Submitted by JHONES LUIZ DE OLIVEIRA (jholuisoliveira@hotmail.com) on 2018-09-21T20:36:12Z No. of bitstreams: 1 Tese_Jhones_Versão_final.docx: 18568915 bytes, checksum: 5f380ac64e8ceaf78f5ca0aadd101a25 (MD5) / Rejected by Lucimara Kurokawa Shinoda null (lucimaraks@sorocaba.unesp.br), reason: Solicitamos que realize correções na submissão seguindo as orientações abaixo: - O arquivo deve estar no formato Portable Document Format (PDF) e não deve estar protegido; - Deve constar o Certificado de Aprovação no lugar da Ata. Agradecemos a compreensão. on 2018-09-24T17:57:56Z (GMT) / Submitted by JHONES LUIZ DE OLIVEIRA (jholuisoliveira@hotmail.com) on 2018-09-25T16:11:04Z No. of bitstreams: 1 Tese_Versão_Final.pdf: 10082969 bytes, checksum: 10f670d91ae97794a59de73275ce0f1d (MD5) / Approved for entry into archive by Lucimara Kurokawa Shinoda null (lucimaraks@sorocaba.unesp.br) on 2018-09-25T18:12:02Z (GMT) No. of bitstreams: 1 oliveira_jl_dr_soro.pdf: 10082969 bytes, checksum: 10f670d91ae97794a59de73275ce0f1d (MD5) / Made available in DSpace on 2018-09-25T18:12:02Z (GMT). No. of bitstreams: 1 oliveira_jl_dr_soro.pdf: 10082969 bytes, checksum: 10f670d91ae97794a59de73275ce0f1d (MD5) Previous issue date: 2018-09-06 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os artrópodes tem sido uma das principais causas de perdas agrícolas em todo o mundo. Só no Brasil essas perdas podem chegar a 7,7 % ao ano. A utilização extensiva de pesticidas sintéticos tem sido a principal forma de controle deste tipo de praga, no entanto, os efeitos adversos destes compostos tanto para o meio ambiente quanto para a saúde humana tem motivado a busca por alternativas menos impactantes. Neste contexto, diversos mecanismos estão sendo estudados a fim de minimizar estes danos, como por exemplo, o desenvolvimento de sistemas de liberação modificada, utilizando polímeros biodegradáveis e proteínas. Aliado a isto, a utilização de pesticidas botânicos também tem demostrado potencialidade para o combate a essas pragas, devido aos menores impactos causados por esses produtos de origem natural. Portanto, o presente trabalho apresenta o desenvolvimento (preparo e caracterização) de sistemas nanocarreadores produzidos a partir dos polímeros quitosana e goma arábica e da proteína zeína para os compostos botânicos (geraniol, citronelal, eugenol e cinamaldeído), bem como, os potenciais efeitos cito e fitotóxicos destes sistemas. Ademais foram também realizados ensaios de atividade biológica destes sistemas em pragas agrícolas (mosca-branca, ácaro-rajado e lagarta falsamedideira). Os compostos botânicos apresentaram elevada eficiência de encapsulação em ambos os sistemas carreadores, sendo que os sistemas foram capazes de proteger os compostos contra uma degradação prematura e também contra a radiação ultravioleta. Os resultados de fito e citotoxicidade mostraram que a encapsulação diminuiu o efeito tóxico dos ativos. Os sistemas também apresentaram atividade biológica contra as pragas agrícolas testadas. As nanopartículas de zeína contendo os compostos botânicos mostraram efeito repelente contra o ácaro-rajado (Tetranychus urticae) em condições laboratoriais e de semi-campo, além de efeito subletal em largarta falsa-medideira (Chrysodeixis includes). Já as nanopartículas de quitosana/goma arábica contendo geraniol mostraram efeito atrativo para mosca-branca, sendo promissora para aplicações em sistemas de armadilha. A importância desta tese reside na dimensão que o setor agrícola representa para a economia brasileira e mundial, aliado a isto o mercado de defensivos agrícolas cresce anualmente, sendo o Brasil um dos líderes no consumo destes produtos. Desta forma, o desenvolvimento de tecnologia com elevado valor agregado à área de controle de pragas em agricultura é promissora uma vez que podem ser produzidos sistemas mais eficientes no controle de pragas, menos impactantes ao ambiente e consequentemente à saúde humana. / Arthropods have been a major cause of agricultural losses worldwide. Only in Brazil can these losses reach 7.7% per year. The extensive use of synthetic pesticides has been the main form of control of this type of pest, however, the adverse effects of these compounds for both the environment and human health have motivated the search for less impactful alternatives. In this context, several mechanisms are being studied in order to minimize these damages, such as the development of modified release systems using biodegradable polymers and proteins. In addition to this, the use of botanical pesticides has also shown potential for combating these pests, due to the lower impacts caused by these products of natural origin. Therefore, the present work showed the development (preparation and characterization) of nanocarrier systems produced from chitosan and gum arabic polymers and zein protein for the botanical compounds (geraniol, citronellal, eugenol and cinnamaldehyde), as well as the potential effects and phytotoxic systems. In addition, tests of the biological activity of these systems on agricultural pests (whitefly, two-spotted spider mite and soybean looper) were also carried out. The botanical compounds showed high encapsulation efficiency in both carrier systems, and the systems were able to protect the compounds against premature degradation and also against ultraviolet radiation. The phyto and cytotoxicity results showed that encapsulation decreased the toxic effect of the active compounds. The systems also showed biological activity against the agricultural pests tested. The zein nanoparticles containing the botanicals showed a repellent effect against the brindle two-spotted spider mite (Tetranychus urticae) under laboratory and semi-field conditions, as well as a sublethal effect on soybean looper (Chrysodeixis includes). The chitosan/gum arabic nanoparticles containing geraniol showed attractive effect for whitefly, being promising for applications in trap systems. The importance of this thesis lies in the dimension that the agricultural sector represents for the Brazilian and world economy, in addition to that the market for agricultural pesticides grows annually, in special as Brazil is one of the leaders in the consumption of these products. In this way, the development of new technologies to pest control in agriculture is promising since more efficient pest control systems can be produced, less impacting the environment and consequently to human health. / FAPESP: 2014/20286-9

