NOVEL ELECTROSPUN POLYHYDROXYALKANOATE BASED HIGH BARRIER AND ACTIVE BIOPAPERS OF INTEREST IN FOOD PACKAGING

Tesis por compendio[ES] La presente tesis doctoral tuvo como objetivo desarrollar nuevos materiales biodegradables hechos a base de fibras obtenidas mediante la técnica de electroestirado, denominadas "biopapers" o biopapeles, con barrera a agua y a gases y propiedades de secuestro de oxígeno para su posible aplicación en recubrimientos de papel o como capas intermedias en envases alimentarios basados en papel y cartón. En un primer estudio, se desarrollaron biopapeles de PHB mediante electroestirado, usando dos tipos de colectores, colectores de placa plana y rotativo, para evaluar la influencia del alineamiento de las fibras. Con posterioridad se aplicó un tratamento de recocido por debajo del punto de fusión del polímero a diferentes temperaturas, tiempos y procesos de enfriamiento para obtener películas continuas por coalescencia de las fibras, lo que a su vez condujo a la adhesión entre capas, y a una mejora en las propriedades barrera y ópticas. En un segundo estudio, se depositaron biopapeles monocapa y multicapa hechos de PHB, PVOH y PLA sobre un sustrato de papel no estucado, utilizando los dos colectores citados; y el tiempo de procesamiento por electrospinning se varió para producir espesores diferentes. Para mejorar la adhesión al sustrato de papel, y las propiedades ópticas y de barrera de las multicapas, los biopapeles se sometieron a un proceso de recocido como se describe y optimiza en el primer estudio. Con respecto a la barrera al agua, el sistema de papel/ PVOH/PHB presentó las mejores propriedades. En un tercer estudio, se obtuvieron dos nanopapeles de alta barrera hechos a base de nanofibras de celulosa de dos tipos, nanofibras de celulosa (CNF) y nanofibras de lignocelulosa (LCNF) y se recubrieron con biopapeles de PHA electroestirados con barrera a agua. Como resultado, el carácter hidrófobo de los nanopapeles se mejoró significativamente. Por otra parte, estos también exhibieron un rendimiento mecánico más equilibrado. En un cuarto estudio, se desarrollaron biopapeles de PHA con capacidad activa de secuestro de oxígeno, para lo cual se usaron nanopartículas de paladio (PdNP) como catalizadores de la respuesta activa. La principal dificultad asociada con las nanopartículas es mantenerlas dispersas, por lo que en este trabajo evaluamos el uso de surfactantes CTAB y TEOS como sustancias permitidas en contacto con alimentos para ayudar a la dispersión y distribución de PdNP dentro de las fibras de PHA. Como resultado, se prepararon nanocompuestos electroestirados con capacidad de secuestro de oxígeno hechos de PHB y PdNP, seguidos de un tratamiento de recocido para obtener capas continuas y autoadhesivas. La capacidad de secuestro de oxígeno de los biopapeles, medida a un 100% de humedad relativa (HR), mostró un mejor rendimento para el material en forma de fibra que en forma de film. En cualquier caso, los resultados indicaron una cinética de absorcion relativamente baja. Con el fin de mejorar aún más la cinética de secuestro de oxígeno, incluso a una humedad intermedia y en forma de película, un quinto estudio, desarrolló biopapeles multicapa hechos de PCL y PHA aplicados sobre papel no estucado. Los nanocompuestos de PCL/PdNP mostraron uma cinética de secuestro de oxígeno mucho mayor que la del sistema PHA / PdNP anterior. Este resultado se atribuye a la mayor fración de volumen libre del PCL que permite que la humedad, el hidrógeno y la permeación de oxígeno desencadenen la reacción de eliminación catalítica de forma más eficiente. Finalmente, un sexto estudio, desarrolló un nuevo concepto de capa con capacidad de secuestro de oxígeno y con alta barrera passiva a gases y vapores orgánicos basado en PdNP, CNC y EVOH. Así, CNC y CNC oxidado com TEMPO (TEMPO oxidized CNC), se utilizaron para producir PdNP in situ sobre el nanorefuerzo, que se incorporaron en la matriz del polímero EVOH. El TEMPO oxidized CNC demostró poseer una mayor absorción de oxígeno