Made available in DSpace on 2016-06-02T19:22:57Z (GMT). No. of bitstreams: 1 4611.pdf: 1042877 bytes, checksum: b9b33a5c88aa13696432ae2d728a0a21 (MD5) Previous issue date: 2012-05-22 / Financiadora de Estudos e Projetos / Previous animal s research has shown that many protocols with aimed to mimic human exercise has been used. The endurance protocols are studied very often however, some difficulties are encountered to produce resistance exercise protocols. Some animal models of resistance training have been used, as jumping exercise. Among these, stands out the rat model performed on ladder with healthy and unhealthy animals. However, the energy system and acute physiological responses associated with this protocol have not been determined. Thus, the aim of the present study was to evaluate the acute metabolic characteristics and the acute effects on indirect biomarkers of muscular microtrauma of acute resistance exercise performed on ladder. Fifty males Wistar rats were randomly divided into two groups: Exercise (E) and Control (C). The animals of E group climbed a vertical ladder with weights attached to their tails. The session was performed once with 4 9 climbs. The lactate concentration increased at the beginning of training and there was a tendency to stabilize the blood lactate during the exercise session. Serum corticosterone found in E group was significantly higher (59%; p<0.05) when compared to C group. There was no difference between free fatty acids (24% p=0.109), in the liver (8%; p=0.575) and in the gastrocnemius fatty acids content (17%; p=0.219). The glycogen in liver (42%; p<0.05) and soleus (56%; p<0.05) were different between groups. Lactate Dehydrogenase (LDH) and Creatine Kinase (CK) activities were significantly higher (LDH 32%; CK 27%; p<0.05) in the E than in the C group. The results suggest that this protocol is a high intensity exercise able to induce an increase in the lactate concentration at the beginning of exercise. Moreover, there were increases in indirect markers of muscle microtrauma in rats after a single exhaustive session. However, the lactate concentration was low, suggesting that the aerobic metabolism is an important factor during the intervals between the series of climbing. / Atualmente, pesquisas com animais usam muitos protocolos de exercícios, com o objetivo de mimetizar as condições de exercícios realizados por humanos. Os protocolos de endurance (aeróbios) são estudados com grande frequência, no entanto algumas dificuldades são encontradas no sentido de produzir um protocolo de exercício resistido para animais. Alguns protocolos foram criados, utilizando principalmente modelos onde os animais realizam saltos. Um protocolo que tem se destacado é o de escalada e tem sido largamente utilizado em animais saudáveis e não saudáveis. Entretanto, as respostas fisiológicas agudas desse protocolo não foram determinadas até o momento. Portanto, o objetivo do presente estudo foi avaliar as características metabólicas agudas do exercício resistido realizado em escada, e examinar os efeitos agudos em marcadores indiretos de lesão muscular. Foram utilizados 50 ratos Wistar divididos randomicamente em dois grupos: Controle (C) e Exercício Resistido (ER). Os animais do grupo ER escalaram uma escada vertical de 1,1 m com pesos fixados em suas caudas. Foi realizada somente uma sessão com 4-9 escaladas. Os níveis de lactato foram maiores nas primeiras escaladas em relação ao repouso, e se mantiveram constantes até o final do exercício. As concentrações de corticosterona encontradas no grupo ER foram maiores (59%; p<0,05) quando comparadas ao grupo C. Não houve diferença significativa no conteúdo de ácidos graxos do plasma (24% p=0,109), do fígado (8%; p=0,575) e do músculo gastrocnêmio (17%; p=0,219). O conteúdo de glicogênio hepático (42%; p<0,05) e muscular (sóleo) (56%; p<0,05) foi diferente entre os grupos. Os níveis de Lactato Desidrogenase (LDH) e Creatina Kinase (CK) foram maiores (LDH 32%; CK 27%; p<0,05) no grupo ER quando comparados ao grupo C. Os resultados sugerem que esse protocolo de exercício resistido é um exercício de alta intensidade, visto que a concentração de lactato aumentou no início do exercício e houve um maior nível de microlesão muscular após o exercício. No entanto, a concentração do lactato foi baixa, sugerindo que o metabolismo aeróbio contribui de forma importante durante os intervalos entre as séries de escalada.

