L'extraction par CO2 supercritique démontre les avantages d'un procédé de chimie verte en comparant ce procédé à la méthode d'extraction par solvant organiques et en tenant compte du degré de toxicité et de pollution du solvant. L'extraction par solvants organiques met en évidence l'influence du solvant d'extraction alors que l'extraction par CO2-SC met en évidence l'influence de différents paramètres dont la pression, la température, le temps de contact entre la matrice végétale et le CO2-SC, le diamètre moyen des particules et l'ajout d'un co-solvant. L'analyse chromatographique a permis d'identifier et de quantifier les flavonolignanes (silychristine, silydianine, silybine, taxifoline) dans les extraits de graines obtenus par solvants organiques et par CO2-SC avec co-solvant. A 220 bar, les concentrations en silydianine (38,87 mg/g) et en silybine (45,91mg/g) sont les plus élevés et à 40°C les concentrations en silychristine (31,97mg/g), en silydianine (38,87 mg/g) et en silybine (45,91mg/g) sont les plus importantes. Les extraits huileux obtenus à 220 bar et à 40°C des graines de Silybum marianum sont riches en acides gras : acide linoléique (65,22%), acide oléique (27,01%), acide palmitique (12,12%). L'activité antioxydante a été évaluée par deux tests : test DPPH et test ABTS. Ces deux tests sont complémentaires et ont permis de conclure que l'extrait ayant un effet antioxydant le plus important est l'extrait obtenu par CO2-SC à 220 bar et à 40°C. L'activité biologique de cet extrait est mise en évidence par rapport à une lignée cellulaire cancéreuse du colon Caco-2. La silychristine, la silydianine et la silybine ainsi que l'extrait obtenu par CO2-SC avec co-solvant (éthanol) à 220 bar et à 40°C ont été testés vis à vis de cette lignée cancéreuse. Ces expérimentations in vitro reflètent une activité cytotoxique quantifiable et une mortalité cellulaire des Caco-2 des flavonolignanes allant jusqu'à 71% / The supercritical CO2 extraction demonstrates the benefits of green chemistry process comparing with the method of organic solvents extraction and depending to toxicity and pollution solvent degree. Organic solvents extraction shows the solvent extraction influence, so that the SC-CO2 extraction highlights different parameters including pressure, temperature, contact time between the plant matrix and CO2 SC, the average particle diameter and the addition of a cosolvent. Chromatographic analysis identified and quantified four flavonolignans (silychristin, silydianin, silybin, taxifolin) in seed extracts obtained by organic solvents and SC-CO2 with cosolvent. At 220 bar, silydianin (38.87 mg / g) and silybin (45.91 mg / g) have highest concentrations and at 40°C silychristin (31.97 mg / g), silydianin (38.87 mg / g) and silybin (45.91 mg / g) have the most important concentrations. The oily extracts obtained at 220 bar and 40°C of Silybum marianum seeds are rich in fatty acids: linoleic acid (65.22%), oleic acid (27.01%), palmitic acid (12.12%). The antioxidant activity measured by two tests: DPPH and ABTS test. These two tests are complementary and confirm that the extract with the higher antioxidant effect is the extract obtained by SC-CO2 at 220 bar and 40°C. The biological activity of this extract is demonstrated with respect to a colon cancer cell line Caco-2. Silychristin, silydianin and silybin and the extract obtained by CO2-SC with co-solvent (ethanol) at 220 bar and 40°C were tested with respect to this line cancer. These experiments in vitro cytotoxic activity reflect estimable and cell death of Caco-2 flavonolignans of up to 71%

O araçá é um fruto, pertencente à espécie Psidium grandifolium Mart. ex DC, nativo da mata atlântica brasileira pouco caracterizado pela literatura ciêntífica. Esta pesquisa visou estudar o rendimento de extração e avaliar as atividades antioxidante e antimicrobiana do óleo essencial de araçá obtido por extração com dióxido de carbono supercrítico (SFE) e dos diferentes extratos obtidos por extração com etanol pressurizado (PLE) seguindo um delineamento composto central rotacional com temperatura e tempo estático como variáveis independentes estudadas. Avaliou-se também o perfil de voláteis do óleo essencial, o teor de compostos fenólicos totais dos extratos etanólicos e as alterações causadas na matriz vegetal por diferentes processos de extração. Com a SFE conseguiu-se extrair toda a fração lipídica do fruto (2,33% ± 0,04.10-2%), a análise dos compostos voláteis do óleo essencial obtido permitiu inferir que este possui diversos compostos com potencial bioativo tais como E-cariofileno (17.56%), α-humuleno (16,26%) e β-sesquifelandreno (14.27%); porém este óleo essencial não apresentou atividade antioxidante relevante. O extrato etanólico com maior rendimento (17, 49%) foi obtido a 74 °C por 6 min, mesma condição em que obteve-se a maior atividade antioxidante (EC50 = 6,37 mg/mL), porém o maior teor de compostos fenólicos totais (136,95 mg EGA/100 g de massa seca) foi obtido quando aplicou-se 60°C por 9 min. Em relação à atividade antimicrobiana, tanto os extratos obtidos