Three dimensional printing (3DP) is one of the most important solid freeform fabrication (SFF) methods that can produce any material with desired 3D shape by using suitable powder-binder formulations. It differs from the standard molding operations in that it can produce a complicated shapes by a software driven instrument in a laminated fashion and the cost is lower. This method can be applied in a very wide area including drug release operations, biomaterial production especially for bone fixation, prototype production for all purposes, wound dressing etc. It can also be used in obtaining edible objects by using natural polysaccharides with water based binders. In this study, it is aimed to understand the gelling behaviour of some of the gelling materials, which are alginates, pectins and carageenans, and effect of various factors on the production of confectionary objects by means of 3DP process. Effect of multivalent cations, especially Ca2+ ion, on the gelling behaviour of these materials are investigated. The egg-box structure obtained between the polymer segments increases the water holding capacity of the materials and much more chewy structures can be obtained. The molecular changes are followed by Fourier Transform infrared spectroscopy (FTIR). In 3DP applications, the composition of powder and binder, pH, temperature, relative humidity (RH) and machine parameters are important factors affecting the texture of the final object. The texture of the produced specimens is examined by using a texture analyzer and maximum force values are given as g/cm at failure. Alginate and carrageenans are found to be more effective in obtaining chewy textures with Ca2+ ion content in sugar based matrices and optimization of machine parameters are performed to obtain a higher resolution on the specimens.

The present work was undertaken to develop a composite osmotic distillation (OD) membrane consisting of a thin hydrogel coating on a microporous hydrophobic substrate for the concentration of aqueous feeds containing surface-active agents. The range of OD applications using the hydrophobic membrane alone have been severely limited by the propensity for membrane wet-out when contacted by amphiphilic agents such as oils, fats and detergents. Wet-out allows the feed solution to track freely through the membrane pores with a resulting loss of solutes and a decrease in selectivity. The rationale for the approach taken was based on the hypothesis that the high water selectivity of the hydrophilic coating would maintain good water mass transfer to the underlying hydrophobic substrate but exclude other components including surface-active agents. The first stage of this work involved the identification of potential coating materials and the fabrication and structural characterization of films of these materials to determine their suitability. The second stage involved the development of techniques to facilitate adhesion of the hydrophilic coatings to the hydrophobic substrate, and the testing of the resulting composite membranes for OD performance and resistance to wet-out by surface-active agents. Sodium alginate was selected as the major coating component on the basis of its non-toxicity and its potential for stable hydrogel formation. Structural characterization of noncrosslinked films and films crosslinked using a water-soluble carbodiimide (WSC) was carried out using differential scanning calorimetry (DSC), Fourier Transform infrared spectroscopy (FT-IR) and swelling measurements. Maximum crosslinking through esterification of hydroxyl and carboxylic acid groups on adjacent polymer strands using the film immersion method was achieved with a non-solvent (ethanol) concentration of 60 vol % and a WSC concentration of 100 mM at pH 4. These conditions resulted in a hydrogel with an equilibrium water content of 60 wt %. DSC measurements of noncrosslinked and crosslinked alginate films showed an increase in crystallinity and hence rigidity on crosslinking. Therefore, several coatings were prepared as blends of sodium alginate and amorphous highly flexible carrageenan gum in order to meet the flexibility requirements of a membrane subjected to varying operating pressures in an industrial OD plant. Structural characterization with respect to polymer blend ratio was carried out using scanning electron microscopy (SEM), DSC, X-ray diffraction (XRD). The optimisation for crosslinking conditions was undertaken as for sodium alginate alone. Optimum conditions for film preparation were 20 wt % carrageenan content and a crosslinking medium containing 60 vol % non-solvent (ethanol) and 120 mM WSC at pH 4. These conditions produced a hydrogel with an equilibrium water content of 85 wt %. Two different techniques were employed to anchor the coatings on substrate PTFE membranes. For membranes with a nominal diameter of 0.2 µm, the technique involved surface tension adjustment of the coating solution by ethanol addition in order to enhance penetration of the coating solution meniscus into the substrate pores. This was followed by polymer precipitation by the selective removal of water using OD to provide structural interlocking. T-peel strength measurements showed that this technique resulted in a ten-fold increase in adhesion strength when compared with a coating cast without surface tension adjustments. For membranes with a nominal diameter of 0.1µm, an interfacial bonding agent, myristyltrimethylammonium bromide (MTMA), was used. This technique gave a three-fold increase in adhesion strength relative to that of coating cast without the use of MTMA. The composite membranes were tested in extended OD trials using pure water and feeds containing limonene, the major surface-active components of orange oil. The sodium alginate-carrageenan blend membrane, which was the preferred membrane based on flexibility and water sorption considerations, was also tested against full-cream milk and an industrial detergent, sodium dodecylbenzene sulfonate (DBS). The results indicated that the coatings offered little resistance to water transport and were effective in providing protection against membrane wet-out. Durability trials showed that the composite membranes retained their integrity in water for a minimum of 30 days. Overall, this study has expanded the potential applications of OD to include many important industrial concentration steps that are currently being undertaken by conventional processes with unsatisfactory results. These include the concentration of citrus juices, full-cream milk and nuclear power plant liquid waste. These feeds contain limonene, fats and detergents respectively, all of which wet out unprotected hydrophobic membranes.