Orientador: Ana Lúcia Barretto Penna / Banca: Susana Marta Isay Saad / Banca: Roberto da Silva / Resumo: O parmesão é um queijo típico italiano e possui como características peculiares o baixo teor de umidade, a textura granular e o sabor picante. Seu processamento é sempre lembrado pelo longo período de maturação e durante esta etapa ocorrem numerosas reações bioquímicas de degradação de seus componentes pelas enzimas oriundas do leite e do coalho e daquelas produzidas pelas bactérias, causando mudanças na textura e sabor desse produto. A autólise espontânea de microrganismos termófilos, como Lactobacillus helveticus, é uma característica tecnológica importante para a escolha de culturas com potencial de aplicação na fabricação de queijos de massa dura como o Parmesão. Desta forma o objetivo do presente trabalho é avaliar, durante a maturação do queijo Parmesão, o desempenho autolítico de culturas de Lb. helveticus autóctones, previamente isoladas de soro fermento. Foram utilizadas as culturas autóctones de Lb. helveticus, E5 com perfil autolítico elevado e A e D1 com perfil autolítico intermediário. A cultura comercial Cc1 (Lh-B02, Chr. Hansen) com perfil autolítico elevado foi utilizada como controle. A atividade das enzimas intracelulares LDH e PepX, bem como a viabilidade foram realizadas durante 48 horas de crescimento das culturas. Após a elaboração dos queijos com as diferentes culturas, mensalmente, foi determinada a contagem de lactobacilos termófilos, a atividade das enzimas LDH e PepX, a evolução dos teores de acidez, tirosina, triptofano e índice de maturação no queijo Parmesão ao longo de 180 dias de maturação. A maior liberação das enzimas LDH e PepX in vitro foi observada na cultura comercial Cc1 e autóctone E5 e comportamento semelhante entre as análises de CDM e cultivo em placa foi observado apenas para a cultura autóctone A e cultivo comercial Cc1. A maior população de lactobacilos termófilos nos queijos experimentais... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The Parmesan is a typical Italian cheese and has peculiar characteristics such as low moisture level, a granular texture and spicy flavor. Its processing involves long period of ripening and during this stage there are many biochemical reactions produced by enzymes from the raw milk, rennet and those produced by bacteria, resulting in changes in texture and taste of this product. The spontaneous autolysis of thermophilous microorganisms, such as Lactobacillus helveticus, is an important technological feature for the choice of cultures with potential application in the production of hard cheeses, such as Parmesan. The objective of this study was to assess the autolytic performance of cultures of autochthonous Lb. helveticus, previously isolated from natural whey starter during the ripening of Parmesan cheese. Autochthonous cultures of Lb. helveticus, E5 with high autolytic profile and A and D1 with intermediary autolytic profile were used. The commercial culture Cc1 (Lh-B02, Chr. Hansen) with high autolitic profile was used as control. The activity of in situ intracellular enzymes LDH and PepX, and the cell viability after 48 hours of growth were determined. Every month during the 180 days of ripening the population of thermophilous lactobacilli, the activity of enzymes LDH and PepX, the acidity, tyrosine, tryptophan contents and the index of ripening on Parmesan cheese were determined. The highest release in vitro of the LDH and PepX enzymes was observed in the commercial culture Cc1 and autocthonous E5 and similar culture A and the commercial culture Cc1. The highest population of thermophilous lactobacilli in the experimental cheeses was observed at the 30 days of ripening. In all cheeses samples it was observed in the cheeses produced with cultures with higher autolytic profile. There was a significant increase in acidity, tyrosine and tryptophan contents and IR in all samples... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2014-06-11T19:23:27Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-02-17Bitstream added on 2014-06-13T19:50:10Z : No. of bitstreams: 1 azevedo_ac_me_sjrp.pdf: 656743 bytes, checksum: a6e979d66c4af6a14eac14b66178875e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O parmesão é um queijo típico italiano e possui como características peculiares o baixo teor de umidade, a textura granular e o sabor picante. Seu processamento é sempre lembrado pelo longo período de maturação e durante esta etapa ocorrem numerosas reações bioquímicas de degradação de seus componentes pelas enzimas oriundas do leite e do coalho e daquelas produzidas pelas bactérias, causando mudanças na textura e sabor desse produto. A autólise espontânea de microrganismos termófilos, como Lactobacillus helveticus, é uma característica tecnológica importante para a escolha de culturas com potencial de aplicação na fabricação de queijos de massa dura como o Parmesão. Desta forma o objetivo do presente trabalho é avaliar, durante a maturação do queijo Parmesão, o desempenho autolítico de culturas de Lb. helveticus autóctones, previamente isoladas de soro fermento. Foram utilizadas as culturas autóctones de Lb. helveticus, E5 com perfil autolítico elevado e A e D1 com perfil autolítico intermediário. A cultura comercial Cc1 (Lh-B02, Chr. Hansen) com perfil autolítico elevado foi utilizada como controle. A atividade das enzimas intracelulares LDH e PepX, bem como a viabilidade foram realizadas durante 48 horas de crescimento das culturas. Após a elaboração dos queijos com as diferentes culturas, mensalmente, foi determinada a contagem de lactobacilos termófilos, a atividade das enzimas LDH e PepX, a evolução dos teores de acidez, tirosina, triptofano e índice de maturação no queijo Parmesão ao longo de 180 dias de maturação. A maior liberação das enzimas LDH