Master of Science / Food Science Institute / Karen Schmidt / Flour is essential to bread production as it provides structure, texture, and flavor. The most common, wheat flour, is unique compared to other cereal flours as it forms gluten that is capable of forming viscoelastic dough, which retains gas produced during fermentation and helps create cohesive dough, all of which are critical to bread development. However, a certain percentage of the population has a rare autoimmune disorder, celiac disease, which is triggered by gluten. A gluten-free diet is the only remedy for celiac disease. Traditionally, in gluten-free breads, hydrocolloids, or gums have been used to mimic the behavior of gluten. However, the lack of a protein structure in breads made with hydrocolloids leads to an almost batter-like viscosity. Therefore, research has focused on gluten-free alternatives, particularly non-wheat cereal proteins that can be altered to mimic gluten’s dough forming properties. For example, zein has an average molecular weight and larger peptides than gluten, which contribute to its hydrophobic behavior. In fact, zein from maize flour is an ideal alternative as it can be manipulated to behave like gluten under certain conditions. The main difference between gluten and zein is that zein does not exhibit a large disulfide-linked polymer. Zein is also more hydrophobic than gluten. However, zein has been found to exhibit viscoelastic properties similar to gluten’s at temperatures higher than its glass transition. Other research has found the secondary structure of zein, in particular the β-sheet structure, increases at temperatures above its glass transition. This suggests that temperature and shear are not the only factors necessary to form and maintain the viscoelastic properties of zein; apparently, the β-sheet structures also affect viscoelasticity. Finally, differences such as maize variety and particle size also affect the properties of zein in bakery applications.

No description available.

Doctor of Philosophy / Food Science Institute / Fadi Aramouni / Scott Bean / Zein, the storage protein of corn, has been shown to form a wheat-like dough; however the exact mechanism is unknown since zein lacks the large polymeric proteins found in wheat. To understand how zein forms a dough, different reagents were added during mixing of zein. Salts from the Hofmeister series were used to determine how hydrophobic interactions influence zein’s dough forming ability. In addition, urea, ethanol, and beta mercaptoethanol (β-ME) were also tested to evaluate the effects of protein denaturation and disulfide bonds on zein dough formation and bread quality. Kosmotropic salts had a negative effect on zein dough formation indicating that increasing hydrophobic interactions prevented dough formation. Surface hydrophobicity was found to decrease significantly (p < 0.05) when zein was exposed to 1M or 2M of the kosmotropic salts. Conversely, chaotropic salts had a slight positive effect on zein dough formation as did urea and ethanol. Interestingly, -ME had little effect on zein dough formation demonstrating that disulfide bonds played no role in zein dough development, and that large disulfide linked polymeric protein complexes were not present as found in wheat dough. Specific volumes of zein-starch bread increased as NaCl content in the bread formula decreased. Likewise, including 5% ethanol (v/v) in the bread formula was found to increase bread quality. Experiments were also conducted to compare the functionality of isolated sorghum proteins (kafirins) to commercially available zein produced during wet milling of corn. The effect of steeping, the first step in wet milling, on kafirin functionality was investigated. Sorghum flour was steeped for 0, 72, or 96 hours. Unsteeped sorghum flour was digested with Alcalase for 90 min at 50°C. After steeping or digestion with Alcalase, kafirins were isolated from the remaining material. Both groups of Kafirins had the ability to form a zein-like visco-elastic resin when mixed with warm water by hand. This is the first time that kafirin has been reported to form a visco-elastic resin using only water as a plasticizer.

