Starch and microbial exo-polysaccharides produced by prokaryotes (i.e. Eubacteria and Archaebacteria) and eukaryotes (i.e. phytoplankton, fungi, and algae) are recognized as a permanent source of biopolymers for the packaging industry. However, the unsuitable mechanical properties for thermoplastic applications and/or high cost of production have restricted their generalized use. Fungal isolates of the genus Ophiostoma are able to produce exo-polysaccharides or protein-like compounds in a medium containing starch as the substrate. Various analytical techniques were used as an approach to investigate the interaction between starch and the fungal extracellular metabolites and the effect of the molecular-structural modifications on the functional properties of the materials. Native starches were used as control in all experiments. Analyses performed by dynamic mechanical thermal analysis (DMTA), which provides information related to the viscoelastic properties, showed that the storage modulus (E') increased substantially after the modification of the starch showing a process of chain stiffness. The determination of the glass transition temperature (Tg) by tan  and loss modulus (E'') peaks showed various thermal transitions indicating a complex molecular aggregation due to the potential presence of dissimilar amorphous polymers. Experiments performed in DSC confirmed the presence of the various thermal transitions associated to the Tg of these materials. The first derivative of mass loss with respect to temperature during the thermogravimetric (TG) analysis was slightly lower compared with native starches (at ~630 and 650°C). However, modified starches can withstand high temperatures showing residues up to 20% at 1000°C. Studies on the characterization of the flow properties of the polymers by capillary rheology showed in both samples a shear thinning behavior. The double logarithmic plot of the shear rate vs. shear viscosity produced a straight line and in consequence a power law equation was used to describe the rheological behavior ( = K'n). The results showed that in order to achieve the same shear rate (') in both samples (modified and native starches) it is necessary to apply a higher shear stress () in the fungal treated materials. As a result, the consistency power law index (n) decreased and the consistency value increased (K). The practical consequence is that the melting point of these polysaccharides shifted to higher temperatures. By using various analytical techniques (including chromatography, spectroscopy, spectrometry) it was found that these phenomena may be due to the interaction of starch with protein-like or exo-polysaccharides or both which may influence the viscosity, bind adjacent molecules (i.e. network-like) and restrict the molecular motion. Evidences of the presence of pendant groups attached to high molecular weight compounds were also found. This information will give guidance to further structural studies and it is intended to pave the way for a variety of industrial applications.

Starch and microbial exo-polysaccharides produced by prokaryotes (i.e. Eubacteria and Archaebacteria) and eukaryotes (i.e. phytoplankton, fungi, and algae) are recognized as a permanent source of biopolymers for the packaging industry. However, the unsuitable mechanical properties for thermoplastic applications and/or high cost of production have restricted their generalized use. Fungal isolates of the genus Ophiostoma are able to produce exo-polysaccharides or protein-like compounds in a medium containing starch as the substrate. Various analytical techniques were used as an approach to investigate the interaction between starch and the fungal extracellular metabolites and the effect of the molecular-structural modifications on the functional properties of the materials. Native starches were used as control in all experiments. Analyses performed by dynamic mechanical thermal analysis (DMTA), which provides information related to the viscoelastic properties, showed that the storage modulus (E') increased substantially after the modification of the starch showing a process of chain stiffness. The determination of the glass transition temperature (Tg) by tan  and loss modulus (E'') peaks showed various thermal transitions indicating a complex molecular aggregation due to the potential presence of dissimilar amorphous polymers. Experiments performed in DSC confirmed the presence of the various thermal transitions associated to the Tg of these materials. The first derivative of mass loss with respect to temperature during the thermogravimetric (TG) analysis was slightly lower compared with native starches (at ~630 and 650°C). However, modified starches can withstand high temperatures showing residues up to 20% at 1000°C. Studies on the characterization of the flow properties of the polymers by capillary rheology showed in both samples a shear thinning behavior. The double logarithmic plot of the shear rate vs. shear viscosity produced a straight line and in consequence a power law equation was used to describe the rheological behavior ( = K'n). The results showed that in order to achieve the same shear rate (') in both samples (modified and native starches) it is necessary to apply a higher shear stress () in the fungal treated materials. As a result, the consistency power law index (n) decreased and the consistency value increased (K). The practical consequence is that the melting point of these polysaccharides shifted to higher temperatures. By using various analytical techniques (including chromatography, spectroscopy, spectrometry) it was found that these phenomena may be due to the interaction of starch with protein-like or exo-polysaccharides or both which may influence the viscosity, bind adjacent molecules (i.e. network-like) and restrict the molecular motion. Evidences of the presence of pendant groups attached to high molecular weight compounds were also found. This information will give guidance to further structural studies and it is intended to pave the way for a variety of industrial applications.