e PepX in vitro foi observada na cultura comercial Cc1 e autóctone E5 e comportamento semelhante entre as análises de CDM e cultivo em placa foi observado apenas para a cultura autóctone A e cultivo comercial Cc1. A maior população de lactobacilos termófilos nos queijos experimentais... / The Parmesan is a typical Italian cheese and has peculiar characteristics such as low moisture level, a granular texture and spicy flavor. Its processing involves long period of ripening and during this stage there are many biochemical reactions produced by enzymes from the raw milk, rennet and those produced by bacteria, resulting in changes in texture and taste of this product. The spontaneous autolysis of thermophilous microorganisms, such as Lactobacillus helveticus, is an important technological feature for the choice of cultures with potential application in the production of hard cheeses, such as Parmesan. The objective of this study was to assess the autolytic performance of cultures of autochthonous Lb. helveticus, previously isolated from natural whey starter during the ripening of Parmesan cheese. Autochthonous cultures of Lb. helveticus, E5 with high autolytic profile and A and D1 with intermediary autolytic profile were used. The commercial culture Cc1 (Lh-B02, Chr. Hansen) with high autolitic profile was used as control. The activity of in situ intracellular enzymes LDH and PepX, and the cell viability after 48 hours of growth were determined. Every month during the 180 days of ripening the population of thermophilous lactobacilli, the activity of enzymes LDH and PepX, the acidity, tyrosine, tryptophan contents and the index of ripening on Parmesan cheese were determined. The highest release in vitro of the LDH and PepX enzymes was observed in the commercial culture Cc1 and autocthonous E5 and similar culture A and the commercial culture Cc1. The highest population of thermophilous lactobacilli in the experimental cheeses was observed at the 30 days of ripening. In all cheeses samples it was observed in the cheeses produced with cultures with higher autolytic profile. There was a significant increase in acidity, tyrosine and tryptophan contents and IR in all samples... (Complete abstract click electronic access below)

La pollution des eaux constitue actuellement une préoccupation majeure aussi bien d’un point de vue sanitaire qu’environnemental. Afin d’y remédier, des procédés de dépollution efficaces, économiques et durables sont constamment développés et l’adsorption reste une méthode largement utilisée dans le traitement des eaux usées. De nombreux travaux sont consacrés à l’adsorption des polluants cationiques, mais le développement de supports adaptés pour interagir avec les contaminants anioniques est moins abordé. L’objectif principal de ce travail de thèse est de mettre en forme deux adsorbants anioniques : l’HDL (hydroxyde double lamellaire) Mg/Al et la ferrihydrite deux-lignes, et les associant à un gel d’alginate pour produire des matériaux composites pouvant être mis en oeuvre dans des réacteurs spécialisés pour l’élimination de contaminants anioniques. Les résultats de l’adsorption en réacteur batch sur les HDL et la ferrihydrite ont montré une bonne efficacité pour l’élimination de certains anions. La ferrihydrite possède une capacité plus importante que les HDL pour l’élimination des anions inorganiques. L’augmentation du rapport Mg/Al dans l’HDL a favorisé l’adsorption du méthyl orange (MO) ; un rapport Mg/Al de 3 (L3) a été séléctionné pour la suite du travail. Deux protocoles ont été évalués pour associer les solides à un gel d’alginate : l’encapsulation et la synthèse interne dans le gel. La nature des cations réticulant et la création de la macroporosité ont été étudiées. L’encapsulation du solide a diminué légèrement la capacité d’adsorption des anions, cependant, la création de la macroporosité permet de compenser cet effet du gel d’alginate. Les études sur l’adsorption du MO avec les billes encapsulées ont montré que l’augmentation de la taille des billes et de la quantité du solide L3 encapsulée a été accompagnée par une diminution de la capacité d’adsorption du MO. Le remplacement du réticulant Ca2+ par Ba2+ a permis de renforcer la structure du gel et améliorer la cinétique d’adsorption du MO, mais a entrainé une diminution de la capacité d’adsorption. La caractérisation des supports préparés par synthèse interne a montré une structure des solides différente des matériaux attendus (L3 ou ferrihydrite) avec par conséquence une réactivité différente. Des mécanismes d’élimination des anions organiques et inorganiques ont été proposés selon les différents adsorbants étudiés. Les billes ferrihydrite/alginate préparées par encapsulation ont présentés globalement une bonne capacité de rétention des anions notamment pour les anions inorganiques (phosphate, chromate et arséniate). Tandis que celles préparées par synthèse interne ne fixent que les arséniates et les phosphates par différents mécanismes essentiellement la précipitation des anions à la surface des oxyde et oxy-hydroxydes de fer. L’adsorption du MO en réacteur filtrant ouvert a montré que l’augmentation du débit d’alimentation a un effet négatif sur l’adsorption alors qu’une concentration initiale plus grande favorise l’adsorption ce qui est en concordance avec les résultats obtenus en réacteur batch. Un taux de régénération de 30% des billes ferrihydrite/alginate macroporeuse (BPENFh-Ba) a été observé en réacteur batch en utilisant une solution de chlorure d’ammonium avec la possibilité de réutiliser l’adsorbant plusieurs fois.Ce travail confirme les performances et la possibilité d’utiliser des matériaux composite d’HDL ou ferrihydrite dans un gel d’alginate pour l’élimination de composés anioniques contenus dans des eaux usées. / Water pollution is currently a