University of Macau / Institute of Chinese Medical Sciences

This thesis describes the convenient routes and the preparation conditions (temperature, oxygen partial presssure) which lead to the formation of single phase materials within the quaternary system Cu-Ni-Fe-O. The investigated compositions are the solid solutions CuxNi1-xFe2O4, the ferrites occurring in the phase triangle Cu0.5Ni0.5Fe2O4 -Cu0.9Fe2.1O4 - Cu0.5Fe2.5O4 and some copper-nickel oxide solid solutions. Three synthesis routes have been used, namely (i) the preparation and the thermal decomposition of freeze-dried carboxylate precursors, (ii) the preparation and the oxidation of intermetallic phases and (iii) the preparation and the heat treatment in air of mixed oxide/metallic powders. The thermal decomposition of freeze-dried Cu-Ni-Fe formate has been found as a suitable method for preparing single spinel phases within the Cu-Ni-Fe-O system. In comparison with the conventional solid state reaction, the required temperature is much lower. Concerning the solid solution CuxNi1-xFe2O4 , a single phase spinel is formed at 1000¢XC for x < 0.7; for CuO is identified as second phase. In this latter range the formation of a pure phase required an increase of the iron content in the mixture. The other single spinel phases in the phase triangle Cu0.5Ni0.5Fe2O4 - Cu0.9Fe2.1O4 - Cu0.5Fe2.5O4 have been synthesized under special synthesis p(O2)/T-conditions. For copper ferrites Cu1-xFe2+xO4 with x ?­ 0.1, 0.2, 0.33, 0.4 and 0.5, the change in the conductivity with the temperature is irreversible. The deviation from the linearity of the conductivity ?ã as a function of the temperature occurs due to the thermal history of these samples. The saturation magnetic moment (nB) at 5K, of some synthesized CuxNi1-xFe2O4 compounds has been determined. It has been found that nB increases with the nickel content in the ferrite sample.

La présente étude concerne l’évaluation de l’impact du séchage par air chaud (HAD), lyophilisation (FD) et « swell drying » (SD), procédé couplant le séchage par air chaud avec le procédé de Détente Instantanée Contrôlée (DIC), sur les fraises (Fragaria var. Camarosa). Il s’agit de comparer et de contraster les performances des procédés et la qualité du produit fini séché en termes des cinétiques de séchage et de réhydratation, de contenus en molécules bioactives et activité antioxydante, et des paramètres caractéristiques de texture comme croquant et croustillant. Les résultats obtenus ont montré que le procédé de SD comparé aux procédés classiques de séchage et de lyophilisation, réduit d’une façon importante le temps de séchage ainsi que les coûts d’opération. D’autre part, SD conserve la qualité nutritionnelle des fraises en gardant leur contenu en composants bioactifs et en augmentant leur disponibilité. De plus, une corrélation importante entre la capacité antioxydante et le contenu total d’anthocyanes a été établie. D’autre part, les fraises séchées par SD ont montré une très intéressante macro et micro-structure. Les produits ont présenté une haute expansion et une croustillance significative due au phénomène de micro-alvéolation par décompression instantanée par DIC. D’ailleurs, il a été possible de mesurer les caractéristiques instrumentales de croustillance/croquance des échantillons finaux séchés. Grâce à la possibilité de modifier, contrôler et optimiser les paramètres opératoires du procédé DIC, il a été possible d’obtenir un produit du type « snack » croustillant avec une très haute valeur nutritionnelle. / The aim of this study was to evaluate the effect of hot air drying (HAD), freeze-drying (FD) and swell drying (SD), which is a coupling of hot air drying to instant controlled pressure drop, (DIC) on the strawberry (Fragaria var. Camarosa) to compare and to contrast its quality in terms of drying and rehydration kinetics, bioactive compounds and its antioxidant activity, and texture parameters as crunchy and crispy features. The obtained results shown that SD method helped to reduce the drying time leading to a low-cost processing compared with classical hot air drying and freezedrying. SD globally preserved the strawberry’s nutritional value and bioactive compounds, increasing their availability. Moreover, a strong correlation between antioxidant activity and total anthocyanin content was established in SD strawberries. On the other hand, the swell-dried strawberries showed an interesting macro and micro-structure. They presented a high expansion ratios and significant crispness provoked by the micro-alveolation phenomenon induced as consequence of the instant decompression process in the DIC treatment. Moreover, it was possible to instrumentaly measure the crispy/crunchy features of the final dried samples. By assessing such crispy and healthy contents of fruit “snacking”, it was possible to modify, control, and optimize DIC operating parameters. And, it can be designed according to the industrial or consumer needs.