debido a los grupos car[CA] La present tesi doctoral va tindre com a objectiu desenvolupar noves capes biodegradables actives obtingudes mitjançant electrospinning, denominades "biopapers" o biopapeles, amb barrera a aigua i a gasos i propietats de segrest d'oxigen per a la seua possible aplicació en recobriments de paper o com a capes intermèdies en envasos alimentaris basats en paper i cartó. En un primer estudi, es van desenvolupar bio-papers de PHB mitjançant electrospinning, utilitzant dos tipus de col·lectors, col·lectors de placa plana i rotatiu, per a avaluar la influència de l'alineament de les fibres. Amb posterioritat es va aplicar un tractament de recuita per davall del punt de fusió del polímer a diferents temperatures, temps i processos de refredament per a obtenir pel·lícules contínues per coalescència de les fibres, la qual cosa al seu torn va conduir a l'adhesió entre capes, i a una millora en les propietats barrera i òptiques. En un segon estudi, es van depositar bio-papers monocapa i multicapa fets de PHB, PVOH i PLA sobre un substrat de paper no estucat, utilitzant els dos col·lectors citats; i el temps de processament per electrospinning es va variar per a produir grossàries diferents. Per a millorar l'adhesió al substrat de paper, i les propietats òptiques i de barrera de les multicapes, els biopapers es van sotmetre a un procés de recuita com es descriu i optimitza en el primer estudi. Respecte a la barrera a l'aigua, el sistema de paper/PVOH/PHB va presentar les millors propietats. En un tercer estudi, es van obtenir dos nano-papers d'alta barrera fets a base de nanofibres de cel·lulosa de dos tipus, nanofibres de cel·lulosa (CNF) i nanofibres de lignocel·lulosa (LCNF) i es van recobrir amb bio-papers de PHA electro-estirats amb barrera a aigua. Com a resultat, el caràcter hidròfob dels nano-papers es va millorar significativament. D'altra banda, aquests també van exhibir un rendiment mecànic més equilibrat. En un quart estudi, es van desenvolupar bio-papers de PHA amb capacitat activa de segrest d'oxigen, per a això es van usar nanopartícules de pal·ladi (PdNP) com a catalitzadors de la resposta activa. La principal dificultat associada amb les nanopartícules és mantenir-les disperses, per la qual cosa en aquest treball avaluem l'ús de surfactants CTAB i TEOS com a substàncies permeses en contacte amb aliments per a ajudar la dispersió i distribució de PdNP dins de les fibres de PHA. Com a resultat, es van preparar nano-compostos electro-estirats amb capacitat de segrest d'oxigen fets de PHB i PdNP, seguits d'un tractament de recuita per a obtenir capes contínues i autoadhesives. La capacitat de segrest d'oxigen dels bio-papers, mesurada a un 100% d'humitat relativa (HR), va mostrar un millor rendiment per al material en forma de fibra que en forma de film. En qualsevol cas, els resultats van indicar una cinètica de absorció relativament baixa. Amb la finalitat de millorar encara més la cinètica de segrest d'oxigen, fins i tot a una humitat intermèdia i en forma de pel·lícula, un cinquè estudi, va desenvolupar bio-papers multicapa fets de PCL i PHA aplicats sobre paper no estucat. Els nano-compostos de PCL/PdNP van mostrar una cinètica de segrest d'oxigen molt major que la del sistema PHA/PdNP anterior. Aquest resultat s'atribueix a la major fracció de volum lliure del PCL que permet que la humitat, l'hidrogen i la permeància d'oxigen desencadenen la reacció d'eliminació catalítica de forma més eficient. Finalment, un sisè estudi, va desenvolupar un nou concepte de capa amb capacitat de segrest d'oxigen i amb alta barrera passiva a gasos i vapors orgànics basat en PdNP, CNC i EVOH. Així, CNC i CNC oxidat com TEMPO (TEMPO oxidat CNC), es van utilitzar per a produir PdNP in situ sobre el nano-reforç, que es van incorporar en la matriu del polímer EVOH. El TEMPO oxidat CNC va demostrar posseir una major absorció d'oxigen degut als grups carboxílics generats.