Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 ZilvamMS_TESE_reduzido.pdf: 9108618 bytes, checksum: 613dad3fd1a359dce84e2af73b067934 (MD5) Previous issue date: 2013-02-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Surfactant-polymer interactions are widely used when required rheological properties for specific applications, such as the production of fluids for oil exploration. Studies of the interactions of chitosan with cationic surfactants has attracted attention by being able to cause changes in rheological parameters of the systems making room for new applications. The commercial chitosan represents an interesting alternative to these systems, since it is obtained from partial deacetylation of chitin: the residues sites acetylated can then be used for the polymer-surfactant interactions. Alkyl ethoxylated surfactants can be used in this system, since these non-ionic surfactants can interact with hydrophobic sites of chitosan, modifying the rheology of solutions or emulsions resultants, which depends on the relaxation phenomenon occurring in these systems. In this work, first, inverse emulsions were prepared from chitosan solution as the dispersed phase and cyclohexane as the continuous phase were, using CTAB as a surfactant. The rheological analysis of these emulsions showed pronounced pseudoplastic behavior. This behavior was attributed to interaction of "loops" of chitosan chains. Creep tests were also performed and gave further support to these discussions. Subsequently, in order to obtain more information about the interaction of chitosan with non-ionic surfactants, solutions of chitosan were mixed with C12E8 and and carried out rheological analysis and dynamic light scattering. The systems showed marked pseudoplastic behavior, which became less evident when the concentration of surfactant was increased. Arrhenius and KWW equations were used to obtain parameters of the apparent activation energy and relaxation rate distribution, respectively, to which were connected to the content of surfactant and temperature used in this work / As intera??es tensoativo-pol?mero s?o amplamente usadas quando s?o necess?rias propriedades reol?gicas para aplica??es espec?ficas, como a produ??o de fluidos para explora??o do petr?leo. Estudos das intera??es de quitosana com tensoativos cati?nicos tem chamado aten??o por serem capazes de causar mudan?as nos par?metros reol?gicos dos sistemas abrindo espa?o para novas aplica??es. A quitosana comercial representa uma alternativa interessante para estes sistemas, uma vez que ela ? obtida a partir da desacetila??o parcial da quitina: os s?tos acetilados residuais podem, ent?o, ser usados para as intera??es pol?mero-tensoativo. Tensoativos alquil etoxilados podem ser utilizados neste sistema, pois estes tensoativos n?o i?nicos podem interagir com s?tios hidrof?bicos da quitosana, modificando a reologia de solu??es ou emuls?es resultantes, os quais dependem do fen?meno de relaxa??o ocorrendo nestes sistemas. Neste trabalho, primeiramente, foram preparadas emuls?es inversas de solu??o de quitosana como fase dispersa e cicloexano como fase cont?nua usando CTAB como tensoativo. A an?lise reol?gica destas emuls?es mostrou pronunciado comportamento pseudopl?stico. Esta pseudoplasticidade foi atribu?da ? intera??o por la?os loops de cadeias de quitosana. Ensaios de flu?ncia tamb?m foram executados e deram maior suporte a estas discuss?es. Em seguida, a fim de se obter maiores informa??es sobre as intera??es da quitosana com tensoativos n?o i?nicos, solu??es de quitosana foram misturadas com C12E8 e levadas ?s an?lises reol?gica e de espalhamento din?mico de luz. Os sistemas tiveram elevado comportamento pseudopl?stico, o qual se tornava menos evidente, quando o teor de tensoativo foi aumentado. Equa??es de Arrhenius e de KWW foram usadas para obter par?metros de energia de ativa??o aparente e de distribui??o da taxa de relaxa??o, respectivamente, aos quais foram relacionados em fun??o do teor de tensoativo e da temperatura, usados neste trabalho

