Dissertationen zum Thema „Biodegradable oils“

El gran desenvolupament que actualment estan experimentant els biopolímers es deu fonamentalment als alts preus i a la disminució de les reserves de petroli, juntament amb la preocupació que existeix avui en dia en matèria de sostenibilitat ambiental. Entre els polímers d'origen renovable, els polièsters alifàtics són dels més estudiats ja que es consideren molt adequats per aplicacions com a biomaterials a causa de la seva biocompatibilitat i biodegradabilitat. En aquesta tesi s'han preparat polièsters renovables mitjançant química sostenible i utilitzant derivats de l'oli de ricí, com a producte de partença. Concretament, s'han fet servir reaccions amb àcid 10-undecenoïc per obtenir els monòmers, que contenen grups funcionals àcid carboxílic i epòxid o alcohol. Tots dos tipus de monòmer són capaços d'experimentar polimerització, obtenint així polímers lineals i ramificats amb grups hidroxilo funcionalitzables. S'ha demostrat que aquests polímers són degradables enzimàtica i hidrolíticament. A més a més s'han modificat aquests polièsters amb diferents biomolècules com els aminoàcids. Finalment, utilitzant enzims com a catalitzador s'han sintetitzat copoliésters de bloc i d’empelt a partir d'aquests monòmers o polièsters i derivats del polietilenglicol. Com a resultat s’han obtingut polímers amfifílics capaços de formar micel·les en les quals és possible encapsular drogues per ser alliberades de forma controlada.
El gran desarrollo que están experimentando actualmente los biopolímeros se debe fundamentalmente a los altos precios y disminución de las reservas de petróleo, junto con la preocupación que existe hoy en día en materia de sostenibilidad ambiental. Entre los polímeros de origen renovable los poliésteres alifáticos son los que se han estudiado en mayor profundidad por ser los más adecuados como biomateriales, debido a su biocompatibilidad y biodegradabilidad. En esta tesis se han preparado poliésteres renovables mediante química sostenible y el uso de derivados de aceite de ricino como materia de partida. Concretamente, se han usado reacciones a partir del ácido 10-undecenoico para obtener monómeros que contienen grupos funcionales ácido carboxílico y epóxido o alcohol. Ambos monómeros son capaces de experimentar polimerización, obteniendo así polímeros lineales y ramificados con grupos hidroxilo funcionalizables. Se ha demostrado que estos polímeros son degradables enzimática e hidrolíticamente. Además, estos poliésteres se han modificado con diferentes biomoléculas como aminoácidos. Finalmente, utilizando enzimas como catalizador se han sintetizado copoliésteres de bloque y de injerto a partir de estos monómeros o poliésteres y derivados del polientilenglicol. Como resultado, se han obtenido polímeros amfifílicos capaces de formar micelas, en las cuales es posible encapsular drogas para ser liberadas de forma controlada.
Currently biopolymers experienced a great development due to the high prices and decrease of petroleum reserves along with the concern increasing in terms of environmental sustainability. Aliphatic polyesters are among the most studied polymers from renewable resources, because they are considered very suitable for applications as biomaterials due to their biocompatibility and biodegradability. In this thesis, renewable polyesters have been prepared from derivatives of vegetable castor oil and using sustainable chemistry. Specifically, 10-undecenoic acid has been used to synthesize the monomers which contain carboxylic acid and epoxide or alcohol. These monomers by polymerization lead to linear or branched polymers with available reactive hydroxyl groups. It has been shown that these polymers are enzymatically and hydrolytically degradable. In addition, these polyesters have been modified with different biomolecules as aminoacids. Finally, using enzymes as catalyst have been synthesized block and grafted copolyesters from these monomers or polyesters and polyethylene glycol derivatives. As result, amphiphilic polymers capable of forming micelles have been synthesized, which can encapsulate drugs to be released.

El desarrollo de materiales de envase biodegradables activos es uno de los retos de la sociedad para resolver los problemas medioambientales asociados a los residuos plásticos y mejorar la conservación de los alimentos, alargando su vida útil. En la presente Tesis Doctoral, se han analizado diferentes estrategias para la obtención y caracterización de películas biodegradables a base de hidrocoloides (almidón de yuca (A) y quitosano (Q)) con características antimicrobianas. Se obtuvieron películas bioactivas gracias a la incorporación de aceites esenciales de capacidad antimicrobiana comprobada: hoja de canela (AC), orégano (AO) y eugenol (EU). Los agentes activos se incorporaron en la matriz polimérica de quitosano por homogenización o encapsulación en liposomas de lecitina o microesferas de alginato, y las películas se obtuvieron mediante casting. Las propiedades fisicoquímicas de las películas se analizaron en función de su composición, así como su actividad antimicrobiana mediante análisis in vitro e in vivo. Se obtuvieron películas por termo- compresión, a base de mezclas A-Q, con dos proporciones polímeros: plastificante (70:30 y 60:40). Las propiedades estructurales, térmicas y físicas de las películas de almidón de yuca obtenidas se vieron afectadas por la incorporación de Q y la proporción polímero: plastificante. Las películas con la mayor proporción de plastificante tuvieron mayor contenido en humedad y fueron más permeables al vapor de agua, menos rígidas y menos resistentes a la rotura. La incorporación de Q tuvo un efecto positivo sobre las propiedades mecánicas de las películas, que aumentaron su rigidez y resistencia a la fractura, reduciéndose su extensibilidad. Sin embargo, el A y Q presentaron una miscibilidad limitada por mezclado en fundido, y las películas exhibieron una estructura heterogénea. A su vez, el polietilenglicol se cristalizó en gran medida en las películas, lo que limitó su efecto plastificante. La incorporación de quitosano proporcionó a las películas sólo una ligera actividad antimicrobiana. Se obtuvieron películas bicapa por procesado en seco de A y vertido/secado de una capa de Q. Ambos polímeros mostraron buena adhesión interfacial, y las bicapas mostraron mejor resistencia mecánica que las monocapas de almidón, aunque fueron menos extensibles debido al efecto de la interfase sobre la fractura. El quitosano fue efectivo en el control del crecimiento bacteriano en carne picada de cerdo, aunque su eficiencia se vio reducida debido al tratamiento térmico en las bicapas, lo que parece indicar la pérdida de grupos amino durante el tratamiento. La incorporación de los aceites esenciales (AC y AO) no mejoró la acción antimicrobiana en las monocapas y bicapas de CH al aplicarse sobre carne de cerdo picada. Se incorporaron aceite esencial de hoja de canela (AC) y eugenol (EU) en películas de Q utilizando nanoliposomas de lecitina. La encapsulación permitió una elevada proporción de retención de compuestos volátiles. La migración total de las películas en simulantes hidrofílicos superó el límite legal establecido para materiales de envase en contacto con alimentos. Sin embargo, la encapsulación en nanoliposomas redujo la migración en todos los simulantes. En ensayos in vitro de eficacia antimicrobiana, todas las películas fueron efectivas frente a L. innocua y E. coli, sin efecto significativo del compuesto activo ni del modo de incorporación. Sin embargo, la encapsulación propició una liberación controlada y sostenida en el tiempo en muestras de carne de cerdo almacenadas durante 13 días a 10 ºC. Se obtuvieron microesferas de alginato con eugenol y se incorporaron en películas de quitosano, cuyas propiedades físicas y estructurales se vieron afectadas. Las microesferas fueron visibles en la estructura de las películas por SEM. La incorporación de las microesfereas promovió una mejora significativa en las propiedad
El desenvolupament de materials d'envàs biodegradables actius és un dels reptes de la societat per a resoldre els problemes mediambientals associats als residus plàstics i millorar la conservació dels aliments, allargant la seua vida útil. En la present Tesi Doctoral, s'han analitzat diferents estratègies per a l'obtenció i caracterització de pel·lícules biodegradables de hidrocoloids (midó de mandioca i quitosano amb característiques antimicrobianes. Es van obtenir pel·lícules bioactives gràcies a la incorporació d'olis essencials de capacitat antimicrobiana comprovada: fulla de canyella (AC), orenga (AO) i eugenol (EU). Els agents actius es van incorporar en la matriu polimèrica de quitosano per homogenització o encapsulació en liposomes de lecitina o microesferes d'alginato, i les pel·lícules es van obtenir per "casting". Les propietats fisicoquímiques de les pel·lícules es van analitzar en funció de la seua composició, així com la seua activitat antimicrobiana mitjançant anàlisi in vitro i in vivo. Es van obtenir pel·lícules per termo- compressió de mescles midó-quitosano, amb dues proporcions polímers:plastificant (70:30 i 60:40). Les propietats estructurals, tèrmiques i físiques de les pel·lícules de midó de yuca obtingudes es van veure afectades per la incorporació de quitosano i la proporció polímer:plastificant. Les pel·lícules amb la major proporció de plastificant van tenir major contingut en humitat i van ser més permeables al vapor d'aigua, menys rígides i menys resistents al trencament. La incorporació de quitosano va tenir un efecte positiu sobre les propietats mecàniques de les pel·lícules, que van augmentar la seua rigidesa i resistència a la fractura, reduint-se la seua extensibilitat. No obstant açò, el midó i quitosano van presentar una miscibilidad limitada per termoprocessat, i les pel·lícules van exhibir una estructura heterogènia. El polietilenglicol va cristal·litzar en gran manera en les pel·lícules, la qual cosa va limitar el seu efecte plastificant. La incorporació de quitosano va proporcionar a les pel·lícules només una lleugera activitat antimicrobiana. Es van obtenir pel·lícules bicapa formades per una capa de midó obtinguda per processament en sec i un altra capa de quitosano obtinguda per "casting". Tots dos polímers van mostrar bona adhesió interfacial, i les bicapes van mostrar millor resistència mecànica que les monocapes de midó, encara que van ser menys extensibles a causa de l'efecte de la interfase sobre la fractura. El quitosano va ser efectiu en el control del creixement bacterià en carn picada de porc, encara que la seua eficiència es va veure reduïda a causa del tractament tèrmic en les bicapes, la qual cosa sembla indicar la pèrdua de grups amino durant el tractament. La incorporació dels olis essencials (AC i AO) no va millorar l'acció antimicrobiana en les monocapes i bicapes de CH en aplicar-se sobre carn de porc. Es van incorporar oli essencial de fulla de canyella (AC) i eugenol (EU) en pel·lícules de quitosano utilitzant nanoliposomes de lecitina. L'encapsulació va permetre una elevada proporció de retenció de compostos volàtils. La migració total de les pel·lícules en simulants hidrofílics va superar el límit legal establert per a materials d'envàs en contacte amb aliments. No obstant açò, l'encapsulació en nanoliposomes va reduir la migració en tots els simulants. En assajos in vitro d'eficàcia antimicrobiana, totes les pel·lícules van ser efectives enfront de L. innocua i E. coli, sense efecte significatiu del compost actiu ni de la manera d'incorporació. No obstant açò, l'encapsulació va propiciar un alliberament controlat i sostinguda en el temps en mostres de carn de porc emmagatzemades durant 13 dies a 10 ºC. Es van obtenir microesferes d'alginato amb eugenol i es van incorporar en pel·lícules de quitosano, les propietats físiques i estructurals de les quals es v
Valencia Sullca, CE. (2017). Different strategies to obtain antimicrobial biodegradable films for food applications, using starch and/or chitosan with or without essential oils [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/89094
TESIS