Submitted by Cássia Santos (cassia.bcufg@gmail.com) on 2015-01-30T10:32:30Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao - Fabiola Alves Lino - 2014.pdf: 1246990 bytes, checksum: edde456da4f6d52fbe0571bf1f519d20 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-01-30T12:19:19Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao - Fabiola Alves Lino - 2014.pdf: 1246990 bytes, checksum: edde456da4f6d52fbe0571bf1f519d20 (MD5) / Made available in DSpace on 2015-01-30T12:19:19Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao - Fabiola Alves Lino - 2014.pdf: 1246990 bytes, checksum: edde456da4f6d52fbe0571bf1f519d20 (MD5) Previous issue date: 2014-02-28 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The objective was to evaluate the physical chemical characteristics of the corn grains and if these affect the ruminal degradability of grain harvested at half milk line. Six corn hybrids were used: AG 1051, BJ 9450 PRO, AG 4051 PRO, IMPACTO VIP, BM 3061 e SG 3060YG. The randomized block design with five replications was used. The experimental plot consisted of four rows of 5.0 m and spaces between rows of 0.6 m. Cobs of the central rows of each plot were harvested when the grains were at half milk line. Posteriorly were dried in a forced air at 55 °C until the grains achieve content of humidity ideal for storing around 13%. The grains were threshed and submitted to analysis of dry matter (DM), crude protein (CP), starch, prolamin (zein) and de nsity. The in situ degradability was conducted in four Nelore cattle fitted with rumen cannula. polyester bags were incubated in size 5.0 x 10.0 cm with a porosity of 50 ± 10 μm (Ankom Technology) containing 2.0 g samples of grain broken into four parts. We evaluated the following incubation times: 6, 12, 24 and 72 hours. Analysis of variance and the Scott-Knott test at 5% significance was conducted (R CORE TEAM, 2012).Hybrids farinaceous texture AG 1051, AG 4051 PRO and BM 3061 showed lower DM content (P<0.05) compared to hard (IMPACT VIP) and semi-hard hybrids (BJ 9450 PRO) except SG 6030 YG. The hard and semi-hard hybrids showed higher density than the hybrid farinaceous (P <0.05). Thus, defining two classes of hardness, hard or high density group (IMPACTO VIP, BJ 9450 PRO and SG 6030YG) and farinaceous or low density group (AG 1051, AG 4051 PRO and BM 3061). The low density group showed the highest CP (P <0.05). The starch content ranged from 68.0% in the hybrid IMPACTO VIP until 75.6% in the hybrid AG 1051. The hybrids of the low density showed the highest levels of zein in g/100g DM and also in relation to starch g/100g of starch. There were no differences in the in situ ruminal degradation of corn hybrids in the time of incubation evaluated. / Objetivou-se avaliar as características físicas e químicas dos grãos de milho e se estas afetam a degradabilidade ruminal dos grãos colhidos na metade da linha do leite. Foram utilizados seis híbridos de milho: AG 1051, BJ 9450 PRO, AG 4051 PRO, IMPACTO VIP, BM 3061 e SG 3060YG. O delineamento foi em blocos casualizados com cinco repetições. A parcela experimental foi formada por quatro linhas de 5,0 m de comprimento e espaçamento entre linhas de 0,6 m. Foram colhidas espigas das linhas centrais de cada parcela quando os grãos estavam na metade da linha do leite. Posteriormente foram secas em estufa de ventilação forçada a 55°C até os grãos atingirem teor de umidade ideal para o armazenamento, em torno de 13%. Os grãos foram debulhados e submetidos a análise de matéria seca (MS), proteína bruta (PB), amido, prolamina (zeína) e densidade. A degradabilidade ruminal in situ foi realizada em quatro bovinos da raça Nelore munidos de cânula ruminal. Foram incubados sacos de poliéster no tamanho 5,0 x 10,0 cm com porosidade de 50±10 μm (Ankom Technology) contendo 2,0 g de amostras dos grãos quebrados em quatro partes. Avaliaram-se os seguintes tempos de incubação: 6, 12, 24 e 72 horas. Foi realizado análise de variância e teste de Scott-Knott ao nível de significância de 5% (R CORE TEAM, 2012). Os híbridos de textura farinácea AG 1051, AG 4051 PRO e BM 3061 apresentaram menor teor de MS (P<0,05) em comparação aos híbridos duro (IMPACTO VIP) e semiduro (BJ 9450 PRO) com exceção do SG 6030 YG. Os híbridos duro e semiduros apresentaram densidade superior à observada nos híbridos farináceos (P<0,05). Dessa forma, definindo duas classes de dureza, tipo duro ou grupo de alta densidade (IMPACTO VIP, BJ 9450 PRO e SG 6030YG) e farináceo ou grupo de baixa densidade (AG 1051, AG 4051 PRO e BM 3061). O grupo de baixa densidade apresentou o maior teor de proteína bruta (PB) (P<0,05). O teor de amido variou de 68,0% no híbrido IMPACTO VIP a 75,6% no híbrido AG 1051. Os híbridos de baixa densidade apresentaram os maiores teores de zeína em g/100g de MS e também em relação ao amido g/100g de amido. Não houve diferenças na degradação ruminal in situ dos híbridos de milho nos tempos de incubação avaliados.