por PLE quanto por SFE apresentaram atividade contra cepas de P. aeruginosa, S. aureus e B. cereus, somente extratos etanólicos apresentaram atividade contra cepas de L. monocytogenes e nenhum dos extratos apresentaram atividade contra cepas de B. subtilis, E. coli e Salmonella. Em ambos os extratos foi possível identificar compostos com potencial aplicação farmacológica. O estudo de processos de extração que envolvam inovação tecnológica na obtenção extratos com atividade biológica visa contribuir com o extrativismo consciente ou estimular o plantio em maior escala de mais um fruto tropical empregado na medicina popular brasileira. / The araçá is a fruit, belonging to the species Psidium grandifolium Mart. ex DC, native of the Brazilian Atlantic Forest, is not largely characterized by the scientific literature. This research work aimed to study the extraction yield and to evaluate the antioxidant and antimicrobial activities of the araçá essential oil obtained by supercritical carbon dioxide extraction (SFE) and the different extracts obtained by pressurized ethanol extraction (PLE) following a central composite design with temperature and static time as independent variables studied. It was also evaluated the volatile profile of the essential oil, the content of total phenolic compounds of the ethanolic extracts and the changes caused in the vegetal matrix by different extraction processes. SFE was able to extract the whole lipid fraction of the fruit (2.33% ± 0.04.10-2%), the analysis of the volatile compounds of the essential oil obtained allowed to infer that it has several compounds with bioactive potential such as E-caryophyllene (17.56%), α-humulene (16.26%) and β-sesquipelandene (14.27%); but this essential oil had no relevant antioxidant activity. The highest ethanolic extract (17, 49%) was obtained at 74 °C for 6 min, the same condition in which the highest antioxidant activity was obtained (EC50 = 6.37 mg/mL), but the higher content of total phenolics contente (136.95 mg EGA / 100 g dry mass) was obtained when 60 °C was applied for 9 min. In relation to the antimicrobial activity, both extracts obtained by PLE and SFE showed activity against P. aeruginosa, S. aureus and B. cereus strains, only ethanolic extracts showed activity against L. monocytogenes strains and none of the extracts presented activity against B. subtilis, E. coli and Salmonella strains. In both extracts it was possible to identify compounds with potential pharmacological application. The study of extraction processes that involve technological innovation in obtaining extracts with biological activity aims to contribute to the conscious extraction or stimulate the larger scale cultivation of another tropical fruit used in Brazilian popular medicine.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-05-03T11:34:42Z No. of bitstreams: 1 disserta??o Roger vers?o biblioteca.pdf: 9741593 bytes, checksum: 510807346e33704b6f1650648b1f1b19 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-05-14T11:17:02Z (GMT) No. of bitstreams: 1 disserta??o Roger vers?o biblioteca.pdf: 9741593 bytes, checksum: 510807346e33704b6f1650648b1f1b19 (MD5) / Made available in DSpace on 2018-05-14T11:48:12Z (GMT). No. of bitstreams: 1 disserta??o Roger vers?o biblioteca.pdf: 9741593 bytes, checksum: 510807346e33704b6f1650648b1f1b19 (MD5) Previous issue date: 2018-01-15 / Developing technologies for the capture and geological storage of CO2 has been a constant challenge of the scientific community in the search for solutions that can reduce the environmental impacts caused by the release of this gas into the atmosphere. However, its storage in depleted oil wells has been shown to be a very important point, since the materials applied in wells can suffer degradation in the presence of CO2 in the supercritical state and at high pressures. The objective of this work is to evaluate the performance of the class G cement paste used in cementation of wellbore under conditions of geological carbon storage with replacement of part of the cement by pozoanic materials such as fly ash from the fossil fuel burning of the Candiota Thermoelectric Plant, and synthetic zeolites (4A-1 e 4A-2). The contents of the pozalanas used in substitution of the cement were 5% and 10% in weight. The medium in which samples were submitted for degradation tests was CO2 saturated water at 15 MPa pressure and 90 ?C for 7 and 14 days. Scanning Electron Microscopy (SEM), XRay Diffraction (XRD) and compressive strength tests were the characterization techniques used in this work. The results showed that the use of fly ash increased the compressive strength of the samples after 14 days, mainly for higher percentage of cement replacement by this material (10%), but its chemical degraded layer increased. In case of zeolites 4A-1 use, a lower compressive strength was observed compared to the standard paste, but the degraded layer was reduced. When zeolites 4A-2 were used significant loss of compressive strength was observed from 7 to 14 days, mainly for the proportion of the mixture of 10% and