Neste trabalho, foram desenvolvidas estratégias para modular a composição de elastômeros biodegradáveis da família dos polihidroxialcanoatos (PHA), produzidos por Pseudomonas, a partir de ácidos graxos ou óleos vegetais, para diversificar suas aplicações, sobretudo pela inserção de monômeros insaturados. A composição do PHA produzido variou com o tipo de ácido graxo fornecido e com sua proporção em misturas. Em genomas seqüenciados, detectaram-se dois genes fadH (codificador de 2,4-dienoilCoA hidratase) em P. aeruginosa e apenas um em outras Pseudomonas. Observou-se uma correlação entre o número de cópias de fadH no genoma e maior eficiência na oxidação de ácidos graxos insaturados. Mutantes afetados no metabolismo de ácidos graxos insaturados foram obtidos utilizando-se transposon, alguns destes mutantes apresentaram maior eficiência na incorporação de monômeros insaturados ao PHA. A clonagem e seqüenciamento de fragmentos de DNA interrompidos pelo transposon permitiram a identificação dos genes afetados nesses mutantes.
Different strategies were applied to modulate the composition of biodegradable elastomeric polyhydroxyalkanoates (PHA) accumulated by Pseudomonas from fatty acids and plant oils, in order to improve the applications of this material, mainly by unsaturated monomer insertion. PHA composition varied both with fatty acid type and fatty acids ratio in mixtures supplied. Analysis of genome sequences revealed two fadH (encoding 2,4-dienoyl-CoA hydratase) copies in Pseudomonas aeruginosa and only one in other Pseudomonas species. The number of fadH copies in the genome was related to the higher oxidation of unsaturated fatty acids. Transposon-induced mutants affected on unsaturated fatty acids metabolism were obtained, some of them showing higher efficiency to incorporate unsaturated monomers do the PHA. Cloning and sequencing of transposon-disrupted DNA regions allowed to identify the genes affected in those mutants.

[ES] El envasado activo es una de las tecnologías emergentes más relevantes de la industria alimentaria. Su objetivo es interactuar con el espacio de cabeza del envase para controlar las reacciones enzimáticas, químicas, físicas y microbiológicas que deterioran los alimentos por medio de la absorción o liberación. La actual tesis doctoral trata originalmente del desarrollo y la caracterización de estructuras de envasado de alimentos activas y biodegradables mono y multicapa basadas en materiales de polihidroxialcanoatos (PHA) electroestirados derivados de estrategias de bioeconomía circular. Con el fin de dotar con propiedades activas los materiales de envasado, se incorporaron a los PHA aceites esenciales, extractos naturales, nanopartículas metálicas o combinaciones de los mismos mediante electrospinning de soluciones. Las fibras resultantes de PHA por electrospinning se recocieron para obtener monocapas continuas que, posteriormente, se combinaron con películas de polímeros biodegradables fundidas, sopladas o fundidas con disolventes y/o con revestimientos de barrera de nanocristales de celulosa bacteriana (CNC) para desarrollar novedosos sistemas multicapa con propiedades antimicrobianas y de barrera. Estos sistemas multicapas basados en PHA presentaron un buen rendimiento térmico y mecánico, así como altas propiedades de barrera a los vapores y gases. Las películas activas también mostraron mejores propiedades antioxidantes y una alta actividad antimicrobiana contra las bacterias transmitidas por los alimentos tanto en sistemas abiertos como, lo que es más importante, en sistemas cerrados, que pueden imitar las condiciones de envasado en casos reales. Por lo tanto, los materiales y prototipos desarrollados en este trabajo pueden ser muy prometedores como materiales de envasado, para constituir bandejas, flow packs y tapas, siendo completamente renovables y también biodegradables, con una potencial capacidad de aumentar tanto la calidad, como la seguridad de los productos alimenticios en el nuevo contexto de la Bioeconomía Circular.
[CA] L'envasament actiu és una de les tecnologies emergents més rellevants de la indústria alimentària. El seu objectiu és interactuar amb l'espai de cap de l'envàs per controlar les reaccions enzimàtiques, químiques, físiques i microbiològiques que deterioren els aliments per mitjà de l'absorció o alliberament. L'actual tesi doctoral tracta originalment de el desenvolupament i la caracterització d'estructures d'envasat d'aliments actives i biodegradables mono i multicapa basades en materials de polihidroxialcanoatos (PHA) electroestirados derivats d'estratègies de bioeconomia circular. Per tal de dotar amb propietats actives dels materials d'envasat, es van incorporar als PHA olis essencials, extractes naturals, nanopartícules metàl·liques o combinacions dels mateixos mitjançant electrospinning de solucions. Les fibres resultants de PHA per electrospinning es recocieron per obtenir monocapes contínues que, posteriorment, es van combinar amb pel·lícules de polímers biodegradables foses, bufades o foses amb dissolvents i / o amb revestiments de barrera de nanocristalls de cel·lulosa bacteriana (CNC) per desenvolupar nous sistemes multicapa amb propietats antimicrobianes i de barrera. Aquests sistemes multicapes basats en PHA van presentar un bon rendiment tèrmic i mecànic, així com altes propietats de barrera als vapors i gasos. Les pel·lícules actives també van mostrar millors propietats antioxidants i una alta activitat antimicrobiana contra bacteris transmeses pels aliments tant en sistemes oberts com, el que és més important, en sistemes tancats, que poden imitar les condicions d'envasament en casos reals. Per tant, els materials i prototips desenvolupats poden ser molt prometedors com materials d'envasat, per constituir safates, flow packs i tapes, sent completament renovables i també biodegradables, amb la capacitat potencial final d'augmentar tant la qualitat, com la seguretat de els productes alimentaris en el nou context de l'Bioeconomia Circular.
[EN] Active packaging is one of the most relevant emerging technologies in the food industry. It aims to interact with the packaging headspace to control the enzymatic, chemical, physical, and microbiological reactions that deteriorate food through scavenging or releasing means. The current PhD thesis originally deals with the development and characterization of mono and multilayer active and biodegradable food packaging structures based on electrospun polyhydroxyalkanoates (PHA) materials derived from circular bioeconomy strategies. In order to provide the packaging materials with active properties, essential oils, natural extracts, metallic nanoparticles or combinations thereof were incorporated into PHA by solution electrospinning. The resultant electrospun PHA mats were annealed to obtain continuous monolayers that were, thereafter, combined with cast-extruded, blown or solvent-casted biodegradable polymer films and/or barrier coatings of bacterial cellulose nanocrystals (CNCs) to develop novel multilayer systems with antimicrobial and barrier properties. These PHA-based multilayers systems presented good thermal and mechanical performance as well as high barrier properties to vapors and gases. The active films also showed improved antioxidant properties and high antimicrobial activity against food-borne bacteria in both open and, more importantly, closed systems, which can mimic real case use packaging conditions. Therefore, the here-developed materials and prototypes can be very promising as packaging materials, to constitute trays, flow packs and lids, being completely renewable and also biodegradable, with the final potential capacity to increase both quality and safety of food products in the new Circular Bioeconomy context.
Al programa Santiago Grisolía de la Generalitat Valenciana (0001426013N810001A201) por concederme la beca Predoctoral. Al proyecto EU H2020 YPACK “High Performance Polyhydroxyalkanoates Based Packaging to Minimise Food Waste” (Grant agreement 773872) de la Comisión Europea. Al proyecto RTI2018-097249-B-C21 financiado por el Ministerio de Ciencia e Innovación de España. A la Unidad Asociada IATA-UJI en “Polymer Technology”.
Figueroa López, KJ. (2021). Biodegradable Mono and Multilayer Materials with Antimicrobial Capacity Based on Circular Bioeconomy of Application Interest in Food Packaging [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/168439
TESIS