A oxidação é um método que visa a modificação do amido por agentes oxidantes diversos, introduzindo grupamentos funcionais e realizando cisão das ligações glicosídicas. Seus objetivos são reduzir a viscosidade do polissacarídeo, elevar a transparência da pasta e limitar sua retrogradação. O objetivo do presente estudo foi modificar os amidos de milho com diferentes teores de amilose e o amido de mandioca pelo tratamento com ozônio e também caracterizar as amostras oxidadas quanto às características moleculares, estruturais e funcionais, correlacionando-as entre si. O processo de oxidação foi efetivo em alterar diversas propriedades e funcionalidades dos amidos estudados, contudo de modos distintos para as diferentes fontes. Tais diferenças decorrem da composição e estrutura granular peculiares de cada um, promovendo diferentes taxas de degradação das lamelas amorfas e cristalinas e da presença de grupos carboxilas. A oxidação pelo ozônio nas condições estudadas reduziu a viscosidade apenas do amido de milho normal; no caso dos amidos de milho ceroso e de mandioca, a viscosidade foi ligeiramente aumentada. O amido de milho de alta amilose não apresentou viscosidade nas condições de analisadas pelo Rapid Visco Analyser, tanto antes como após a oxidação. O setback foi reduzido pelo processo oxidativo com o ozônio para os três amidos, tornando-os mais estáveis. A oxidação aumentou a claridade de pasta de todos os amidos. A ozonização também causou alterações no amido de milho ceroso e no de mandioca, de modo a proporcionar capacidade de expansão no forno, em índices próximos àqueles de amostras comerciais de polvilho azedo. Os demais amidos não se expandiram significativamente. A propriedade de expansão no forno foi afetada principalmente pela variação de entalpia de gelatinização dos amidos, mas também pelos teores de carboxilas e de carbonilas, fator de inchamento, quebra de viscosidade, setback, cristalinidade relativa e tamanho das cadeias ramificadas de amilopectina (cadeias B2 e B3 e tamanho médio). O uso do ozônio, portanto, poderá ser útil nesta modalidade de modificação dos amidos e, em especial para o amido de mandioca ou de milho ceroso, capacitando-os para a expansão no forno, o que poderia gerar produtos panificáveis mais padronizados do que os obtidos pelo polvilho azedo, ou sem as consequências da oxidação por métodos químicos mais agressivos, como o uso do hipoclorito de sódio. / Oxidation is a method which aims the starch modification by various oxidizing agents, introducing functional groups and performing the cleavage of glycosidic linkages. Its objectives are to reduce the polysaccharides viscosity, raising the transparency paste and minimizing retrogradation. The aim of this study was to modify the corn starch with different levels of amylose and the cassava starch using ozone and also to characterize the samples oxidized as the molecular, structural and functional characteristics, relating them with each other. The oxidation process was effective changing several properties and features of the studied starches, however, in different ways for the different sources. These differences come from having starches different composition and granular structure, providing different rates of degradation of amorphous and crystalline lamellae and the presence of carbonyl groups, and carboxyl formed. A reduction in viscosity was observed for the normal corn starch after oxidation, and an increase for the waxy maize and cassava starches. The high amylose corn starch showed no viscosity by Rapid Visco Analyser, before or after oxidation. The setback was reduced by the oxidation process with ozone for the three starches, rendering them more stable. Oxidation by ozone under the conditions studied increased paste clarity of all starches. Ozonation caused changes in the waxy corn and cassava starches, providing baking properties, in indices close to those of commercial samples of sour cassava starch. The other starches are not expanded significantly in the oven. The baking property was mostly affected by enthalpy of gelatinization of starches, but also by carboxyl and carbonyl contents, swelling factor, breakdown, setback, relative crystallinity and size of amylopectin branched chains (B2, B3 and medium size). So, the use of ozone may be useful in this starch modification modality, and in particular for cassava or waxy maize starches, enabling the expansion in oven, which could generate more standardized baking products than those obtained by sour cassava starch, or without consequences of oxidation using more aggressive chemical methods, such as sodium hypochlorite.