OLIVEIRA, Gleison Silva. Aplicação do processo de liofilização na obtenção de cajá em pó: avaliação das características físicas, físico-químicas e higroscópicas. 2012. 83 f. : Dissertação (mestrado) - Universidade Federal do Ceará, Centro de Ciências Agrárias, Departamento de Tecnologia de Alimentos, Fortaleza-CE, 2012 / Submitted by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-09T12:17:09Z No. of bitstreams: 1 2012_dis_gsoliveira.pdf: 1196468 bytes, checksum: a8572b9d75384ed2a57b461af4d5a3bf (MD5) / Approved for entry into archive by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-09T12:17:20Z (GMT) No. of bitstreams: 1 2012_dis_gsoliveira.pdf: 1196468 bytes, checksum: a8572b9d75384ed2a57b461af4d5a3bf (MD5) / Made available in DSpace on 2016-06-09T12:17:20Z (GMT). No. of bitstreams: 1 2012_dis_gsoliveira.pdf: 1196468 bytes, checksum: a8572b9d75384ed2a57b461af4d5a3bf (MD5) Previous issue date: 2012 / The yellow mombin due to its distinctive flavor and pleasant, is a fruit highly appreciated and consumed in various regions of the country. But by presenting a high perishability, it becomes necessary to use processing techniques to extend its availability for consumption throughout the year. Dehydration by freeze-drying has the advantage of an excellent retention of nutritional and sensory characteristics of fresh fruit. To increase retention and to prevent agglomeration of the powder, for example, can be made the use of adjuvants drying such as maltodextrin. In this context, the work aimed at the implementation of the lyophilization process to obtain the pulp of yellow mombin powder, physical characterization and physicochemical pulp and powder yellow mombin, tracking stability during storage and hygroscopic behavior of the tests. With the tests of the experimental design was chosen to test lower humidity, with 17% maltodextrin and 24 hours of freeze drying. The pulp presented characteristics similar to reported by literature, and a concentration of constituents occurred with the pulp dehydration. As for storage, the test control (dried whole) had a useful life of 60 days, unlike the test containing maltodextrin that showed good characteristics throughout the period analyzed. In addition, maltodextrin exerted protective function, preventing further loss of chemical constituents and physical reactions to the product, such as lower rate of increase of hygroscopicity, moisture and water activity. The adsorption isotherms were the characteristics of type III. The mathematical models of BET, GAB and Oswin were the best fit to experimental data of moisture sorption for the full hog plum powder, and powder of hog plum pulp with maltodextrin, the Henderson model was the best fit to experimental points of work. / O cajá, devido ao seu sabor diferenciado e agradável, é um fruto bastante apreciado e consumido em diversas regiões do país. Mas por apresentar uma elevada perecibilidade, torna-se necessário o uso de técnicas de processamento para estender sua disponibilidade para o consumo durante todo o ano. A desidratação por liofilização apresenta como vantagem uma excelente retenção das características nutricionais e sensoriais do fruto “in natura”. Para um aumento desta retenção e evitar aglomerações no pó, por exemplo, pode ser feita a utilização de adjuvantes de secagem como a maltodextrina. Neste contexto, o trabalho teve como objetivo a aplicação do processo de liofilização para obtenção da polpa de cajá em pó, caracterização física e físico-química da polpa e do pó de cajá, acompanhamento da estabilidade durante o armazenamento e comportamento higroscópico dos ensaios. Com a realização dos ensaios do planejamento experimental, foi escolhido o ensaio de menor umidade, com 17% de maltodextrina e 24 horas de liofilização. A polpa apresentou características semelhantes às reportadas pela literatura, e uma concentração dos constituintes ocorreu com a desidratação da polpa. Quanto ao armazenamento, o ensaio controle (pó integral) teve uma vida útil de 60 dias, diferentemente do ensaio contendo maltodextrina que apresentou boas características durante todo período analisado. Além disso, a maltodextrina exerceu função protetora, evitando maiores perdas de constituintes químicos e reações físicas no produto, como menor taxa de aumento de higroscopicidade, umidade e atividade de água. As isotermas de adsorção foram características às do tipo III. Os modelos matemáticos de BET, GAB e Oswin foram os que melhor se ajustaram aos dados experimentais de sorção de umidade para o pó de cajá integral, e no pó da polpa de cajá com maltodextrina, o modelo de Henderson foi o que melhor se ajustou aos pontos experimentais do trabalho.