Particles and macromolecular components, including biopolymers (protein and carbohydrate), are viewed as the main foulants in the complex feed submerged membrane filtration systems such as membrane bioreactor (MBR). This work focused on two aspects of fouling in complex fluids: 1- Assessing fouling propensity and mechanisms for various model solutions. 2- Using of two specific solutions modelling biomass found in MBR for a better understanding of the fouling mechanisms in submerged MBR processes. Filtrations were carried out with 0.22 ??m PVDF hollow fibre membrane. Alginate was used as a model for polysaccharide, bovine serum albumin (BSA) as a model for protein, (un)washed yeast and bentonite were representing suspended solid contents. According to the data obtained during this study the fouling propensity of each model solution was classified as follow in a decreasing order: Alginate &gt unwashed yeast &gt washed yeast &gt BSA &gt bentonite for one-component solutions; and Alginate-washed yeast &gt Alginate-BSA &gt Alginate-bentonite &gt Alginate-unwashed yeast for two-component solutions. Introducing the alginate increased the reversible fouling (except BSA). Passive adsorption had a significant effect on fouling of alginate even before the beginning of the filtration. Washed yeast and a mixture of washed yeast + BSA were then used as model solutions to simulate the activated sludge found in MBR. The concentration of washed yeast and BSA used in this study were calculated in order for the characterisations of the two model solution to match (in terms of biopolymer contents) those of MBR biomasses reported in the literature. By rinsing, backwashing and chemical cleaning of the membrane, three fouling layers of upper, intermediate and lower were defined respectively. Results obtained from the analysis of the biopolymers found in the cleaning solutions allow a better understanding of the fouling mechanisms occurring for the two model solutions used in this study: for washed yeast, the lower layer and for washed yeast + BSA , the upper and intermediate layers were found to have relatively high biopolymeric composition. This was explained by higher concentration of solids on the membrane surface and by higher biopolymer interactions when washed yeast was mixed with BSA.

Made available in DSpace on 2016-08-12T19:15:20Z (GMT). No. of bitstreams: 1 LaianeTS_DISSERT.pdf: 999860 bytes, checksum: 8dc5867c70f5fc730dd9ff2cb969005b (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The responses to mechanical damage caused by minimal processing can accelerate the loss of quality and modify the sensory attributes. Besides cooling, which is considered the main technique available to retard the undesirable effects of minimal processing, the use of barriers to O2/CO2 and water vapor can contribute in controlling senescence, maintaining the quality and extending the shelf-life. The objective of this study was to develop an edible coating based on mango puree and sodium alginate with minimal permeability to water vapor and the potential to form a thin gel layer around 'Tommy Atkins' minimally processed mango slices (MPM), capable of controlling gas exchange and water loss by the product, in order to maintain its quality and retain volatile compounds for a longer time. Eleven films were prepared, according to a central composite design with two variables, namely alginate concentration in the coatings and immersion time in calcium chloride. In a second part of the experiment, 'Tommy Atkins' mangoes, bought in the market, were washed, sanitized, peeled and cut into slices. MPM were immersed in the film forming solution for 30 seconds, and then in calcium chloride (1%) for 15 seconds, subsequently being disposed for 60 minutes on stainless steel sieve to drain. After this processing, 200g MMP were packed in polyethylene terephthalate trays with lids and stored under refrigeration (10 ± 2ºC) for six days. Every three days samples were collected to quantify the mass loss, pH, titratable acidity (TA), soluble solids (SS), SS/TA ratio, vitamin C, total sugars, polyphenoloxidase activity and volatile compounds. The experiment was conducted using CRD in 3 x 3 factorial design, with three treatments (control plus two coatings) in three storage times (1, 3, and 6 days). Data was subjected to analysis of variance; means of analysis of volatile compounds were compared by the method of Scott-Knott at 