine) et des cations monovalent (Na+) et divalents (Ca2+, Zn2+, Ba2+, Mg2+) en régime dilué (c < c*) et concentré (c ≈ c*). Ainsi, une pectine faiblement méthylée (LMP) a été étudiée en comparaison avec l’acide polygalacturonique (PGA). L’affinité de ces polyosides pour fixer les ions calcium diminue quand la concentration en NaCl augmente. Elle est plus élevée dans le cas du Ca-polyGal en comparaison avec Ca-LMP ; ceci peut être expliqué par la faible rigidité des chaînes observée pour le polyGal. Les interactions entre les quatre cations divalents (Ca2+, Zn2+, Ba2+, Mg2+) et les deux biopolymères (PolyGal et LMP) en régime dilué ont été étudiées afin d’obtenir des informations sur la structure du réseau, le mode d’association et l’énergie d’association. Nous avons donc proposé un mécanisme d’association qui est composé de deux étapes : i) formation de monocomplexes et de réticulations ponctuelles et ii) formation de dimères. Le passage de l’étape (i) à l’étape (ii) est caractérisé par un ratio molaire critique (R*=[M2+]/[Gal]) qui dépend du nombre et de la stabilité des réticulations ponctuelles entre le polymère et le cation. Pour le Mg-polyGal, l’association est due à une condensation des ions magnésium autour des chaînes du polyGal. Les résultats de simulations ont montré que l’association de 4 cations Zn2+ avec 2 chaînes composées de 8 unités Gal est similaire à une structure de type « boîte à œuf ». Ce modèle n’est pas applicable à la structure obtenue par l’association des cations Ca2+ et Ba2+. Les associations entre les polyGals et les cations divalents à une concentration en polymère proche de la concentration de recouvrement (c*) permettent d’obtenir des gels uniquement pour les trois cations (Ca2+, Zn2+, Ba2+). Les propriétés viscoélastiques de ces gels ainsi que la cinétique de gélification ont été étudiés. Dans le cas des gels, la première étape du mécanisme d’association proposé (formation de monocomplexes et de réticulations ponctuelles) s’accompagne d’une augmentation de l’épaisseur du gel ; alors que la deuxième étape (formation de dimères) conduit à une densification du gel. Nous avons remarqué que le coefficient de diffusion du front de gel suit l’ordre suivant : Ba2+ > Ca2+ > Zn2+ > Mg2+ ; ceci peut être relié à l’affinité entre les molécules d’eau de la sphère de coordination et le cation. En effet, l’affinité du cation pour l’eau augmente selon l’ordre inverse : Ba2+ < Ca2+ < Zn2+ < Mg2+. Enfin, nous avons utilisé ces trois polyosides (PGA, LMP et ALMP - pectine faiblement méthylée amidée) en association à des ions calcium pour fabriquer des microparticules contenant la rutine afin de cibler sa libération au niveau intestinal. Nous avons ainsi relié la cinétique de libération de la rutine à la structure du réseau mis en place lors de l’étape de gélification. Les microparticules à base de pectine ALMP présentent une capacité à fixer l’eau et un taux de libération de la rutine plus élevés que les microparticules à base de LMP et PGA. Le gel Ca-ALMP est plus flexible et présente des modules viscoélastiques plus faibles que les gels Ca-PGA et Ca-LMP. Nous avons attribué ceci à la distribution aléatoire des groupements ester et/ou amide dans ALMP qui gênerait la formation des dimères : les liaisons hydrogènes entre les fonctions amines et les fonctions carboxylates seraient donc responsables de la flexibilité du réseau formé. / In this thesis, we studied the interactions between an anionic polysaccharide (pectin) and monovalent cation (Na+) and divalent cations (Ca2+, Zn2+, Ba2+, Mg2+) in dilute regime (c < c*) and concentrate regime (c ≈ c *). Thus, a low methoxy pectin (LMP) was studied in comparison with a polygalacturonic acid (PGA). The affinity to bind calcium ions for these polysaccharides decreases as the NaCl concentration increases. This binding affinity was higher for Ca-polyGal than for Ca-LMP due to the low rigidity of chains observed in the polyGal. The interactions between four divalent cations (Ca2+, Zn2+, Ba2+, Mg2+) and the two biopolymers (polyGal and LMP) in the dilute regime were studied in order to obtain information about the network structure, the mode of association and the binding energy. Therefore, we propose a mechanism of the binding which consists of two steps: i) formation of monocomplexations and point-like cross-links ii) formation of dimers. The threshold molar ratio (R* = [M2+]/[Gal]), between these two steps depends on the number and the stability of the point-like cross-links between polyGal chains and the cation. Mg2+ interacts so strongly with water that is remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. Molecular dynamic simulations of galacturonate chains in explicit water showed that the « egg-box » model is more adapted for zinc cations than for calcium and barium. When the concentration of the polyGal is close to the overlap concentration (c*), the addition of divalent cations allows to obtain gels for only three cations (Ca2+, Zn2+, Ba2+). The viscoelastic properties of these gels and the gelation kinetics were studied. In the case of gel