its degraded layer also reduced. / Desenvolver tecnologias para a captura e armazenamento geol?gico de CO2 tem sido um desafio constante da comunidade cient?fica na busca de solu??es que possam reduzir os impactos ambientais provocados pela libera??o desde g?s na atmosfera. Por?m, seu armazenamento em po?os depletados de petr?leo tem se mostrado o ponto mais desafiador, pois os materiais aplicados nestes po?os podem sofrer degrada??o na presen?a de CO2 em estado supercr?tico e em altas press?es. Este trabalho tem como objetivo avaliar o desempenho da pasta de cimento classe G, utilizada na cimenta??o e tamponamento dos po?os, em condi??es de armazenamento geol?gico de carbono com substitui??o de parte do cimento por materiais pozol?nicos. O material utilizado foi as cinzas volantes, oriundas da queima de carv?o mineral da Usina Termoel?trica de Candiota, e ze?litas 4A comerciais sint?ticas (4A-1 e 4A-2). Os teores utilizados das pozalanas em substitui??o ao cimento foram 5% e 10% em massa. O meio em que foram submetidas as amostras foi de ?gua saturada com CO2 a 15 MPa de press?o a 90? C por 7 e 14 dias. A Microscopia Eletr?nica de Varredura (MEV), a Difra??o de Raios X (DRX) e o teste de resist?ncia ? compress?o foram as t?cnicas de caracteriza??o utilizadas neste trabalho. Os resultados obtidos mostram que o uso de cinzas volantes aumentou aos 14 dias a resist?ncia ? compress?o das amostras, principalmente para maior a porcentagem de substitui??o do cimento por este material (10%), por?m a camada alterada quimicamente aumentou. Quando utilizadas as ze?litas 4A-1, notou-se uma menor resist?ncia ? compress?o que a pasta padr?o, mas a camada degradada reduziu. No caso das ze?litas 4A-2, foi constatada a perda significativa de resist?ncia ? compress?o dos 7 para 14 dias, principalmente para a amostra contendo 10% dessa zeolita, sendo que a camada alterada quimicamente tamb?m reduziu.

Ces travaux de thèse constituent une contribution au développement de composites chanvre/époxy 100% bio-sourcés. Les enjeux environnementaux actuels favorisent l'émergence de matériaux issus de ressources renouvelables telles que les fibres végétales mais conduisant aussi à une large gamme de synthons bio-sourcés, notamment à l'origine de prépolymères époxydiques. Une étude approfondie des deux constituants (fibres de chanvre et matrices polyépoxydiques) est réalisée avant l'étape d'élaboration des composites. Un traitement au CO2 supercritique est appliqué sur les fibres de chanvre utilisées comme renfort dans les matériaux composites. Le résultat de ce traitement mène à une meilleure individualisation ainsi qu'à une baisse du pouvoir hygroscopique des fibres. Ces aspects, décisifs pour garantir de bonnes propriétés pour le composite final, sont néanmoins nuancés par une baisse des propriétés ultimes en traction à l'échelle des fibres mais également à l'échelle du composite. De la même façon, la diminution du pouvoir hygroscopique des fibres après traitement se répercute à l'échelle du composite, permettant ainsi d'améliorer la durabilité du composite. La synthèse des résines époxydiques utilisées dans cette étude est réalisée à partir de ressources renouvelables et abondantes telles que la lignine. Les polyépoxydes thermodurcissables ainsi préparés présentent de bonnes performances, compatibles avec le cahier des charges pour des applications composites à renfort végétal. Au regard des résultats obtenus, les composites 100% bio-sourcés sont des matériaux d'avenir. Leur développement nécessite néanmoins une étude approfondie de leur durabilité. / This thesis contributes to the development of 100% bio-based hemp/epoxy composites. Current environmental issues favor the emergence of materials derived from renewable resources such as plant fibres and a wide range of bio-based building-blocks, source of epoxy prepolymers in particular. An intensive investigation of the two constituents (hemp fibres and polyepoxidic matrix) is carried out before the composites manufacturing. Supercritical CO2 treatment is applied to hemp fibres used as reinforcement in composite materials. This treatment, not optimized, leads to better individualization as well as a decrease in the hygroscopic power of the fibres. These aspects, which are essential in order to guarantee good properties for the final composite, are nevertheless qualified by a loss of mechanical properties at the fibre scale but also at the composite scale. In the same way, the decrease in the hygroscopic power of the hemp fibres after treatment is reflected at the composite scale, thus improving the durability of the crosslinked material. The synthesis of the epoxy resins used in this study is made from abundant resources such as lignin. The thermosetting polyepoxides prepared in this study have good performance, compatible with the specification for composite applications with plant fibres reinforcement. In view of the results obtained, 100% bio-based composites are materials with a high future potential. Nevertheless, their development requires a comprehensive sustainability study.