A hidrolipodistrofia ginóide, popularmente denominada de celulite, é caracterizada como um processo distrófico que produz alterações estruturais dos elementos presentes na pele, como: modificações no tecido conjuntivo, comprometimento da microcirculação periférica cutânea, hipertrofia e hiperplasia dos adipócitos e edema. Os flavonóides são utilizados como substâncias ativas em preparações anticelulíticas por reduzirem a permeabilidade capilar. Os objetivos estabelecidos para esta pesquisa foram: (1) desenvolver emulsões cosméticas com finalidades anticelulíticas; (2) validar metodologia analítica para o doseamento de flavonóides totais, equivalentes em rutina, por espectrofotometria na região do ultravioleta; (3) avaliar a estabilidade física, físico-química e química das formulações. Formulações cosméticas anticelulíticas foram desenvolvidas contendo o extrato vegetal comercial de Trichilia catiguá Adr. Juss (e) Ptychopetalum olacoides Bentham (Slimbuster® H1), padronizado em flavonóides totais, equivalentes em rutina, e avaliadas quanto à estabilidade física, físico-química e química. Para sua quantificação, o método espectrofotométrico na região do ultravioleta a 361,0 nm foi empregado, comparando-se com rutina padrão secundário de referência (T = 96,1%). A avaliação da estabilidade envolveu três condições distintas de temperatura (5,0 + 0,5; 24 + 2 e 40,0 + 0,5 °C), pelo período de três meses, e as variáveis analisadas foram as características organolépticas, valor de pH, viscosidade aparente e teor de flavonóides totais. A metodologia foi validada quanto à linearidade, limites de detecção e quantificação, especificidade e pesquisa de interferentes, recuperação do padrão, precisão e exatidão intra e inter-dias. Os resultados da estabilidade indicaram que o teor de flavonóides totais, equivalentes em rutina, sofreu decaimento inferior a 10% nas condições de exposição à luz solar direta e/ou indireta, à temperatura ambiente (24 + 2 °C) e de refrigerador (5,0 + 0,5 °C), sendo que a 40,0 + 0,5 °C, condição de estufa, ocorreu redução de, aproximadamente, 35%. / Gynoid hydrolipodystrophy, popularly known as cellulite, is characterized as a dystrophic process that generates structural alterations of skin elements, as: connective tissue modifications, cutaneous microcirculation abnormalities, hypertrophy and hyperplasia of adipocytes and edema. Flavonoids are employed as raw materials in anticellulitic products by their capability to reduce capillary permeability. The objectives established for this research were: (1) development of anticellulitic cosmetic emulsions; (2) analytical method validation for total flavonoids, expressed in rutin, by ultraviolet spectrophotometry; (3) physical, physicochemical and chemical stability assay for the preparations. Anticellulitic cosmetic formulations containing the Trichilia catigua Adr. Juss (and) Ptychopetalum olacoides Bentham commercial extract (Slimbuster® H1), standardized in total flavonoids, expressed in rutin, were developed and their physical, physicochemical and chemical stability was assessed. Flavonoids were quantified within the ultraviolet spectrophotometric method at 361.0 nm as rutin equivalents by comparison with secondary standard rutin (T = 96.1%). Stability assay was conducted in three temperature conditions (5.0 + 0.5; 24 + 2 e 40.0 + 0.5 °C) and the following parameters were analyzed: aspect, color and odor, pH and apparent viscosity values and flavonoid content. Analytical methodology was validated determining linearity, limits of detection and quantification, specificity and interferent assay, recovery and intra and inter-run precision and accuracy. Results from stability evaluation have indicated decrease of flavonoid content inferior than 10% at sunlight exposure (room temperature, 24 + 2 °C) and at 5.0 + 0.5 °C; high temperature (40.0 + 0.5 °C) has reduced the flavonoid content at, approximately, 35%.