The dissertation thesis deals with the analysis of prospective environmentally compatible electrical insulating fluids for electrical engineering in relation to their chemical structure. The thesis starts with the overview of the current state of the art and of the latest trends in the use of synthetic and biodegradable natural oils. In the experimental part were studied these oils: mineral oils, rapeseed oil, sunflower oils, soybean oil, methyl oleate, peanut oil, MCT oil, castor oil and other. Dielectric properties were measured using LRC meter Agilent 4980A including dielectric liquid test fixture Agilent 16452A and also by the Novocontrol Alpha-A analyzer. Electrical properties are presented in the frequency range 10 mHz – 1 MHz range in the temperature interval 253 K to 363 K. The work goes on with the study of the suitability of individual oils for lower temperature, including the impact of the chemical structure and formulation on electrical properties.

Ce travail porte sur la caractérisation physico-chimique de l'huile de Jatropha Curcas et sa capacité à remplacer l'huile minérale dans les transformateurs de puissance. Ce produit présente plusieurs avantages sur les autres huiles végétales comme l'huile de palme ou l'huile de colza, qui recommandent sa production et son utilisation. En effet, la plante de Jatropha Curcas peut être cultivée sur des sols pauvres à faibles précipitations, évitant ainsi d'utiliser des sols plus fertiles pour sa culture permettant ainsi aux petits exploitants de réserver leurs terres aux cultures de base. Cette plante peut pousser facilement dans des zones où les niveaux de précipitations annuelles sont nettement inférieures à celles requises par d'autres espèces telles que le colza, le tournesol, le soja, le maïs, le palmier à huile et d'autres. Elle peut être cultivée sur tous les types de sol en Indonésie, même sur des terres arides, dans de nombreuses régions de l'Indonésie orientale, inexploitées en raison des difficultés à planter d'autres cultures. En outre, l'huile de Jatropha Curcas est un produit non alimentaire. En faisant subir à l’huile de Jatropha Curcas brute une estérification à base alcaline avec de l'hydroxyde de potassium (KOH), on obtient de l’huile de méthylester de Jatropha Curcas (JMEO) dont la viscosité et l’acidité sont acceptables pour les équipements à haute tension en particulier pour les transformateurs de puissance. Les propriétés physico-chimiques et électriques de JMEO ont été mesurées ainsi que celles de l'huile minérale (MO) pour la comparaison. Pour les propriétés physico-chimiques, il s’agit de la densité relative, la teneur en eau, la viscosité, l'acidité, l'indice d'iode, la corrosivité, le point d'éclair, le point d'écoulement, la couleur, l'examen visuel, et la teneur en ester méthylique. Quant aux propriétés électriques, elles concernent la rigidité diélectrique sous différentes formes de tension (alternative, continu et choc de foudre), les phénomènes de pré-claquage et de claquage sous choc de foudre, les décharges glissantes sur les surfaces de carton comprimé, immergé dans JMEO et MO. Les résultats obtenus montrent que les tensions de claquage moyennes en continu et en choc de foudre des huiles JMEO et MO sont très proches ; la tension de claquage moyenne de JMEO est même plus élevée que celle de l'huile minérale (de type naphténique). La mesure des tensions de claquage des mélanges d'huiles «80% JMEO + 20% MO» et «50% JMEO et 50% MO» montrent que la tension de claquage du mélange «80% JMEO + 20% MO» est toujours supérieure à celle de l'huile minérale sous tensions alternative et continue. Cela indique que le mélange d'huile minérale et de JMEO avec un rapport de 20:80 ne dégrade pas ses performances. Le mélange d'huiles peut se produire lors du remplacement de l'huile minérale par JMEO dans les transformateurs installés et en exploitation. L'analyse des caractéristiques des streamers (la forme, le temps d'arrêt, le courant associé et la charge électrique) se développant dans les huiles JMEO et MO sous tension impulsionnelle de foudre, montre une grande similitude. Aussi, la longueur finale (Lf) et la densité des branches des décharges surfaciques se propageant sur le carton comprimé immergé dans l'huile de Jatropha Curcas de méthylester (JMEO) et de l'huile minérale (MO), sous tensions de choc de foudre positif et négatif (1,2/50 μs), pour deux configurations d'électrodes divergentes (électrode pointe haute tension perpendiculaire et tangente au carton, respectivement), sont fortement influencées par l'épaisseur du carton comprimé. Pour une épaisseur donnée, Lf augmente avec la tension et décroît lorsque l'épaisseur augmente. Lf est plus long lorsque la pointe est positive que lorsque la pointe est négative. Pour une tension et une épaisseur du carton comprimé donnée, les valeurs de Lf dans l’huile minérale et l’huile JMEO sont très proches. [...]
This work is aimed at the investigation of the physicochemical characterization of Jatropha Curcas seeds oil and its capacity to be an alternative option to replace mineral oil in power transformers. This product presents several advantages that recommend both its production and usage over those of other vegetable oils as crude palm oil and rapeseeds oil. Indeed, it may be grown on marginal or degraded soils avoiding thus the need to utilize those more fertile soils currently being used by smallholders to grow their staple crops; and it will readily grow in areas where annual rainfall levels are significantly lower than those required by other species such as palm oil, rape-seeds oil, sunflower oil, soybeans oil, corn oil and others. For instance, these plants can grow on all soil types in Indonesia, even on barren soil. The barren soil types can be found in many parts of eastern Indonesia that remain untapped because of the difficulty planted with other crops. Moreover, jatropha curcas oil is nonfood crops. Jatropha Curcas oil was processed by alkali base catalyzed esterification process using potassium hydroxide (KOH) to produce Jatropha Curcas methyl ester oil (JMEO) has a viscosity and a acidity that are acceptable for high voltage equipment especially in power transformer. The physicochemical and electrical properties of JMEO were measured as well as those of mineral oil (MO) for comparison. The physicochemical properties cover relative density, water content, viscosity, acidity, iodine number, corrosivity, flash point, pour point, color, visual examination, and methyl ester content. Meanwhile the electrical properties cover dielectric strength under AC, DC and lightning impulse voltages, pre-breakdown / streamers under lightning impulse voltage, creeping discharge over pressboard immersed in JMEO and MO. The obtained results show that the average DC and lightning impulse breakdown voltages of JMEO and MO are too close, even the average AC breakdown voltage of JMEO are higher than that of mineral oil (napthenic type). The measurement of breakdown voltages of two oil mixtures namely “80% JMEO + 20% MO” and “50% JMEO and 50% MO” shows that the breakdown voltage of the first mixture (i.e., “80%JMEO+20%MO”) is always higher than that of mineral oil under both AC and DC voltages. This indicates that mixing 20:80 mineral oil to JMEO ratio does not degrade its performance. The mixing of oils can occur when replacing mineral oil by JMEO in installed transformers. The analysis of the streamers characteristics (namely; shape, stopping length, associated current and electrical charge) developing in JMEO and MO under lightning impulse voltages, shows that these are too close (similar). It is also shown that the stopping (final) length Lf and the density of branches of creeping discharges propagating over pressboard immersed in Jatropha Curcas methyl ester oil (JMEO) and mineral oil (MO), under positive and negative lightning impulse voltages (1.2/50 μs), using two divergent electrode configurations (electrode point perpendicular and tangential to pressboard), are significantly influenced by the thickness of pressboard. For a given thickness, Lf increases with the voltage and decreases when the thickness increases. Lf is longer when the point is positive than with a negative point. For a given voltage and thickness of pressboard, the values of Lf in mineral oil and JMEO are very close. It appears from this work that JMEO could constitute a potential substitute for mineral oil for electrical insulation and especially in high voltage power transformers