Made available in DSpace on 2016-06-02T19:56:39Z (GMT). No. of bitstreams: 1 3124.pdf: 1709285 bytes, checksum: 01aa5e6d0190ca5658a75e9fefae9b2b (MD5) Previous issue date: 2010-05-28 / Financiadora de Estudos e Projetos / The cultivation of pepper is widespread in Brazil since its colonization. This plant, besides being much appreciated in the cuisine has proven pharmacological effects such as lowering cholesterol, inhibiting appetite and the presence of antioxidants such as ascorbic acid and beta-carotene. It is a product whose demand increases every year, but generally still produced handmade diminish the ability of producers to meet the needs of commerce. To contribute to improving the production of pepper dedo-de-moça, it was the behavior of this plant in analyzing the influence of drying process on the nutritional composition and physical qualities of the dried product. For this, drying kinetics were obtained and certain structural properties (apparent density, real density and porosity) as a function of moisture content during drying. Assessing the quality of the final product was performed by quantification of ascorbic acid and study of rehydration. The convective drying and freeze-drying was compared with respect to product quality parameters such as shrinkage, structural properties, vitamin C retention and rehydration characteristics. To describe the kinetics of drying and rehydration were used empirical and semiempirical equations. The characterization of the rehydration process was carried out from the indices that take account of the capacity of water absorption and loss of solutes. The use of seed from the drying of peppers to obtain seedlings was studied by checking the germination through standardized tests. The samples of convective drying at 60 ºC had the best results in terms of nutritional quality, rehydration characteristics and structural properties, comparing with those obtained from freezedrying. In assessing the use of seeds of peppers after processing to obtain new seedlings, the most suitable temperature was 40 oC to cause less damage to germination. / A cultura da pimenta está bem difundida no Brasil desde a sua colonização. Esse vegetal, além de ser muito apreciado na culinária possui efeitos farmacológicos comprovados como o de redutor do colesterol, inibidor do apetite e a presença de substâncias antioxidantes como o ácido ascórbico e o beta-caroteno. É um produto cuja demanda aumenta a cada ano, mas que a forma como é produzido continua, em sua maioria, artesanal diminuindo a capacidade dos produtores de atender às necessidades do comércio. Visando contribuir para o melhoramento da produção da pimenta dedo-de-moça, verificou-se o comportamento desse vegetal na secagem analisando a influência do processo na composição nutricional e qualidades físicas no produto seco. Para isso, foram obtidas as cinéticas de secagem e a determinação das propriedades estruturais (densidade aparente, densidade real e porosidade) em função do teor de umidade durante a secagem. A avaliação da qualidade do produto final foi realizada pela quantificação de ácido ascórbico e estudo da reidratação. A secagem convectiva foi comparada com a secagem em liofilizador com relação a parâmetros de qualidade do produto como encolhimento, propriedades estruturais, retenção de vitamina C e características de reidratação. Para descrever a cinética de secagem e de reidratação foram utilizados modelos empíricos e semi-empíricos. A caracterização do processo de reidratação foi realizada a partir dos índices que levam em conta a capacidade de absorção de água e a perda de solutos. Avaliou-se também o aproveitamento das sementes resultantes do processamento para obtenção de novas mudas através da verificação da capacidade germinativa por meio de testes padronizados. As amostras obtidas da secagem por convecção a 60oC tiveram os melhores resultados em termos de qualidade nutricional, características de reidratação e propriedades estruturais, comparando-se com aquelas obtidas da liofilização. Na avaliação do uso das sementes após o processamento das pimentas para obtenção de novas mudas, a temperatura mais adequada foi de 40oC por causar menos prejuízo a capacidade germinativa.