major concern from both health and environmental point of view. In order to solve this problem, efficient decontamination processes, economic and sustainable are constantly being developed and adsorption process remains a widely used method in the wastewater treatment. Many studies are devoted to the adsorption of cationic pollutants, but the development of suitable supports able to interact with the anionic contaminants is less discussed. The main objective of this work is to form two anionic adsorbents: the LDH (Layered Double Hydroxide) Mg/Al and two-line ferrihydrite. These adsorbents were associated with an alginate gel in order to produce composite materials that can be implemented in continuous reactors for the removal of anionic contaminants. The adsorption studies in batch reactor on LDH and ferrihydrite confirmed good removal efficiency for some anions. Ferrihydrite showed a higher adsorption capacity than LDH for the removal of inorganic anions. Increasing the Mg/Al ratio was favorable for the methyl orange (MO) adsorption, and an Mg/Al ratio of 3 (L3) was selected for the following work. Two protocols were evaluated for the integration of adsorbent into alginate gel: encapsulation and direct synthesis in the gel structure. The effect of crosslinking cation and the making of macroporosity were studied. The encapsulation of solids decreased slightly the adsorption ability of anions; however, the macroporosity counterbalances this negative effect of alginate gel. The MO adsorption studies with encapsulated beads showed that the increase of the bead size and the amount of solid in the beads were accompanied with a decrease in the adsorption capacity. The replacement of Ca2+ by Ba2+ strengthened the gel structure and improved the adsorption kinetics but decreased the adsorption capacity. The characterization of the support material prepared by direct synthesis in alginate gel showed a different structure from the expected materials (L3 or ferrihydrite), and therefore a different reactivity. The sorption mechanisms of various organic and inorganic anions were proposed for the studied adsorbents. The ferrihydrite/alginate beads prepared by encapsulation showed a good adsorption for all the anions used in this work, especially for inorganic anions (phosphate, chromate and arsenate); while those produced by direct synthesis in alginate gel removed only arsenate and phosphate essentially by a precipitation mechanism of the anions at the surface of the iron oxides and oxy-hydroxides. The sorption of MO in a continuous reactor showed that the increasing of the flow rate had a negative effect on sorption while higher initial concentration presented a favorable effect on the sorption, which is in accordance with results obtained in batch reactor. A desorption ratio of 30% for ferrihydrite/alginate macroporous beads (BPENFh-Ba) was observed in batch reactor with the possibility of reusing the adsorbent.This study confirms the performance and the possibility to use the composite materials of LDH or ferrihydrite in an alginate gel for the removal of anionic compounds contained in wastewater.

The intercalation of surfactant anions, namely sodium dodecyl sulphate, sodium benzene sulphonate and lauric acid, into commercial layered double hydroxides (LDH-CO3) with approximate composition [Mg0.654AI0.346 (OH)2](CO3)0.173.0.5H2O] was explored. LDH-CO3 is commercially available in bulk form owing to its large scale applications as a PVC stabiliser and acid scavenger in polyolefins. It is therefore of interest to investigate intercalation methods using LDH-CO3 as starting material. The intercalation method used was compared with the pre existing procedures, for instance the co-precipitation, ion exchange and regeneration methods. Due to the tenacity with which the carbonate ion is held in LDH-CO3, direct ion exchange is an intricate matter. Hence, in the regeneration method the carbonate ion is removed by thermal treatment and the LDH-surfactant is obtained by reaction of the LDH and surfactant in an aqueous medium. Nevertheless, the resulting products are impure and poorly crystallised, and only partial intercalation is achieved. The underlying principle of the current method is protonation of the carbonate anion to a monovalent anion that is easily exchanged with surfactant anions. Improved results were obtained when water-soluble organic acids were used, the most suitable being lower aliphatic carboxylic acids, e.g. acetic, butyric and hexanoic acid. In contrast, higher linear aliphatic carboxylic acids are preferentially intercalated to the anionic surfactants. In both cases the carboxylic acids are assumed to assist intercalation by facilitating the elimination of the carbonate ions present in the anionic clay galleries. X-ray diffraction analysis, thermal analysis and infrared spectroscopy confirmed the monolayer intercalation of LDH-dodecyl sulphate and LDH-dodecylbenzene sulphonate. In contrast, LDH-laurate featured a bilayer structure. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

Hierarchical arrangement of biological composites such as nacre and bone containing high filler (ceramic) content results in high strength and toughness of the natural material. In this study we mimic the design of layered bone microstructure and fabricate an optimal multifunctional bio-nanocomposite having strength, toughness and corrosion resistance. Poly (butylene adipate-co-terephthalate) (PBAT), a biodegradable polymer was used as a substrate material with the reinforcement of LDH (Layered double hydroxide) as a nanofiller in different concentrations to achieve enhancement in mechanical properties as well as processing related thermostability. Corrosion resistance was increased by mimicking a layered structured which incorporated a tortuous diffusion path.