The effects of adding a biodegradable litter amendment (AmmoSoak), developed from steam exploded corncobs, to poultry litter prior to pyrolysis on the product yields and qualities were investigated. Mixtures of litter and AmmoSoak were pyrolyzed in a bench-scale fluidized bed reactor. The objective of the second phase was to start-up a pilot-scale fluidized bed reactor unit. The poultry litter had a lower higher heating value (HHV), higher moisture, ash, nitrogen, sulfur, and chlorine contents than AmmoSoak. Analysis of the poultry litter indicated a mixture of volatiles, hemicelluloses, cellulose, lignin, ash, and proteins. AmmoSoak had a simpler composition than the litter; mainly hemicelluloses, cellulose, and lignin. Bench-scale studies indicated that adding AmmoSoak affected the yields and characteristics of the products. Addition of Ammosoak increased the bio-oil and syngas yields and decreased char yields. Adding AmmoSoak to the feed decreased the pH, water contents, initial viscosity, and the rate at which the viscosity increased with time, while densities and HHVs increased. The addition of Ammosoak to poultry litter also increased the carbon and oxygen contents of the boi-oils while nitrogen, hydrogen, sulfur, chlorine and ash contents decreased. A pilot-scale fluidized bed reactor was designed, constructed, installed and investigated for the pyrolysis of poultry litter. Fluidization and thermal equilibrium of the reactor were successfully demonstrated. The reactor was heated by combustion of propane. To ensure complete combustion, the combustion water was collected and compared to the stoichiometric yield. Complete combustion was achieved. Bio-oil yields on the pilot scale were lower than those obtained on the bench-scale pyrolysis unit. The water soluble fractions of the bio-oils were rich in oxygen. Water insoluble fractions were rich in carbon and ash.
Master of Science

[EN] In the present Doctoral Thesis, different strategies to improve functional properties of starch films for food packaging applications were analysed: study of the effect of amylose:amylopectin ratio, blend with other polymers poly(vinyl alcohol) (PVA), and incorporation of different fillers (rice bran and cellulose nanocrystals-CNCs) and antimicrobial agents (neem oil-N, oregano essential oil-O and silver nanoparticles-AgNPs). Likewise, a biodegradation study of the films as affected by antimicrobials was carried out. Among different starches with distinct amylose:amylopectin ratio, pea starch was selected with higher values of this ratio. The high content of amylose gave rise to stiffer and more resistant to fracture films, with lower oxygen permeability, which decreased during storage. Pea starch-PVA (S-PVA) blend films represented a good strategy to improve film properties without a notable increase in cost. The PVA addition led to films which were less water soluble and not as sensitive to water sorption, more extensible and resistant than neat starch films, while they maintained the high oxygen barrier and provided stability to the matrix during ageing. In this sense, S-PVA ratios near to 1:1 are recommendable. When rice bran with the smallest particle size was used as filler, it improved the elastic modulus of the films, but reduced the film stretchability and barrier properties, due to the enhancement of the water binding capacity and the introduction of discontinuities in the matrix. Incorporation of CNCs into S-PVA films, as a reinforcing material, enhanced phase separation of polymers, did not imply changes in water vapour barrier of the films but improved the film mechanical performance: they became stiffer and more stretchable, while crystallization of PVA was partially inhibited. Silver loaded S-PVA films exhibited antimicrobial activity against the fungi (Aspergillus niger and Penicillium expansum) and bacteria (Listeria innocua and Escherichia coli) genera, depending on the silver concentration. Silver nanoparticles provoked notable changes in the film colour and transparency but no relevant changes in the other physical properties. Silver was completely delivered to aqueous simulants within the firsts 60 minutes of contact, but the film release capacity drastically decreased in the non-polar simulant, where the overall migration limit for food contact packaging materials (60 mg/Kg simulant) was accomplished. So, the use of the developed films as food packaging materials should be restricted to fat-rich foodstuffs. The incorporation of oregano essential oil (O), as antimicrobial agents, into the S-PVA matrix gave rise to active films against bacteria and fungi, whereas films containing neem oil (N) were not effective. Higher O concentration in the films was required to observe antifungal effect with respect to the antibacterial activity. Oils did not notably affect water sensitivity and water barrier properties of the films, but at high ratio, oils implied weaker film networks, affecting their mechanical performance. Blend of starch with PVA significantly improved PVA biodegradation and disintegration behaviour. Incorporation of silver species to S-PVA films slowed down their biodegradation kinetics while increased their degradation ratio. However, no significant effect of O was observed on the biodegradability indices despite the antimicrobial activity detected for this oil. N even promoted biodegradation of S-PVA films. Finally, a food application of biopolymer coatings was studied, using chitosan and essential oils (oregano or rosemary) to prevent weight loss and fungal development of semi-hard goat's milk cheeses. Coating were highly effective at reducing fungal growth and cheese weight loss while slightly reduced lipolytic and proteolytic activities in the cheese. Sensory evaluation revealed that the cheeses double coated with chitosan-oregano oil were the best evaluated in terms of aroma and flavour.
[ES] En la Tesis Doctoral, se han analizado diferentes estrategias para mejorar las propiedades funcionales de películas de almidón para aplicaciones de envasado de alimentos: el estudio del ratio amilosa:amilopectina, mezclas con otros polímeros (alcohol de polivinilo-PVA), y la incorporación de diferentes refuerzos (salvado de arroz y nanocristales de celulose-CNCs) y agentes antimicrobianos (aceite de neem-N, aceite esencial de orégano-O y nanopartículas de plata-AgNPs). También se realizó un estudio de biodegradación de las películas observando el efecto de los antimicrobianos. Entre los diferentes almidones con distinto ratio amilosa:amilopectina, se seleccionó el almidón de guisante con altos valores de amilosa. El alto contenido en amilosa dio lugar a películas más rígidas y resistentes a la fractura, con baja permeabilidad al oxígeno, la cual disminuyó durante el almacenamiento. Las películas de mezcla de almidón-PVA (S-PVA) representaron una buena estrategia para mejorar las propiedades de las películas sin incrementar notablemente el precio. La adición de PVA dio lugar a películas menos solubles en agua, menos sensibles a su absorción y más extensible y resistentes que las de almidón puro, mientras mantuvieron alta barrera al oxígeno y dieron estabilidad a la matriz durante el envejecimiento. Son recomendables los ratios de S-PVA cercanos a 1:1. El salvado de arroz con menor tamaño de partícula, mejoró el modulo elástico de las películas, pero su extensibilidad y propiedades barrera empeoraron debido a la mejor capacidad de retención de agua y a las discontinuidades introducidas. La incorporación de CNCs en las películas de S-PVA incrementó la separación de fases de los polímeros, sin cambios en la permeabilidad al vapor de agua, y mejoró las prestaciones mecánicas: películas más rígidas y extensibles, mientras que inhibió parcialmente la cristalización del PVA. Las películas de S-PVA con partículas de plata exhibieron actividad antimicrobiana contra dos hongos y dos bacterias, dependiendo de la concentración de plata. Las AgNPs provocaron cambios en el color de las películas así como en su transparencia. La plata fue completamente liberada en los primeros 60 minutos en contacto con simulantes acuosos, sin embargo la liberación disminuyó en simulantes no polares, donde se cumple el límite de migración global. Por lo tanto, el uso de las películas desarrolladas para envasado de alimentos debe ser restringido a productos alimenticios ricos en grasas. La incorporación de O en la matriz de S-PVA dio lugar a películas activas contra bacterias y hongos, mientras que las películas con N no fueron efectivas. Se necesitaron concentraciones más altas de O en las películas para observar un efecto antifúngico respecto a la actividad bactericida. Los aceites no afectaron notablemente la sensibilidad ni las propiedades barreras al agua de las películas, aunque la mayor proporción de aceite dio lugar a películas con una red más débil, afectando sus prestaciones mecánicas. La mezcla de S con PVA mejoró significativamente el comportamiento de biodegradación y desintegración de las películas. La incorporación de AgNPs a películas de S-PVA disminuyó su cinética de biodegradación mientras aumentó su ratio de degradación. La adición de O no presentó efecto significativo en el índice de biodegradación a pesar de la actividad antimicrobiana detectada. El N incluso mejoró la biodegradación de las películas. Finalmente, se realizó una aplicación de recubrimientos basados en biopolímeros, usando quitosano-CH y aceite esencial de orégano o romero para evitar la pérdida de peso y el desarrollo de hongos en quesos de cabra semicurados. Los recubrimientos fueron efectivos en la reducción del crecimiento fúngico y la pérdida de peso de los quesos, mientras que la actividad lipolítica y proteolítica ligeramente disminuyó. El análisis sensorial reveló q
[CAT] S'han analitzat diferents estratègies per a millorar les propietats funcionals de pel·lícules de midó per a aplicacions d'envasat d'aliments: l'estudi de la ràtio amilosa:amilopectina, mescles amb altres polímers (alcohol polivinílic-PVA), i la incorporació de diferents reforços (segó d'arròs i nanocristalls de celulosa-CNCs) i agents antimicrobians (oli de neem-N, oli essencial d'orenga-O i nanopartícules de plata). També es va fer un estudi de biodegradació de les pel·lícules per observar l'efecte dels antimicrobians. Entre els diferents midons amb distint ràtio amilosa:amilopectina, es va seleccionar el midó de pèsol amb alts valors d'amilosa. L'alt contingut en amilosa va donar lloc a pel·lícules més rígides i resistents a la fractura, amb baixa permeabilitat a l'oxigen, la qual va disminuir durant l'emmagatzemament. Les pel·lícules de mescla de S-PVA van representar una bona estratègia per a millorar les propietats de les pel·lícules sense incrementar notablement el preu. L'addició de PVA va donar lloc a pel·lícules menys solubles en aigua, menys sensibles a la seua absorció i més extensible i resistents que les de midó pur. A més van mantenir l'alta barrera a l'oxigen i van donar estabilitat a la matriu durant l'envelliment. Son recomanables les ràtios de S- PVA pròxims a 1:1. El segó d'arròs amb menor tamany de partícula, va millorar el mòdul elàstic de les pel·lícules, però la seua extensibilitat i propietats barrera van empitjorar. La incorporació de CNCs en les pel·lícules de S-PVA, va incrementar la separació de fases dels polímers, sense implicar canvis en la permeabilitat al vapor d'aigua, però millorant les prestacions mecàniques: pel·lícules més rígides i extensibles, al mateix temps que es va inhibir parcialment la cristal·lització del PVA. Les pel·lícules de S-PVA amb partícules de plata van exhibir activitat antimicrobiana front a dos de fongs i dos bacteris, depenent de la concentració de plata. Les AgNPs van provocar canvis en el color de les pel·lícules així com en la seua transparència. La plata va ser completament alliberada en els primers 60 minuts en contacte amb simulants aquosos. La capacitat d'alliberament va disminuir en simulants no polars, on es complix el límit de migració global. Per tant, l'ús de les pel·lícules desenvolupades per a l'envasat d'aliments ha de ser restringit a productes alimentaris rics en greixos. La incorporació d'O en la matriu de S-PVA va donar lloc a pel·lícules actives front a bacteris i fongs. Pel contrari les pel·lícules amb N no van ser efectives. Van ser necessàries concentracions més elevades d'O en les pel·lícules per a observar un efecte antifúngic respecte a l'activitat bactericida. Els olis no van afectar la sensibilitat a l'aigua ni les propietats barrera a l'aigua de les pel·lícules, però la major proporció d'oli va donar lloc a pel·lícules amb una xarxa més dèbil, afectant les seues prestacions mecàniques. La mescla de S amb PVA va millorar significativament el comportament de biodegradació i desintegració. La incorporació de partícules de plata a pel·lícules de S-PVA va disminuir la seua cinètica de biodegradació mentre que va augmentar la seua ràtio de degradació. No obstant això, l'addició d'O no va presentar un efecte significatiu en els índexs de biodegradació a pesar de l'activitat antimicrobiana detectada. L'N fins i tot va millorar la biodegradació de les pel·lícules de S-PVA. Finalment, es va realitzar una aplicació de recobriments basats en biopolímers, fent ús de quistosà-CH i olis essencials de orenga i romer per evitar la pèrdua de pes i el desenvolupament de fongs en formatges de cabra semi-curats. Els recobriments van ser altament efectius en la reducció del creixement fúngic i la pèrdua de pes dels formatges. L'activitat lipolítica i proteolítica en els formatges va disminuir suaument. L'anàlisi sensorial va revelar que els form
Cano Embuena, AI. (2015). Different strategies to improve the functionality of biodegradable films based on starch and other polymers [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/55383
TESIS
Premiado