Brazil is one of the greatest producers of fruits in the world which involves the generation of a large amount of agro-industrial residues whose potential still needs to be better studied. The yellow passion fruit (Passiflora edulis f. flavicarpa) is rich in minerals, vitamins and fibers and its production generates a large number of by-products as peels and seeds, which can reach 70% of the fruit weight. Within this reality, the methods of dehydration stand out as an alternative to remove moisture of this material, preventing the proliferation of microorganisms and creating opportunities for its reutilization. In this work, it was studied the impact of four techniques of dehydration in the passion fruit s residue: hot air, infrared, microwaves and freeze drying. In all was possible to obtain a material with satisfactory final moisture levels, highlighting the use of microwaves as the most efficient in terms of time. Dehydration by hot air was positively affected by velocity and temperature conditions, but the bioactive compounds had impact of temperature and time (80oC and 7 hours). The temperature of 95oC was the most efficient for the moisture removal and contends of bioactive compounds in the dehydration of infrared, but an overexposure to this radiation beyond the observed limits must be avoided. The use of microwaves show that is possible to obtain a material with good final quality and quickly, since intermediate levels of powers (480 W) are used to avoid over exposure. Freezer drying produced a final product with better visual appearance but its great operation times and the final content of bioactive compounds found wasn t better to other methods, in exception of pectin contents. Analyzing the bioactive compounds, phenolics and flavonoids were positively impacted by dehydration, reach values near and above of the residue in natura in all techniques. Citric acid showed deterioration in all conditions observed, indicating its sensibility to thermal processes as much as freeze drying. The ascorbic acid was strongly influenced by heat exposure an increased its levels, except in the freeze drying samples. Overall, the best dehydration methodology was the microwave technique, indicating a potential future use of this method in the use of passion fruit residues. / O Brasil é um dos maiores produtores de frutas do mundo, o que implica na geração de uma grande quantidade de resíduos agroindustriais cujo potencial ainda necessita ser melhor estudado. O maracujá-amarelo (Passiflora edulis f. flavicarpa) é um fruto rico em minerais, vitaminas e fibras e sua produção gera uma grande quantidade de subprodutos como cascas e sementes, que podem chegar até 70% do peso do fruto. Dentro dessa realidade, destacam-se as metodologias de desidratação como alternativa para remoção de umidade desse material, impedindo a proliferação de micro-organismos e abrindo oportunidades para seu posterior aproveitamento. Neste trabalho foram verificados os impactos de quatro metodologias de desidratação no resíduo de maracujá: o uso de ar quente, infravermelho, micro-ondas e liofilização. Em todos foi possível obter um material com níveis de umidade final satisfatórios, destacando-se o uso de micro-ondas como o mais eficiente em termos de tempo. A desidratação por ar quente se mostrou impactada positivamente pela velocidade e temperatura de operação, mas os compostos bioativos sofreram maior impacto da temperatura e do tempo (80oC e 7 horas). A temperatura de 95oC se destacou como a mais eficiente tanto em remoção de umidade quanto nos teores de compostos bioativos para a desidratação por infravermelho, mas verificou-se que uma superexposição a essa radiação além dos limites observados deve ser evitada. O uso de micro-ondas indicou que é possível obter um material final de qualidade e rapidamente, desde que sejam utilizadas potências intermediárias (480 W) e evitado o excesso de exposição. A liofilização resultou em um produto final com melhor aspecto visual, porém seus tempos de operação elevados e o nível de compostos bioativos finais encontrados não obtiveram destaque perante os demais métodos, com exceção aos teores de pectina. Quanto aos compostos bioativos, os fenólicos e flavonoides foram impactados positivamente pela desidratação, atingindo valores próximos e superiores ao do resíduo in natura em todas as metodologias. O ácido cítrico apresentou degradação em todas as condições a que foi submetido, indicando a sensibilidade do mesmo tanto a processos térmicos quanto à liofilização. Já o ácido ascórbico se mostrou fortemente influenciado pela exposição ao aquecimento, apresentando aumento em seus teores, com exceção das amostras liofilizadas. Globalmente, o melhor método de desidratação obtido foi o micro-ondas, indicando um potencial uso do mesmo no aproveitamento do resíduo de maracujá. / Mestre em Engenharia Química

Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2016-11-23T15:47:14Z No. of bitstreams: 2 Dissertação - Monick Cristina Braga - 2016.pdf: 3023233 bytes, checksum: 1cca73525c76930a1072da12ee837400 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2016-11-30T15:45:17Z (GMT) No. of bitstreams: 2 Dissertação - Monick Cristina Braga - 2016.pdf: 3023233 bytes, checksum: 1cca73525c76930a1072da12ee837400 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-11-30T15:45:17Z (GMT). No. of bitstreams: 2 Dissertação - Monick Cristina Braga - 2016.pdf: 3023233 bytes, checksum: 1cca73525c76930a1072da12ee837400 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-09-26 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The aim of this study was to evaluate the physical and chemical quality Curcuma Longa L. leaf submitted to three drying methods: hot air drying, freezedrying and microwave drying, as well as the study of kinetic drying methods by convection and microwave. For the kinetic study the leaves were dried by hot air (60 °C) and microwave drying (900W power). Mathematical modeling using various models was performed, as follows: Lewis, Page, Henderson and Pabis, Wang and Singh, and logarithmic models were used to adjust experimental kinetic data. The results showed that the drying time of microwave was 60 times lower than hot air drying. Page model was the best adjusted the drying kinetics data by both methods. The phenol content was higher in the dry leaf (185.42mg/100g-1±0,65) by microwave (p <0.05) than in the hot air dried leaf (183,76 mg/100g-1±0,60), showing phenolic content greater than three times the fresh leaf (54,88mg/100g-1±0,76). It was observed that the drying process does not influence the color variation (ΔE) of the dried leaf. To study the physical and chemical characterization of Curcuma longa L. leaves by studying the chemical composition of the fresh leaf, mineral composition, antinutritional factors and evaluation of the color change of fresh and dry leaf, they were dehydrated by methods microwave, hot air drying and freezedrying. The chemical composition showed appreciable amounts of protein (39,5g (100g) -1 ± 0.91), carbohydrates (44,74g (100g) -1 ± 1.04), total fiber (34,47g (100g) -1 ± 0.98), and soluble fiber (22,65g (100g) -1 ± 0.65), insoluble fiber (11,81g (100g) -1 ± 0.34), ash (13,81g (100g) - 1 ± 1.05), and low in lipids (2,47g (100g) -1 ± 0.12). The mineral composition showed higher amounts of Na, Mg, K, Ca, P, and Mn. Other minerals are Fe and Zn. It was observed low levels of nitrate 0.05 mg / g ± 0.00 (fresh leaf) and 0,46-0,47mg / g (dry leaves) and showed no cyanogenic compounds in its composition. It was observed that the drying process influence on color variation of the dry leaves, increasing the brightness, diminindo the intensity of green color and causing the change in the shade of green to yellowish green. To study the effect of different methods of preservation (hot air drying, in a microwave and freezedrying) the content of bioactive compounds and antioxidant capacity of turmeric leaves, they were dehydrated by drying in an oven (60 ° C) in microwaves (900 W) and lyophilizing (vacuum of 300 mmHg) until equilibrium moisture content (0.030 kgágua.kgsolido dry- 1 ). The content of total phenolics, tannins hydrolysates and condensates and antioxidant activity (DPPH scavenging, reducing and iron chelation) of dried and fresh Curcuma longa leaves were evaluated. The drying methods led to reduction of all the characteristics assessed on a dry basis (2.77 to 73.86%) and antioxidant capacity compared to fresh leaf (67 to 98%). The microwave drying was preservation method studied which produced the best dry leaves, based on the content of bioactive compounds and antioxidant capacity (top being 0.9 to 612% compared to other methods). / O objetivo desse trabalho foi avaliar