Made available in DSpace on 2014-06-11T19:23:28Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-08-13Bitstream added on 2014-06-13T18:50:38Z : No. of bitstreams: 1 tavares_ll_me_sjrp.pdf: 1771695 bytes, checksum: ae4d9f94fd6915f2e3ae8fda69b172e0 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O propósito deste estudo foi verificar alterações na estrutura e em algumas propriedades funcionais de biofilmes produzidos com zeína adicionados de argilas modificadas. As argilas modificadas Cloisite® 15A e Cloisite® 30B foram adicionadas na solução filmogênica sob agitação nas proporções de 1, 2 e 4% em relação à massa de zeína e os filmes formados pelo método “casting”. Ácido oléico e glicerol foram utilizados como agentes plasticizantes. Para a caracterização da microestrutura dos biofilmes foram realizadas as análises de Microscopia Eletrônica de Varredura (MEV), Ótica (MO) e Espectroscopia no Infravermelho (FTIR) e as propriedades funcionais avaliadas foram Opacidade, Solubilidade e Permeabilidade ao Vapor d’Água. Por meio das imagens obtidas na MEV observou-se que os acréscimos de argilas nos filmes resultaram na formação de uma microestrutura heterogênea, ou seja, estrutura de fase separada chamada de microcompósito ou tactóide, uma vez que as argilas não dispersaram no filme, o que proporcionou a formação de agregados. No entanto, por meio das imagens obtidas com a MO, observou-se uma distribuição uniforme dos glóbulos de lipídeos na matriz protéica, para todos os filmes. Em concordância com a característica da microestrutura dos filmes elaborados identificados na MEV, o FTIR foi capaz de identificar número de onda referente às argilas, indicando que a mesma não estabeleceu estruturação com a proteína, confirmando a formação de uma estrutura de fase separada tipo tactoide. Todos os filmes elaborados apresentaram maior opacidade quando comparados com o polietileno em razão da presença de pigmentos carotenóides. Pequenas diferenças na espessura das amostras e a quantidade de argila adicionada não influenciaram na transparência dos materiais. Os testes... / The purpose of this study was to evaluate changes in the structure and some functional properties of zein edible films added with modified clays. The modified clays Cloisite® 15A and Cloisite® 30B were added in the solution under agitation in the proportions of 1, 2 and 4% based on the weigh of zein. The films were formed pouring the solution on a surface to dry by casting method. Oleic acid and glycerol were used as plasticizer agents. Analyses of Scanning Electron Microscopy (SEM), Optical Microscopy (MO) and Infrared Spectroscopy (FTIR) were performed to characterize the microstructure of biofilms. The functional properties evaluated were opacity, solubility and permeability of water vapor. SEM images showed that the additions of clays in the films resulted in the formation of a heterogeneous microstructure, i.e. the phase separated structure called microcomposite or tactoids, since the clays were not dispersed in the film, which forms points of aggregates. However, the images obtained with MO showed an even distribution of lipids globules in the protein matrix, for all films. In agreement with the characteristic of the microstructure of the films showed by SEM, FTIR analyses pointed out the absence of wave number related to the clays, indicating that it was not established a really binding of the clays with the protein molecule. This confirms the formation of a material with phase separated, tactoid type. All the films prepared showed higher opacity when compared with polyethylene because of the presence of carotenoid pigments. Little differences in thickness of the samples and the amount of clay added did not influence the transparency of materials. Statistical mean tests of water solubility of the samples showed no differences among those films added with clay and the control. Water... (Complete abstract click electronic access below)

Most seed storage proteins accumulate in protein bodies which are derived from the vacuole. Zeins, the major corn storage proteins, however, are retained in the endoplasmic reticulum (ER) and their protein bodies are derived from the ER. There are circumstantial and preliminary data indicating that 27K zein, the proline-rich zein, may span the ER membrane. This potential transmembrane feature is considered very significant to understand the mechanism for zeins' ER retention. The transmembrane feature may retain the 27K zein in the ER where it could serve as an anchor for other classes of zein through specific protein interactions. In this study, a heterologous system (<i>Xenopus laevis</i> oocytes) was used to investigate the potential transmembrane domain of 27K zein. This study utilized physical assays of proteolytic digestion (proteinase K) and chemical modification (biotinylation) on isolated protein vesicles from <i>Xenopus</i> oocytes injected with <i>in vitro</i> transcribed 27K zein mRNA. In addition, the transmembrane features were analyzed by monitoring the protein's mobility in the lumen of the ER by pulse-chase experiments. The results showed that the possibility of 27K zein as a transmembrane protein was consistently refuted in this study. The 27K zein protein was not affected by the proteinase K treatment or biotinylation. Moreover, 27K zein and total zeins moved freely in the lumen of the ER similar to a secretory protein (ovalbumin), totally different from an ER membrane protein (a mutant transmembrane hemagglutinin envelope protein). The free movement, within the ER lumen, of total zeins under conditions where zein aggregates should form necessitates a reevaluation of the mechanisms responsible for zein polypeptides' ER retention and protein body formation. This study, therefore, concludes that 27K zein is not a protein body nucleating factor by virtue of an ER transmerrlbrane feature or association with the ER membrane and that the significance of zein solubility should be reconsidered to explain the zeins' ER retention leading to protein body formation in the ER. / Ph. D.