O araçá é um fruto, pertencente à espécie Psidium grandifolium Mart. ex DC, nativo da mata atlântica brasileira pouco caracterizado pela literatura ciêntífica. Esta pesquisa visou estudar o rendimento de extração e avaliar as atividades antioxidante e antimicrobiana do óleo essencial de araçá obtido por extração com dióxido de carbono supercrítico (SFE) e dos diferentes extratos obtidos por extração com etanol pressurizado (PLE) seguindo um delineamento composto central rotacional com temperatura e tempo estático como variáveis independentes estudadas. Avaliou-se também o perfil de voláteis do óleo essencial, o teor de compostos fenólicos totais dos extratos etanólicos e as alterações causadas na matriz vegetal por diferentes processos de extração. Com a SFE conseguiu-se extrair toda a fração lipídica do fruto (2,33% ± 0,04.10-2%), a análise dos compostos voláteis do óleo essencial obtido permitiu inferir que este possui diversos compostos com potencial bioativo tais como E-cariofileno (17.56%), α-humuleno (16,26%) e β-sesquifelandreno (14.27%); porém este óleo essencial não apresentou atividade antioxidante relevante. O extrato etanólico com maior rendimento (17, 49%) foi obtido a 74 °C por 6 min, mesma condição em que obteve-se a maior atividade antioxidante (EC50 = 6,37 mg/mL), porém o maior teor de compostos fenólicos totais (136,95 mg EGA/100 g de massa seca) foi obtido quando aplicou-se 60°C por 9 min. Em relação à atividade antimicrobiana, tanto os extratos obtidos por PLE quanto por SFE apresentaram atividade contra cepas de P. aeruginosa, S. aureus e B. cereus, somente extratos etanólicos apresentaram atividade contra cepas de L. monocytogenes e nenhum dos extratos apresentaram atividade contra cepas de B. subtilis, E. coli e Salmonella. Em ambos os extratos foi possível identificar compostos com potencial aplicação farmacológica. O estudo de processos de extração que envolvam inovação tecnológica na obtenção extratos com atividade biológica visa contribuir com o extrativismo consciente ou estimular o plantio em maior escala de mais um fruto tropical empregado na medicina popular brasileira. / The araçá is a fruit, belonging to the species Psidium grandifolium Mart. ex DC, native of the Brazilian Atlantic Forest, is not largely characterized by the scientific literature. This research work aimed to study the extraction yield and to evaluate the antioxidant and antimicrobial activities of the araçá essential oil obtained by supercritical carbon dioxide extraction (SFE) and the different extracts obtained by pressurized ethanol extraction (PLE) following a central composite design with temperature and static time as independent variables studied. It was also evaluated the volatile profile of the essential oil, the content of total phenolic compounds of the ethanolic extracts and the changes caused in the vegetal matrix by different extraction processes. SFE was able to extract the whole lipid fraction of the fruit (2.33% ± 0.04.10-2%), the analysis of the volatile compounds of the essential oil obtained allowed to infer that it has several compounds with bioactive potential such as E-caryophyllene (17.56%), α-humulene (16.26%) and β-sesquipelandene (14.27%); but this essential oil had no relevant antioxidant activity. The highest ethanolic extract (17, 49%) was obtained at 74 °C for 6 min, the same condition in which the highest antioxidant activity was obtained (EC50 = 6.37 mg/mL), but the higher content of total phenolics contente (136.95 mg EGA / 100 g dry mass) was obtained when 60 °C was applied for 9 min. In relation to the antimicrobial activity, both extracts obtained by PLE and SFE showed activity against P. aeruginosa, S. aureus and B. cereus strains, only ethanolic extracts showed activity against L. monocytogenes strains and none of the extracts presented activity against B. subtilis, E. coli and Salmonella strains. In both extracts it was possible to identify compounds with potential pharmacological application. The study of extraction processes that involve technological innovation in obtaining extracts with biological activity aims to contribute to the conscious extraction or stimulate the larger scale cultivation of another tropical fruit used in Brazilian popular medicine.