a qualidade físico-química e caracterizar os compostos bioativos e capacidade antioxidante da folha da Cúrcuma Longa L. submetida a três métodos de secagem: estufa, liofilização e micro-ondas, assim como o estudo cinético pelos métodos de secagem por convecção e micro-ondas. Para o estudo cinético as folhas foram secas por convecção (temperatura de 60°C) e micro-ondas (potência de 900 W). Foi realizada a modelagem matemática utilizando vários modelos, sendo eles: Lewis, Page, Henderson e Pabis, Wang & Singh e logarítmico, ajustando os modelos aos dados experimentais cinéticos. Os resultados obtidos revelaram que o tempo de secagem por micro-ondas foi 60 vezes inferior ao de secagem convectiva. O modelo de Page foi o que melhor ajustou os dados de cinética de secagem pelos dois métodos. O conteúdo de fenólicos foi superior na folha seca (185,42mg/100g-1±0,65) pelo método micro-ondas (p<0,05) que na folha seca por convecção (183,76 mg/100g-1±0,60), apresentando conteúdo de fenólicos maior que três vezes o da folha in natura (54,88mg/100g-1±0,76). Observou-se que o processo de secagem não influenciou na variação de cor (ΔE) da folha seca. Para o estudo da caracterização física e química de folhas de Curcuma longa L. através do estudo da composição centesimal da folha fresca, composição de minerais, presença de fatores antinutricionais e avaliação da variação de cor da folha fresca e seca, estas foram desidratadas pelos métodos de micro-ondas, estufa e liofilização. A composição centesimal apresentou quantidades apreciáveis de proteínas (39,5g (100g)-1 ±0,91), carboidratos (44,74g (100g)-1±1,04), fibras totais (34,47g (100g)-1±0,98), sendo fibra solúvel (22,65g (100g)-1±0,65), fibra insolúvel (11,81g (100g)-1±0,34) , cinzas (13,81g (100g)-1±1,05), e baixo teor de lipídeos (2,47g (100g)-1±0,12). A composição mineral mostrou maiores valores de Na, Mg, Ca, K, P e Mn. Outros minerais foram Fe e Zn. Observou- se baixos teores de nitrato 0,05 mg/g±0,00 (folha fresca) e 0,46-0,47mg/g (folhas secas) e não apresentou compostos cianogênicos em sua composição. Observou-se que o processo de secagem influenciou na variação de cor das folhas secas, aumentando a luminosidade, diminindo a intensidade da cor verde e provocando a mudança da tonalidade verde para verde amarelada. Para o estudo do efeito de diferentes métodos de conservação (secagem em estufa, em micro-ondas e liofilização) no conteúdo de compostos bioativos e na capacidade antioxidante de folhas de cúrcuma, estas foram desidratadas por secagem em estufa (60ºC), em micro-ondas (900 W) e liofilização (vácuo de 300 mmHg) até umidade de equilíbrio (0,030 kgágua.kgsólido seco -1 ). O conteúdo de fenólicos totais, taninos hidrolisados e condensados e atividade antioxidante (sequestradora de DPPH, redução e quelação de ferro) de folhas cúrcuma secas e fresca foram avaliados. Os métodos de secagem provocaram redução de todas as características avaliadas, em base seca (2,77 a 73,86%) e capacidade antioxidante em relação à folha fresca (67 a 98%). A secagem por micro-ondas foi o método de conservação estudado que produziu as melhores folhas secas, com base no conteúdo de compostos bioativos e capacidade antioxidante (sendo superior de 0,9 a 612% em relação aos outros métodos utilizados).

L‘intérêt de développer de nouvelles applications de la nanotechnologie pharmaceutique dans les soins de santé augmente année après année. Le rôle des nanosystèmes est devenu évident, surtout après que certains d'entre eux aient contribué à des solutions révolutionnaires dans des maladies graves. Dans notre projet, nous avons cherché à synthétiser des nanoparticules (NPs) intelligentes capables de livrer, de façon sélective, des agents anticancéreux. Les NPs ont été synthétisées afin de cibler des cellules cérébrales atteintes par le glioblastome multiforme (GBM), un cancer du cerveau présentant un mauvais pronostic et un taux de survie médian très faible. À cet effet, nous avons planifié de synthétiser et analyser ces nanoparticules et également d’étudier les preuves de concept de leur efficacité. Tout d'abord, nous avons sélectionné avec soin, la procédure de formulation ainsi que les polymères avant d’optimiser les caractéristiques physico-chimiques des nanogels (NGs) formulés à base de chitosane. Après l'optimisation de la taille, du PdI et du potentiel de surface des NGs, nous avons