Although work on the prolamins of pearl millet (Pennisetum glaucum) has revealed partial amino acid sequences for several alcohol-soluble storage proteins (Marcellino et al. 2002) the genes encoding them have not yet been isolated. We constructed a cDNA library from developing P. glaucum seed tissue and screened it using maize zein gene probes to isolate several α-prolamin-like gene sequences. The proteins encoded by these genes generally fall into two size classes: 20.6kD and 27.1kD, which we call the 21kD and 27kD pennisetins. Both proteins are similar in composition and sequence to α-prolamins from maize, sorghum and Coix. Protein bodies that appear as occlusions within the rough ER of P. glaucum endosperm cells are also very similar in size and shape to maize and sorghum protein bodies. The SDS-PAGE gel of the alcohol soluble protein fraction shows two distinct bands in the region corresponding to the 19kD and 22kD of maize α-zein. Both classes of pennisetins appear to be more similar to the 19kD α-zein of maize than to the 22-kD α-zein judging from sequence homology and maize antibody binding. Phylogenetic reconstruction suggests that P. glaucum may have branched from maize prior to the gene duplication which created the 19kD and 22kD α-zein families.

O objetivo deste trabalho foi a produção de blendas a partir de zeína e amido de milho, procurando unir de forma otimizada as propriedades dos polímeros e suas características de processabilidade e o entendimento da correlação estrutura-propriedades destas blendas. Misturas de amidolzeína foram preparadas nas proporções de 0/100, 10190, 20180, 30170, 50150, 80120 e 10010 massa/massa%, utilizando glicerol como plastificante nas proporções de 22, 30 e 40% em relação a massa total dos polímeros. As formulações foram processadas em um misturador interno, tipo Haake, conectado ao reômetro de torque a 160°C. As misturas obtidas foram moldadas por compressão a 160°C. As propriedades das blendas foram aliadas por ensaios de absorção de umidade, difração de raios X, ensaios mecânicos (tração), calorimetria exploratória diferencial (DSC), termogravimetria (TG), análise termo dinâmica-mecânica, microscopia eletrônica de varredura (MEV) e microscopia ótica. As blendas com 22% de glicerol foram avaliadas também quanto a biodegradabilidade, utilizando a técnica de biodegradação aeróbia. A adição da zeína facilitou o pmcessamento das misturas, conforme o observado durante o processamento no reômetro de torque. A presença da zeína não afeta a cristalinidade do amido nas blendas e não ocorre a formação de novas estruturas cristalinas devido a mistura. As blendas amidolzeína apresentaram menor estabilidade térmica que o amido termoplástico e zeína plastificada separadamente e a estabilidade térmica das blendas diminuiu com o aumento do teor de glicerol. As propriedades mecânicas das blendas foram dependentes do teor de zeína e de glicerol. A adição de zeína na lenda provocou aumento no módulo de elasticidade e na resistência a tração e diminuição da deformação , enquanto que o gliceml provocou diminuição em todas estas propriedades. As blendas apresentaram-se imiscíveis em todas as composições estudadas. A zeína plastificada mostrou biodegradação mais acentuada que o amido termoplástico e as blendas apresentaram biodegradação intermediária entre o amido e a zeína. / In this work were investigated blends from zein, which is a com protein, with com starch. The objective of this work was optimizing the polymers properties and their processing characteristics and looking for a structure-properties correlation of these blends. The mixtures of pure polymers and starchlzein blends were prepared using glycerol as plasticizer in a batch mixer connected to a torque rheometer. The zein content varied from 20 to 80% and three levels of glycerol were used, 22, 30 and 40 % of total starch plus zein weight, on a dry basis. The mixtures obtained were molded by compression at 160 OC. The blends were characterized by water absorption experiments, wide-angle X-ray diffraction, thermogravimetry (TG), differential scanning calorimetry (DSC), tensile test, dynamical mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), optical microscopy. Additionally the biodegradability of starchtzein blends were evaluated by aerobic test. The torque behavior of the starchtzein blends shows that zein acts as a processing agent, reducing the melt viscosity of the mixture and facilitating the plasticization of starch. No evidence of the zein affecting the type or amount of crystal structure of thermoplastic starch was observed. The zein proved to be effective to reduce the water absorption of the blends. Mechanical properties of blends depends on the glycerol and zein contents. Young\'s modulus and ultimate tensile strength increase sharply with increasing zein content, while that the glycerol caused reduction on these properties. The blends were immiscible and phase invesion was observed. The results of biodegradation aerobic showed that after 45 days the zeína unfastened greater COz mass than the starch. This indicates that the zein biodegradation occurs more easily than the starch. The blends presented intermediate biodegradtion between the starch and the zein.