Master of Science / Department of Animal Sciences and Industry / J.S. Drouillard / A series of experiments were conducted in which wheat gluten film forming solutions were modified by various means to produce films that would improve resistance to ruminal degradation. There was an interaction between pH and temperature, whereby low pH (pH 3) and high temperature (75°C) of film forming solution resulted in films that had highest resistance to microbial degradation. Strategies that proved unsuccessful in improving resistance to ruminal degradation included use of the cross-linking enzyme, transglutaminase; induction of a Maillard reaction; and increasing the time of heating film forming solutions. Utilizing HCl versus acetic acid as the means to lower the pH of the film forming solution resulted in poor film formation, which can be attributed to glutenin‟s solubility in acetic acid. When acetic acid was replaced with 25% HCl, however, no compromise in film formation was observed and ruminal degradability was not affected. In order to develop an economical and effective means of encapsulating lysine for rumen bypass, wheat gluten and corn zein were evaluated as encapsulation materials. Coating soybean meal with either wheat gluten or zein resulted in superior protection against ruminal degradation when compared to unprotected soybean meal. Compared to wheat gluten, zein was observed to have greater resistance to ruminal degradation in vitro. Lysine was encapsulated by the spray dry method with wheat gluten or zein. Results from an in vitro ammonia release experiment were inconclusive with respect to effectiveness of the encapsulation process. Wheat gluten films were approximately 59% degraded in pepsin solution. Our results suggest that 72% of the wheat gluten film will bypass the rumen and 59% of the bypass fraction of the film will be degraded in the abomasum. Wheat gluten and zein are suitable candidates for development of encapsulated nutrients for ruminal protection.

Doctor of Philosophy / Department of Chemical Engineering / Jennifer L. Anthony / Ionic liquids are low melting salts composed of an organic cation and an inorganic or organic anion. Ionic liquids are of interest for their wide range of applications and unique properties, such as the negligible vapor pressure of some types of ionic liquids, and the ability to modify ionic liquid properties by selection of the cation or anion. It has been hypothesized that over one million binary ionic liquids (meaning a single cation/anion pair) are possible. Due to the vast number of potential combinations, it should be possible to design ionic liquids specifically for an application of interest. One potential application is their use as protein solvents. However there is little understanding of how ionic liquids affect proteins. This research examined the solubility and secondary structure of the hydrophobic corn protein zein in seven ionic liquids and three conventional solvents as a function of temperature and solvent properties. Zein’s solubility in the solvents was measured gravimetrically from 30 to 60 degrees Celsius. Solubility was then related to solvent properties to gain an understanding of what solvent properties are important, and how to design an ionic liquid to dissolve zein. It was found that a good solvent for zein has a small molecular volume, a low polarity, and is a weak hydrogen bond acceptor. Infrared spectroscopy with curve fitting was used to examine the secondary structure of zein as a function of both solvent and temperature from 25 to 95 degrees Celsius. It was found that most of the ionic liquids change zein’s secondary structure, but those secondary structure changes were not affected by temperature. Aprotic ionic liquids increase the amount of β-turn secondary structure through non-polar interactions between the mixed aromatic-alkyl imidazolium cations and the non-polar portions of the zein. Strong hydrogen bond accepting molecules were found to increase the amount of β-turn secondary structure. It is hypothesized from this research that suitable solvents for zein will have a small molar volume, low polarity, and be poor hydrogen bond acceptors. This combination of properties will enhance zein’s solubility and limit secondary structure changes that can harm protein properties.