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

A rutina é empregada como antioxidante e na prevenção da fragilidade capilar. Pode ser veiculada em emulsões tópicas adequadas para atingir o local de ação. Estudos de penetração in vitro através da pele humana seria a situação ideal, entretanto, há dificuldades de sua obtenção e manutenção de sua viabilidade. Entre os demais modelos de membrana, a muda de pele de cobra apresenta-se como estrato córneo puro, fornecendo barreira similar ao humano e é obtida sem a morte do animal. Os objetivos desta pesquisa foram: (1) desenvolver e avaliar a estabilidade de emulsões cosméticas, contendo rutina e promotores de penetração cutânea, tais como, uréia (U), isopropanol (IP) e propilenoglicol (PG); (2) avaliar a liberação da referida substância ativa das emulsões e; (3) avaliar a penetração e a retenção cutânea in vitro da rutina da formulação de melhor desempenho. Emulsões foram desenvolvidas com rutina a 5,0% p/p e U, IP e PG, associados ou não e em proporções distintas, segundo planejamento fatorial com dois níveis com ponto central. Quantificou-se a rutina das emulsões por espectrofotometria a 361,0 nm, método previamente validado. A liberação da rutina nas formulações foi realizada em células de difusão vertical com membrana de acetato de celulose e água destilada e álcool etílico absoluto 99,5% (1:1), como fluido receptor. O experimento foi conduzido em um período de seis horas, a 37,0 ±. 0,5 &#176;C e agitação constante de 300 rpm.>f. emulsão de melhor desempenho quanto à liberação foi estudada quanto à estabilidade (Testes de Estabilidade Acelerada). Para o estudo de penetração e retenção cutânea da rutina dessa formulação foi utilizada muda de pele de cobra de Crotalus durissus. Empregou-se o método espectrofotométrico validado a 410,0 nm para a quantificação da rutina após liberação, penetração e retenção cutânea. Todas as emulsões foram consideradas adequadas após desenvolvimento das formulações. A uréia (isolada e em associação com IP e PG) e o isopropanol (isolado e em associação com PG) influenciaram negativamente a liberação da rutina das emulsões em diversos parâmetros. A rutina liberada e acumulada da formulação contendo PG a 5,0% p/p possuiu valor de 648,80 ±. 53,01 &#181g/cm2. Fora do esperado, a preparação contendo o número maior de promotores (U 5,0% p/p, IP 5,0% p/p e PG 5,0% p/p) resultou em liberação de menor magnitude igual a 419,76 ±. 17,98 &#181g/cm2. A presença do PG apresentou-se mais eficiente na liberação da rutina, mas não na sua penetração através da muda de pele de C. durissus, retendo 0,931 ± 0,0391 &#181;g de rutina/mg de muda de pele de cobra. Nas condições de armazenamento a 25,0 ±2,0 &#176;C; 5,0 ±0,5 &#176;C e 45,0 ±. 0,5 &#176;C, a emulsão com PG e rutina apresentou-se quimicamente estável durante 30 dias. De acordo com os resultados, a emulsão contendo PG apresentou liberação mais expressiva da rutina, no entanto, não ocorreu a penetração cutânea, mas apenas sua retenção no estrato córneo de C. durissus. A preparação manteve-se estável em todas as condições de armazenamento. / Rutin is employed as antioxidant and to prevent the capillary fragility and, when incorporated in cosmetic emulsions, it must target the action site. In vitro cutaneous penetration studies through human skin is the ideal situation, however, there are difficulties to obtain and to maintain this tissue viability. Among the membrane models, the shed snake skin presents itself as pure stratum corneum, providing barrier function similar to human and it is obtained without the animal sacrifica. The objectives of this research were: (1) development and stability evaluation of cosmetic emulsions containing rutin and penetration enhancers, as urea (U), isopropanol (IP) and propylene glycol (PG); (2) release evaluation of the mentioned active substance from the emulsions and; (3) evaluation of rutin in vitro cutaneous penetration and retention from the emulsion of the best performance. Emulsions were developed with rutin 5.0% w/wand U, IP and PG, associated or not according to factorial design with two levels and central point. Active substance on the formulations was quantified by a validated spectrophotometric method at 361.0 nm. Rutin release from emulsions was performed in vertical diffusion cells with cellulose acetate membrane and distilled water and ethanol 99.5% (1:1), as receptor fluid. The experiment was conducted for six hours, at 37.0 ± 0.5 °c with constant stirring of 300 rpm. Formulation with best profile of rutin release had its