<p>Ispitivani su dvostruki slojeviti hidroksidi, LDH i me&scaron;oviti oksidi nastali njihovom<br />razgradnjom, sa različitim sadržajem Mg-Al-Fe i pro&scaron;irenom supstitucijom aluminijuma.<br />Koprecipitacione metode male i velike prezasićenosti odabrane su za sintezu LDH op&scaron;te<br />formule [Mg1_-xM(III)_x(OH)₂](CO₃)_x/2 &sdot; mH₂O, gde M(III) pretstavlja Al i/ili Fe, a x udeo<br />trovalentnih anjona, x = M(III) / [M(II) + M(III)], variran u intervalu 0,15 &lt; x &lt; 0,7.<br />Katalizatori na bazi me&scaron;ovitih oksida sa gvožđem pogodni za upotrebu u redoks<br />reakcijama, formirani su nakon termičke aktivacije - razlaganja LDH. Izvr&scaron;ena je<br />karakterizacija me&scaron;ovitih oksida nastalih iz LDH, kao i netretiranih LDH, ispitivanjem<br />kristalne strukture (XRD), termičke stabilnosti (TG-DTA), teksture (adsorpcija N₂), redoks<br />(H₂ TPR) i kiselo-baznih karakteristika (NH₃ TPD), a utvrđena je i priroda prisutnih vrsta<br />gvožđa (Moessbauer spektroskopija). Pokazano je kako metoda pripreme i obim<br />supstitucije M(III) jona utiču na strukturne, povr&scaron;inske i redoks karakteristike LDH i<br />njihovih me&scaron;ovitih oksida u korelaciji sa katalitičkim svojstvima u odabranim test<br />reakcijama (razgradnja N₂O i redukcija sa NH₃). Utvrđeno je da na katalitičku aktivnost<br />dominantno utiču redoks karakteristike i priroda vrste gvožđa u me&scaron;ovitom oksidu, ali<br />takođe i strukturne karakteristike polaznog LDH, pri čemu je povr&scaron;inska struktura aktivnih<br />centara intervalentnog Fe²⁺-Fe³⁺gvožđa ključna za redoks procese ispitivanih reakcija.<br />Kod svih me&scaron;ovitih oksida dobijenih iz LDH aktivni centri imaju relativno jednake jačine,<br />dok razlike u katalitičkom pona&scaron;anju potiču od razlika u dostupnosti aktivnih centara.<br />Najbolje performanse u katalitičkim reakcijama pokazali su uzorci sa najmanjom<br />stabilno&scaron;ću inicijalnih LDH kod kojih je količina supstituisanih M(III) jona bila blizu<br />granice za inkorporaciju u LDH matricu (x = 0,5), a naročito uzorak sintetisan metodom<br />velike prezasićenosti sa malom količinom dodatne Al(OH)₃ faze.</p> / <p>Layered double hydroxides (LDHs) and derived mixed oxides with different Mg-Al-Fe content and extended aluminum substitution were investigated. High and low supersaturation precipitation methods were used for the synthesis of LDHs with general formula [Mg1_-x M(III)_x (OH)₂](CO₃)_x/2 &sdot; mH₂O where M(III) presents Al and/or Fe and x the content of trivalent ions, x = M(III) / [M(II) + M(III)], varied between 0.15 &lt; x &lt; 0.7. Iron-containing mixed oxides, suitable as catalysts for redox reactions, were formed after thermal activation - decomposition of LDH. Both, LDHs and derived mixed oxides were characterized with respect to crystalline structure (XRD), thermal stability (TG-DTA), textural (N₂ adsorption), redox (H₂ TPR) and acid-base properties (NH₃ TPD) as well as the nature of the iron species (Moessbauer spectroscopy). It was demonstrated how preparation method and the extent of M(III) substitution influence the structure, surface and redox properties of LDHs and derived mixed oxides in correlation to catalytic properties in chosen test reactions (N₂O decomposition and reduction with NH3). The catalytic behavior is mainly determined by the redox properties and the nature of the iron species in mixed oxides, but also by the structural properties of initial LDHs. It was confirmed that surface structure of intervalent Fe²⁺-Fe³⁺ iron active sites is crucial for the redox processes in chosen reactions. The strength of active sites is similar for all mixed oxides derived from LDH, but the differences in catalytic behavior arise from the differences in active sites accessibility. The best catalytic results were obtained when the stability of the initial LDH matrix was lowest e.g. when the amount of substituted M(III) was near the limit for the incorporation into LDH matrix (x = 0.5), especially for the sample synthesized with high superasaturation method containing a small amount of additional Al(OH)₃ phase.</p>