Os fertilizantes são as fontes de nutrientes mais comuns utilizados no mundo, mas, esses insumos agrícolas apresentam sérias desvantagens quanto a perdas na aplicação (volatilização, lixiviação e/ou imobilização nos solos). Essas desvantagens podem ser controladas e/ou minimizadas pelo uso de revestimentos poliméricos sobre os grânulos. A efetividade desta estratégia depende que o polímero formado apresente boa aderência, reatividade com a superfície do grânulo e homogeneidade na aplicação. Porém, apesar da literatura especializada apresentar vários exemplos de materiais para estes fins, o tema é pouco explorado com relação às propriedades de liberação, tais como avaliação do mecanismo envolvido e de fenômenos (abertura de poros, biodegradação, entre outros fenômenos) que ocorrem no polímero de recobrimento. Assim, o controle cinético da liberação nestes sistemas ainda precisa ser elucidado. Portanto, este estudo avaliou os mecanismos de liberação associados ao uso de barreiras (filmes) protetivas em fertilizantes com enfoque na dinâmica de difusão dos nutrientes, a partir da aplicação de filmes protetivos de poliuretanas (PU) à base de óleo vegetal (mamona) e zeínas em grânulos de fertilizantes nitrogenados e fosfatados. Analisou-se a influência da espessura aplicada, a estabilidade do revestimento, a interface de deposição e o tempo total de liberação em imersão em água e em solo. Os resultados demonstraram que é possível se obter revestimentos com bom desempenho de liberação. Considerando o caso de fertilizante nitrogenado (ureia) notou-se que o uso de revestimento polimérico pode ser preparado para controlar a liberação do nutriente, de maneira satisfatória, conseguindo-se liberação prolongada acima de 40 dias, quando imersos em água. Também, os resultados, em plantio semeado com milho, mostraram que é possível promover menor emissão de N2O (um dos gases do efeito estufa) e melhores rendimentos das culturas, como reduzir, a produção média de N2O por kg de colheita, significativamente. Assim, como observado nos experimentos envolvendo a ureia, também é possível notar para os fertilizantes fosfatados que os resultados obtidos nos experimentos com solo concordaram com os perfis de liberação de fósforo (P) em água, refletindo uma correlação positiva entre os testes de liberação. Em ambos nutrientes (N e P) verificou-se que o controle na liberação é diretamente associado à espessura do revestimento sobre o grânulo. A boa interface apresentada pela resina PU derivada de óleo de mamona sugere que este material possa produzir revestimentos de boa qualidade e longo tempo de liberação com espessura mínima, maximizando assim o aproveitamento de teor total de N e P presente no grânulo. / Fertilizers are the most common source of nutrients used in the world, but it has serious disadvantages in application losses (volatilization, leaching and/or immobilization) which can be controlled or minimized by polymer coatings. The effectiveness of this strategy depends on the formed polymer presenting good adhesion, reactivity with the surface of the granule and homogeneity in the application. However, although the literature presents several examples of materials for these purposes, little is known about the release properties such as evaluation of the mechanism involved and phenomena (pore opening, biodegradation, etc.) in the coating polymer. Thus, the kinetic control of the release in these systems still needs to be elucidated. Therefore, this study evaluated the release mechanisms associated with the use of protective barriers (films) in fertilizers with a focus on nutrient diffusion dynamics. We prepare fertilizer granules coated with polyurethane (PU) based on castor oil and zein. The influence of the applied thickness, coating stability, deposition interface and total release (immersion and soil) time were analyzed. The results demonstrated that it is possible to obtain coatings with good release performance. For nitrogen fertilizer (urea), it has been noted that the use of polymeric coating can be prepared to control the release of the nutrient, achieving prolonged release over 40 days when immersed in water. In addition, the results showed that it is possible to promote lower N2O emission (one of greenhouse gases) and better crop yields as it significantly reduces the production of N2O per kg of grain. Thus, as observed in the experiments involving urea, it is also possible to observe, for phosphate fertilizers, that the results obtained in the soil experiments agreed with the phosphorus (P) release profiles in water, reflecting a positive correlation between water and soil release. In both nutrients (N and P) it was noted that the release control is directly associated with the coating thickness on granule. The good interface presented by PU resin derived from castor oil suggests that this material can produce coatings of good quality and long release time with minimum thickness, thus maximizing the use of N and P total content present in the granule.