stability studied by the Accelerated Stability Assays. Rutin cutaneous penetration and retention from the mentioned emulsion was performed with shed snake skin from Crotalus durissus. Spectrophotometry at 410.0 nm, previously validated, determined the active substance after release and cutaneous penetration/retention. Ali emulsions were considered apparently stables after development. Urea (isolated and associated with IP and PG) and isopropanol (isolated and associated with PG) have influenced negatively the rutin release in several parameters. Emulsion with PG 5.0% w/w presented rutin released and accumulated equal to 648.80 ± 53.01 &#181;g/cm2. Unexpectedly, the formulation containing all enhancers (U 5.0% w/w, IP 5.0% w/w and PG 5.0% w/w) has decreased the amount released of the active substance (419.76 ± 17.98 &#181;g/cm2). Emulsion with PG presented more adequate for rutin release, but PG did not provide rutin cutaneous penetration through C. durissus skin, retaining 0.931 ± 0.0391 &$181;g rutin/mg shed snake skin. The referred formulation was chemically stable for 30 days after they have been stored at 25.0 ± 2.0 &#176;c, 5.0 ± 0.5 &#176;c and 45.0 ± 0.5 &#176;C. In conclusion, emulsion with PG provided rutin release more expressively, although, it has not been verified the active cutaneous penetration, but only its retention on the Crotalus durissus stratum corneum. Formulation was stable in all storage conditions.

[ES] Las microalgas son organismos unicelulares fotosintéticos microscópicos que se encuentran en gran variedad de ambientes y son muy eficientes en la transformación de energía solar en biomasa. Los estudios realizados hasta el momento hacen referencia a posibles beneficios de la incorporación de microalgas en la dieta, por la mejora del sistema cardiovascular, las propiedades adelgazantes y energizantes, capacidad antioxidante, o la reducción del colesterol y los triglicéridos. La forma más habitual de consumir las microalgas es como suplemento dietético en forma de tabletas, cápsulas o polvo. La incorporación de biomasa de microalgas en productos tradicionales se ha enfrentado al reto de la aparición de colores verdes fuertes, así como su consistencia pulverulenta que puede afectar la textura y percepción del producto. Todos estos aspectos constituyen las principales áreas de mejora para conseguir un mayor grado de aceptación de productos con microalgas, y son la base del reto de este proyecto. El objetivo de la presente tesis doctoral fue el desarrollo de nuevos productos alimentarios incorporando las propiedades nutricionales de la biomasa de microalgas, incrementando o mejorando con ello, las propiedades nutricionales del alimento original. Para conseguir este objetivo se evaluaron a nivel fisicoquímico, reológico y textural, la incorporación de diferentes especies de microalgas (Arthrospira platensis (Spirulina), Chlorella vulgaris, Dunaliella salina y Nannochloropsis gaditana) en distintas matrices alimentarias (productos horneados, emulsiones y extrusionados). Por otra parte, se evaluó y caracterizó la incorporación de las microalgas utilizando diferentes tecnologías como la impresión 3D o la extrusión. Además de cómo afecta la incorporación de las microalgas a los productos obtenidos, se evaluaron los aspectos nutricionales de su incorporación, en cuanto al aporte de minerales y su biodisponibilidad. Las propiedades reológicas de las masas y emulsiones enriquecidas con microalgas (Spirulina, Chlorella y Dunaliella) indicaron que su comportamiento viscoelástico fue modificado y mejorado, mostrando características aptas para este tipo de productos. La adición de microalgas (Spirulina y Chlorella) a las masas utilizadas para la impresión 3D de galletas y snacks, permitió una mejor extrusión o impresión de éstas, obteniendo muestras impresas en 3D de forma cilíndrica, más precisas en cuanto a sus dimensiones con respecto a la estructura cilíndrica diseñada. Además, las muestras impresas presentaron mayor estabilidad y resistencia, antes y después del proceso de horneado comparadas con la muestra control. Para los productos horneados, tanto para las rosquilletas como los snacks impresos en 3D, la adición de microalgas (Spirulina y Chlorella) permitió mayor estabilidad en términos de textura. Ligeros cambios en los parámetros fisicoquímicos y de expansión se produjeron por la adición de Spirulina y Chlorella en los productos extrusionados. Además, los extrusionados enriquecidos con Nannochloropsis, mostraron parámetros similares a los de la muestra de control. Todos los