[EN] The present PhD thesis aimed to develop novel active fiber based biodegradable layers obtained by electrospinning, so-called biopapers, with water and gas barrier and oxygen scavenging properties for their potential use as paper coatings or packaging interlayers in fiber based packaging. In a first study, PHB biopapers were obtained by electrospinning, by means of two types of collectors namely, flat plate and rotation drum collectors, to evaluate the influence of the alignment of fibers. Annealing post-processing below the polymer melting point was carried at different temperatures, isothermal times and cooling processes to obtain transparent and pore free continuous films by fibers coalescence which in turn led to interlayer adhesion, enhanced barrier and optical properties. In a second study, mono and multilayer biopapers comprising PHB, PVOH and PLA were deposited onto a conventional uncoated paper substrate, using the cited two collectors; and the electrospinning processing time was varied to produce different thickneses. To enhance adhesion to the paper substrate, optical and barrier performance of the multilayer, the biopapers were subjected to an annealed process as described and optimized in the first study. Regarding water barrier, the system paper/PVOH/PHB presented the highest barrier performance. In a third study, environmentally friendly materials such as cellulose based nanopapers, i.e. gas barrier layers made of cellulose nanofibrils (CNFs) and lignocellulose nanofibrils (LCNFs), were obtained and coated with the water barrier electrospun PHA biopapers. As a result, the hydrophobic character of the nanopapers was significantly improved by the electrospun biopapers. Moreover, these also exhibited a more balanced mechanical performance. In a fourth study, active oxygen scavenging PHA biopapers were developed, in which palladium nanoparticles (PdNP) were used as catalysts to scavenge oxygen from the headspace. The main difficulty associated with nanoparticles is to keep them dispersed, so in this work we assessed the use of CTAB and TEOS surfactants as food contact permitted substances to help dispersion and distribution of the PdNP within the PHA fibers. As a result, oxygen scavenging nanocomposite biopapers made of electrospun PHB and PdNP were prepared, followed by annealing treatment to obtain homogeneous and continuous active layers. The oxygen scavenging capacity at 100% relative humidity (RH) of the biopapers in fiber form showed better performance than their annealed specimens as expected, but in general this was not considered optimal. In order to improve further the oxygen scavenging capacity, even at a low relative humidity and in film form, a fifth study, developed multilayered biopapers made of PCL and PHA coated on conventional cellulose paper. The PCL/PdNP nanocomposites showed much more enhanced oxygen scavenging performance in comparison with the above PHA/PdNP system. This result is attributed to the higher fractional free volume of the PCL polymer that allows moisture, hydrogen and oxygen permeation to trigger the catalytic scavenging reaction. Finally, a sixth study, developed a solvent casting high gas barrier and active oxygen scavenging layer concept based on PdNP, CNC and EVOH. Thus, CNC and TEMPO oxidized CNC, were used to produce in situ PdNP, which were incorporated into the EVOH polymer matrix. The TEMPO oxidized CNC exhibited higher oxygen absorption due to the generated carboxylic groups.Spanish Ministry of Economy and Competitiveness (MINECO) project AGL2015-63855-C2-1-R for financial support. A. Cherpinski also would like to thank the Brazilian Council for Scientific and Technological Development (CNPq) of Brasilian Government for her predoctoral grant (205955/2014-2). A. Cherpinski also acknowledges the European Cooperation in Science and Technology (COST) Action FP1405 for funding through a Short Term Scientific Mission (STSM)Cherpinski Correa, A. (2019). NOVEL ELECTROSPUN POLYHYDROXYALKANOATE BASED HIGH BARRIER AND ACTIVE BIOPAPERS OF INTEREST IN FOOD PACKAGING [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/123064TESISCompendi