Orientador: Yoon Kil Chang / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-06T15:58:59Z (GMT). No. of bitstreams: 1 Pontes_AnaElisaRomanide_M.pdf: 395267 bytes, checksum: ebcf7fcfc2404c4c594d5bec165805f6 (MD5) Previous issue date: 2006 / Resumo: As sociedades modernas têm apresentado um crescente interesse por alimentos saudáveis, com teor calórico reduzido e livres de ingredientes, como açúcares, gorduras saturadas e ácidos graxos trans, mas que mantenham as características sensoriais agradáveis dos produtos originais. Este trabalho tem como objetivo apresentar uma alternativa de pão de forma sem adição de açúcar, gordura e emulsificantes, com a utilização de amido modificado por ligações cruzadas (fosfatado), acetilado e pré-gelatinizado de mandioca (AMPM) e das enzimas a-amilase, amiloglucosidase (AMG) e fosfolipase (FOSFO). Para tanto, foi elaborado um planejamento experimental do tipo composto central rotacional com três variáveis independentes: dosagem de amido modificado AMPM (x1), de amiloglucosidase AMG (x2) e fosfolipase FOSFO (x3). Analisaram-se as matérias-primas principais e os pães de forma foram elaborados pelo método de massa direta. Além dos parâmetros L*a*b de coloração do miolo e o volume dos pães após a produção, efetuou-se também a análise da umidade e da textura durante a vida de prateleira, após 24, 72 e 120 horas de estocagem. Dentro das faixas estudadas para as três variáveis, foi possível verificar que nenhuma delas teve influência estatisticamente significativa nas respostas analisadas, apesar do erro puro ter sido adequado para o processo de panificação utilizado, mostrando uma boa reprodutibilidade. Algumas amostras foram submetidas a um painel sensorial de consumidores para avaliação dos parâmetros de sabor e textura, sendo que a amostra com menores concentrações de AMPM, AMG e FOSFO recebeu a menor pontuação. Já as demais amostras apresentaram pontuação estatisticamente igual ao padrão, utilizando gordura, açúcar e emulsificante. De maneira geral, a melhor relação entre a aceitação dos consumidores, o custo da formulação e a porcentagem de retenção de umidade dos pães foram obtidos com a formulação utilizando 1,5% do amido modificado e atividade de fosfolipase de 960 PLU por kg de farinha de trigo / Abstract: Modern societies are presenting a growing interest in healthy foods, low calories and free from undesirable ingredients such as sugar, saturated and ¿trans¿ fatty acids but maintaining sensorial characteristics of the original foods. This work intends to present an option of sliced bread with total substitution of sugar, fat and emulsifiers, with the use of a instant cross linked acetylated tapioca starch (AMPM) , a-amylase, amyloglucosidase (AMG) and phospholipase (FOSFO). For this, an experimental design with three independents variable was done: the dosage of modified starch (AMPM ¿ x1), amyloglucosidase (AMG ¿ x2) and phospholipase (FOSFO ¿ x3). The raw materials were analyzed and the bread was produced using straight dough process. Besides the color of the crumb and bread volume after the production the moisture content and texture during the shelf-life (24, 72 and 120 hours) were measured. None of the three variables had statistically significant effects on the results, even though the process showed good reproductibility. However, the same samples were tested in a sensorial panel for taste and texture attributes and the sample with the lower amounts of AMPM, AMG and FOSFO showed the worst score. The remaining samples received the same punctuation as the standard bread. Thus, the recipe with the best combination of cost, consumer acceptance and moisture retention was the bread with 1.5% of modified tapioca starch (AMPM) and phospholipase activity of 960 PLU / kg of wheat flour / Mestrado / Mestre em Tecnologia de Alimentos