productos presentaron colores luminosos y apariencias innovadoras y atractivas. En cuanto a los minerales, se observó un aumento de P, K, Ca, Na, Mg, Fe y Se con la adición de Spirulina y Chlorella, junto con el aumento de la concentración adicionada de microalgas. Siguiendo la normativa sobre etiquetado nutricional de los alimentos, el enriquecimiento con microalgas en rosquilletas se puede clasificar como un alimento "rico en hierro (Fe)". De igual forma, las rosquilletas y galletas enriquecidas con microalgas pueden considerarse un alimento "alto en selenio (Se)". Además, la incorporación de Spirulina y Chlorella en las formulaciones de galletas, permitió una mayor bioaccesibilidad del contenido de P, K, Ca, Mg, Fe, Zn y Se para la absorción en el cuerpo comparado con las muestras control. / [CAT] Les microalgues són organismes unicellulars fotosintètics microscòpics. Són molt eficients a l'hora de transformar l'energia solar en biomassa. Els estudis realitzats fins ara fan referència a possibles beneficis de la incorporació de microalgues en la dieta per produir una millora del sistema cardiovascular, per presentar propietats per aprimar i donar energia, per mostrar capacitat antioxidant o per afavorir una reducció del colesterol i els triglicèrids. La forma més habitual de consumir microalgues és com a suplement dietètic en forma de tauleta, càpsula o en pols. La incorporació de biomassa de microalgues en productes tradicionals s'ha afrontat al repte de l'aparició d'un color verd fosc i d'una consistència polsosa que pot afectar a la textura i, per tant, a la percepció del producte. Aquests aspectes constituïxen les principals àrees de millora per aconseguir un major grau d'acceptació de productes amb microalgues i són la base del repte d'aquest projecte. L'objectiu d'aquesta tesi doctoral és el desenvolupament de nous productes alimentaris que incorporen les propietats nutricionals de la biomassa de microalgues, de manera que s'incrementen o es milloren les propietats nutricionals de l'aliment original. Per aconseguir aquest objectiu s'avaluaren a escala fisicoquímica, reològica i de textura la incorporació de diferents espècies de microalgues (Arthrospira platensis (Spirulina), Chlorella vulgaris, Dunaliella salina i Nannochloropsis gaditana) en diferents matrius alimentàries (productes fornejats, emulsions i extrudits). D'altra banda, s'avaluà i caracteritzà la incorporació de les microalgues utilitzant diferents tecnologies com la impressió en 3D o l'extrusió. A banda de valorar com afecta la incorporació de microalgues als productes elaborats, s'avaluaren els aspectes nutricionals, pel que fa a l'aportació i biodisponibilitat de minerals. Les propietats reològiques de les masses i emulsions enriquides amb microalgues (Spirulina, Chlorella i Dunaliella) indicaren que el seu comportament viscoelàstic fou modificat i millorat, de tal manera que mostrà característiques aptes per aquest tipus de productes. L'addició de microalgues (Spirulina i Chlorella) en les masses utilitzades per a la impressió 3D de galetes i snacks permeté una millor impressió, ja que s'obtingueren mostres impreses de forma cilíndrica amb unes dimensions més precises respecte a l'estructura cilíndrica dissenyada. A més, les mostres impreses presentaren una major estabilitat i resistència abans i després del procés de fornejat en comparació amb la mostra control. Respecte als productes fornejats, l'addició de microalgues (Spirulina i Chlorella) a les rosquilletes i els snacks impresos en 3D permeté una major estabilitat en termes de textura. Lleugers canvis als paràmetres fisicoquímics i d'expansió es produïren per l'addició d'Spirulina i Chlorella en els productes extrudits. A més, els extrudits que foren enriquits amb Nannochloropsis mostraren paràmetres similars als de la mostra control. Tots els productes presentaren colors lluminosos i aparences innovadores i atractives. Pel que fa als minerals, s'observà un augment de P, K, Ca, Na, Mg, Fe i Se quan s'afegí Spirulina i Chlorella, directament relacionat amb l'augment de la concentració de microalgues. Seguint la normativa sobre etiquetatge nutricional dels aliments, l'enriquiment amb microalgues en rosquilletes ens permet classificar-les com a aliment "ric en ferro (Fe)". De la mateixa manera, les rosquilletes i galetes enriquides amb microalgues poden considerar-se un aliment "alt en seleni (Se)". A més a més, la incorporació de Spirulina i Chlorella en les formulacions de galetes, permeté una major bioaccessibiltat del contingut de P, K, Ca, Mg, Fe, Zn i Se comparat amb