O FALSO PAGANISMO DE RICARDO REIS

This paper addresses aspects of the poetry of Pessoa Ricardo Reis heteronomous. Restricted to research the analysis of denial of Christianity in some odes, since the genesis of his poetry is linked to paganism, Epicureanism and Stoicism. The survey should detect the belief "hidden" in kings and religious issue. The denial of the master away from paganism insistently, nicely demonstrates his knowledge of Christianity. It is precisely these vestiges of a past that Christianity will be pointed in some odes of Kings. We will analyze some excerpts from odes denouncing the religious aspect addressed, as well as their influences.O presente estudo aborda aspectos da poesia do heterônimo pessoano Ricardo Reis. Restringe-se a pesquisa à análise da negação do Cristianismo em algumas odes, uma vez que a gênese de sua poesia está ligada ao paganismo, epicurismo e estoicismo. A pesquisa deverá detectar a crença “escondida” e a questão religiosa em Reis. A negação afasta o mestre do paganismo insistentemente, demonstra muito bem o seu conhecimento do cristianismo. São justamente estes resquícios de um cristianismo passado que serão apontados em algumas odes de Reis. Serão analisados alguns trechos de odes que denunciam o aspecto religioso abordado, bem como suas influências.&nbsp

Um Narrador “Quase” Oral

O propósito deste artigo é identificar marcas do narrador de tradição oral na obra literária Quase de verdade, de Clarice Lispector, destinada ao público infanto-juvenil. Como âncora teórica, deteve-se, especificamente, no narrador da tradição oral defendido por Walter Benjamin (1994), e que se encontra na iminência de desaparecer. Observou-se que o cão Ulisses, narrador da produção literária clariceana, selecionada para este estudo, apresenta diversas características da oralidade, culminando assim em evidente dialogismo com as especificidades do narrador benjaminiano

RESSONÂNCIAS ONOMATOPEICAS E INTERJETIVAS NO EPISÓDIO “SEREIAS”, DE ULYSSES

Este estudo busca analisar os efeitos de sentido das onomatopeias e interjeições presentes no episódio “Sereias”, de Ulysses. Após breve apresentação dos pilares que constituem o bloomsday e do episódio selecionado, os vocábulos encontrados revelam que os sons espalhados no entremeio da narrativa auxiliam o leitor na compreensão dos fatos apresentados. Os aspectos metodológicos correspondem a um estudo bibliográfico, amparados em autores da área, tais como Mikhail Bakhtin e Caetano W. Galindo. A obra Estética da criação verbal, de Bakhtin, fundamenta a análise de diferentes vozes em dialogia. Galindo é o tradutor da edição utilizada na análise, bem como autor da obra Sim, eu digo sim: uma visita ao Ulisses de James Joyce, a qual subsidiou as discussões expostas.PALAVRAS-CHAVE: Ulysses. Bloom. Onomatopeias.DOI: https://doi.org/10.47295/mgren.v7i2.165

Multilayer structures based on annealed electrospun biopolymer coatings of interest in water and aroma barrier fiber-based food packaging applications

In this research work, for the first time, a fiber-based packaging material was coated by annealed electrospun ultrathin fibers of poly(3-hydroxybutyrate), poly(vinyl alcohol), and polylactide. The resultant mono- and multilayer structures self-adhered to the paper substrate and were characterized in terms of morphology, optical, and barrier properties. Additionally, the use of a static flat plate and rotating mandrel collector as well as the application of different electrospinning deposition times were analyzed. The thermally treated electrospun biopolymers yielded totally transparent films while, due to the opaque nature of the uncoated paper substrate, the developed packaging materials were also opaque but with a glossier surface finish provided by the bioplastic coating. The annealed films obtained from random electrospun fibers, that is, the mats of ultrathin fibers collected on the static plate, presented higher transparency and thickness and also enhanced barrier performance. On the overall, the developed annealed electrospun biopolymer coatings resulted in a significant improvement of the paper barrier properties to water and limonene vapors, being the paper/poly(vinyl alcohol)/poly(3-hydroxybutyrate) film the best performing multilayer packaging structure

Electrospun Oxygen Scavenging Films of Poly(3-hydroxybutyrate) Containing Palladium Nanoparticles for Active Packaging Applications