Two-phase flow in porous media is an important subsurface process that has significant impacts on the global economy and environments. To study two-phase system in porous media, capillary pressure (Pc ), relative permeability (Kr), bulk electrical conductivity (σb) and bulk relative permittivity (εb) are often employed as characterization parameters. Interestingly, all of these parameters are functions of water saturation (S). However, the non-uniqueness in the Pc -S, Kr-S,σb-S and εb-S relationships pose considerable challenges in employing them for effective monitoring and control of the two-phase flow processes. In this work, laboratory scale experiments and numerical simulations were conducted to investigate the factors and conditions contributing to the non-uniqueness in the above relationships for silicone oil-water and supercritical CO2-water flow in porous media, with a special emphasis on geological carbon sequestration. Specifically, the dynamic capillary pressure effect, which indicates the dependence of the Pc - S relationship on the rate of change of saturation (αS/αt) during two-phase flow in porous media was investigated. Using a silicone oil-water system, the dynamic capillary pressure effect was quantified in term of the parameter named the dynamic coefficient, τ , and it was found to be dependent on the domain scale and the viscosity ratio of the two fluids. It was found that τ increases with the domain scale and the viscosity ratio. It is inversely affected by αS αt , which is related to the degree of resistance to the fluid motion, namely, viscosity. In almost all cases, τ was found to decrease monotonically with an increase in water saturation, S. An order increase in magnitude of τ was observed as the domain scale increases from 4cm scale to 8cm in height. A similar order of increase in τ was observed in the 12cm high domain scale. There is an order increase in the value of τ for the silicone oilwater system as the viscosity ratio increases from 200 to 500. For the supercritical CO2 (scCO2) and water system in porous media, the experiments and numerical simulations showed that τ increases with rising system temperature and decreasing porous media permeability. Dimensionless analysis of the silicone oil-water experimental results showed that by constructing non-dimensional groups of quantities expressing a relationship among different variables on which τ depends, it is possible to summarise the experimental results and determine their functional relationship. A generalised scaling relationship for τ was derived from the dimensionless analysis which was then validated against independent literature data. The exercise showed that the τ-S relationship obtained from the literature and the ii scaling relationship match reasonably well. This work also demonstrated the applicability of an artificial neural network (ANN) as an alternative computational platform for the prediction of the domain scale dependence of τ . The dependence of the Kr-S relationship on αS/αt was also investigated. The results showed that the Kr-S curve under dynamic flow condition is different from that under the quasi-static condition. Kr for water (Krw) increases with increasing water saturation and decreases with the increase in viscosity ratio while Kr for silicone oil (Krnw) increases with decreasing water saturation as well as with the increase in viscosity ratio. Also, Krw decreases while Krnw increases with the increasing boundary pressure. However, the εb-S and σb-S relationships were found to be independent of αS/αt for the scCO2-water system in carbonate and silicate porous media. Nevertheless, the εb and σb values decrease as the water saturation decreases in the two porous media samples. While εb decreases with increase in temperature in silica sand, the trend in the limestone showed a slight increase with temperature, especially at high water saturation. Also, the εb-S relationship is shown to be affected by pressure in silica sand increasing with the pressure of the domain. On the contrary, the σb-S relationship increases as the temperature increases with more significance at higher water saturation in the silica sand sample. This work further demonstrated the application of a membrane in the monitoring of the CO2 in geological sites used for carbon sequestration. Commercial silicone rubber coupled