Orientador: Leonardo Fernandes Fraceto / Resumo: Considerando os danos causados pelas arboviroses disseminadas pelo vetor Aedes aegypti, o Brasil vem sofrendo, porém buscando estratégias de combate a tal realidade, uma vez que teve um custo total de R$ 2,3 bilhões, apenas no ano de 2016, distribuídos no combate ao vetor, em inseticidas e larvicidas e nos custos diretos e indiretos. Valor esse, correspondente a cerca de 2 % do montante investido na Saúde no mesmo ano. Esse quadro ressalta a necessidade de novas ações e táticas na procura de minimizar a situação, como a elaboração de repelentes que possuam um sistema mais efetivo no combate do vetor responsável pela disseminação do vírus Zika, da Dengue, do Chikungunya e da Febre Amarela. Hoje, sabe-se que um dos ativos repelentes mais eficientes é a icaridina, porém, ela pode causar intoxicação nos organismos não alvos. Também, tem-se o geraniol, que é um ativo de origem botânica, bastante eficaz em sua atuação repelente. E, na busca de aprimorar a ação dos ativos, existe a opção da utilização de sistemas de liberação lenta, o que resulta no aumento da faixa de efeito biológico do ativo de interesse, devido ao prolongamento da liberação do mesmo. No entanto, nota-se a existência de intensa preocupação e responsabilidade na elaboração de sistemas que, além de se mostrarem mais eficientes, sejam, também, focados na diminuição de possíveis mecanismos de resistência que o vetor possa desenvolver. Dessa forma, o presente estudo teve por objetivo o desenvolvimento de sistemas de l... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Considering the damage caused by arboviruses disseminated by the vector Aedes aegypti, Brazil has been suffering, but seeking strategies to combat this reality, since it had a total cost of R$ 2.3 billion, only in the year 2016, distributed in combat to the vector, in insecticides and larvicides and in direct and indirect costs. This amount corresponds to approximately 2 % of the amount invested in Health in the same year. This scenario highlights the need for new actions and tactics in order to minimize the situation, such as the elaboration of repellents that have a more effective system in the fight against the vector responsible for the spread of the Zika virus, Dengue, Chikungunya and Yellow Fever. It is now known that one of the most effective repellent actives is icaridin, but it can cause intoxication in non-target organisms. Also, one has the geraniol, that is an active of botanical origin, quite effective in its action repellent. And, in the search to improve the action of the assets, there is the option of using slow release systems, which results in the increase of the biological effect range of the asset of interest, due to the prolongation of the release of the same. However, we note the existence of intense concern and responsibility in the elaboration of systems that, in addition to being more efficient, are also focused on the reduction of possible mechanisms of resistance that the vector can develop. Thus, the present study aimed at the development of sustai... (Complete abstract click electronic access below) / Mestre

<div>Zein is major nitrogen storage protein that accounts for nearly half of the protein content of the corn grain. As a byproduct of starch and ethanol processing, it is generally recognized as safe (GRAS) and soluble in up to 70% ethanol. Historically, zein has been used for films and coatings. However, usage of the corn protein has diminished in recent years. New advances in food nanotechnology has renewed interest in zein. By forming the protein into stable nanoparticles capable of being dispersed in aqueous solution, zein can be used in many applications ranging from improving stability and digestion of functional ingredients or active biodegradable packaging. Developing novel applications for this protein would then add value to a waste product during the processing of corn.</div><div><br></div><div>The formation of hydrophobic zein nanoparticles (ZNPs) would allow for easier dispersion in aqueous systems without further modification to increase hydrophilicity. However, their dispersibility and subsequent stability in aqueous systems is important for its functionality in food. Addition of sufficient ι-carrageenan (ι-CGN) prevented aggregation in the pH range of 5.25 to 6.75 and limited aggregation at pH 7.0. Enhanced stability was attributed to the adhesion of ι-CGN to the nanoparticle surface, as the ZNPs surface charge became significantly negative with introduction of ι-CGN. These particles remained stable for up to 30 days with significantly lower turbidity and greater resistance to gravitational separation when compared to ZNPs alone.</div><div><br></div><div>Lutein was encapsulated in zein nanoparticles, and the bioaccessibility was determined by quantifying lutein content after exposure to in vitro gastric and intestinal conditions. It was found that ZNPs provided a protective environment for lutein in aqueous dispersions and would release the carotenoid into the small intestine by rapid breakdown of ZNP structure during intestinal digestion. However, the process or residual components must have limited uptake of lutein into mixed micelles. ZNPs can be a promising encapsulating agent to improve the digestive stability of lutein.</div><div><br></div><div>Composite films composed of methylcellulose (MC) and zein nanoparticles (ZNPs) were prepared as a potential biodegradable alternative for synthetic packaging. The effects of ZNP aggregation on mechanical and moisture barrier properties as affected by drying temperature, pH, and stabilizers were tested. The phase separation of composite films was determined to be detrimental to both its mechanical and moisture barrier properties. The drying temperature, pH, and composition of the solvent casting solution all affected the distribution of ZNPs dispersed in MC films. Drying films at 23°C or setting the pH to 6.5 resulted in ZNP aggregation and weaker, brittle films that were poor moisture barriers. The presence of CGN was able to provide stability to ZNPs at both pH 4 and 6.5, thus improving its mechanical and moisture barrier properties.</div>