Three continuously stirred tank reactors (CSTR) were operated in semi continuous mode treating swine waste using anaerobic digestion. The reactors were used to test the effect of solid retention time (SRT) on CH4 yield, total ammonia nitrogen (TAN) concentrations, % volatile solids (VS), chemical oxygen demand (COD) and volatile fatty acids (VFA) removal, readily biodegradable COD concentration and the denitrification potential for the effluent in a biological nutrient removal (BNR) system. During Phase I of the study, the three reactors were operated at the same 28 day SRT for 16 weeks. SRTs were then changed during the 12 week Phase II period. The SRTs studied were 14, 21 and 28 days, with the same organic loading rate (OLR) of 1.88 ± 0.2 kg VS/ m3-day. The reactor with the lowest SRT (14 days) had the highest VS and VFA removal at 73.6 and 67.6% and lowest TAN concentration at 0.78 g NH4+-N/L, followed by the 21 day and 28 day reactors. This was likely due to the fast microbial growth rates and substrate utilization rates in this reactor compared with the other two. The 14 day reactor had the highest CH4 yield at 0.33 m3CH4/kg VS added and readily biodegradable COD concentration at 0.93 COD/L. The variations in CH4 yield and readily biodegradable COD concentrations between the three reactors were not statistically significant. Denitrification potential for the reactors was 1.20, 0.73 and 0.56 g COD/g N for 14, 21 and 28 day reactors, respectively, and the differences were statistically significant. None of the reactors achieved a denitrification potential of 5 g COD/g N, the amount required to use effluent of anaerobically digested swine waste as an internal carbon source in a BNR. This was attributed to operating conditions such as freezing and thawing of the raw swine waste that maximized CH4 yield and lowered the readily biodegradable COD concentration. In addition the 14 day reactor had low TAN concentrations thus increasing the denitrification potential of the centrate from that reactor.

O consumo abusivo de embalagens plásticas tem causado diversos problemas ambientais, visto que as mesmas são produzidas a partir de fontes não renováveis de energia e são resistentes à degradação. Neste contexto, o desenvolvimento de filmes biodegradáveis ativos para aplicação em alimentos é de grande importância pois, além de serem produzidos a partir fontes renováveis e mais sustentáveis, os mesmos podem interagir com o produto embalado e proporcionar benefícios extras em relação aos filmes convencionais. Este trabalho utilizou o bagaço de uva proveniente do processo de vinificação como fonte de antocianinas para o desenvolvimento de filmes biodegradáveis com propriedades antioxidantes. A microencapsulação das antocianinas, realizada com a finalidade de aumentar sua estabilidade, utilizou maltodextrina e goma arábica como agentes encapsulantes. Diferentes formulações de filmes biodegradáveis foram desenvolvidas com as microcápsulas produzidas. Goma arábica, maltodextrina e a combinação das mesmas foram eficientes no processo de microencapsulação (>90% de retenção de antocianinas). Apesar de apresentarem o mesmo teor de antocianinas - quantificadas via cromatografia líquida de alta eficiência - a atividade antioxidante das microcápsulas de goma arábica foi maior. A diferença entre a atividade antioxidante das cápsulas foi atribuída às diferentes solubilidades destas em água, onde maiores solubilidades poderiam liberar mais facilmente as antocianinas encapsuladas. O filme desenvolvido a partir de antocianinas encapsuladas com maltodextrina apresentou melhores propriedades mecânicas e ofereceu maior proteção ao óleo de girassol frente às reações de oxidação, e portanto foi utilizado na produção de sachês de azeite de oliva extra-virgem. O filme desenvolvido apresentou biodegradabilidade comprovada e propiciou maior estabilidade oxidativa ao azeite de oliva nele embalado quando comparado a um azeite embalado em polipropileno comercial. Os resultados obtidos neste trabalho comprovam a potencialidade da utilização de maltodextrina como encapsulante de antocianinas e como ingrediente na produção de filmes biodegradáveis, aplicados principalmente em produtos gordurosos.
The abuse of plastic packaging has caused various environmental problems, since they are produced from non-renewable sources of energy and are resistant to degradation. In this context, the development of active biodegradable films for application in foods is of great importance, since they are produced from renewable and sustainable sources, besides they may interact with the packaged product and provide additional benefits over conventional films. This study used the wine grape pomace as a source of anthocyanins for the development of biodegradable films with antioxidant properties. Microencapsulation of anthocyanins, which was carried out with the purpose of increasing its stability, used maltodextrin and gum arabic as wall materials. Different formulations of biodegradable films were developed with the obtained microcapsules. Gum arabic, maltodextrin and their combination were effective in the microencapsulation process (> 90% retention of anthocyanins). Despite being provided with the same anthocyanins content - quantified by highperformance liquid chromatography - the antioxidant activity of gum arabic microcapsules was greater. The difference between the antioxidant activity of the capsules was attributed to their different solubility in water, so that capsules with higher solubility could release more easily the encapsulated anthocyanins. The film containing anthocyanins encapsulated with maltodextrin showed better mechanical properties and offered greater protection to sunflower oil against oxidation reactions, and so was used in the production of extra-virgin olive oil pouches. The developed film, which was proven to be biodegradable, increased the oxidative stability of the olive oil when compared to olive oil packaged in a commercial polypropylene. The results of this study demonstrate the potential usage of maltodextrin as wall material on encapsulation of anthocyanins and as an ingredient in the production of biodegradable films, mainly applied in fatty products.