with a pressure transducer showed potential in the detection of CO2 leakage from geological sites. The response of the device in terms of the mass of permeated gas, permeability and gas flux were investigated for both CO2 and N2. In addition, the monitoring of potable water contamination in a shallow aquifer by the migrating or leaking of CO2 is demonstrated with the combination of the pH analysis, geoelectrical measurement techniques and the membrane-sensor system. Overall, the work in this PhD research demonstrated robust applications of two-phase systems'characterization parameters under different scenarios in the porous media. Implications of the findings in this work to the monitoring and control of two-phase systems in porous media are expatiated.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The main objective of this work was to evaluate the antioxidant and antibacterial activities of extracts of Brassica oleracea var. capitata, obtained by supercritical CO2 and ultrasound-assisted extractions, as well as to carry out the characterization of these extracts using gas chromatography coupled with mass detector. For supercritical CO2, five extractions were performed to investigate the influence of pressure (10-25 MPa) and temperature (20-60°C) on the extraction yield, chemical composition and antioxidant activity towards peroxyl, superoxide and hydroxyl radicals. The highest extraction yield was 0.47% at 60 °C and 25 MPa. In the characterization of the extracts was possible to identify compounds like sulforaphane and iberin nitrile. All extracts showed antioxidant activity for the three radicals, although the highest activity for all radicals was obtained using the extract obtained at 60 °C and 25 MPa (run 2). For the ultrasound-assisted extraction were evaluated the effects of solvent concentration and temperature. The extracts obtained in the optimized extraction condition, were subjected to different hydrolysis conditions before use in biological assays. It was evaluated the antioxidant activity against DPPH, superoxide and peroxyl radicals, besides the antibacterial activity against S. aureus and E. coli. Both crude and hydrolyzed extracts were characterized by gas chromatography coupled with mass detector. The best condition for extraction was 30 ° C and 60% (w /v) of ethanol. All extracts showed antioxidant activity towards DPPH, superoxide and peroxyl radicals, but the use of hydrolyzed extracts improved considerably the antioxidant activities. Antibacterial activity was detected only in extracts hydrolysates Brassica oleracea var. capitata. The main contributions of this work were that the use of supercritical CO2 extraction to obtain bioactive compounds from Brassica oleracea var. capitata showed a promising alternative to conventional methods of extraction, since it allowed the extraction of compounds of interest in science and industry. Besides, in this work was demonstrated that the hydrolysis of extracts can increase the antioxidant activity of plant extracts. / O objetivo principal deste trabalho foi avaliar a atividade antioxidante e antibacteriana de extratos de Brassica oleracea var. capitata, obtidos a partir de extração supercrítica e extração por ultrassom, além de caracterizá-los por cromatografia gasosa acoplada à detector de massas. Para os compostos bioativos apolares de Brassica oleracea var. capitata, utilizou-se extração com CO2 supercrítico e avaliou-se o potencial antioxidante dos extratos. Foram realizadas cinco extrações para investigar a influência da pressão (10 - 25 MPa) e temperatura (20 - 60°C) no rendimento da extração, na composição química e na atividade antioxidante frente os radicais peroxila, superóxido e hidroxila. Obteve-se o maior rendimento de extração 0,47% a 60 °C e 25 MPa. Na caracterização dos extratos foi possível a identificação de compostos como sulforafano e iberin nitrila. Todos os extratos apresentaram atividade antioxidante para os três radicais, porém a maior atividade para todos os radicais foi o extrato obtido a 60°C e 25 MPa. Para os compostos bioativos polares, otimizou-se a extração assistida por ultrassom. Os extratos obtidos nas melhores condições de extração foram submetidos a diferentes condições de hidrólise, antes da sua utilização nos ensaios biológicos. Avaliou-se a atividade antioxidante, frente ao radical DPPH, superóxido e