CAVALCANTE, Rosane Souza. Avaliação das características estruturais de bolos com redução calórica. 2012. 50 f. : Dissertação (mestrado) - Universidade Federal do Ceará, Departamento de Tecnologia de Alimentos, Programa de Pos-Graduação em Ciências e Tecnologia de Alimentos, Fortaleza-CE, 2012 / Submitted by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-23T13:35:25Z No. of bitstreams: 1 2012_dis_rscavalcante.pdf: 1129788 bytes, checksum: 8f3b16ba9d7215549d158094e9a448d0 (MD5) / Approved for entry into archive by Nádja Goes (nmoraissoares@gmail.com) on 2016-06-23T13:35:40Z (GMT) No. of bitstreams: 1 2012_dis_rscavalcante.pdf: 1129788 bytes, checksum: 8f3b16ba9d7215549d158094e9a448d0 (MD5) / Made available in DSpace on 2016-06-23T13:35:40Z (GMT). No. of bitstreams: 1 2012_dis_rscavalcante.pdf: 1129788 bytes, checksum: 8f3b16ba9d7215549d158094e9a448d0 (MD5) Previous issue date: 2012 / The consumption of cakes with calorie reduction is growing, but has presented challenges to be overcome in the formation of its structure when the sugar or fat are replaced by sweeteners, gums, thickeners or fat substitutes. The present study was to investigate the internal characteristics of cakes with calorie reduction and viability of producing the same pattern similar to conventional cake. Initially, we defined the mixing time and mass of fat source to be used in the formulation, using as parameter the specific volume. Next, we determined the pattern of the cake formulation from a factorial experimental design of the simple type, measuring the specific volume and cell count. From this formulation, sucrose and fat were partially substituted for the production of calorie reduced cake. Replacement of sugar was made in proportion of a mixture of xanthan gum (1.5%) and sucralose (1%), while the zein was used to replace fat. In cakes with sugar lowering evaluated the specific volume (VE), the cell count (CC) of the cakes, the apparent viscosity of the mass and its thermal properties by differential scanning calorimetry (DSC). In cakes with reduced fat content, the analyzes were VE, CC and apparent viscosity. It was found that the cake with increased VE was prepared with one hydrogenated vegetable fat and one (1) minute of mixing the dough. The standard formulation was defined as having 155.88 and 28.78 shares of sugar and fat, respectively. As the sugar content decreased (10.00 to 52.17%) were reduced specific volume (1.94 to 0.7 ml / g) and cell counts (from 36.2 to 4.0 cells / cm ²) the cake and the apparent viscosity of the mass (337.56 to 631.40 cP). By reducing the fat content, there were no significant differences between the samples for VE, CC and viscosity, and viable to produce cake with reduced calorie fat replacing up to 46.86%. For the results, it was observed that replacement of sugar contributed more sharply than the replacement of fat in the formation of defects in the structure of the cake. Thermograms of the mass of standard and cakes with reduced sucrose suggested that the presence of sucralose can reduce the starch gelatinization temperature, accelerating the process and causing a compression of the structure during baking, thereby facilitating the coalescing of bubbles dispersed in mass. / O consumo de bolos com redução calórica vem crescendo, mas tem apresentado desafios a serem superados na formação da sua estrutura quando o açúcar ou a gordura são substituídos por adoçantes, gomas, espessantes ou substitutos de gordura. O presente trabalho propôs avaliar as características internas de bolos com redução calórica e a viabilidade de produção do mesmo com características similares ao bolo convencional. Inicialmente, foram definidos o tempo de mistura da massa e a fonte de gordura a ser utilizada na formulação, utilizando-se o volume específico como parâmetro. Em seguida, determinou-se a formulação do bolo padrão a partir de um delineamento experimental do tipo fatorial simples, medindo-se volume específico e a contagem de células. A partir dessa formulação, a sacarose e a gordura foram parcialmente substituídos para a produção de bolos com valor calórico reduzido. A substituição do açúcar foi feita proporcionalmente por uma mistura de goma xantana (1,5%) e sucralose (1%), enquanto a zeína foi usada para substituir a gordura. Nos bolos com redução de açúcar avaliou-se o volume específico (VE), a contagem de células (CC) dos bolos, a viscosidade aparente da massa e as suas propriedades térmicas por meio de calorimetria diferencial de varredura (DSC). Nos bolos com redução do teor de gordura, as análises realizadas foram VE, CC e viscosidade aparente. Verificou-se que o bolo com maior VE foi aquele elaborado com gordura vegetal hidrogenada e 1 (um) minuto de mistura da massa. A formulação padrão foi definida como tendo 155,88 e 28,78 partes de açúcar e de gordura, respectivamente. À medida que o teor de açúcar decresceu (10,00-52,17%) foram reduzidos o volume específico (1,94-0,7 mL/g) e a contagem de células (36,2 – 4,0 cél/cm²) do bolo e a viscosidade aparente da massa (337,56-631,40 cP). Com a redução do teor de gordura, não foram observadas diferenças significativas entre as amostras para VE, CC e viscosidade aparente, sendo viável a produção do bolo com redução calórica substituindo-se a gordura em até 46,86%. Pelos resultados encontrados, foi observado que a substituição do açúcar contribuiu mais acentuadamente que a substituição da gordura na formação de defeitos na estrutura do bolo. Os termogramas das massas dos bolos padrão e com redução de sacarose sugeriram que a presença de sucralose pode reduzir a temperatura de gelatinização do amido, acelerando esse processo e causando uma compactação da estrutura durante o assamento, favorecendo assim a coalescência das bolhas dispersas na massa.