5% probability, and the average remaining analyses were compared by Tukey test at 5%. The edible films resulted in different water vapor permeabilities (WVP) as a function of the variables analyzed. The lowest WVP under the conditions used was 0.31 kPa mm-1 m-2, for 1% alginate and 15 seconds of immersion in CaCl2, and was therefore adopted as reference for the preparation of edible coatings. Analyses in gas chromatography-mass spectrometry revealed -3-carene as major constituent in mango aroma, and the same was used in this study as an indicator to assess the retention of volatile compounds of edible coatings. The mangoes coated with mango puree + sodium alginate (1%) exhibited the highest levels of this compound (64.47%). The edible coating (mango puree + sodium alginate) was efficient in maintaining the quality and retaining the -3-carene in mangos 'Tommy Atkins , stored at 10ºC for six days / As respostas aos danos mecânicos provocados pelo processamento mínimo podem acelerar a perda de qualidade e modificar os atributos sensoriais. Além da refrigeração, que é considerada a principal técnica disponível para retardar os efeitos indesejáveis do processamento mínimo, o uso de barreiras ao O2/CO2 e vapor d água pode contribuir no controle dos processos de senescência, na manutenção da qualidade e no prolongamento da vida útil o suficiente para a distribuição, comercialização e consumo. O objetivo desse trabalho foi elaborar um revestimento comestível à base de purê de manga e alginato de sódio com mínima permeabilidade ao vapor d água e com potencial para formar uma fina camada de gel capaz de controlar as trocas gasosas e a perda de água pelo produto, visando manter a qualidade e principalmente reter os compostos voláteis em manga Tommy Atkins minimamente processada (MMP) por maior período de tempo. Foram elaborados onze filmes, de acordo com um delineamento composto central, com duas variáveis, a saber, concentração de alginato nos filmes e tempo de imersão em cloreto de cálcio. Mangas Tommy Atkins , compradas no mercado, foram lavadas, sanitizadas, descascadas e cortadas em fatias. A MMP foi imersa na solução filmogênica, por 30 segundos, e em seguida, em cloreto de cálcio (1%), por 15 segundos, sendo posteriormente disposta, por 60 minutos, em peneira de inox para drenagem. Após esse processamento, 200g de MMP foram acondicionadas em bandejas PET com tampa e armazenadas sob refrigeração (10±2ºC), por seis dias. A cada três dias foram retiradas amostras para a quantificação da perda de massa, pH, acidez titulável, sólidos solúveis, relação SS/AT, vitamina C, açúcares totais, atividade da polifenoloxidase e compostos voláteis. O experimento foi instalado usando DIC em esquema fatorial 3 x 3, com três tratamentos (controle mais dois filmes) em três tempos de armazenamento (1, 3, e 6 dias). Os dados foram submetidos à análise de variância e as médias da análise dos compostos voláteis foram comparadas entre si pelo método de Scott-Knott à 5% de probabilidade, e as médias das demais análises foram comparadas entre si pelo teste de Tukey à 5%. Os filmes confeccionados apresentaram diferentes taxas de permeabilidade ao vapor d água (PVA) em função das variáveis analisadas. A menor PVA dentro das condições utilizadas foi de 0,31 mm kPa-1 m-2, com 1% de alginato e 15 segundos de imersão em CaCl2, portanto, foi adotada como referência para a elaboração de revestimentos comestíveis. Análises em cromatografia gasosa acoplada a espectrometria de massas revelaram -3-careno como constituinte majoritário no aroma da manga, e o mesmo foi utilizado nesse trabalho como indicativo para avaliar a retenção dos compostos voláteis dos revestimentos comestíveis. As mangas revestidas com purê de manga + alginato de sódio (1%) exibiram os maiores teores desse composto (64,47 %). O revestimento comestível (purê de manga + alginato de sódio) se mostrou eficiente em manter a qualidade e em reter o -3-careno, em mangas Tommy Atkins minimamente processadas, armazenadas à 10ºC, por seis dias