Mes recherches s’inscrivent dans une problématique de remédiation des sols pollués par deshydrocarbures aromatiques polycycliques (HAP) avec comme modèle de polluant organiquepersistant le benzo[a]pyrène (BaP). La persistance de ce type de molécules dans les sols estprincipalement due à deux paramètres limitants : leur faible biodisponibilité en raison de leur faible solubilité aqueuse et la difficulté pour les microorganismes d’amorcer l’oxydation de molécules aussi stables. Notre approche a consisté en l’utilisation de polysaccharides à base d’amidon comme matrice permettant de stimuler la solubilisation du BaP et comme support à la réaction de Fenton (Fe²⁺ + H2O2 → Fe³⁺ + OH- + OH⁺) en tant que producteur d’un puissant oxydant : le radical hydroxyl OH⁺. Une étude théorique de modélisation moléculaire a permis de mettre en évidence dans lamolécule d’amidon des sites de fixation préférentiels aussi bien pour le BaP que pour le cation Fe ²⁺. Par la suite, l’étude expérimentale a eu pour objectif la synthèse chimique d’amidon modifié utilisantdeux types d’agent alkylant, des époxydes et des anhydrides d’acides carboxyliques. Après la caractérisation chimique de ces molécules par spectroscopie RMN et FTIR, les études de relation structure activité (par fluorescence, MEB et MEB-EDS) entre les amidons modifiés, le BaP et le cation Fe ²⁺ ont permis le criblage d’une vingtaine de molécules d’amidons modifiés et la sélection des amidons modifiés les plus solubles et les plus efficaces dans la solubilisation du BaP. Par exemple, la molécules d’amidon (P17) bialkylé par un époxyde à trois carbones et un anhydride à onze carbones présente une solubilité aqueuse de 4,41 g/l (amidon natif 0,4 g/l) et une capacité à stimuler la solubilité du BaP d’un facteur 20. La dernière étape de mon travail de thèse aborde, in vitro, les applications potentielles des amidons modifiés pour la dégradation du BaP. Les essais réalisés avec la réaction de Fenton nous ont suggéré une hypothèse originale dans laquelle il semblerait que la matrice polysaccharique produirait des radicaux carbohydrates possédant un temps de demi-vie largement supérieur comparé à celui de l’hydroxyl radical leur conférant une meilleure capacité à atteindre et à oxyder le BaP. Les premiers essais couplant l’oxydation chimique et les potentialités de dégradation par des champignons saprotrophes doivent être encore optimisés afin d’utiliser tout le potentiel de la biodiversité des champignons. / My researchs concern remediation of polluted soil by polycyclic aromatic hydrocarbons (PAH) with the benzo[a]pyrene (BaP) as a model of persistent organic pollutant. The persistence of these molecules into soil is mainly due to both limiting parameters: their weak biodisponibility due to their low aqueous solubility and the difficulty for microorganisms of starting the oxidation of such stable molecules. Our approach consisted in the use of polysaccharides like starch matrix for stimulating the solubilization of BaP and allowing on such support the Fenton reaction (Fe²⁺+H2O2 → Fe ³⁺+ OH -+ OH ⁺) as a producer of high oxidant i.e. the hydroxyl radicals OH ⁺. A theoretical computer modelling study conducted on potato starch permits to identify the preferential sites for BaP and iron complexation. Thereafter, the experimental study aimed the chemical modification of starch using two types of alkylated agents i.e. epoxides and anhydrides of carboxylic acids. After the chemical characterization of these molecules by NMR and FTIR spectroscopy, the structure activity relationship between the modified starches, BaP and Fe2+ (as studied by fluorescence, SEM and SEM-EDS) allowed the screening of modified starches and the selection of the most soluble starches and the most effective one in BaP solubilization. For example, the molecule of starch (P17) bi-alkyl substituted by an epoxy group with three carbons and an anhydride with eleven carbons has an aqueous solubility of 4,41 g/L (native starch 0,4 g/L) and a capacity to stimulate the BaP solubility by a 20-factor. The last step of this work approaches, in vitro, the potential application of the modified starch for BaP degradation. The tests carried out with Fenton reaction suggested an original hypothesis based on the production of carbohydrate radicals having a higher half-life time compared with that of the hydroxyl radical itself, conferring them a better capacity to reach and to oxidize BaP. The first tests coupling chemical oxidation and the potentialities of fungal degradation must be still optimized in order to use all the potential biodiversity of fungi. / Cercetările acestei teze se înscriu în cadrul unei probleme de remediere a solurilor poluate cu hidrocarburi aromatice policiclice (HAP),având ca model de poluare benzo [a] pirenul (BaP). Persistenţa acestor moleculelor, de acest tip, în soluri este dată în principal de doi parametri limitanţi: biosponibilitatea lor scăzută, datorită solubilităţii apoase scăzute, şi dificultatea, pentru microorganisme de a oxida aceste molecule stabile. Abordarea nostră constă în utilizarea polizaharidelor, având ca suport amidonul: ca matrice permanentă de stimulare