O objetivo deste trabalho foi a produção de blendas a partir de zeína e amido de milho, procurando unir de forma otimizada as propriedades dos polímeros e suas características de processabilidade e o entendimento da correlação estrutura-propriedades destas blendas. Misturas de amidolzeína foram preparadas nas proporções de 0/100, 10190, 20180, 30170, 50150, 80120 e 10010 massa/massa%, utilizando glicerol como plastificante nas proporções de 22, 30 e 40% em relação a massa total dos polímeros. As formulações foram processadas em um misturador interno, tipo Haake, conectado ao reômetro de torque a 160°C. As misturas obtidas foram moldadas por compressão a 160°C. As propriedades das blendas foram aliadas por ensaios de absorção de umidade, difração de raios X, ensaios mecânicos (tração), calorimetria exploratória diferencial (DSC), termogravimetria (TG), análise termo dinâmica-mecânica, microscopia eletrônica de varredura (MEV) e microscopia ótica. As blendas com 22% de glicerol foram avaliadas também quanto a biodegradabilidade, utilizando a técnica de biodegradação aeróbia. A adição da zeína facilitou o pmcessamento das misturas, conforme o observado durante o processamento no reômetro de torque. A presença da zeína não afeta a cristalinidade do amido nas blendas e não ocorre a formação de novas estruturas cristalinas devido a mistura. As blendas amidolzeína apresentaram menor estabilidade térmica que o amido termoplástico e zeína plastificada separadamente e a estabilidade térmica das blendas diminuiu com o aumento do teor de glicerol. As propriedades mecânicas das blendas foram dependentes do teor de zeína e de glicerol. A adição de zeína na lenda provocou aumento no módulo de elasticidade e na resistência a tração e diminuição da deformação , enquanto que o gliceml provocou diminuição em todas estas propriedades. As blendas apresentaram-se imiscíveis em todas as composições estudadas. A zeína plastificada mostrou biodegradação mais acentuada que o amido termoplástico e as blendas apresentaram biodegradação intermediária entre o amido e a zeína. / In this work were investigated blends from zein, which is a com protein, with com starch. The objective of this work was optimizing the polymers properties and their processing characteristics and looking for a structure-properties correlation of these blends. The mixtures of pure polymers and starchlzein blends were prepared using glycerol as plasticizer in a batch mixer connected to a torque rheometer. The zein content varied from 20 to 80% and three levels of glycerol were used, 22, 30 and 40 % of total starch plus zein weight, on a dry basis. The mixtures obtained were molded by compression at 160 OC. The blends were characterized by water absorption experiments, wide-angle X-ray diffraction, thermogravimetry (TG), differential scanning calorimetry (DSC), tensile test, dynamical mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), optical microscopy. Additionally the biodegradability of starchtzein blends were evaluated by aerobic test. The torque behavior of the starchtzein blends shows that zein acts as a processing agent, reducing the melt viscosity of the mixture and facilitating the plasticization of starch. No evidence of the zein affecting the type or amount of crystal structure of thermoplastic starch was observed. The zein proved to be effective to reduce the water absorption of the blends. Mechanical properties of blends depends on the glycerol and zein contents. Young\'s modulus and ultimate tensile strength increase sharply with increasing zein content, while that the glycerol caused reduction on these properties. The blends were immiscible and phase invesion was observed. The results of biodegradation aerobic showed that after 45 days the zeína unfastened greater COz mass than the starch. This indicates that the zein biodegradation occurs more easily than the starch. The blends presented intermediate biodegradtion between the starch and the zein.

<p>Zein is a major storage protein of corn, with unique amphiphilic film forming properties. It is insoluble in water, but soluble in 70% ethanol and acetic acid, and has been declared ‘generally recognized as safe’ (GRAS) by the FDA. Due to new advances in food nanotechnology, zein is being investigated for various applications such as biodegradable packaging, oral delivery of proteins and peptides, scaffold for tissue engineering, as well as biodegradable sensor platforms. The time consuming and highly complicated methods for toxin and allergen analysis in the food industry necessitates the need for a rapid, selective, compact and easy-to-use method of detection for analytes. In the scope of this dissertation, we investigated the feasibility of functional zein nanocomposite films and formation of a zein nanocomposite sensor assembly for rapid and highly selective electrochemical measurements of food toxins and allergens. Fabrication of a zein based electrochemical amperometric sensor assembly was studied, first through the comparison of various zein film characteristics changes with the application of Laponite®, graphene oxide and carbon nanotube nanoparticles, followed by a proof-of-concept study by detecting the gluten allergen protein gliadin. </p> <p>To mechanistically study the functional zein nanocomposite films, Laponite®, a silica nanoparticle, was added in the presence of 70% ethanol solvent and oleic acid plasticizer. The films were studied using various characterization techniques like transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), water contact angle measurements etc. Through Si-N bond formation between Laponite® and zein, fabricated zein nanocomposite films showed increase in surface hydrophobicity, water vapor barrier properties, tensile strength and Young’s modulus. Graphene oxide (GO), a carbon nanoparticle, was also incorporated into zein through the solvent casting process. Uniform dispersion of GO nanoparticles within zein matrix were confirmed up to 1% GO loading, and covalent and hydrogen bonding mechanisms were proposed. Similar to zein-Laponite® (Z-LAP) nanocomposites, zein-GO (Z-GO) showed increase in hydrophobic tendencies, rougher surface and a 300% improvement in Young’s modulus and 180% improvement in tensile strength at only 3% GO loading. Both nanoparticles increased tensile strength, thermal stability and water vapor barrier property of the films, indicating a potential for food packaging as an alternative application for the nanocomposite films.