formation, the first step (formation of monocomplexations and point-like cross-links) is accompanied by an increase in the gel thickness; while the second step (formation of dimers) leads to a densification of the gel. We found that the diffusion coefficient of the gel front increased according the following order: Ba2+ > Ca2+ > Zn2+ > Mg2+; this may be related to the affinity between the water molecules from the coordination sphere and the cation. Indeed, the affinity of the cation for water molecules increases in the reverse order: Ba2+ < Ca2+ < Zn2+ < Mg2+. Finally, we have used the three polysaccharides (PGA, LMP and ALMP - amidated low methoxyl pectin) in association with calcium ions to produce microparticles containing rutin to target drug release in the intestine. We have linked the rutin release kinetics to the network structure established in the gelation step. ALMP microparticles had higher ability to uptake water and thus higher drug release rate than two others microparticles (Ca-LMP and Ca-PGA). The Ca-ALMP gel was more flexible and had the lower viscoelastic modulus than Ca-PGA and Ca-LMP gels. We attributed this to the random distribution of ester and/or amide groups in ALMP, which hinders the formation of dimers: the hydrogen bonds between the amine groups and carboxylate groups are responsible for the flexibility of the network formed.

La puissance de la biopile enzymatique à glucose/oxygène est limitée par sa partiecathodique. Afin de contourner cette limitation, nous avons étudié les enzymescathodiques : les Bilirubine oxydases (BODs). Dans le but de mieux appréhender ces BODs, lemécanisme réactionnel, la nature de l’étape limitante et l’effet des sels ont alors été étudiés.Deux mécanismes différents sont retrouvés en fonction du mode de transfert des protons etdes électrons (4 fois 1H+/1e- ou 2 fois 2H+/2e-). De plus, nous avons démontré que l’étapelimitante est l’oxydation du substrat pour les trois substrats testés et que les sels agissent auniveau du cuivre T1. Les principales limitations des BODs sont leur stabilité à 37 °C ainsi queleur inhibition par le NaCl. Deux techniques ont alors été utilisées pour identifier des BODsplus résistantes. La première méthode est l’extraction de nouvelles enzymes à partird’organismes extremophiles. Elle a permis d’isoler la BOD d’Anaerophaga thermohalophilaqui possède une bonne résistance au NaCl mais une densité de courant faible. Dans unsecond temps, afin de reconstruire des séquences ancestrales, la phylogénie de la familledes Bacillus Bacterium a été effectuée. Cette technique a permis l’identification de troisBODs possédant des caractéristiques très intéressantes : la BOD de Bacillus nakamurai etdeux BODs ancestrales (Noeud 10 et Noeud 13). Par exemple, après une heure à 37°C et 140mM de NaCl, le Noeud 10 possède une meilleure densité de courant que la BOD de Bacilluspumilus, qui est l’enzyme utilisée comme base de la phylogénie. La seconde technique estdonc une méthode de choix permettant la découverte de nouvelles enzymes à la fois plusstables et plus résistantes que les enzymes actuelles. Elle ouvre de grandes perspectivespour l’utilisation des BODs comme enzymes cathodiques ou pour d’autres applicationsbiotechnologiques. Enfin, nous avons montré que l’immobilisation de la BOD de B. pumilusdans le matériau Si-(HIPE) permet la décoloration cyclique de colorants chimiques surplusieurs mois. / Power of glucose/oxygen enzymatic biofuel cell is limited by the cathodic part. In order to prevent this limitation, we studied cathodic enzymes: Bilirubin oxidases (BODs). For this purpose, the kinetic mechanism, rate-limiting step and salts effect were determined. Two different mechanisms are observed depending on the electron/proton transfer (4 times1H+/1e- or 2 times 2H+/2e-). We also demonstrated that the rate-limiting step is the substrate oxidation for the three substrates tested and salts act around the T1 copper. Main BODs limitations are their stability at 37°C and their inhibition by NaCl. Two methods were used toidentify the most resistant BODs. The first one was the identification of new enzymes from extremophile organisms. It allows to isolate BOD from Anaerophaga thermohalophila whichhas good NaCl resistance but low current density. In addition, in order to reconstructancestral sequences, phylogeny of Bacillus Bacterium family was performed. This methodidentified three BODs with interesting features: BOD from Bacillus nakamurai and twoancestral BODs (Noeud 10 and Noeud 13). For example, after one hour at 37°C and 140 mMNaCl, Noeud 10 has a better current density than the BOD from Bacillus pumilus, which is theenzyme used as basis for the phylogeny. This second method allowed the discovery of newenzymes that were both more stable and more resistant than actual enzymes. Thistechnique opens up valuable prospects for the use of BODs as cathodic enzymes or for otherbiotechnological applications. In the end, we demonstrated that BOD from B. pumilusimmobilization in Si-(HIPE) materials allows cyclic discoloration of chemical dyes duringseveral months.