a solubilităţii BaPului şi ca suport în reacţia Fenton (Fe²⁺+H2O2 → Fe ³⁺+ OH -+ OH ⁺) producătoare de un oxidant foarte puternic precum radicalul hidroxil OH ⁺. Un studiu teoretic de modelare moleculară a permis punerea în evidenţă în molecula de amidon a unor site-uri de fixare preferenţiale atât pentru BaP cât şi pentru cationul Fe²⁺. Apoi, un studiu experimantal a avut ca obiectiv sinteza chimică a amidonului modificat utilizând două tipuri de agenţi de alchilare: epoxizii şi anhidridele acizilor carboxilici. După caracterizarea chimică a acestor molecule prin spectroscopie RMN şi FTIR, studiile de relaţie structură-activitate (prin fluorescenţă, MEB şi MEB-EDS) între amidonurile modificate, BaP şi cationul Fe²⁺ au permis verificarea a douăzeci de molecule de amidon modificate şi selecţionarea amidonurilor modificate cele mai solubile şi mai eficace în solubilizarea BaPului. De exemplu, molecula de amidon (P17) bialchilată printr-un epoxid cu trei atomi de carbon şi o anhidridă cu unusprezece carboni, prezintă o solubilitate apoasă de 4,41 g/L (faţă de amidonul nativ 0,4 g/L) şi o capacitate de stimulare a solubilităţii BaP de un factor 20. Ultima etapă a acestei teze de doctorat abordează, in vitro, aplicaţiile potenţiale ale amidonurilor modificate pentru degradarea BaPului. Încercările realizate cu reacţia Fenton ne sugerează o ipoteză originală în care se pare că matricea polizaharidică produce radicali carbohidraţi posedând un timp de viaţă superior, comparativ cu cel al radicalului hidroxil, conferind o mai bună capacitate de captare şi oxidare a BaPului. Primele încercări cuplând oxidarea chimică şi potenţialitatea de degradare prin fungi saprotrofi mai trebuie încă optimizată pentru utilizarea întregului potenţial de biodiversitate a fungilor.

A oxidação é um método que visa a modificação do amido por agentes oxidantes diversos, introduzindo grupamentos funcionais e realizando cisão das ligações glicosídicas. Seus objetivos são reduzir a viscosidade do polissacarídeo, elevar a transparência da pasta e limitar sua retrogradação. O objetivo do presente estudo foi modificar os amidos de milho com diferentes teores de amilose e o amido de mandioca pelo tratamento com ozônio e também caracterizar as amostras oxidadas quanto às características moleculares, estruturais e funcionais, correlacionando-as entre si. O processo de oxidação foi efetivo em alterar diversas propriedades e funcionalidades dos amidos estudados, contudo de modos distintos para as diferentes fontes. Tais diferenças decorrem da composição e estrutura granular peculiares de cada um, promovendo diferentes taxas de degradação das lamelas amorfas e cristalinas e da presença de grupos carboxilas. A oxidação pelo ozônio nas condições estudadas reduziu a viscosidade apenas do amido de milho normal; no caso dos amidos de milho ceroso e de mandioca, a viscosidade foi ligeiramente aumentada. O amido de milho de alta amilose não apresentou viscosidade nas condições de analisadas pelo Rapid Visco Analyser, tanto antes como após a oxidação. O setback foi reduzido pelo processo oxidativo com o ozônio para os três amidos, tornando-os mais estáveis. A oxidação aumentou a claridade de pasta de todos os amidos. A ozonização também causou alterações no amido de milho ceroso e no de mandioca, de modo a proporcionar capacidade de expansão no forno, em índices próximos àqueles de amostras comerciais de polvilho azedo. Os demais amidos não se expandiram significativamente. A propriedade de expansão no forno foi afetada principalmente pela variação de entalpia de gelatinização dos amidos, mas também pelos teores de carboxilas e de carbonilas, fator de inchamento, quebra de viscosidade, setback, cristalinidade relativa e tamanho das cadeias ramificadas de amilopectina (cadeias B2 e B3 e tamanho médio). O uso do ozônio, portanto, poderá ser útil nesta modalidade de modificação dos amidos e, em especial para o amido de mandioca ou de milho ceroso, capacitando-os para a expansão no forno, o que poderia gerar produtos panificáveis mais padronizados do que os obtidos pelo polvilho azedo, ou sem as consequências da oxidação por métodos químicos mais agressivos, como o uso do hipoclorito de sódio. / Oxidation is a method which aims the starch modification by various oxidizing agents, introducing functional groups and performing the cleavage of glycosidic linkages. Its objectives are to reduce the polysaccharides viscosity, raising the transparency paste and minimizing retrogradation. The