peroxila, além da atividade antibacteriana, frente a S.aureus e E.coli. Tanto os extratos brutos quanto os hidrolisados, foram caracterizados por cromatografia gasosa acoplada à detector de massas. A melhor condição de extração foi a 30ºC e 60% (m/v) de etanol. Todos os extratos apresentaram atividade antioxidante frente aos radicais DPPH, superóxido e peroxila, mas o uso de extratos hidrolisados melhorou consideravelmente a atividade antioxidante. Em relação à atividade antibacteriana, apenas uma amostra, que foi submetida à condição de hidrólise alcalina apresentou ação frente a E.coli. Uma das principais contribuições deste trabalho foi que a utilização de extração com CO2 supercrítico, para obtenção de compostos bioativos de Brassica oleracea var. capitata, mostrou ser uma alternativa promissora em relação aos métodos convencionais de extração, pois permitiu a extração de compostos com interesse científico e industrial. Além disso, foi demonstrado que a hidrólise dos extratos pode aumentar consideravelmente a atividade antioxidante de extratos vegetais em relação aos extratos brutos.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Rice husk is a fairly abundant agro-industrial waste in the state of Rio Grande do Sul, hence the same has been suggested and studied to be used as in lignocellulosic hydrolysis to produce fermentable sugars material. However, processes of hydrolysis in most cases are more expensive and impractical. In this context, this work aimed to study which evaluated acid and enzymatic hydrolysis of rice hulls to obtain fermentable sugars using some alternative technologies such as ultrasound and supercritical CO2 to increase the yields of sugars. In the acid hydrolysis, the yields obtained at optimized conditions were 113.0 and 162.0 g.kg-1 for conventional and ultrasound-assisted hydrolysis, where the yield obtained by ultrasound-assisted hydrolysis was around 43% higher than for the conventional hydrolysis. In the enzymatic hydrolysis, it was evaluated the use of supercritical CO2 as co-solvent and ultrasound-assisted hydrolysis and the results were compared with conventional procedure. Maximum yield of fermentable sugar obtained was about 16 g.kg-1using conventional or ultrasound-assisted hydrolyses. The yield obtained in the hydrolysis using supercritical CO2 as co-solvent was around 4.2 g.kg-1. Enzymatic hydrolysis using conventional procedure showed to be the best alternative to obtain fermentable sugar from rice hulls since the innovative technologies employed did not lead to better results. For acid hydrolysis, it was possible to obtain high yield using less acid and low temperature, in a manner that ultrasound can be used as a device for process intensification. / A casca de arroz é um resíduo agroindustrial bastante abundante no estado do Rio Grande do Sul, deste modo à mesma vem sendo sugerida e estudada para ser usada como material lignocelulósico em hidrólises para a produção de açúcares fermentescíveis. Entretanto, processos de hidrólises na maioria das vezes não possuem um alto rendimento o que torna o processo ainda mais caro e inviável. Dentro desse contexto o presente trabalho teve o intuito de realizar um estudo onde avaliou hidrólise ácida e enzimática da casca de arroz para a obtenção de açúcares fermentescíveis utilizando algumas tecnologias alternativas, como o banho de ultrassom e CO2 supercrítico para aumentar os rendimentos de açúcares. Os ensaios foram realizados em diferentes condições de temperatura, concentrações de ácido e umidade, pressão e concentrações de enzima do meio. Na hidrólise acida convencional obteve-se um rendimento de 113,0 g.kg-1 e na hidrólise ácida assistida por ultrassom o rendimento foi de 162,0 g.kg-1, com base nesses resultados dos rendimentos de açúcares foi possível concluir que o uso do ultrassom intensificou o processo ocorrendo um aumento do rendimento em cerca de 43% quando comparado com o rendimento de açúcares fermentescíveis da hidrólise convencional. Já na hidrólise enzimática utilizando o CO2 Supercrítico o rendimento foi de 4.2 g.kg-1 enquanto que o rendimento da hidrólise enzimática convencional e assistida por ultrassom foi de 16 g.kg-1, neste caso o uso do CO2 supercrítico não foi uma alternativa promissora, uma vez que a mesma causou uma desnaturação das enzimas causando uma diminuição na eficiência do processo.