Ce projet de thèse avait pour objectif l’élaboration de glyconanocapsules à cœur huileux par nanoprécipitation à partir de polymères biocompatibles et biodégradables. Dans ce but, nous avons tout d’abord élaboré une série de glycopolymères à base de poly(alcool vinylique) (PVA) par copolymérisation radicalaire de type RAFT suivie d’une réaction d’alcoolyse sélective. En parallèle, nous avons synthétisé une seconde famille de glycopolymères en hydrolysant partiellement des chaînes de poly(2-ethyl-2-oxazoline) (PEOX) et d’autre part, en réalisant une réaction d’animation réductrice entre les amines secondaires obtenues (PEOX-co-PEI) et le lactose. S’appuyant sur les diagrammes de phase des systèmes ternaires eau/acétone/huile et eau/acetone/polymère, nous avons ensuite identifié les conditions de basculement de solvant (dans les domaines Ouzo et SFME) permettant simultanément la formation de nanogouttelettes d’huile et l’adsorption de chaînes polymère à l’interface, conditions essentielles à l’obtention de nanocapsules à cœur huileux. Afin d’assurer leur pérennité en milieu aqueux, l’écorce de ces nano-objets a été réticulée chimiquement et/ou physiquement, dans le cas des nanocapsules à base de PVA par ajout de Na2SO4 (salting out). Enfin, moyennant l’ajout de réactifs et de principes actifs dans les phases aqueuse et organique respectivement, ce procédé de basculement en une étape a permis de construire des glyconanocapsules contenant des molécules de principe actif dissoutes dans le cœur huileux et possédant une membrane polymère réticulée dégradable en conditions réductrices Enfin, Il a été démontré que ces glyconanocapsules sont capables de libérer un principe actif encapsulé en réponse à un stimulus et d’interagir avec certaines lectines
In this PhD work, we designed a series of precisely-defined water-soluble PVAbased glycopolymer chains with tunable compositions using RAFT copolymerization and selective alcoholysis reactions. In a second approach, we prepared a library of poly(2-ethyl-2-oxazoline)-based glycopolymers by partial acidic hydrolysis and reductive amination reactions with sugar residues. Relying on the establishment of phase diagrams for water/acetone/oil and water/acetone/polymer ternary systems (commercial PVA, PVA or polyoxazoline-based glycopolymers), we identified the conditions of solvent shifting (in the Ouzo and /or the SFME domains) for which oil-filled nanocapsules can be constructed in one step thanks to spontaneous emulsification of the oil and concomitant adsorption of the polymer chains at the interface. Stabilization of the nanocapsules in water was typically achieved by covalent cross-linking of the shell or, in the case of PVA-based materials, by addition of Na2SO4 (salting out). This straightforward nanoprecipitation process was further effortlessly implemented to confer redox-sensitivity to the polymer shell (to trigger the release of actives), decorate the nanocapsules with diverse molecules of interest and to entrap hydrophobic actives within the oily core. Release of the drugs and bioactivity of the nanocapsules were demonstrated

La quantité de déchets augmente depuis plusieurs décénies, issus principalement de l'industrie du plastique. La production cumulée de matières plastiques au cours des dix dernières années est supérieure que pendant le dernier millénaire. Une des solutions pour réduire les impacts écologiques et économiques est de dévelopement de films et enrobages biodégradables et/ou comestibles.L'objectif de cette thèse est d'étudier des films et enrobages comestibles à base d'amidon. Quinze types de solutions filmogènes ont été formulés: 3 types d’amidons, amidon + protéines, amidon + huile de colza, amidon + plastifiant. Afin de mieux comprendre le rôle des constituants et les interactions mises en jeu, les propriétés physico-chimiques et structurales des films ont été réalisées. Enfin, les films présentant les meilleurs compromis ont été appliqués sur des prunes.L’étude physico-chimique des films à base d’amidon de maïs, de pommes de terre et de de blé ont permis de retenir l’amidon de blé pour les études suivantes. Une quantité de plastifiant de 50% (par rapport à la masse sèche de biopolymère) a été sélectionnée car elle permet d'obtenir des films souples et resistants sans blanchiment. Afin d'améliorer l'efficacité barrière à l'humidité, de l'huile de colza a été ajoutée par laminage sur le film d’amidon. Les observations de la microstructure montrent une dispersion de gouttelettes d’huile dans la matrice à la place d’une structure multicouche amidon-huile-amidon. Diverses proportions amidon/protéine ont été testées pour améliorer les propriétés fonctionnelles des films. Plus la teneur en protéines est élevée, meilleure est l'efficacité barrière à la vapeur d'eau, à l'oxygène ou aux arômes. En effet, les films sont plus denses et homogènes en présence des protéines. A partir de la meilleure compréhension du rôle de la composition et de la structure sur les performances des films, plusieurs formulations ont été testées comme enrobage ou film sur des prunes fraîches. L’analyse thermographique a été utilisée pour étudier le comportement des prunes pendant le stockage, l’enrobage/film composé de l’amidon enrobage s’est avéré efficace pour retarder la dégradation des fruits
The amount of waste increased annually, mainly from plastic industry. Plastic materials were more produced during the only last ten years than during the last millennium. A potential solution of the ecological and economic problems can be biodegradable or edible films and coatings. The goal of this thesis was to study edible films and coatings based on starch. Fifteen types of film-forming solutions were made: 3 types of starch, starch + different amounts of plasticizer, starch + proteins, starch + oil. To better understanding the interaction between film components, physical, chemical and functional tests were done. Finnaly, validation on real foods (plums) as coatings and films helped to improved edible barrier films for fruit and vegetable preservation.Preliminary physico-chemical studies of corn, potato and wheat starch film properties allowed choosing the wheat starch-based films further experiments. Then, a 50% amount of plasticizer related to dry biopolymer weight was selected aiming to obtain films being not too rigid, that did not break and without blooming. To prove the barrier moisture efficacy, rapeseed oil was added as multilayers films. Microstructure observations displayed that oil was dispersed as droplets instead of layer, thus emulsion-based films were obtained instead of multilayer starch-oil-starch films. Various ratios of starch/protein were assessed to improve functional properties of films. The more the protein content was, the better the barrier efficiency against water vapour, oxygen or aroma were. Indeed, higher protein content films were more dense and homogeneous. From these data obtained on films, and the better understanding how composition and structure affect film performances, several recipes were tested as coatings or films for wrapping fresh plums. Thermographic analysis was used to study the plums behavior during storage, and starch coating was efficient to delay fruit degradation
Z każdym rokiem wzrasta liczba produkowanych odpadów, w szczególmości tych z plastiku. W ciągu pierwszych dziesięciu lat wyprodukowano więcej tworzyw sztucznych niż w przeciągu całego ubiegłego tysiąclecia. Rozwiązaniem tych ekologicznych i ekonomicznych problemów mogą okazać się filmy i powłoki do żywności. Celem tej pracy były studia nad jadalnymi filmami i powłokami na bazie skrobi. Piętnaście rodzajów roztworów powłokotwórczych zostało wytworzonych: z 3 typów skrobi, skrobia + różne stężenia plastyfikatora, skrobia + białka, skrobia + olej. W celu lepszego zrozumienia interakcji pomiędzy komponentami filmu właściwości fizyczne, chemiczne i funkcjonalne zostały zmierzone. W ostatnim etapie walidacja na prawdziwej żywności (powlekanie i pakowanie śliwek) pomogła w udowodnieniu istnienia właściwości barierowych owoców i warzyw podczas przechowywania.Próbne testy fizyko-chemiczne skrobi kukurydzianej, ziemniaczanej i pszenicznej pomogły w wyborze skrobi otrzymywanej z pszenicy do dalszych badań. Następnie wybrano zawartość plastyfikatora. 50% glicerolu względem suchej masy substancji powłokotwórczej nie powodowało twardości i pękania filmów ani też tzw. efektu kwitnienia (intensywnie żółty/ pomarańczowy kolor filmów). W celu poprawy właściwości barierowych olej rzepakowy został dodany. Zdjęcia mikroskopowe obrazują zawieszone krople oleju w matrycy jako emulsja zamiast dodatkowej warstwy, której oczekiwano. Do skrobi zostały dodane również białka serwatkowe w kilku proporcjach. Im więcej białek jest w stosunku procentowym skrobia/proteiny tyym lepsze są właściwości barierowe dla pary wodnej, tlenu i aromatów. Dodatkowo filmy zawierające więcej protein w stosunku procentowym są bardziej gęste i jednolite. Uzyskane informacje pozwoliły na lepsze zrozumienie wpływu kompozycji i struktury filmów i powłok na pakowanie świeżych śliwek. Analiza z użyciem kamery termowizyjnej pozwoliła na ocenę zmian w owocach podczas przechowywania, zaś powłoka skrobiowa efektywnie opóźniała procesy degradacyjne w owocach