Ces travaux décrivent l'élaboration de latex hybrides de polymère / nanotubes d'Imogolite et polymère / nanofeuillets d'hydroxydes doubles lamellaires (HDL) en milieu aqueux dispersé. Les deux charges inorganiques ont été choisies pour leurs propriétés thermiques, mécaniques et pour leur anisotropie de forme, ce qui pourrait permettre l'élaboration de films nanostructurés. Les latex ont été synthétisés par une stratégie originale basée sur le procédé de polymérisation RAFT en émulsion. Cette stratégie consiste à utiliser des copolymères hydrophiles (macroRAFT), comportant à la fois des unités d'acide acrylique et un groupe trithiocarbonate terminal, comme agents de couplage et stabilisants. Dans un premier temps, ces macroRAFTs ont été adsorbés à la surface des nanoparticules inorganiques, puis l'extension de ces chaînes a été réalisée par la polymérisation d'un monomère hydrophobe selon un procédé semi-batch. Des nanotubes d'Imogolite décorés de particules de latex ou des nanotubes d'Imogolite encapsulés ont été obtenus, selon les conditions de synthèse adoptées. L'effet de différents paramètres sur la morphologie finale des particules hybrides a été étudié. La nature de l'agent macroRAFT s'est avérée être un paramètre clé pour le succès de l'encapsulation. La même stratégie a été utilisée en vue de l'encapsulation des HDL. Quelles que soient les conditions investiguées, des latex stables contenant des particules d'HDL encapsulées par du polymère ont été formés. Dans tous les cas, la morphologie des latex nanocomposites a été caractérisée par MET et cryo-MET et reliée à la méthode de modification de la surface et aux conditions de polymérisation. Enfin, les propriétés mécaniques ainsi que la microstructure des films hybrides de polymère / nanotubes d'Imogolite ont été étudiées par DMA et MET, respectivement, et reliées à la morphologie des particules de latex / This work describes the elaboration of hybrid latexes of polymer / Imogolite nanotubes and polymer / layered double hydroxyde (LDH) nanosheets in aqueous dispersed media. The two inorganic materials were chosen as fillers for their thermal and mechanical properties and especially for their shape anisotropy, which could lead to the formation of nanostructured films. The latexes were synthesized through an original polymerization strategy based on the RAFT process in emulsion. The strategy consists in the use of hydrophilic random copolymers, containing acrylic acid units and a thiocarbonylthio end group, as both coupling agents and stabilizers. These copolymers, herein named macroRAFT agents, were tethered to the surface of the inorganic nanoparticles and chain extended by the polymerization of a hydrophobic monomer in a semi-batch process. Polymer-decorated Imogolite nanotubes or encapsulated nanotube bundles were obtained according to the process conditions. The effect of different parameters on the final morphology and latex stability was studied, and the macroRAFT nature was proven to be the key factor to achieve encapsulation. The same strategy was then applied to LDH materials. The different conditions tested all led to the encapsulation of the nanosheets. In both cases, the morphology of the nanocomposite latexes was characterized by TEM and cryo-TEM and correlated with the surface modification and the experimental conditions. The mechanical properties and the microstructure of hybrid films of polymer / Imogolite were studied by DMA and TEM, respectively, and correlated with the latex particles morphology

Os Hidróxidos Duplos Lamelares (HDL) constituem uma classe de materiais que apresentam estrutura lamelar, consistindo de camadas positivamente carregadas de um hidróxido duplo, intercaladas com ânions hidratados no domínio interlamelar. Estes materiais têm recebido bastante atenção nos últimos tempos, devido ao baixo custo e relativa simplicidade de preparação, a possibilidade de combinação de uma variedade de cátions e ânions, aliados às propriedades que os HDL podem apresentar como: propriedades ácidas e básicas, \"efeito memória\", elevada área superficial, etc. Os HDL também podem ser utilizados em combinação com outros materiais, como por exemplo, óxido de grafeno, formando compósitos, com a finalidade melhorar as propriedades destes materiais. Podem ainda serem utilizados para a preparação de outros compósitos e/ou réplicas de carbono, por tratamento térmico de um HDL intercalado com um monômero, por