Made available in DSpace on 2016-08-12T19:18:42Z (GMT). No. of bitstreams: 1 LaianeTS_DISSERT.pdf: 999860 bytes, checksum: 8dc5867c70f5fc730dd9ff2cb969005b (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The responses to mechanical damage caused by minimal processing can accelerate the loss of quality and modify the sensory attributes. Besides cooling, which is considered the main technique available to retard the undesirable effects of minimal processing, the use of barriers to O2/CO2 and water vapor can contribute in controlling senescence, maintaining the quality and extending the shelf-life. The objective of this study was to develop an edible coating based on mango puree and sodium alginate with minimal permeability to water vapor and the potential to form a thin gel layer around 'Tommy Atkins' minimally processed mango slices (MPM), capable of controlling gas exchange and water loss by the product, in order to maintain its quality and retain volatile compounds for a longer time. Eleven films were prepared, according to a central composite design with two variables, namely alginate concentration in the coatings and immersion time in calcium chloride. In a second part of the experiment, 'Tommy Atkins' mangoes, bought in the market, were washed, sanitized, peeled and cut into slices. MPM were immersed in the film forming solution for 30 seconds, and then in calcium chloride (1%) for 15 seconds, subsequently being disposed for 60 minutes on stainless steel sieve to drain. After this processing, 200g MMP were packed in polyethylene terephthalate trays with lids and stored under refrigeration (10 ± 2ºC) for six days. Every three days samples were collected to quantify the mass loss, pH, titratable acidity (TA), soluble solids (SS), SS/TA ratio, vitamin C, total sugars, polyphenoloxidase activity and volatile compounds. The experiment was conducted using CRD in 3 x 3 factorial design, with three treatments (control plus two coatings) in three storage times (1, 3, and 6 days). Data was subjected to analysis of variance; means of analysis of volatile compounds were compared by the method of Scott-Knott at 5% probability, and the average remaining analyses were compared by Tukey test at 5%. The edible films resulted in different water vapor permeabilities (WVP) as a function of the variables analyzed. The lowest WVP under the conditions used was 0.31 kPa mm-1 m-2, for 1% alginate and 15 seconds of immersion in CaCl2, and was therefore adopted as reference for the preparation of edible coatings. Analyses in gas chromatography-mass spectrometry revealed -3-carene as major constituent in mango aroma, and the same was used in this study as an indicator to assess the retention of volatile compounds of edible coatings. The mangoes coated with mango puree + sodium alginate (1%) exhibited the highest levels of this compound (64.47%). The edible coating (mango puree + sodium alginate) was efficient in maintaining the quality and retaining the -3-carene in mangos 'Tommy Atkins , stored at 10ºC for six days / As respostas aos danos mecânicos provocados pelo processamento mínimo podem acelerar a perda de qualidade e modificar os atributos sensoriais. Além da refrigeração, que é considerada a principal técnica disponível para retardar os efeitos indesejáveis do processamento mínimo, o uso de barreiras ao O2/CO2 e vapor d água pode contribuir no controle dos processos de senescência, na manutenção da qualidade e no prolongamento da vida útil o suficiente para a distribuição, comercialização e consumo. O objetivo desse trabalho foi elaborar um revestimento comestível à base de purê de manga e alginato de sódio com mínima permeabilidade ao vapor d água e com potencial para formar uma fina camada de gel capaz de controlar as trocas gasosas e a perda de água pelo produto, visando manter a qualidade e principalmente reter os compostos voláteis em manga Tommy Atkins minimamente processada (MMP) por maior período de tempo. Foram elaborados onze filmes, de acordo com um delineamento composto central, com duas variáveis, a saber, concentração de alginato nos filmes e tempo de imersão em cloreto de cálcio. Mangas Tommy Atkins , compradas no mercado, foram lavadas, sanitizadas, descascadas e cortadas em fatias. A MMP foi imersa na solução filmogênica, por 30 segundos, e em seguida, em cloreto de cálcio (1%), por 15 segundos, sendo posteriormente disposta, por 60 minutos, em peneira de inox para drenagem. Após esse processamento, 200g de MMP foram acondicionadas em bandejas PET com tampa e armazenadas sob refrigeração (10±2ºC), por seis dias. A cada três dias foram retiradas amostras para a quantificação da perda de massa, pH, acidez titulável, sólidos solúveis, relação SS/AT, vitamina C, açúcares totais, atividade da polifenoloxidase e compostos voláteis. O experimento foi instalado usando DIC em esquema fatorial 3 