synthétisés des NGs chargés en substance active. Deux molécules thérapeutiques ont été retenues La première était la doxorubicine HCl (DOX) qui est trop hydrophile pour passer la BHE, bien qu’ayant démontré une efficacité in vitro contre le GBM. Le deuxième médicament était le témozolomide (TMZ) qui est déjà utilisé dans le traitement de GBM, comme adjuvant à la radiothérapie, après l’intervention chirurgicale. Les méthodes d'analyses ont ensuite été développées pour déterminer l’efficacité du taux d'encapsulation (EE%) et l'efficacité de chargement de médicament (DLE%) des deux médicaments. Pour la préparation des nanogels théranostiques, nous avons suivi les mêmes procédures après l’addition de l’agent de contraste USPIO, durant la synthèse des NGs. Ensuite, nous avions besoin d’assurer la qualité de nos NGs lors du stockage à long terme. Pour atteindre cet objectif, nous avons développé une procédure de lyophilisation en utilisant différents sucres de nature et de concentrations variables. Les sucres ont été ajoutés pour cryoprotéger les NGs contre les contraintes mécaniques et physiques mises en jeu lors de la lyophilisation. Les sucres qui ont démontré des résultats satisfaisants avec NGs vides ont été utilisés, par la suite, dans la cryoprotection des NGs chargées de médicament au cours de leur lyophilisation. Finalement, nous avons étudié la libération de la DOX à partir des NGs chargées avant et après lyophilisation. Cette étude, en particulier avait deux objectifs. Le premier était de comparer l'effet de la lyophilisation sur le comportement de la libération de DOX des NGs, en observant l’impact de cette procédure sur la cinétique de libération Le deuxième but de l'étude de relargage était de tester la capacité des NGs à libérer leur contenu à trois pH différents : 5.8 (pH intracellulaire des cellules tumorales), 6.8 (espace interstitiel de la tumeur) et 7.4 (plasma sanguin). / The interest in developing new applications of nanotechnology in the pharmaceutical health care increases year after year. The role of nanosystems became clearer, especially after some of them contributed to revolutionary solutions in serious diseases. In our project, we sought to synthesize ‘intelligent’ nanoparticles (NPs) capable of selectively delivering anticancer agents. NPs were synthesized to target brain cells affected by glioblastoma multiforme (GBM), a brain cancer with a poor prognosis and a very low rate of median survival. To this end, we planned to synthesize and analyze these nanoparticles and also to study the proof-of-concept of their efficiency. First, we carefully selected the formulation process and the polymers prior to optimize physicochemical characteristics of the nanogels (NGs) formulated with chitosan. After optimization of the NGs size, PDI and surface potential, we synthesized NGs loaded with active substances. Two therapeutic molecules were selected. First we chose doxorubicin HCl (DOX) which is too hydrophilic to cross the BBB, whereas demonstrating in vitro efficacy against GBM. The second drug was temozolomide (TMZ), already used in the treatment of GBM as an adjuvant to radiotherapy after surgery. Analytical methods were then developed to determine the encapsulation efficiency (EE %) and drug loading efficiency (DLE %) of both drugs. For the preparation of theranostic nanogels, we followed the same procedures after the addition of the USPIO contrast agent during the NGs synthesis. Next, we needed to ensure the quality of our NGs during long-term storage. To achieve this goal, we developed a freeze-drying process using different kind of sugar cryoprotectants at varying concentrations, in order to protect NGs against mechanical and physical stresses at play during freeze-drying. Most promising sugars used with unloaded NGs were subsequently used to cryoprotect DOX-loaded NGs. Finally, we studied the release of DOX from DOX-loaded NGs before and after freeze-drying. This study in particular had two objectives. The first was to compare the effect of the freeze-drying process on the behavior of the DOX-loaded NGs, observing the impact of this procedure on the release kinetics. The second purpose of the release study was to test the ability of NGs to release their contents at three different pH: 5.8 (intracellular pH of tumor cells), 6.8 (interstitial space of the tumor) and 7.4 (blood plasma).