[EN] This paper reports on the development and characterization of oxygen scavenging films made of poly(3-hydroxybutyrate) (PHB) containing palladium nanoparticles (PdNPs) prepared by electrospinning followed by annealing treatment at 160 degrees C. The PdNPs were modified with the intention to optimize their dispersion and distribution in PHB by means of two different surfactants permitted for food contact applications, i.e., hexadecyltrimethylammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS). Analysis of the morphology and characterization of the chemical, thermal, mechanical, and water and limonene vapor barrier properties and the oxygen scavenging capacity of the various PHB materials were carried out. From the results, it was seen that a better dispersion and distribution was obtained using CTAB as the dispersing aid. As a result, the PHB/PdNP nanocomposites containing CTAB provided also the best oxygen scavenging performance. These films offer a significant potential as new active coating or interlayer systems for application in the design of novel active food packaging structures.This research has received funding from the Spanish Ministry of Economy and Competitiveness (MINECO, project AGL2015-63855-C2-1-R) and the EU H2020 project YPACK (reference number 773872). A.C. and S.T.-G. would like to thank the Brazilian Council for Scientific and Technological Development (CNPq) and MINECO for her predoctoral grant (205955/2014-2) and his Juan de la Cierva contract (IJCI-2016-29675), respectively.Cherpinski, A.; Gozutok, M.; Turkoglu Sasmazel, H.; Torres-Giner, S.; Lagaron, JM. (2018). Electrospun Oxygen Scavenging Films of Poly(3-hydroxybutyrate) Containing Palladium Nanoparticles for Active Packaging Applications. Nanomaterials. 8(7):1-19. https://doi.org/10.3390/nano8070469S11987Puglia, D., Fortunati, E., D’Amico, D. A., Manfredi, L. B., Cyras, V. P., & Kenny, J. M. (2014). 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HANÓI: A REPRESENTAÇÃO DO SUJEITO EM CONDIÇÕES EXÍLICAS

O propósito deste artigo é analisar o romance contemporâneo Hanói (2013), de Adriana Lisboa, explorando o conceito de exílio para observar como o processo de pertencimento identitário se desenvolve na obra recortada para o estudo, a partir da representação dos protagonistas e seus familiares em espaços geográficos multiculturais em consequência do exílio. Considera-se que a prática exílica reformula as experiências e promove o assujeitamento das pessoas que passam por situação de deslocamentos, rupturas e renúncias, no ultrapasse de fronteiras. Constatou-se que os personagens principais e seus familiares buscam o sentimento de pertença em local exílio, sem atingi-lo por completo, visto que as identidades são (des)construídas constantemente e anacronicamente

Sensory profile and drivers of liking of cashew beverage (Anacardium ocidentale L.) with dietary purpose, added psyllium