Made available in DSpace on 2014-12-17T14:06:55Z (GMT). No. of bitstreams: 1 CarinaGMM_DISSERT.pdf: 2881294 bytes, checksum: 3b5fb2cb077e76e3477ec04b95724ee5 (MD5) Previous issue date: 2009-12-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel?s salt, where free chlorine is bonded to tricalcium aluminate / Atualmente, um dos grandes desafios para as empresas petrol?feras ? a explora??o de petr?leo em bacias dominadas por estruturas salinas, mais conhecidas por zonas evapor?ticas. A camada de sal ? formada pela evapora??o da ?gua do mar, cuja composi??o qu?mica inclui altas concentra??es de cloreto de s?dio (NaCl). Reservat?rios profundos s?o encontrados abaixo de espessas camadas de sal que vedam o fluxo de ?leo para fora da rocha, aprisionando hidrocarbonetos e aumentando, assim, a probabilidade de sucesso na prospec??o de ?leo e g?s. Atendendo ?s condi??es de po?o, s?o utilizadas pastas de cimento do tipo Portland para isolar, promover resist?ncia mec?nica ao po?o e impedir a intercomunica??o zonal das forma??es rochosas produtoras. Deste modo, as pastas de cimento devem atender ?s necessidades do sal, pois este se encontra na natureza com distintas caracter?sticas. Assim, este trabalho teve como objetivo avaliar o comportamento de sistemas de pastas saturadas com NaCl, em concentra??es de 5% a 25%, frente as propriedades f?sicas e qu?micas das mesmas. Tais propriedades foram analisadas atrav?s de ensaios laboratoriais de reologia, tempo de espessamento, ?gua livre e resist?ncia ? compress?o (UCA), bem como com o uso de t?cnicas de caracteriza??o t?rmica, difra??o de raios X e microscopia eletr?nica de varredura. Os resultados mostraram que a presen?a do NaCl, quando em pequenas concentra??es (at? 10%) atua como acelerador de pega. J? quando em altas concentra??es (a partir de 20%), n?o s? apresenta efeito oposto em rela??o ? pega, retardando-a, bem como atua deleteriamente na resist?ncia ? compress?o. Foi observada, tamb?m, a forma??o de uma nova fase denominada sal de Friedel, resultado da liga??o dos cloretos livres ao aluminato tric?lcico, incorporado ?s fases s?lidas do cimento hidratado

L’utilisation des alliages de titane dans de nombreuses applications (transport, énergie, chimie,...) permet des gains de masse importants en tirant profit du rapport propriétés mécaniques/masse volumique qui est avantageux pour ce type de matériaux. L’utilisation de ces alliages dans des environnements à hautes températures (T>500°C) nécessite de se préoccuper de leur comportement et de comprendre les mécanismes de dégradation dans ces conditions sévères. Certains facteurs peuvent influencer le comportement des alliages de titane en oxydation, comme l’application de cycles de chauffage/refroidissement, la présence de vapeur d’eau ou la présence de sels, selon les conditions d’utilisation.Ce travail de thèse s’est attaché à comprendre les mécanismes d’oxydation d’un alliage de titane utilisé dans l’aéronautique : l’alliage Ti6242S. Il a été étudié à 560°C sous air, sous air humide et en présence de dépôts solides de sel(s) de type NaCl et/ou Na2SO4. Pour cela, des oxydations de longues durées avec et sans dépôts solides de sels ont été réalisées. Les résultats obtenus montrent que la présence de NaCl provoque une dégradation importante du comportement en oxydation des échantillons. La dissolution d’oxygène dans le métal observée sous air ne se produit plus en présence de dépôts de sels. En revanche, une oxydation interne de l’alliage a lieu et des fissures apparaissent dans la profondeur du substrat métallique. La dégradation du matériau est attribuée à la présence de dichlore et à la formation de chlorures métalliques volatiles. Un mécanisme réactionnel a été