aim of this study was to modify the corn starch with different levels of amylose and the cassava starch using ozone and also to characterize the samples oxidized as the molecular, structural and functional characteristics, relating them with each other. The oxidation process was effective changing several properties and features of the studied starches, however, in different ways for the different sources. These differences come from having starches different composition and granular structure, providing different rates of degradation of amorphous and crystalline lamellae and the presence of carbonyl groups, and carboxyl formed. A reduction in viscosity was observed for the normal corn starch after oxidation, and an increase for the waxy maize and cassava starches. The high amylose corn starch showed no viscosity by Rapid Visco Analyser, before or after oxidation. The setback was reduced by the oxidation process with ozone for the three starches, rendering them more stable. Oxidation by ozone under the conditions studied increased paste clarity of all starches. Ozonation caused changes in the waxy corn and cassava starches, providing baking properties, in indices close to those of commercial samples of sour cassava starch. The other starches are not expanded significantly in the oven. The baking property was mostly affected by enthalpy of gelatinization of starches, but also by carboxyl and carbonyl contents, swelling factor, breakdown, setback, relative crystallinity and size of amylopectin branched chains (B2, B3 and medium size). So, the use of ozone may be useful in this starch modification modality, and in particular for cassava or waxy maize starches, enabling the expansion in oven, which could generate more standardized baking products than those obtained by sour cassava starch, or without consequences of oxidation using more aggressive chemical methods, such as sodium hypochlorite.

<p dir="ltr">Baked goods are one of the primary sources of added sugar in the American diet. Excessive consumption of added sugar can lead to diseases such as obesity, heart disease, and diabetes. As information pertaining to the link between health and diet becomes more available to consumers, the demand for products with lower calories, fat, and sugar continues to rise. The obstacle in formulating baked goods with alternative sweeteners is that these sweeteners have different effects on the physicochemical properties of the starch in the products than that of sucrose, leading to differences in texture, color (browning), texture, and flavor between the sucrose-containing products consumers are accustomed to and the new reduced sugar products. Previous studies done by the Mauer lab have found that interactions between the sweeteners that enter the amorphous region of the starch granule alter physicochemical properties of the starch, including the gelatinization temperature (T_gel) and pasting properties of the starch. The purpose of this project was to investigate how the presence of oligosaccharides (OS) used as sucrose replacers in starch-containing products alters the functionality of the starch through modification of its thermal and physicochemical properties. Different botanical sources of starch were preconditioned in solutions containing different concentrations of select OS, varying temperature during preconditioning. The preconditioned starches were then analyzed by differential scanning calorimetry (DSC), rapid visco analysis (RVA), and x-ray diffraction (XRD). Results demonstrated that several OS are less effective plasticizers of starch (all botanical sources) than sucrose, meaning T_gel is higher in the presence of these OS and less pasting occurs. This is advantageous for formulating low moisture baked goods that rely on inhibition of starch gelatinization for desirable product quality.</p>