exemplo, 4-vinil benzeno sulfonato (VBS), que pode ser polimerizado \"in situ\" e posteriormente carbonizado produzindo a réplica de carbono. A utilização dos materiais descritos anteriormente como suporte para imobilização de enzimas pode proporcionar uma plataforma alternativa para construção de dispositivos biossensores. O objetivo geral do trabalho foi a preparação e caracterização de materiais como HDL, Compósitos e/ou Réplicas de Carbono derivadas de HDL ou compósitos de HDL/ óxido de grafeno, como suporte da enzima Glicose Oxidase, estudando suas propriedades eletroquímicas, visando as potenciais aplicações destes materiais como biossensores. Para isto, foram preparados e caracterizados HDL de Mg-Al e Zn-Al intercalados com o ânion carbonato, pelo método de coprecipitação a pH variável; compósitos e/ou réplicas de carbono derivadas de um HDL precursor de Mg-Al-VBS, preparados, por coprecipitação a pH constante e compósitos de Mg-Al/óxido de grafeno que também foram preparados por coprecipitação a pH constante. Estes materiais foram utilizados na imobilização da enzima Glicose Oxidase (GOx), em eletrodos modificados e foi realizado o estudo eletroquímico dos mesmos e de suas potenciais aplicações. Foi possível observar que os HDL de Mg-Al-CO3, Zn-Al-CO3, Mg-Al-VBS e o compósito Mg-Al/óxido de grafeno exibiram boa cristalinidade, estabilidade térmica, e outras características como porosidade e superfícies positivamente carregadas, viabilizando a xiii utilização dos mesmos para a imobilização e estudo eletroquímico da enzima Glicose Oxidase. O estudo eletroquímico dos eletrodos modificados com estes materiais e a enzima Glicose Oxidase mostrou que os mesmos apresentam boa resposta catalítica frente ao substrato glicose e a importância destes materiais na atividade desta enzima. Os eletrodos modificados apresentaram boa sensibilidade, estabilidade à longo prazo e reprodutibilidade do método, podendo estes serem aplicados para a preparação de biossensores. / Layered Double Hydroxides (LDH) constitute a class of materials with a layered structure consisting of positively charged layers of a double hydroxide and hydrated anions intercalated in the interlayer domain. These materials have received much attention lately because they offer many advantages: they display acidic and basic properties, \"memory effect\", and high surface area; are inexpensive and easy to prepare; and can combine with a variety of cations and anions. Combination of LDH with materials like graphene oxide affords composites with improved properties as compared to the starting organic component. Heat treatment of LDH intercalated with a monomer such as 4-vinyl-benzene sulfonate (VBS), followed by \"in situ\" polymerization and carbonization, produces composites and/or carbon replica. The materials described above could be applied as support to immobilize enzymes and may provide an alternative platform for biosensor devices. In this study, we aimed to prepare and characterize LDH, composites and/or carbon replica derived from LDH, and LDH/graphene oxide composites and support glucose oxidase enzyme (GOx) on these matrixes. We investigated the electrochemical properties of the resulting materials and evaluated their potential application as biosensors. More specifically, we prepared and characterized Mg-Al and Zn-Al LDH systems intercalated with carbonate ion by the coprecipitation method; composites and/or carbon replica derived from a precursor LDH Mg-Al-VBS by coprecipitation at constant pH; and Mg-Al/graphene composites by coprecipitation at constant pH. We used these materials to immobilize GOx on modified electrodes and assessed the electrochemical activity and potential application of the immobilized enzyme as biosensor. Mg-Al-CO3, Zn-Al-CO3, Mg-Al-VBS LDH and Mg-Al/graphene oxide composite were crystalline, thermally stable, and porous and exhibited positively charged surface, which favored immobilization and electrochemical investigation of the GOx enzyme. The modified electrodes displayed good catalytic response to glucose, as substrate, and improved the activity of the enzyme as compared to GOx alone. Additionally, the modified electrodes were sensitive, stable, and reproducible, paving the way for their use in the design of biosensors.