proposé afin d’expliquer l’effet néfaste des dépôts de NaCl. L’effet d’un dépôt de sels mixte NaCl/Na2SO4 sur l’oxydation de l’alliage Ti6242S est cependant moins marqué.L’évolution des propriétés mécaniques de l’alliage Ti6242S a également été étudiée après oxydation. Une simple oxydation de 100 h sous air provoque une diminution importante de la ductilité du matériau à cause de la zone de dissolution d’oxygène formée pendant l’oxydation. En présence d’un dépôt de NaCl et après 100h d’oxydation à 560°C, la perte de ductilité est encore plus importante et la rupture de l’éprouvette intervient dès la fin du domaine élastique. Dans ces conditions, la pièce perd une partie de sa section porteuse et la limite élastique et le module élastique du matériau restant sont fortement impactés. La présence d’un dépôt mixte NaCl/Na2SO4 pendant l’oxydation a un effet moins marqué sur les propriétés mécaniques du matériau, en accord avec la plus faible réactivité de l’alliage Ti6242S avec ce type de dépôt. Les mécanismes inhérents au changement de propriétés mécaniques sont expliqués dans le travail de thèse. / The use of titanium alloys in many applications (transport, energy, chemistry,...) allows significant weight savings in relation to the good mechanical properties/density ratio of these materials. Since titanium alloys are employed at high temperatures (T>500°C), their behavior in such conditions has to be studied in severe conditions in order to understand degradation mechanisms. Moreover, some specific conditions can be met during application, like thermal cycling, water vapour or presence of salts. These parameters are known to influence oxidation behavior of titanium alloys.In this thesis work, oxidation behavior of an aeronautics titanium alloy (Ti6242S) has been studied in air and moist air at 560°C. The effect of solid salt deposits (NaCl and/or Na2SO4) on the oxidation behavior of Ti6242S alloy has also been taken into account. Ti6242S samples were oxidized at 560°C for oxidation times up to 19 000 hours with or without solid salt deposits. NaCl deposit resulted in an important deterioration of Ti6242S alloy behavior at this temperature. Oxygen dissolution in the metal was no longer observed compared to ageing in air, but internal oxidation of the alloy could be evidenced, and cracks were observed deeply into the metallic substrate after oxidation. The corrosion resistance decrease in such conditions was attributed to the presence of chlorine and formation of volatile metallic chlorides due to the presence of NaCl. A degradation mechanism based on active oxidation of Ti6242S alloy exposed to NaCl salt was proposed. The second salt deposit tested consisted in a mixed NaCl/Na2SO4 salt deposit. The harmful effect of this salt deposit on the oxidation behavior of Ti6242S alloy was lower than that of a simple NaCl deposit.Mechanical properties of Ti6242S alloy exposed to solid salt deposits at 560°C were then studied. A simple oxidation in air for 100 hours without salt deposit resulted in an important loss of ductility of the tested samples due to the presence of oxygen solid solution into the metal. The same oxidation time caused an even more important loss of ductility for the samples covered by NaCl deposits. In this case, sample failure occurred at the end of the elastic deformation domain. Elastic modulus and yield strength were also strongly decreased. Mixed NaCl/Na2SO4 deposit exhibited a lower impact on the mechanical properties of the oxidized Ti6242S sample, in accordance with the lower reactivity of Ti6242S alloy with this type of salt deposit. Mechanisms explaining Ti6242S alloy mechanical behavior in such conditions were explained in this thesis work.