x 3, com três tratamentos (controle mais dois filmes) em três tempos de armazenamento (1, 3, e 6 dias). Os dados foram submetidos à análise de variância e as médias da análise dos compostos voláteis foram comparadas entre si pelo método de Scott-Knott à 5% de probabilidade, e as médias das demais análises foram comparadas entre si pelo teste de Tukey à 5%. Os filmes confeccionados apresentaram diferentes taxas de permeabilidade ao vapor d água (PVA) em função das variáveis analisadas. A menor PVA dentro das condições utilizadas foi de 0,31 mm kPa-1 m-2, com 1% de alginato e 15 segundos de imersão em CaCl2, portanto, foi adotada como referência para a elaboração de revestimentos comestíveis. Análises em cromatografia gasosa acoplada a espectrometria de massas revelaram -3-careno como constituinte majoritário no aroma da manga, e o mesmo foi utilizado nesse trabalho como indicativo para avaliar a retenção dos compostos voláteis dos revestimentos comestíveis. As mangas revestidas com purê de manga + alginato de sódio (1%) exibiram os maiores teores desse composto (64,47 %). O revestimento comestível (purê de manga + alginato de sódio) se mostrou eficiente em manter a qualidade e em reter o -3-careno, em mangas Tommy Atkins minimamente processadas, armazenadas à 10ºC, por seis dias

Ces travaux visent à déterminer l‘intérêt de deux types de nanosystèmes (NS) coeur-couronne dans des applications dermatologiques ou cosmétiques. Les nanocapsules lipidiques (LNC) sont obtenues par une méthode déjà décrite dans la littérature. Leur formule est modifiée pour incorporer un actif cosmétique d‘intérêt. Les nanocapsules d‘alginate (ANC) sont développées au moyen de plans d‘expériences. Elles sont composées d‘un coeur huileux et d‘une coque d‘alginate de calcium gélifiée obtenue par gélification ionique de surface d‘une nanoémulsion. Des méthodes basées sur le phénomène de fluorescence nous permettent de mettre en évidence l‘endocytose des ANC par les kératinocytes. Leur contenu est rapidement libéré dans le cytoplasme. Une étude sur différents modèles ex vivo montre que les deux nanosystèmes permettent aux molécules encapsulées d‘atteindre les couches vivantes de l‘épiderme. ANC et LNC sont stables plusieurs mois dispersées dans des formes galéniques semi-solides. Ces deux NS sont donc adaptés à la délivrance de molécules actives dans la peau. / Two types of core-shell nanosystems have been evaluated for dermatological and cosmetic applications. Lipid nanocapsules (LNC) are obtained by a method that has already been described in the literature. Their composition is adapted for incorporation of a specific cosmetic ingredient. Alginate nanocapsules (ANC) are developed with the aid of experimental design. They consist of a triglyceride core with a rigid calcium alginate shell obtained by ionic gelation of the surface of a nanoemulsion. By incorporating fluorophores into these nanosystems, they can be studied by advanced spectral fluorescence imaging methods. We were thus able to show that ANC are first internalized into keratinocytes by endocytosis, and once inside the cells, their contents are rapidly released into the cytoplasm. A study of different ex vivo skin model systems has shown that both nanosystems enable active substances to reach the living epidermis. When incorporated into gels similar to those used as galenic forms for topical administration, LNC and ANC remain stable for months. They can thus be used as vectors for delivering active substances to the skin.

Baker´s yeast (Saccharomyces cerevisiae) were magnetically modified by three different methods, namely, surface modification by magnetic fluid, entrapment of cells into alginate and covalent immobilization on particles of magnetic chitosan. The ability of H2O2 decomposition was tested for all types of modification. It is apparent that the most amount of hydrogen peroxid was degraded by magnetic fluid - modified cells (84-95%), while the efficiency of cell which were modified by other methods was much lower (40-60%). Thanks to immobilization on particles of magnetic chitosan, we made completely new type of magnetic material, which was tested for adsorption of Crystal violet and Safranin O. It was founded that magnetic chitosan adsorbs no dyes, so all adsorption belongs to immobilized yeast. The maximum adsorption capacities were determined using Langmuire isotherm at 69,4 mg/g for Crystal violet and 99,0 mg/g for Safranin O.