Diariamente são descartados no mundo toneladas de resíduos do processamento de frutas que poderiam ser aproveitados pelo seu elevado poder nutricional e funcional, que acabam sendo desperdiçados e podem gerar sérios problemas ao meio ambiente. Outro descarte inadequado que agrava esse problema ambiental é o de embalagens plásticas, que quando não submetidas ao processo de reciclagem trazem enormes danos. Por esses fatores, esse estudo teve como objetivo o aproveitamento de subprodutos da indústria de alimentos para o desenvolvimento de farinhas funcionais e aproveitamento dos resíduos da indústria de capsulas nutracêuticas de gelatina e óleo de chia como matriz para as embalagens biodegradáveis ativas. A quitosana também foi utilizada como matriz no desenvolvimento de filmes aplicados como embalagens. Primeiramente foram avaliados quatro resíduos obtidos de diferentes frutas: resíduo do processamento de suco de mirtilo (bagaço), resíduo do processamento de azeite de oliva (bagaço), cascas de mamão e abacaxi. As propriedades físico químicas, funcionais e antioxidantes desses resíduos foram analisadas, sendo que no geral todos demonstraram alto teor de fibras dietéticas. Em relação às propriedades funcionais a farinha de mamão se destacou pelos elevados valores de capacidade de retenção de água e óleo, pela alta solubilidade e maiores teores de carotenoides (15,56 ± 0,35 mg/100g). A farinha de mirtilo foi a que apresentou o maior poder antioxidante pelo método DPPH (4,62 ± 0,18 IC50 em mg de farinha) e maior teor de compostos fenólicos (23,59 ± 0.85 mg/g GAE), além disso exibiu alto teor de antocianinas. Devido a estas propriedades, a farinha e o extrato do resíduo de mirtilo foram incorporados à gelatina do resíduo do processamento de cápsulas nutracêuticas de óleo de chia para o desenvolvimento de filmes biodegradáveis ativos. Os filmes foram avaliados em relação as suas propriedades mecânicas, de barreira ao vapor da água e luz UV, capacidade antioxidante e aplicação como embalagem em produtos alimentícios. Os resultados sugeriram que a adição de fibras promoveu uma diminuição da resistência à tração e aumento na permeabilidade ao vapor da água. No entanto, a adição de fibra também proporcionou um aumento significativo na barreira de luz UV a 500 nm, sendo eficaz na redução da oxidação lipídica de óleo de girassol. Os filmes com adição de extrato não exibiram alteração nas propriedades mecânicas ou de barreira em comparação com a formulação controle. Além disso, estes filmes exibiram capacidade antioxidante estável por 28 dias. Filmes desenvolvidos com a farinha de mamão e resíduos de gelatina apresentaram comportamento similar aos filmes com resíduos de mirtilo, já que a farinha de mamão também alterou algumas propriedades originais do filme como as propriedades mecânicas e de barreira, e agregaram poder antioxidante. Com o objetivo de melhorar essas propriedades foram então desenvolvidas micropartículas de farinha de casca de mamão em spray drying utilizando o resíduo de gelatina como material de parede. Os resultados indicaram que as micropartículas de casca de mamão ao serem adicionadas na gelatina originaram uma matriz de filme mais contínua e homogênea com aumento da resistência à tração e do módulo de Young. Os filmes com micropartículas (7,5%), quando aplicados como material de embalagem para banha de porco, foram os mais eficientes como barreiras ativas (maior atividade antioxidante), pois um menor teor de peróxidos, dienos e trienos conjugados foram quantificados na amostra após 22 dias. A farinha de resíduos da produção de azeite de oliva também foi utilizada para o desenvolvimento de filmes biodegradáveis, porém o biopolimero utilizado foi a quitosana. A incorporação de farinha de resíduo de oliva na matriz de quitosana também causou alterações na morfologia, tornando o filme mais heterogêneo e áspero. Por esse motivo foram testadas a adição de micropartículas de farinha de oliva nos filmes. A adição de 10% de micropartículas de oliva melhorou significativamente a resistência à tração dos filmes sem alterar as suas propriedades originais. A farinha e as micropartículas de oliva aumentaram a capacidade antioxidante dos filmes, esse aumento foi proporcional à concentração de farinha ou micropartículas adicionadas ao filme. Os filmes com 30% de farinha ou micropartículas foram eficazes como embalagem protetora contra a oxidação de nozes durante 31 dias. A partir dos resultados obtidos neste trabalho fica evidenciado a viabilidade do uso de resíduos da indústria de alimentos e resíduos da indústria de cápsulas nutracêuticas para o desenvolvimento de filmes e uso como embalagens biodegradáveis em diferentes produtos.
Every day tons of fruit processing residues are discarded worldwide that could be harnessed for their high nutritional and functional power and that end up being wasted and generating problems for the environment. Another inadequate disposal that aggravates this environmental problem is the plastic packaging, which when not subjected to the recycling process bring huge damages. Due to these factors, this study aims at the utilization of by-products of the food industry for the development of active biodegradable packaging. Firstly, four residues obtained from different fruits, processing residue of blueberry juice (bagasse), processing residue of olive oil (bagasse), peels of papaya and pineapple were evaluated. The physicochemical, functional and antioxidant properties of these residues were analyzed, and in general, all showed high total dietary fiber content. In relation to the functional properties, papaya flour was distinguished by high water and oil retention capacity, high solubility and higher carotenoid content (15.56 ± 0.35 mg / 100g). The blueberry flour had the highest antioxidant power by the DPPH method (4.62 ± 0.18 IC50 in mg of flour) and a higher content of phenolic compounds (23.59 ± 0.85 mg / g GAE), in addition, it exhibited a high content of anthocyanins. Due to these properties, the flour and extract of the blueberry residue were incorporated into the gelatin from the processing residue of chia oleuroceutical capsules for the development of active biodegradable films for packaging. The films were evaluated in relation to their mechanical properties, water vapor barrier, and UV light, antioxidant capacity and application as packaging in food products. The results suggested that fiber addition promoted a decrease in tensile strength and an increase in water vapor permeability. However, the addition of fiber also provided a significant increase in the UV light barrier at 500 nm being effective in reducing the lipid oxidation of sunflower oil. Films with added extract showed no change in mechanical or barrier properties compared to the control formulation. In addition, these films exhibited a stable antioxidant capacity for 28 days. Films developed with papaya flour and gelatin residues showed similar behavior to films with blueberry residues since papaya flour also altered some of the original properties of the film as mechanical and barrier properties, and added antioxidant power. In order to improve these properties microparticles of papaya peel flour were then developed in spray drying using the gelatin residue as the wall material. The results indicated that the microparticles of papaya peel, when added to gelatin, gave a more continuous and homogeneous film matrix increasing tensile strength and Young's modulus. Microparticles films (7.5%), when applied as packaging material for lard, were the most efficient as active barriers (higher antioxidant activity) because a lower peroxide content was quantified in the sample after 22 days. The residue flour from olive oil production was also used for the development of biodegradable films, but the biopolymer used was chitosan. The incorporation of olive residue flour in the chitosan matrix also caused changes in the morphology, making the film more heterogeneous and rough. For this reason, the addition of olive flour microparticles in the films was tested. The addition of 10% of olive microparticles significantly improved the tensile strength of films without altering their original properties. The flour and the microparticles of olive increased the antioxidant capacity of the films; this increase was proportional to the concentration of flour or micro added to the film. Films with 30% flour or microparticles were effective as protective packaging against Walnut oxidation for 31 days. From the results obtained in this work, it is evident the viability of the use of residues from the food and waste industry of the nutraceutical capsule industry for the development of films and use as biodegradable packaging in different products.

This work deals with the classification and diagnosis of electrical insulating liquids. Furthermore, the theoretical part describes the mathematical and physical principles of these liquids. The automated workplace was compiled with development environment VEE Pro for measurement of viskosity and control thermostat medingen and modifiable components for measuring complex permittivity in the frequency range. In the experimental part was carried out measurements of selected material parameters, investigated the effect of difficult conditions and made the mathematical evaluation of physical phenomena.

Regeneration, a spontaneous response of bones in response to injuries, infections and fractures, is severely compromised in certain clinical circumstances. Unfortunately, several shortcomings are associated with the current treatment of bone grafting method such as donor shortage and immune response for allografts and donor morbidity for autografts. Thus, the development of clinical alternates is essential. One promising adjunct method is bone tissue engineering that includes the implantation of a scaffold containing the cells with the supplementation of suitable growth factors. Among the various classes of materials, biodegradable polymers are commonly preferred because their use does not necessitate a secondary surgery for their removal after the intended use. Commercially available polymers such as poly (lactic- co- glycolic acid) and polycaprolactone are expensive and degrade slowly. This motivates the development of novel synthetic biodegradable polymers that are affordable and can be tuned to tailor for specific biomedical applications. The primary aim of this thesis is to synthesize effective biodegradable polymers for drug delivery and bone tissue engineering. The properties of these polymers such as modulus, hydrophobicity and crosslinking etc. were tailored based on the variations in chemical bonds, chain lengths and the molar stoichiometric ratios of the monomers for specific clinical applications. Based on the above variations, degradation and release kinetics were tuned. The cytocompatibilty properties for these polymers were studied and suitable mineralization studies were conducted to determine their potential for bone regeneration.