Ce travail décrit la synthèse et les propriétés gélifiantes de nouveaux dérivés d’acides aminés de faible poids moléculaire dans des solvants organiques ainsi que l’élaboration d’aérogels correspondants par séchage au CO2 supercritique. Nous avons pu montrer, dans notre cas, que seuls les dérivés de la leucine et de la phénylalanine étaient nécessaires au phénomène de gélation. L’étude des paramètres des solvants a permis de montrer que les paramètres de Hansen h des solvants gélifiés s’inscrivaient dans un domaine étroit de valeurs faibles ; il inclut des solvants aromatiques et des solvants chlorés. L’usage de spectroscopies diverses (IR, RMN, dichroïsme circulaire et fluorescence) a permis de mettre en évidence les interactions responsables du phénomène de gélation. Les liaisons hydrogène permettent l’empilement unidimensionnel des molécules gélatrices, ces empilements s’associent ensuite grâce à des interactions de - stacking intercolonnaires. Des aérogels monolithiques ont pu être obtenus. Ils présentent des propriétés remarquables parmi lesquelles une conductivité thermique sous vide extrêmement faible / This work describes the synthesis and the gelation properties of new amino-acid-based low-molecular-weight derivatives in organic solvents as well as the development of the corresponding aerogels by supercritical CO2 drying. We have proved that in our case the presence of phenylalanine or leucine lateral chains were necessary for gelation. A solvent parameters study led us to define a favourable narrow h Hansen parameter domain for gelation including aromatic and chlorinated solvents. The use of several spectroscopy methods (IR, NMR, circular dihroism and fluorescence) allowed to settle the interactions accountable for gelation phenomenon. Hydrogen bonds enable the unidimensional stacking-up of gelator molecules; next, the stacking-up are associated through intercolumnar - stacking interactions. Monolithic aerogels were obtained. They display noteworthy properties among them an extremely low thermal conductivity under vacuum

Ce travail est dédié à l'étude d'écoulement diphasique sous pression en micro et milli-capillaires pour permettre la mesure efficace de propriétés de mélanges sous pression. Dans un premier temps, un montage expérimental comprenant un micro-dispositif pour des applications allant jusqu'à des pressions de 25 MPa a été développé. Ce micro-dispositif à faible coût et transparent, permet la visualisation de l'écoulement grâce à une caméra rapide. Dans un second temps, l'étude du système diphasique du système CO2 supercritique / liquide ionique (1-Butyl-3-Methyl-Imidazolium hexafluorophosphate, [BMIm][PF6]) sous pression est présentée. L'écoulement est réalisé dans des tubes cylindriques de silice de diamètre intérieur de 536 micromètres. Parmi les différents régimes d'écoulements diphasiques, nous nous sommes intéressés aux écoulements périodiques intermittents ou « Taylor flow ». La zone de conditions opératoires couvertes est la suivante : [308 K - 318 K] x [9 MPa - 18 MPa]. Les films de la caméra rapide sont traités par analyse d'image. Le logiciel« μcap2phase » développé pour traiter les films permet d'accéder aux caractéristiques géométriques de l'écoulement (volume et aire de chaque phase, longueur du motif, longueur de la phase dispersée et vitesse de la phase dispersée). Un comportement atypique est observé avec ce binaire. En effet le transfert unidirectionel du CO2SC dans le [BMIm][PF6] induit des changements importants des propriétés physico-chimiques de la phase continue : abaissement de la viscosité (divisée par 10) et augmentation de la masse volumique (multiplié par 1,5). Ces changements impliquent une modification de la forme et de la taille des bulles au cours de l'écoulement. Une importante vitesse de glissement a été identifiée. Elle est générée par la présence d'un film épais de viscosité plus élevée au niveau des parois du capillaire. Un modèle de transfert de matière prenant en compte certaines des observations expérimentales (variations de la taille du film, de la taille des bulles, et des propriétés de la phase continue tout au long du capillaire) a été développé. Ce modèle intégrera dans le futur la tension interfaciale bulle/phase continue et le facteur de forme de la bulle. / The present work deals with the study of two-phase flow in micro-capillaries under high-pressure to enhance properties measurements. As a first step, an experimental setup consisting of a micro-device has been developed for microfluidics high-pressure applications (P < 25 MPa). The set-up combines good optical access, high-pressure resistance, homogeneous operating conditions, fast process control and detection, and the ability to generate a stable two-phase flow. In the following step, we focused our work on the hydrodynamics features of two-phase flow between supercritical carbon dioxide(SC-CO2) and ionic liquid (1-butyl-3-methyl-imidazolium hexafuorophosphate) ([BMIm][PF6]) .The two-phase flow system is observed with a high-speed camera. The flow is conducted in silica capillary tubing with inner diameter of 536 micrometers. Among the two-phase flow patterns, ours relates to Taylor flow. The range of operating conditions are : [308 K - 318 K] x [9 MPa - 18 MPa]. An image analysis home-made soft, « μcap2phase », has been developed in order to access to the geometric properties and to the velocities of the dispersed phase from images. The two-phase flow presents an unexpected behaviour. In fact, the unidirectional transfer of SC-CO2 in [BMIm][PF6] induces significant changes in physico-chemical properties of continous phase : viscosity decreases(divided by ten) and density increases (1.5 fold). Due to the wide variations of the continuous phase properties along the capillary, size and shape of the dispersed phase bubbles are simultaneously modified. A significant slip velocity has been indentified located between a thick liquid film (at the wall of capillary) and a Taylor flow region (at the center). A mass transfer taking into account some experimental observations (changes in film thickness, in bubble size, and in properties of the continuous phase throughout the capillary) is developed. Further, this model will integrate the interfacial tension between bubbles and continous phase.