Background: Collagens of marine origin are applied increasingly as alternatives to mammalian collagens in tissue engineering. The aim of the present study was to develop a biphasic scaffold from exclusively marine collagens supporting both osteogenic and chondrogenic differentiation and to find a suitable setup for in vitro chondrogenic and osteogenic differentiation of human mesenchymal stroma cells (hMSC). Methods: Biphasic scaffolds from biomimetically mineralized salmon collagen and fibrillized jellyfish collagen were fabricated by joint freeze-drying and crosslinking. Different experiments were performed to analyze the influence of cell density and TGF-β on osteogenic differentiation of the cells in the scaffolds. Gene expression analysis and analysis of cartilage extracellular matrix components were performed and activity of alkaline phosphatase was determined. Furthermore, histological sections of differentiated cells in the biphasic scaffolds were analyzed. Results: Stable biphasic scaffolds from two different marine collagens were prepared. An in vitro setup for osteochondral differentiation was developed involving (1) different seeding densities in the phases; (2) additional application of alginate hydrogel in the chondral part; (3) pre-differentiation and sequential seeding of the scaffolds and (4) osteochondral medium. Spatially separated osteogenic and chondrogenic differentiation of hMSC was achieved in this setup, while osteochondral medium in combination with the biphasic scaffolds alone was not sufficient to reach this ambition. Conclusions: Biphasic, but monolithic scaffolds from exclusively marine collagens are suitable for the development of osteochondral constructs.

Fundação de Apoio a Pesquisa e à Inovação Tecnológica do Estado de Sergipe - FAPITEC/SE / Aedes aegypti is the main vector of the dengue virus, urban yellow fever and emerging arboviruses in Brazil as zika and chikungunya. The use of chemical pesticides is still the main control mechanism vector, their overuse has led to the emergence of resistant insects besides mammalian toxicity and the environment. Essential oils such as essential oil Sizygum aromaticum (OESA) is an alternative in control of Ae. aegypti.In this context , the aim of this study was to develop and characterize nanostructured systems from the use of PPG -5 CETETH -20 ( cetyl alcohol propoxylated 5 OP ethoxylate 20 EO) , water, sodium alginate and essential oil Sizygum aromaticum ( OESA ) with potential application in larvicide control of Ae. aegypti. The systems were obtained by phase diagram composed of water, oleic acid, PPG-5 CETETH-20 (OA)in the ratio 2: 1 and OESA, and characterized by techniques polarized light microscopy (MLP), Smallangle Xray scattering(SAXS) and rheological analysis.In this diagram, we chose a liquid crystalline phase precursor to polymer incorporation of sodium alginate, to increase the physical stability of the system. Were also made in water increases precursor and then characterized by such techniques. The larvicidal activity was evaluated from the determination of the median lethal concentration (LC50) against Ae. aegypti. According to the results the main constituent of OESA was eugenol (76.75 %), oil yield was 3.66% (w / v) and density of 1,04g / ml. We observed four distinct regions of the diagram, liquid crystal (LC) emulsion (ME), microemulsion (ME) and phase separation. Through the images of MLP was observed isotropic systems as (MEs) and anisotropic systems as lamellar CLs.The SAXS measurements confirmed the structures visualized by MLP, showing broad peaks of low intensity for MEs, phase transition and the ratio between CL lamellar peaks of 1: 2: 3. The study showed that the rheological properties of the systems and MEs phase transition are Newtonians and LCs are non-Newtonian. With the aqueous phase the increased phase precursor showed a greater degree of structuring, becoming lamellar liquid crystalline systems. Confirmed through the MLP techniques to display "Maltese crosses '' SAXS with ratios of 1: 2: 3 and rheological analysis with an increase in storage modulus. After incorporating polymer, systems are presented anisotropic with lamellar system characteristics and hexagonal system having more than one set of lamellae observed in the MLP and confirmed by SAXS measurements, which showed ratios of 1: 2: 3 to lamellar CL and 1: 1.73: 2: 2.64 hexagonal CL. In rheological analysis showed an increase in independent storage modulus of the characteristic frequency of structured systems.For the larvicidal activity, A2 and F8 samples showed LC50 8.14 and 3.37 ppm, respectively, indicating the presence of the polymer