Orientador: Helena Maria Andre BoliniDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de AlimentosResumo: As pessoas que necessitam substituir a sacarose em função da dieta devido a doenças como diabetes, obesidade e hipertensão, ou ainda aquelas pessoas interessadas em manter uma alimentação saudável, podem se beneficiar do gosto doce sem a adição de calorias ou com teor reduzido através da utilização de edulcorantes. A falta de tempo do consumidor para seguir uma alimentação balanceada e saudável tem exigido da indústria alimentos adaptados que possam oferecer mais benefícios em um único produto. As bebidas de frutas apresentam-se uma excelente opção para adição de ingredientes prebióticos visando a agregação de propriedades funcionais. Considerando estes fatores, o objetivo deste trabalho foi avaliar a subtituição da sacarose por diferentes edulcorantes (aspartame, estévia, neotame, neosucralose e sucralose) em bebida de caju adicionada de 1,5% de prebiótico psyllium. Foram realizados inicialmente dois testes com 30 consumidores para conhecer a concentração do ideal de suco e ideal de doçura para a preparação da bebida de caju, sendo determinado 1:4 de suco concentrado e 9% de sacarose para bebida de caju com psyllium. Na sequência foram determinadas, através do método de estimativa de magnitude as concentrações de cada edulcorante que iriam proporcionar doçura equivalente ao ideal de sacarose, que apresentaram-se nas seguintes concentrações 0,0496% de aspartame, 0,0908 de estevia, 0,0015 neotame, 0,0226 de neosucralose e 0,0145 de sucralose.Utilizando o método de rede, foram definidos 20 atributos que melhor caracterizaram as amostras. Os provadores participaram de 4 sessões de treinamento e foram selecionados para participação na Análise Descritiva Quantitativa através da análise de pf amostra (0,05) e concenso com a equipe. Avaliou-se o perfil físico químico das amostras através das análises de pH, acidez titulável, sólidos solúveis (ºBrix), e cor utilizando os parâmetros (L*, a*, b*). Os provadores treinados avaliaram as amostras quanto às suas caracteristicas temporais para os gostos doce e amargo, usando a metodologia Tempo Intensidade, sendo que amostra com sacarose apresentou as menores tempos e intensidades, enquanto a amostra com estévia apresentou os maiores tempos e intensidades para os estímulos doce e amargo, indicando a presença de sabor residual doce e amargo. Ja as amostras com aspartame e sucralose, apresentaram perfil de tempo intensidade muito similar ao da sacarose para doçura e amargor, caracterizando-se boas opções como substitutos da sacarose em bebida de caju. As amostras foram avaliadas em relação a aparência, aroma, sabor, textura, impressão global, ideal de doçura, ideal de viscosidade e intenção de compra, através de teste de aceitação com 120 consumidores, sendo que para as amostras com aspartame, neosucralose e sucralose a aceitação foi muito próxima a da sacarose. Os dados obtidos foram avaliados através de análise de variância (ANOVA), teste de médias Tukey, histogramas e análise de regressãoAbstract: People who need to replace of sucrose in function of diet due to diseases like diabetes, obesity, hypertension, or those interested in maintaining a healthy diet, can benefit from the sweet taste without adding calories or reduced their content through the use of sweeteners. The lack of time for consumer to follow a balanced and healthy diet has required the industry to adapt to the foods that can provide more benefits in a single product. The fruit drinks have become a great option for adding prebiotic ingredients in order to aggregate functional properties and many alternatives have been proposed. Soluble fibers can be added to various kinds of products, with the purpose of increasing satiety, improving bowel function or reduce the glycemic response of food, whereas their use is generally recommended for diabetics. But not a product to be just the ideal from nutritional point of view, it must also be acceptable to the public consumer, which is obtained through different sensory tests, where the human being is the measuring instrument. Considering these factors, the aim of this study was to evaluate the sucrose substitution by different sweeteners (aspartame, sucralose, stevia 95 % rebaudiosídio, neotame and neosucralose blend) in cashew drink plus 1.5 % prebiotic psyllium. Initially the ideal sweetness test was conducted to know the preference to the product and the value was found to be 9 %. In the next step the power of these sweeteners as well as the concentrations of each sweetener that would provide the same perception of the ideal sweetness of sucrose was determined, ranging from 99 time for the sample sweetened with stevia to 6000 times for the sample sweetened with neotame. Using the Kelly's repertory grid method, the attributes that best characterize the samples, were selected. The panelists were trained and selected for participation in the Quantitative Descriptive Analysis test. Physicochemical profile of the samples was evaluated through analysis of pH, titratable acidity, soluble solids (° Brix), and using color parameters (L *, a *, b *). Trained panelists evaluated the samples with respect to their temporal characteristics for sweet and bitter tastes, using the Time Intensity method, where sample with sucrose showed the lowest mean, while the sample with stevia showed the largest for time and intensity to both stimuli. Samples with aspartame and sucralose, showed time -intensity profile very similar to that of sucrose sweetness and bitterness, characterized spoiled as sucrose substitutes in cashew drink. The samples were evaluated for appearance, aroma, flavor, texture, global media ideal of sweetness, ideal viscosity and purchase intent through acceptance testing with 120 consumers, and for samples with aspartame , sucralose and neosucralose acceptance was very close to that of sucrose. The data were evaluated using analysis of variance (ANOVA), Tukey test, histograms and regression testingMestradoConsumo e Qualidade de AlimentosMestra em Alimentos e Nutriçã