</p> Finally, the research focused on the fabrication of an electrochemical amperometric sensor, capable of detecting the protein gliadin, which is responsible for the allergic reaction with people having celiac disease. Novel biodegradable coatings made from zein nanocomposites: zein-graphene oxide, zein-Laponite® and zein-multiwalled carbon nanotubes (Z-CNT) using drop casting technique were tested for fabricating the electrochemical sensors using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV) techniques. As Z-CNT produced the strongest signals compared to other nanomaterials, the active tip of the electrochemical sensor was functionalized through a sequence of layer by layer deposition of Z-CNT nanocomposite, antibody and target analyte. Here, Z-CNT acts as a natural linker molecule with large number of functional groups, that causes immobilization of capture antibody and target, to ensure high sensor performance. Both CV curves and SWV curves indicated successful sequential immobilization of gliadin antibody onto the Z-CNT coated electrode. The Z-CNT biosensor was successfully able to give CV signals for gliadin toxins for as low as 0.5 ppm and was highly specific for gliadin in the presence of other interfering molecules, and remained stable over a 30-day period. The low-cost, thin, conductive zein films offered a promising alternative for protein immobilization platforms used in sensors and can be extended to other matrices in biosensors as well as other functional film applications

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / The polymer and their blended fibres provide good surface and intermolecular chemistry that bring additional functionalities and structural changes that can be adapted for new usages. Natural polymers are known to possess desirable qualities in terms of biocompatibility and biodegradability. The natural polymers are chosen due to their abundance but have difficulties in the preparations hence the addition of a synthetic polymer is vital. An important property of the polymer blended fibres is its miscibility which affects the mechanical properties, the morphology and degradation. Metal oxide nanoparticles embedded into polymer blended fibres enhances the performances of the polymer blended fibre permeability, selectivity, strength, and hydrophilicity. This study reports on the synthesis and characterization of zein, collagen nanofibres, zein/PVA fibre blends, iron oxide, manganese oxide nanoparticles, Fe2O3/zein /PVA and Mn2O3/zein/PVA fibre nanocomposite blends. The zein nanofibres and zein/PVA fibre blends were electrospun using electrospinning technique. Parameters such as the concentration and voltage were investigated. These parameters had an effect on the fibre morphology. The electrospun zein nanofibres and zein/PVA fibre blends were characterized using scanning electron microscopy (SEM), UV-Visible spectroscopy, Photoluminescence (PL), X-ray diffraction (XRD), Fourier transformer infrared (FTIR) spectroscopy and Thermal gravimetric analysis (TGA). The SEM results illustrated that an increase in the concentration of zein nanofibres improved the morphology of the fibres into ribbon like shape and had an effect on the average diameter size. The addition of PVA into zein nanofibres enhanced electrospinnabilty and the mechanical strength of zein was dependent on the presence of PVA. The optical properties, XRD, FTIR and thermal studies confirmed that zein/PVA (80/20) blend weight ratio was miscible and the other blend weight ratios remained immiscible, this was due to stronger interaction of hydrophilic performance of zein and PVA through hydrogen bonding. Therefore, fibre blend weight ratios of zein/PVA (90/10, 80/20, 70/30, 60/40 and 50/50) were successfully fabricated. The optimisation of collagen nanofibres favoured electrospraying instead of electrospinning hence collagen nanofibres could not be fabricated. Iron oxide nanoparticles was synthesized using hydrothermal method and manganese oxide nanoparticles was synthesized through co-precipitation method. The TEM results revealed well defined shapes of metal oxide nanoparticles illustrating that the increment of temperature had an influence on the crystallinity and particle size of 𝛼-Fe2O3 , 𝛼-MnO2 and 𝛼-Mn2O3 nanoparticles. The XRD confirmed the crystalline pattern of the metal oxide nanoparticles were of rhombohedral 𝛼-Fe2O3 structures (JCPDS 00-033-0664), cryptomelane phase 𝛼-MnO2 (JCPDS No. 29-1020) and orthorhombic crystalline phase of 𝛼-Mn2O3 (JCPDS No. 04-007-088). The metal oxide nanoparticles were thermally stable. Three different concentrations (4.25 wt%, 4.75 wt% and 5.25 wt %) of 𝛼-Fe2O3 and 𝛼- Mn2O3 were embedded onto zein/PVA (80/20) fibre blends and electrospun. The SEM, optical properties, XRD and TGA confirmed that the embedment of metal oxide nanoparticles enhanced the zein/PVA fibre blends performance, mechanical strength and resistance to wear therefore 5.25 wt% of 𝛼-Fe2O3/zein/PVA and 𝛼-Mn2O3/zein/PVA were explored further for the adsorption of chrysoidine G removal from wastewater. The adsorption studies of zein/PVA (80/20), 𝛼-Fe2O3/zein/PVA and 𝛼-Mn2O3/zein/PVA were carried out in a batch system on the effects of contact time, pH, initial concentration and adsorbent dosage. All the nanoadsorbents could rapidly reach adsorption equilibrium within 30 min at room temperature. The maximum removal efficiency of chrysoidine G of zein/PVA, 𝛼-Mn2O3/zein/PVA was higher than 𝛼-Fe2O3/zein/PVA. The dye adsorption equilibrium data were well-fit with Langmuir isotherm rather than Freundlich isotherm. The comparison of kinetic models revealed that the overall adsorption process was described well by pseudo second-order kinetics. The polymeric materials were cost effective hence regeneration studies were implemented for three cycles. These nanoadsorbents are easily available and are expected to be economical.