les mostres control. / [EN] Microalgae are microscopic unicellular and photosynthetic organisms that can be found in a wide variety of environments. These microorganisms are very efficient when transforming solar energy into biomass, due to their cellular structure, which is completely submerged in an aqueous medium, forming an adequate surface for the exchange of nutrients and gases. Microalgae compounds are now known to exhibit cardioprotective, immunomodulatory, anti-proliferative, anti-inflammatory, cognitive, neurobehavioral and antimicrobial properties, amongst others. Researchers have shown possible benefits of the incorporation of microalgae in the diet so far. The most common way to consume microalgae is as a dietary supplement in the form of tablets, capsules or powder. The incorporation of microalgae biomass in traditional products has faced the challenge of the appearance of strong green colours, as well as its powdery consistency that can affect the texture and perception of the product. All these aspects constitute the main areas for improvement the development of microalgae-based products, and they are the challenges faced of this project. The main objective of this PhD Thesis was the development of novel food products incorporating the nutritional properties of microalgae biomass, thereby increasing or improving the nutritional properties of the original food matrix. To achieve this goal, the effect of the addition of different species of microalgae (Arthrospira platensis (Spirulina), Chlorella vulgaris, Dunaliella salina and Nannochloropsis gaditana) on the physicochemical, rheological and textural properties of different food matrices (baked products, emulsions and extrudates) was evaluated. Furthermore, the effect of the incorporation of microalgae using different technologies such as 3D printing or extrusion to obtain food products was studied. In addition, how the incorporation of microalgae affects the nutritional aspects of the food products in terms of the contribution of minerals and their bioavailability was also evaluated. The rheological properties of doughs, batters and emulsions enriched with microalgae (Spirulina, Chlorella and Dunaliella) indicated that their viscoelastic behaviour was modified and improved, showing characteristics suitable for this type of products. The addition of microalgae (Spirulina and Chlorella) to the doughs and batters used for the 3D printing of cookies and snacks, allowed a better extrusion or printing behaviour. This allowed obtaining cylindrical 3D printed samples, more precise in terms of their dimensions with respect to the designed cylindrical structure. In addition, the 3D microalgae-printed sample structures presented greater stability and resistance, before and after the baking process compared to the control sample. For baked products, both for breadsticks and 3D printed snacks, the addition of microalgae (Spirulina and Chlorella) allowed greater stability in terms of texture. Slight changes in the physicochemical and expansion parameters were produced by the addition of Spirulina and Chlorella in the extruded products. In addition, the extrudates enriched with Nannochloropsis, showed similar parameters to those of the control sample. Microalgae-enriched obtained products showed bright colours with appealing appearances. Regarding minerals, an increase in P, K, Ca, Na, Mg, Fe and Se was observed with the addition of Spirulina and Chlorella, along the increase of concentration of microalgae addition. Following the regulations on nutrition labelling for food stuffs, breadstick enrichment with microalgae are a food "high in iron (Fe)" In the same way, breadsticks and cookies enriched with microalgae can be considered a "high in selenium (Se)" food. Going a step further, Spirulina and Chlorella vulgaris incorporation in cookie formulations allowed for greater bioaccessibility of P, K, Ca, Mg, Fe, Zn, and Se content for absorption in the body than control cookies. / Uribe Wandurraga, ZN. (2020). Microalgae as novel ingredients for the formulation of food products [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/158743 / TESIS