L'objectif de cette thèse est la préparation d’aérogels biosourcés ayant des propriétés de super-isolation thermique. Pour cela, nous avons choisi de développer de nouveaux aérogels à base de nanofibres de cellulose (NFC). Les aérogels ont été préparés par lyophilisation. Dans un premier temps, une analyse des paramètres expérimentaux jouant un rôle sur la morphologie et les propriétés physico-chimiques des aérogels a été réalisée afin d’obtenir les meilleures propriétés d’isolation thermique. Avec une suspension de NFC à 2% en masse, sans ajout de sels et sans faire varier le pH, une lyophilisation réalisée dans des moules d’aluminium à une température de -80°C a permis d’obtenir des aérogels ayant une conductivité thermique de 0,024 W/m.K. Afin de diminuer cette conductivité thermique, nous avons choisi de réduire la taille des pores pour obtenir un effet Knudsen. Pour cela, une nouvelle technique de séchage a été proposée : la lyophilisation par pulvérisation. Les aérogels préparés dans les mêmes conditions expérimentales que précédemment avec cette technique ont des propriétés thermiques super-isolantes (0,018 W/m.K) grâce à la nano-structuration du réseau poreux. Finalement, un nouveau dispositif expérimental a été développé pour caractériser plus finement les propriétés thermiques des aérogels. C’est un dispositif transitoire impulsionnel qui permet d'estimer simultanément la contribution de la conduction solide et gazeuse, l'effet radiatif et la diffusivité thermique grâce à un modèle théorique simple. Ce dispositif permettra d’approfondir l’étude complexe du transfert thermique à travers des matériaux poreux semi-transparents tels que les aérogels. / The objective of this thesis is the preparation of renewable aerogels having thermal super-insulating properties. To do it, we designed new aerogels from nanofibrillated cellulose (NFC) by freeze-drying. This technique is simple and has the advantage of not using organic solvents. First of all, the parameters playing a role on the aerogel morphology and physico-chemical properties of the aerogels were analyzed to get the best thermal insulating properties. Using 2 wt% NFC suspensions, without addition of salts, keeping the initial pH, the obtained freeze-dried aerogels in alumina molds at -80 °C have a thermal conductivity of 0.024 W/m.K. In order to reduce the pore size and to improve the thermal insulating properties by Knudsen effect, a new drying technique was proposed: the spray freeze-drying. Aerogels prepared in the same experimental conditions with this technique have thermal super-insulating properties (0.018 W/m.K) thanks to the nanostructuration of the porous network. Finally, a new device was designed to characterize more precisely the thermal properties of aerogels. This is an impulsive transient device, which can estimate simultaneously the contribution of solid and gas conduction, the radiative effect and thermal diffusivity using a simple theoretical model. This device will allow studying complex heat transfer through porous semi-transparent materials such as aerogels

Tato diplomová práce se zabývá charakterizací 3D porézních kolagenových pěn obsahující vybraná antibakteriální činidla. V literární části jsou shrnuty dosavadní poznatky o biomateriálech a biopolymerech se zaměřením na kolagen a chitosan. Dále jsou v ní popsány antibakteriálních vlastnosti nanočástic v kontextu s využitím selenových nanočástic jako antibakteriální činidla. Pro potřeby této práce byla vybrána antibakteriální aditiva dvojího typu – biopolymerní chitosan a selenové nanočástice. 3D porézní struktury bylo dosaženo metodou lyofilizace. Mechanické vlastnosti biopolymerní matrice byly podpořeny síťováním v prostředí chemického síťovadla na bázi karbodiimidu. K charakterizaci připravených kolagenových pěn byly použity především fyzikálně chemické metody. Na analýzu mikrostruktury a velikosti pórů, vizualizaci nanočástic a jejich distribuci v testovaných materiálech byla využita rastrovací elektronová mikroskopie (SEM) spolu s energiově disperzní analýzou (EDX). Parametry jako je porozita, botnací poměr, úbytek hmotnosti při degradaci ve vodném prostředí a v prostředí enzymů byly zjištěny vhodnými gravimetrickými metodami. Ovlivnění chemické struktury kolagenové matrice před a po přidání antibakteriálních aditiv bylo sledováno za pomocí metody zeslabeného úplného odrazu infračervené spektroskopie s Fourierovou transformací (ATR FTIR). Procentuální uvolnění nanočástic z testovaných vzorků bylo sledováno pomocí optické emisní spektroskopie s indukčně vázanou plazmou (ICP OES). K zhodnocení antibakteriálních vlastností testovaných materiálů byly použity především difúzní agarová disková metoda a makrodiluční bujónová metoda. Provedeným výzkumem jsme zjistili vliv přídavku antibakteriálních činidel na strukturu a některé vlastnosti 3D kolagenových matric. Výsledky antibakteriálních testů ukázaly pozitivní vliv chitosanu i selenových nanočástic na inhibici růstu bakterií v závislosti na koncentraci přidaných aditiv. Navržené materiály mohou být využity pro biomedicínské aplikace především v oblastech zabývající se regenerací měkkých tkání.