[ES] La presente tesis doctoral, titulada "Microportadores inteligentes para la liberación controlada de sustancias de interés nutracéutico", se centra en el diseño y evaluación de sistemas híbridos orgánico-inorgánicos para proteger y liberar controladamente compuestos bioactivos. Dichos sistemas están basados en (i) materiales de sílice, principalmente partículas mesoporosas, como soporte inorgánico para almacenar y proteger la carga bioactiva; y (ii) una capa externa de biomoléculas como puerta molecular, que regula la liberación de la carga ante ciertos estímulos. En el primer capítulo de la tesis se describe el ácido oleico como puerta molecular. Este capítulo se subdivide en tres artículos diferentes, con distintos objetivos. En el primer artículo se emplea por primera vez el ácido oleico como puerta molecular de un soporte mesoporoso, cargado con la molécula modelo rodamina B. El material preparado es capaz de proteger la carga en las condiciones presentes en la boca y en el estómago, e inducir su liberación en el intestino con la acción surfactante de las sales biliares. El sistema se ha empleado para la liberación de vitamina B2, demostrando así la utilidad del diseño para la protección y liberación controlada de nutracéuticos. El segundo artículo evalúa la efectividad de esta puerta molecular en diferentes tipos de partículas mesoporosas de sílice, con diversos tamaños y estructuras de poro (MCM-41, MCM-48, SBA-15 y UVM-7). En todos los sistemas estudiados, la puerta molecular es capaz de mantener protegidas las moléculas cargadas, y liberarlas ante la presencia de sales biliares. El sólido basado en la estructura de UVM-7 se validó in vivo, observándose un retraso en la absorción intestinal de la rodamina gracias a su encapsulación. Por último, el tercer artículo incluido en este capítulo ha estudiado la posibilidad de incorporar puertas moleculares en filosilicatos. Se ha conseguido la protección y liberación controlada de biomoléculas de gran tamaño implicadas en el metabolismo humano (vitamina B12 y hematina) empleando filosilicatos funcionalizados con ácido oleico como puerta molecular. El segundo capítulo describe por primera vez el uso de la proteína zeína (prolamina de maíz) como puerta molecular. La presencia de la prolamina de maíz inhibe la salida de los compuestos antimicrobianos encapsulados (timol, carvacrol y cinamaldehído) liberándolos en presencia de las enzimas proteolíticas excretadas durante el crecimiento bacteriano. De todos los materiales desarrollados, el sistema cargado con cinamaldehído ha demostrado una inhibición del crecimiento de E. coli superior a la del compuesto libre. Finalmente, el tercer capítulo estudia la efectividad de la lactosa como puerta molecular para proteger aceites esenciales y liberarlos solo en las condiciones presentes en el intestino. Se han preparado tres materiales diferentes basados en MCM-41, cargados con timol, eugenol y cinamaldehído, y funcionalizados con lactosa para inhibir la salida de los compuestos. La acción enzimática de la lactasa secretada en el intestino es capaz de hidrolizar la puerta molecular en los correspondientes monosacáridos, liberando la carga a lo largo del lumen intestinal. Los microdispositivos diseñados han sido validados in vitro con células Caco-2, donde se ha observado el aumento de la capacidad citotóxica del cinamaldehído y la disminución de la permeabilidad a través del modelo de membrana intestinal gracias a su encapsulación. Finalmente, el microdispositivo cargado con cinamaldehído se ha validado in vivo ratificándose la disminución de la permeabilidad del compuesto y su mayor permanencia en el lumen intestinal. Así, la presente tesis doctoral ha demostrado la posibilidad de emplear biomoléculas sencillas de grado alimentario como puertas moleculares sobre diversos materiales de sílice. Estos nuevos sistemas han permitido proteger y liberar control / [CA] La present tesi doctoral, titulada "Microportadors intel·ligents per a l'alliberament controlat de substàncies d'interès nutracèutic", se centra en el disseny i avaluació de sistemes híbrids orgànic-inorgànics per a la protecció i alliberament controlat de compostos bioactius. Aquests sistemes estan basats en (i) materials de sílice, principalment partícules mesoporoses, com a suport inorgànic per emmagatzemar i protegir la càrrega bioactiva; i (ii) una capa externa de biomolècules com a porta molecular, que regula l'alliberament d'aquesta càrrega davant de determinats estímuls. En el primer capítol de la tesi es descriu l'àcid oleic com a porta molecular. Aquest capítol se subdivideix en tres articles diferents, amb objectius diferents. En el primer article s'empra per primera vegada l'àcid oleic com a porta molecular d'un suport mesoporós, carregat amb la molècula model rodamina B. El material preparat és capaç de protegir la càrrega en les condicions presents a la boca i a l'estómac, i induir el seu alliberament a l'intestí amb l'acció surfactant de les sals biliars. El sistema s'ha emprat per a l'alliberament de vitamina B2, demostrant així la utilitat del disseny per a la protecció i alliberament controlat de nutracèutics. El segon article avalua l'efectivitat d'aquesta porta molecular en diferents tipus de partícules mesoporoses de sílice, amb diverses mides i estructures de porus (MCM-41, MCM-48, SBA-15 i UVM-7). En tots els sistemes estudiats, la porta molecular és capaç de mantindre protegides les molècules carregades, i alliberar-les davant la presència de sals biliars. El sòlid basat en l'estructura de UVM-7 es validà in vivo, observant-se un retard en l'absorció intestinal de la rodamina gràcies a la seua encapsulació. Finalment, en el tercer article inclòs en aquest capítol s'ha estudiat la possibilitat d'incorporar portes moleculars en fil·losilicats. S'ha aconseguit la protecció i alliberament controlat de biomolècules de grans dimensions implicades en el metabolisme humà (vitamina B12 