碩士
輔仁大學
食品科學系碩士班
103
Oregano essential oil (OEO) is widely used as a food flavoring, and also shows antimicrobial and antioxidative capacities. Additionally, Chitosan (CH) has been demonstrated as an active polymer with antimicrobial activity, which is beneficial to food quality and safety. The objectives of this research aimed to prepare an active packaging material using biodegradable polylactide film incorporating with antimicrobial substances (chitosan and/or oregano), and evaluate its mechanical properties and antimicrobial potential. Solvent casting technique was accomplished to prepare antimicrobial film, then its functionality was determined according to releasing rate and inhibition of microbial growth. Mechanical properties (tensile strength, elongation at break and Young’s module), permeability (water vapor and O2 permeation), and stability (water absorption and degradability), as well as feasibility of food application were evaluated. Results showed that thickness of active films ranged 0.11~0.15 mm. Sufficient antimicrobial agent diffusing into agar plate to cause antimicrobial activity was found within 5 hours. In addition, PLA film incorporated with 3% blend of OEO and CH (1:1, w/w) resulted 4, 3 and 7 log CFU/mL reduction on S. aureus, E. coli and total total viable count, respectively, and those revealed a synergistic effect. With 3% antimicrobial agent incorporation, no significant difference in transparency was found. Moreover, this incorporation led to increase water absorption about 10%, however, no significant difference was found between pure PLA and 3% antimicrobial agent incorporation on degradability. Water vapor permeability increased about 1.5 g/m2/day while O¬2 permeation has 5 mL/m2/day reduction with 3% antimicrobial agent incorporation. Decrease of tensile strength, elongation at break and Young’s module was determined from 360.13 ± 45.12 MPa, 17.04 ± 1.63% and 22.36 ± 4.34 to 286.86 ± 39.89 MPa, 15.01 ± 0.47% and 19.19 ± 1.78, respectively. Antimicrobial films caused 0.5~0.8 and 0.2~0.5 log CFU/mL reduction of growth of S. aureus and E. coli, respectively, on packaged meat; however, the inbhitory effect is not sufficient to meet industrial demand. The findings in the present study demonstrated that antimicrobial film incorporatied with chitosan and oregano essential oil is characterized less substances addition, and no effectiveness on similar mechanical properties and flavor.

Dissertação de Mestrado Integrado em Engenharia Química apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra
Hydrogels are 3D networks of hydrophilic polymers that can absorb and retain significant amounts of water or aqueous solutions without dissolution. These compounds can be synthesized by any technique that leads to a crosslinked polymer, using generally three reagents: an initiator, monomers (or polymers) with water affinity and a crosslinking agent. Hydrogels can be used in several areas, such as hygiene, agriculture, industry, medicine or even in pharmaceutical. In this work the area of interest is agriculture, where the hydrogels can improve and minimize the use of water and the yield in the crop fields without adverse consequences to the environment and the natural resources. Concerning agriculture, it is important to refer the superabsorbent polymers (SAPs), an evolutionary category similar to hydrogels in almost everything except that they have the capacity to absorb greater amounts of water and other fluids (1000 times its own dry weight) in short periods of time comparing to conventional hydrogels. Most of the SAPs used in agriculture are from synthetic source and their degradation contributes for the accumulation of harmful compounds and for the contamination of soils and possibly groundwater. Thus, it would be motivating to develop more biodegradable SAPs with proprieties good enough for a possible application in agriculture, where high capability of absorption and retention of water are essentials. This work had, therefore, as the main goal, the development of a more biodegradable SAPs based in compounds of natural source, such as acrylated epoxidized soybean oil (AESO) and cellulose derivatives, carboxymethyl cellulose sodium salt (CMCss) and hydropropyl cellulose (HPC). In a first stage it was used AESO, comonomers, initiators and crosslinking agents and reaction conditions normally used in SAPs synthesis. It was possible to understand which conditions were the best and which reagents were the most suitable to obtain hydrogels with AESO in their constitution. The most promising and interesting synthesized hydrogels were then evaluated for the capacity of water absorption and it was possible to conclude that those hydrogels had a rather low swelling capacity (3-49 g water/g dry hydrogel). The second stage of this work, were realized two phases. In the first phase, it was reproduced a SAP with good features of swelling and subsequently it was modified with the aim of obtain new SAPs with improved proprieties compared with the base SAP. Among the several synthesised SAPs, the one which had better maximum capacity of absorption of water was the SAP5 with a maximum swelling of 2700 g water/g dry hydrogel. This material was fully characterized, through which it was possible to understand that even for pHs slightly acid or basic, high values for the swelling capacity were achieved. Also, it was possible to observe improvements in the retention of water in the soil caused by the presence of SAP5 and to understand the ability of this material in load high amounts of urea and thereafter to release this fertilizer in a controlled way for the surrounding medium. However it was also possible to have an idea of the negative influence of the ionic strength of the medium on the swelling properties of the SAP5. At last, it was performed the second phase, where it was used the knowledge and the methodology developed in the previous phase, to synthesize more biodegradable SAPs using carboxymethyl cellulose sodium salt and hydropropyl celloluse as comonomers. Those derivatives were also functionalized in order to occur incorporation of functional groups that could help in the synthesis and improve the proprieties of the new SAPs. Through the FTIR analysis it was possible to confirm the success of the performed functionalizations. Despite attempts made, it was not possible to obtain a more biodegradable SAP on this phase. This can be due to various reasons, such as the difficulty of ensure dissolution of the cellulose derivatives in water during the reaction and for the temperatures utilized.
Hidrogéis são uma rede tridimensional de polímeros hidrofílicos que podem absorver e reter grandes quantidades de água ou soluções aquosas, sem dissolver. Estes compostos podem ser sintetizados recorrendo a qualquer técnica que origine um polímero reticulado e utilizando normalmente 3 reagentes: iniciador, monómeros (ou polímeros) e agente reticulante. As áreas de aplicação dos hidrogéis vão desde a higiene até à agricultura, passando pela indústria, medicina e farmacêutica. Neste trabalho em concreto a área de interesse é a agricultura, área onde os hidrogéis podem melhorar e minimizar a utilização de água e a produção nos campos de cultivo sem consequências adversas para o ambiente e para os recursos naturais. Quando a aplicação se trata da agricultura é importante falar em polímeros superabsorventes, uma categoria evolutiva semelhante em tudo aos hidrogéis mas com capacidade de absorver maiores quantidades de água e outros fluidos (1000 vezes o seu peso seco), em curtos períodos de tempo, do que os hidrogéis convencionais. A maior parte dos polímeros superabsorventes utilizados na agricultura são de origem sintética e a sua degradação contribui para a acumulação de compostos prejudiciais e para a contaminação dos solos e possivelmente das águas subterrâneas. Seria interessante então desenvolver polímeros superabsorventes mais biodegradáveis e com propriedades suficientemente boas para uma possível aplicação na agricultura, onde a elevada capacidade de absorção e de retenção de água são essenciais. Este trabalho teve portanto como principal objetivo desenvolver polímeros superabsorventes mais biodegradáveis recorrendo a compostos de origem natural, como o óleo de soja acrilatado e epoxidado (AESO) e os derivados da celulose, carboximetil celulose sal de sódio (CMCss) e hidroxipropil celulose (HPC). Numa primeira etapa recorreu-se ao AESO, a comonómeros, iniciadores e agentes reticulante e a condições de reação normalmente utilizados na síntese de polímeros superabsorventes. Foi possível perceber quais as melhores condições e os reagentes mais apropriados para obter hidrogéis com AESO na sua constituição. Os hidrogéis sintetizados mais promissores e interessantes foram posteriormente avaliados através do cálculo da capacidade máxima de absorção de água e foi possível concluir que esses hidrogéis apresentam uma capacidade de inchamento bastante baixa (3-49 g água/g de hidrogel seco). Na segunda etapa do trabalho foram realizadas duas fases. Uma primeira fase onde se reproduziu um polímero superabsorvente com boas propriedades de inchamento e posteriormente se fez modificações com o objetivo de obter polímero superabsorvente com propriedades melhoradas em relação ao polímero superabsorvente base. Dos vários polímeros superabsorventes sintetizados, o que apresentou melhor capacidade máxima de absorção de água foi o SAP5 com um inchamento máximo de 2700 g água/g hidrogel seco. O material foi caracterizado de forma exaustiva, sendo possível perceber que mesmo para pHs um pouco ácidos ou um pouco básicos eram atingidos elevados valores para a capacidade de inchamento. Também foi possível observar melhorias na retenção de água no solo provocadas pela presença do SAP5 e perceber a capacidade deste composto em carregar elevadas quantidade de ureia e posteriormente libertar este fertilizante de forma controlada para o meio envolvente. No entanto, também foi possível ter uma ideia da negativa influência da força iónica do meio nas propriedades de inchamento do SAP5. Por último foi realizada uma segunda fase onde se utilizou o conhecimento e a metodologia desenvolvida na fase anterior para sintetizar polímeros superabsorventes mais biodegradáveis recorrendo à carboximetil celulose sal de sódio e a hidroxipropil celulose como comonómeros. Esses derivados também foram funcionalizados para haver incorporação de grupos funcionais que ajudassem na síntese e melhorassem as propriedades dos possíveis polímeros superabsorventes obtidos. Através da análise FTIR foi possível confirmar o sucesso das funcionalizações realizadas. Apesar de terem sido realizadas várias tentativas não foi possível obter num polímero superabsorvente mais biodegradável. Isto pode ter ocorrido devido a várias razões, tais como a dificuldade de garantir a dissolução dos derivados da celulose em água durante a reação e para as temperaturas utilizadas.