contributed to a better larvicidal activity. Thereby, it can be concluded that there were obtained phase precusores with a potential use against Ae. aegypti larvae. / Aedes aegypti é o principal vetor dos vírus da dengue, febre amarela urbana e arboviroses emergentes no Brasil, como chikungunya e zika. O uso de inseticidas químicos ainda é o principal mecanismo de controle do vetor, seu uso indiscriminado tem provocado o surgimento de insetos resistentes além da toxicidade aos mamíferos e ao meio ambiente. Os óleos essenciais tais como o óleo essencial de Sizygum aromaticum (OESA) surge como alternativa no controle do Ae. aegypti. Neste contexto, o objetivo deste trabalho foi desenvolver e caracterizar sistemas nanoestruturados a partir da utilização de PPG-5 CETETH-20 (Álcool cetílico propoxilado 5 OP etoxilado 20 OE), água, alginato de sódio e óleo essencial de Sizygum aromaticum (OESA) com potencial aplicação no controle larvicida do Ae. aegypti. Primeiramente, foi feita a extração e a caracterização do OESA. Os sistemas foram obtidos através da construção do diagrama de fases composto por água, PPG-5 CETETH-20: ácido oléico (AO) na proporção 2:1 e OESA, e caracterizados através das técnicas de microscopia de luz polarizada (MLP), espalhamento de raios X a baixo ângulo (SAXS) e análise reológica. Neste diagrama optou-se por um precursor de fase líquido cristalina para incorporação do polímero alginato de sódio, a fim de aumentar a resistência do sistema ao intumescimento. Também foram feitos acréscimos de água no precursor e em seguida caracterizados pelas técnicas citadas. A atividade larvicida foi avaliada a partir da determinação da concentração letal média (CL50) contra as larvas do Ae. aegypti. De acordo com os resultados obtidos o principal constituinte do OESA foi o eugenol (76,75%), o rendimento do óleo foi de 3,66% (p /v) e densidade de 1,04 g/mL. Foram observadas quatro regiões distintas no diagrama, cristal líquido (CL), emulsão (EM), microemulsão (ME) e separação de fases. Através das imagens de MLP foi possível observar sistemas isotrópicos como MEs e sistemas anisotrópicos como CLs lamelares. As medidas de SAXS confirmaram as estruturas visualizadas por MLP, exibindo picos largos e de baixa intensidade para MEs, transição de fase e razão entre os picos de CL lamelar de 1: 2: 3. O estudo das propriedades reológicas demonstrou que os sistemas MEs e transição de fase são newtonianos e os CLs são não-newtonianos. Com o aumento de fase aquosa o precursor de fase apresentou um maior grau de estruturação, transformando-se em sistemas líquidos cristalinos lamelares. Confirmado através das técnicas de MLP com a visualização de “cruzes de malta‟‟, SAXS com razões de 1: 2: 3 e análise reológica apresentando um aumento no módulo de armazenamento. Após a incorporação do polímero, os sistemas apresentaram-se anisotrópicos com mistura de fases, possuindo características de sistema Lamelar e sistema hexagonal, observados na MLP e confirmados pelas medidas de SAXS, onde apresentaram razões de 1: 2: 3 e 1: 1,73: 2: 2,64 característicos de CL lamelares e hexagonais. Através da análise reológica foi possível observar um aumento no módulo de armazenamento independente da freqüência, característico de sistemas estruturados. Para a atividade larvicida, as amostras A2 e F8 demonstraram CL50 de 8,14 e 3,37 ppm, respectivamente, indicando que a presença do polímero contribuiu para uma maior atividade larvicida. Desse modo,pode-se concluir que foram obtidos precursores de fase com potencial uso contra as larvas de Ae. aegypti.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / With the purpose to develop environmentally appropriate materials, scales of the Piau fish and sodium alginate were used as precursor materials for the preparation of new ecomaterials which were used in the removal of the herbicide Paraquat and ions Co(II) and Cu(II). The hybrid material obtained from the reaction between the polysaccharide and scales was designated as ALG/ESC, and the hybrid ALG/ESC-CaCl2 was obtained from the crosslinking of the ALG/ESC with calcium chloride. The materials were characterized by FTIR, TG, SEM, XRD and determination of the point of zero charge (PZC). Changes in the peak observed in the FTIR spectrum of the ALG/ESC confirmed the existence of chemical interactions between Ca(II) of the hydroxyapatite present in fish scales, and the carboxylate groups of the sodium alginate. In the spectrum of ALG/ESC-CaCl2, bands were observed to be considerably narrower, due to crosslinking with the Ca(II) ions and tension of the carboxylate group that increases to accommodate the coordination structure around the