i hematina) emprant fil·losilicats funcionalitzats amb àcid oleic com a porta molecular. El segon capítol descriu per primera vegada l'ús de la proteïna zeïna (prolamina de dacsa) com a porta molecular. La presència de la prolamina de dacsa inhibeix la sortida dels compostos antimicrobians encapsulats (timol, carvacrol i cinamaldèhid) alliberant-los en presència dels enzims proteolítics excretades durant el creixement bacterià. De tots els materials desenvolupats, el sistema carregat amb cinamaldèhid ha demostrat una inhibició de l'creixement d'E. coli superior a la del compost lliure. Finalment, el tercer capítol estudia l'efectivitat de la lactosa com a porta molecular per protegir olis essencials i alliberar-los només en les condicions presents a l'intestí. S'han preparat tres materials diferents basats en MCM-41, carregats amb timol, eugenol i cinamaldèhid, i funcionalitzats amb lactosa per inhibir l'eixida dels compostos. L'acció enzimàtica de la lactasa secretada a l'intestí és capaç d'hidrolitzar la porta molecular en els corresponents monosacàrids, alliberant la càrrega al llarg del lumen intestinal. Els microdispositius dissenyats s'han validat in vitro amb cèl·lules Caco-2, on s'observà l'augment de la capacitat citotòxica del cinamaldèhid i la disminució de la permeabilitat a través del model de membrana intestinal gràcies a la seua encapsulació. Finalment, el microdispositiu carregat amb cinamaldèhid s'ha validat in vivo ratificant la disminució de la permeabilitat del compost i la seua major permanència al lumen intestinal. Així, la present tesi doctoral ha demostrat la possibilitat d'emprar biomolècules senzilles de grau alimentari com portes moleculars sobre diversos materials de sílice. Aquests nous sistemes han permès protegir i alliberar controladament diferents nutracèutics, millorant així la seua biodisponibilitat. / [EN] This PhD thesis, entitled "Smart microdevices for nutraceutical-delivery", is focused on the design and evaluation of organic-inorganic hybrid systems for the protection and controlled release of bioactive molecules. These systems are based on (i) silica materials, mainly mesoporous particles, as inorganic support to store and protect the bioactive cargo; and (ii) an outer layer of biomolecules that regulate the payload release triggered by certain stimuli. In the first chapter of the thesis oleic acid is described as a molecular gate. This chapter is subdivided into three different articles, with different objectives. In the first article, oleic acid is used for the first time as molecular gate of a mesoporous support, loaded with the rhodamine B model molecule. The designed material is capable of protecting the cargo under the conditions present in the mouth and stomach, and inducing its release in the small intestine with the surfactant action of bile salts. The system has been used for the release of vitamin B2, thus demonstrating the validity of the design for the protection and controlled release of nutraceuticals. The second article evaluates the effectiveness of this molecular gate in different types of mesoporous silica particles, with different sizes and pore structures (MCM-41, MCM-48, SBA-15 and UVM-7). In all the systems studied, the molecular gate is capable of keeping cargo molecules protected and releasing them in the presence of bile salts. The solid based on the structure of UVM-7 was validated in vivo, observing a delay in the intestinal absorption of rhodamine thanks to its encapsulation. Lastly, the third article included in this chapter has studied the possibility of incorporating molecular gates onto phyllosilicates. The protection and controlled release of large biomolecules involved in human metabolism (vitamin B12 and hematin) have been achieved using phyllosilicates functionalized with oleic acid as molecular gate. The second chapter describes for the first time the use of the protein zein (corn prolamine) as a molecular gate. The presence of corn prolamine inhibits the release of encapsulated antimicrobial compounds (thymol, carvacrol and cinnamaldehyde) releasing them in the presence of the proteolytic enzymes excreted during bacterial growth. Among all the materials developed, the cinnamaldehyde-loaded system has shown greater inhibition of E. coli growth than the free compound. Finally, the third chapter studies the effectiveness of lactose as a molecular gate to protect essential oils and release them only under the conditions present in the intestine. Three different materials based on MCM-41 loaded with thymol, eugenol, and cinnamaldehyde, and functionalized with lactose to inhibit the release of the compounds have been prepared. The enzymatic action of the lactase secreted in the intestine is capable of hydrolyzing the molecular gate into the corresponding monosaccharides, thus releasing the cargo along the intestinal lumen. The designed microdevices have been validated in vitro with Caco-2 cells, where an increase in the cytotoxic capacity of cinnamaldehyde and a decrease in permeability through the intestinal membrane model have been observed thanks to its encapsulation. Finally, the cinnamaldehyde-loaded microdevice has been validated in vivo, confirming the decrease in the permeability of the compound and its greater permanence in the intestinal lumen. Thus, the present PhD thesis has demonstrated the possibility of using simple food-grade biomolecules as gatekeepers on various silica materials. These new systems have allowed the protection and controlled release of different nutraceuticals, thus improving their bioavailability. / The authors also thank the Electron Microscopy Service at the UPV for support. The authors also thank Prof. Pedro Amorós for his explanations and guidance on the knowledge of phyllosilicates. / Poyatos Racionero, E. (2020). Smart microdevices for nutraceutical-controlled delivery [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/159247 / TESIS