A non-reactive model system comprising a highly concentrated and unstable oil-in-water emulsion was used to investigate the retention of oil by the membrane in producing biodiesel with a membrane reactor. Critical flux was identified using the relationship between the permeate flux and transmembrane pressure along with the separation efficiency of the membrane. It was shown that separation efficiencies above 99.5% could be obtained at all operating conditions up to the critical flux. It was observed that the concentration of oil in all collected permeate samples using the oil-water system was below 0.2 wt% when operating at a flux below the critical flux. Studies to date have been limited to the characterization of low concentrated emulsions below 15 vol.%. The average oil droplet size in highly concentrated emulsions was measured as 3200 nm employing direct light scattering (DLS) measurement methods. It was observed that the estimated cake layer thickness of 20 to 80 mm was larger than external diameter of the membrane tube i.e. 6 mm based on a large particle size. Settling of the concentrated emulsion permitted the detection of a smaller particle size distribution (30-100 nm) within the larger particles averaging 3200 nm. It was identified that DLS methods could not efficiently give the droplet size distribution of the oil in the emulsion since large particles interfered with the detection of smaller particles. The content of the smaller particles represented 1% of the total weight of oil at 30°C and 5% at 70°C. This was too low to be detected using DLS measurements but was sufficient to affect ultrafiltration. In order to study the critical flux in the presence of transesterification reaction and the effect of cross flow velocity on separation, various oils were transesterified in another membrane reactor providing higher cross flow velocity. higher cross flow velocity provides better separation by reducing materials deposition on the surface of the membrane due to higher shearing. The oils tested were canola, corn, sunflower and unrefined soy oils (Free Fatty Acids (FFA< 1%)), and waste cooking oil (FFA= 9%). The quality of all biodiesel samples was studied in terms of glycerine, mono-glyceride, di-glyceride and tri-glyceride concentrations. The composition of all biodiesel samples were in the range required by ASTM D6751 and EN 14214 standards. A critical flux based on operating pressure in the reactor was reached for waste cooking and pre-treated corn oils. It was identified that the reaction residence time in the reactor was an extremely important design parameter affecting the operating pressure in the reactor. / Natural Sciences and Engineering Research Council of Canada (NSERC)

The present work broaches the physics of light-matter interaction, chiefly using nonlinear optical spectroscopy in a newly developed framework termed as Photon Management Concept. This way, existing fragments dealing with specific properties of harmonic and upconversion nanoparticles (HNPs/UCNPs) are consolidated into a full and coherent picture with the primary goal of understanding the underlying physical processes and their impact on the application side, especially in terms of imaging techniques, via suitable experimental and numerical studies. Contemporary optical setups involving contrast-enhancing agents are frequently limited in their excitation and detection configurations owing to a specialization to a select number of markers. As a result, the bandwidth of experimental methods and specimens that may be investigated is severely restricted in a large number of state-of-the-art setups. Here, an alternative approach involving HNPs and UCNPs, respectively, is presented providing an overview from their synthesis to optical characterization and to potential fields of application. Based on their inherent flexibility based on their nonlinear optical response, especially in terms of wavelength and intensity tunability, the PMC alleviates prevalent limitations by dynamically adapting the setup to a sample instead of the preliminary culling to a reduced number of eligible specimens that must not change their optical properties significantly during investigation. The use of HNPs supersedes such concerns due to their nearly instantaneously generated, strongly anti-Stokes shifted, coherent emission capable of producing radiation throughout the visible spectral range, including infrared and ultraviolet wavelengths. This way, HNPs transcend the traditional field of imaging and introduces potential applications in optomanipulation or holographic techniques. Thorough (nonlinear) optical characterization of UCNPs and alkali niobate HNP ensembles is performed to assess the fundamental physical mechanisms interwoven with numerical studies leading to their wide-ranging applicability. Final remarks show that HNPs are ideal candidates for realization of the PMC and yet hold an even further potential beyond current prospects.