Ca(II). It was observed an increase in sample thermal stability of the ALG/ESC-CaCl2 when compared to ALG/ESC, indicating the formation of the "egg box" structure. The SEM micrographs exhibited the presence of hydroxyapatite crystals on the surface of the ALG/ESC, and a homogeneous surface on the ALG/ESC-CaCl2 beads. Comparison between the X-ray diffraction profiles of the precursors (pure scales, ESC, and pure alginate, ALG) and those of the ALG/ESC and ALG/ESC-CaCl2 indicated that changes occurred due to incorporation of the hydroxyapatite structure in the alginate. From the PZC values of the materials, it was suggested that, in a general way, the interactions were controlled by electrostatic attractions between negatively charged surface groups and the cationic paraquat, or free Co(II) and Cu(II) ions, that are present in the solution, or between species of cobalt and copper in their anionic form and the surface groups that presented themselves as positively charged in the investigated pH range. From adsorption experiments carried out using the technique of batch with samples of solutions of the herbicide Paraquat and salts of copper and cobalt, the amount of adsorbed species per gram of adsorbent, Nf was determined. The values of Nf showed the highest affinity of the hybrid ALG/ESC-CaCl2 for the herbicide and the Co(II) and Co(II) ions. The adsorption rates were evaluated using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models. It was found that the data did present a good fit to the traditional intraparticle diffusion model. The data obtained from this model suggested that processes, other than simple intraparticle diffusion, may be occurring simultaneously. / Buscando desenvolver materiais ambientalmente adequados, foram utilizadas escamas do peixe Piau e Alginato de Sódio como materiais precursores para preparação de novos ecomateriais que foram utilizados na remoção do herbicida Paraquat e de íons Co(II) e Cu(II). O material híbrido obtido da reação entre o polissacarídeo e as escamas foi designado como ALG/ESC, sendo o híbrido ALG/ESC-CaCl2 obtido a partir da reticulação do ALG/ESC com Cloreto de Cálcio. Os materiais foram caracterizados por FTIR, TG, MEV, DRX e determinação do ponto de carga zero (PCZ). No espectro de FTIR do ALG/ESC deslocamentos de picos para regiões de maiores comprimentos de onda indicaram a existência da interação química entre íons Ca(II) da hidroxiapatita, presentes na escama de peixe, e os grupos carboxilato do Alginato de Sódio. No espectro do ALG/ESC-CaCl2 foram observadas bandas consideravelmente mais estreitas, devido à ligação cruzada com os íons Ca(II) e pela tensão do grupo carboxilato que aumenta para acomodar a estrutura de coordenação em torno do Ca(II). O material ALG/ESC-CaCl2, quando comparado com o ALG/ESC, apresentou-se mais estável termicamente, indicando a formação da estrutura caixa de ovos . As micrografias evidenciaram a presença de cristais de hidroxiapatita na superfície das esferas de ALG/ESC, e uma superfície homogênea nas esferas ALG/ESC-CaCl2. Foram observadas mudanças nos padrões de difração de raios X, quando comparados aos dos precursores (escamas puras, ESC, e Alginato puro, ALG) que ocorreram devido à incorporação da hidroxiapatita na estrutura do Alginato. A partir dos valores do PCZ dos materiais sugeriu-se que, de um modo geral, as interações ocorrem através de atrações eletrostáticas entre grupos superficiais carregados negativamente e o Paraquat catiônico, ou íons Co(II) e Cu(II) livres que se encontram presentes na solução ou ainda entre espécies de cobalto e cobre na sua forma aniônica e os grupos superficiais que apresentavam-se carregados positivamente na faixa de pH investigada. Através de experimentos de adsorção realizados usando a técnica de batelada com amostras de soluções do herbicida Paraquat e de sais de cobre e cobalto, determinou-se a quantidade de espécie adsorvida por grama de adsorvente, Nf. Os valores de Nf indicaram que o híbrido ALG/ESC-CaCl2 apresentou maior afinidade pelo herbicida e pelos íons Co(II) e Co(II). As taxas de adsorção foram investigadas através dos modelos de pseudo-primeira-ordem, pseudo-segunda-ordem e de difusão intrapartícula. Verificou-se que os dados obtidos não se ajustaram aos modelos cinéticos de pseudo-primeira-ordem e pseudo-segunda-ordem, com exceção dos dados referentes à interação entre os íons Cu(II) e as esferas ALG/ESC-CaCl2. O modelo de difusão intrapartícula ofereceu uma boa correlação. Os dados obtidos através deste modelo sugeriram que os processos de interação são controlados não apenas por difusão intrapartícula, mas também outros processos ocorrem concomitantemente.