A hipóxia-isquemia (HI) neonatal é uma causa importante de deficits neurológicos. Estimativas relatam que 3-5 em cada 1.000 nascidos vivos ocorrem encefalopatia neonatal, sendo que, encefalopatia hipóxico-isquêmica (EHI) moderada ou grave acomete 0,5-1/1000 dos nascidos vivos. Aproximadamente 10 a 60% das crianças com EHI morrem, e pelo menos 25% dos que sobrevivem, apresentam deficiência permanente, como paralisia cerebral, epilepsia e dificuldades na aprendizagem. Evidências clínicas e experimentais sugerem que a exposição a estímulos nocivos no início da vida pode resultar em mudanças duradouras no processamento sensorial. Apesar da magnitude do problema, pouco se conhece sobre a modulação da dor e mecanismos envolvidos durante um processo hipóxico-isquêmico em neonatos e suas conseqüências ao longo da vida. Sendo assim, a presente tese objetivou avaliar respostas comportamentais e bioquímicas de filhotes de ratos submetidos à hipóxia/isquemia no 7°dia de vida, avaliados em diferentes idades. Ninhadas de ratos Wistar machos foram randomizadas em 6 grupos experimentais: controle, hipóxia-isquemia, isquemia, hipóxia, sham-ischemia, sham-hipóxia. O modelo experimental utilizado foi de HI unilateral descrito por Levine (1960) e adaptado por Rice e colaboradores (1981), realizando-se isquemia através da oclusão da carótida esquerda e hipóxia com câmara hipóxica de 92% de nitrogênio e 8% de oxigênio. Avaliaram-se os animais no 14° (P14), 30°(P30) e 60° (P60) dias de vida. Para avaliação da (s) resposta (s): nociceptiva térmica foram utilizados testes de tail-flick e placa quente; e alodinia mecânica utilizou-se teste de Von Frey eletrônico. Para as avaliações dos biomarcadores foram utilizados kits comerciais de BDNF e TNF por métodos ELISA e LDH por espectrofotometria. A ativação neuronal foi quantificada em lâminas de imunoistoquímica de c-fos em regiões CA1 e giro dentado de hipocampo bilateral. Foi observado que ratos com hypoxia e/ou isquemia tiveram diminuição irreversível de neurônios com ativação por c-fos em área CA1 do hipocampo, região ipsilateral do insulto. Maior sensibilidade em animais com HI em P14 foi observado no teste do Von Frey, mas não foi observada em P30 e P60. Independentemente do grupo experimental, a idade do animal desempenhou um papel significativo na resposta de comportamento nociceptivo, bem como sobre o BDNF e dos níveis séricos de TNF-α, mas não sobre os níveis séricos de LDH. Em conclusão, o insulto cerebral da HI induz uma redução significativa e irreversível sobre a ativação neuronal ipisilateral à lesão, com a evidência de uma alteração da resposta comportamental nociceptiva manifestada no curto, mas não a médio ou longo prazo. Biomarcadores de neuroplasticidade, inflamação e danos celulares apresentaram poucas alterações sobre o insulto cerebral, mas mudanças mais pronunciadas foram observadas com relação à idade. / Neonatal hypoxia-ischemia (HI) is an important cause of neurological deficits. It is estimated that 3-5 in 1000 newborns suffer neonatal encephalopathy, and moderate or severe hypoxic-ischemic encephalopathy (HIE) in 0,5-1/1000 of the newborns. Approximately 10 to 60% of the children with HIE die, and at least 25% of the survivors present permanent deficits such as cerebral palsy, epilepsy and learning difficulties. Clinical and experimental evidence suggest that the exposure to noxious stimuli at the beginning of the life might result in long lasting changes in sensorial processing. Despite the magnitude of the problem, few is known regarding pain modulation and its involved mechanisms during the HI process in neonates and its life lasting consequences. Hence, the present thesis aimed to evaluate behavioral and biochemical responses in rats’ litters submitted to HI during their seventh day of life, evaluated at different ages. Male Wistar rats’ litters were randomized into 6 experimental groups: control, HI, ischemia, hypoxia, sham-ischemia and sham-hypoxia. The experimental model was the one of unilateral HI described by Levine (1960) and adapted by Rice et al (1981), inducing ischemia by occlusion of the left carotid artery, and hypoxia using hypoxic chamber with nitrogen 92% and oxygen 8%. Animals were evaluated in their 14th (P14), 30th(P30) and 60th (P60) postnatal day. To assess the thermal nociceptive response the tail flick and hot plate test were employed; and mechanical allodynia was assessed by means of the digital Von Frey test. To evaluate biomarkers, commercial BDNF and TNF kits with ELISA, and LDH kits with spectrophotometry were used. Neuronal activation was quantified by c-fos immunohistochemistry in CA1 and dentate gyrus of bilateral hippocampi. It was observed that rats with hypoxia and/or ischemia had irreversible diminution of neurons with c-fos activation in the CA1 area of the hippocampus ipsilateral to the insult. Higher sensitivity in animals with HI at P14 was observed in the Von Frey test, but was not observed at P30 or at P60. Irrespective of the experimental group, animals’ age played a significant role in the nociceptive behavioral response, as well as on the BDNF and TNF-α serum levels, but not on the LDH serum levels. In conclusion, cerebral HI insult induces a significant and irreversible reduction on neuronal activation ipsilateral to the insult, with evidence of a significant alteration on the nociceptive behavioral response manifested in the short, but not in the medium or long term. Biomarkers of neuroplasticity, inflammation and cellular damage present few alterations after the cerebral insult, however more pronounced changes were observed related with age.