Submitted by Maria Beatriz Vieira (mbeatriz.vieira@gmail.com) on 2017-01-05T13:10:39Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) tese_fabio_schaun_harter.pdf: 3557391 bytes, checksum: 5b6d3757e05c02956957ee671553ba7f (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-01-09T11:55:09Z (GMT) No. of bitstreams: 2 tese_fabio_schaun_harter.pdf: 3557391 bytes, checksum: 5b6d3757e05c02956957ee671553ba7f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-01-09T11:56:59Z (GMT) No. of bitstreams: 2 tese_fabio_schaun_harter.pdf: 3557391 bytes, checksum: 5b6d3757e05c02956957ee671553ba7f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-01-09T11:57:10Z (GMT). No. of bitstreams: 2 tese_fabio_schaun_harter.pdf: 3557391 bytes, checksum: 5b6d3757e05c02956957ee671553ba7f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-02-28 / Sem bolsa / O objetivo do trabalho foi avaliar a produção de sementes de arroz de diferentes cultivares, sob estresse salino. O experimento foi realizado em duas safras agrícolas; no primeiro ano foram avaliados cinco genótipos (IRGA 417, Avaxi CL, SCSBRS Tio Taka, Inov CL e IAS 12-9 - Formosa) submetidos a doses de 0, 12,5; 25; 37,5; 50; 75 e 100 mM. No segundo ano utilizou-se quatro genótipos (IRGA 417, Epagri 109, BRS Querência e IAS 12-9 - Formosa) nas doses 0, 4, 8, 12 e 16 mM. Avaliou-se a qualidade fisiológica das sementes sob estresse salino pelos testes de germinação, primeira contagem de germinação, teste frio, envelhecimento acelerado, índice de velocidade de emergência, emergência, área foliar, comprimento de parte aérea e sistema radicular, fitomassa seca parte aérea e sistema radicular. Os genótipos foram cultivados sob as mesmas condições de salinidade, avaliando-se no final do ciclo as características agronômicas e a qualidade da semente produzida da seguinte forma: número de panículas, peso total, peso de sementes cheias, peso de sementes chochas, porcentagem de sementes cheias e chochas, e peso de mil sementes; e qualidade fisiológica pelos teste de germinação, primeira contagem de germinação e teste de frio. Conclui-se que a qualidade fisiológica de sementes de arroz apresenta redução com o aumento dos níveis de estresse salino; cultivares de arroz mostram respostas diferenciadas sob condições de estresse salino; as cultivares de arroz IRGA 417, Epagri 109, BRS Querência e IAS 12-9 (Formosa) apresentam redução da produção de sementes sob condições de estresse salino; a qualidade fisiológica de sementes de arroz das cultivares IRGA 417, Epagri 109, BRS Querência e IAS 12-9 (Formosa), não são afetadas negativamente em concentrações salinas até 16 mM. / The objective of this work was to evaluate the production of rice seeds of different cultivars under salt stress. The experiment was conducted in two growing seasons, in the first year, the following five rice genotypes (IRGA 417, Avaxi CL, SCSBRS Tio Taka, Inov CL e IAS 12-9 - Formosa) were evaluated to salt tolerance and they were submitted to doses of 0; 12.5; 25; 37.5; 50; 75 and 100 mM. In the second year, four genotypes (IRGA 417, Epagri 109, BRS Querência e IAS 12-9 - Formosa) were used at dosages of 0; 4; 8; 12 and 16 mM. The following tests were performed to evaluate seed quality under stress: germination, first count, cold test, accelerated aging, emergence speed index, emergence, leaf area, shoot and root length, stem and root dry biomass. All genotypes were grown under the same salinity conditions and the agronomic characteristics and quality of seed produced were evaluated at the end of the cycle as follows: number of panicles, total weight, weight of full seeds, weight of empty seeds, percentage of full and empty seeds and thousand seed weight. Physiological seed quality was evaluated by tests of germination, first count and cold test. It can be concluded that physiological quality of rice seeds showed a decrease with the increase in salt stress levels. Rice cultivars show different responses under salt stress; salt stress reduce the production of seed of the cultivars IRGA 417, Epagri 109, BRS Querência and IAS 12-9 (Formosa) and the physiological quality of rice seeds of the cultivars IRGA 417, Epagri 109, BRS Querência and IAS 12-9 (Formosa), are not affected in salt concentrations up to 16 mM .