Master of Science / Department of Grain Science and Industry / D.L. Wetzel / Chemical imaging enables displaying the distribution of different substances within a field of view based on their fundamental vibrational frequencies. Mid-IR bands are generally strong and feature direct correlation to chemical structure, while near IR spectra consist of overtones and combinations of mid-IR bands. Recently, mid-IR microspectroscopy has enabled determination of the relative substitution of hydroxyl groups with the modifying agent for individual waxy maize starch granules by using synchrotron source. The brightness and non-divergence of the synchrotron source and confocal masking enabled obtaining individual spectra with 5 [mu]m[superscript]2 masking and 1 [mu]m raster scanned steps. Each 1 [mu]m step results from the coaddition of hundreds of scans and lengthy data collection is required to produce data. The recent breakthrough at the Synchrotron Research Center uses a multi-beam synchrotron source combined with a focal plane array microspectrometer. This major improvement in localized detection of the modifying agent within single waxy maize starch granules is the increased efficiency of focal plane array detection and an effective spatial resolution of 0.54 [mu]m. Mixtures of granular solids represent an analytical challenge due to the range of heterogeneity and homogeneity within samples. Near IR imaging provides deeper sample penetration allowing for solid mixture analysis. However, the broad, overlapping bands present in the near IR necessitates statistical data treatment. This requires imaging specimens representative of the individual components to create spectral libraries for classification of each component. Partial least squares analysis then allows characterization and subsequent pixel analysis provides quantitative results. The primary break system for wheat milling was studied as it is key in releasing endosperm to be further ground into fine flour in subsequent processes. The mass balance of endosperm throughout individual unit processes was determined by obtaining flow rates of incoming and outgoing millstreams and calculating endosperm content through pixel identification. The feed milling industry requires the use of a tracer to determine adequate mixing and mix uniformity to limit the time and energy in processing. Near IR imaging allows individual components of a formula feed to serve as a self-tracer, eliminating the need of an inorganic tracer.

Orientador: Célia Maria Landi Franco / Banca: Magali Leonel / Banca: Mieko Kimura / Resumo: O tratamento ácido-alcoólico tem sido proposto para modificar a estrutura do grânulo de amido e obter a máxima conversão de amido nativo em amido solúvel. Este amido modificado torna-se frágil quando submetido à moagem em moinho de bola produzindo pequenos cristais que podem ser usados como substitutos de gordura. Neste trabalho, características físico-químicas, estruturais e morfológicas de amidos tratados com ácido-etanol (0,36% HCl em etanol anidro por 1 e 12 h a 30, 40 e 50oC) submetidos ou não a moagem em moinho de bola por 1 h foram analisados e comparados. A recuperação dos amidos foi alta atingindo em média 98%, independente do tempo e temperatura de tratamento. A solubilidade aumentou com o aumento da temperatura e tempo de tratamento e os amidos tratados a 40oC/12h e 50oC/12h tornaram-se totalmente solúveis a 95oC. O tamanho médio dos grânulos de amido de mandioca reduziu com o aumento do tempo e da temperatura de modificação, passando de 25,2 mm para 20,0 mm após 12 h de tratamento a 50oC. A moagem reduziu o tamanho médio dos grânulos de amido nativo e daqueles submetidos a tratamentos ácido-alcoólicos mais brandos (1 h a 30 ou 40oC), enquanto o tamanho médio dos grânulos tratados por 12 h, independente da temperatura, permaneceu inalterado. Os grânulos de amido de mandioca, observados em microscópio eletrônico de varredura, apresentaram forma arredondada e após tratamento com ácido-álcool a 50oC por 12h antes e após moagem, mostraram superfície áspera e rugosa sugerindo erosão com conseqüente solubilização das camadas mais externas dos grânulos. Alguns grânulos mostraramse disformes sugerindo gelatinização parcial que foi mais intensa após moagem. O índice de cristalinidade relativa (IC) dos amidos, determinados por difração de raios- X, aumentou quanto maior o tempo e temperatura de tratamento, enquanto o teor de amilose... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Acid-alcohol treatment has been proposed to modify starch granule structure and obtain maximum conversion of raw starch into soluble starch. Acid-alcohol starch becomes fragile when submitted to the milling in ball mill producing small crystals, which can be used as fat substitute. In this work, physicochemical, structural and morphological characteristics of acid-ethanol cassava starch (0,36% HCl in anhydrous ethanol during 1 and 12 h at 30, 40 e 50oC) followed by milling in ball milling for 1 h were analyzed and compared. The recovery of the modified starches was high reaching 98% independent of time and temperature. The solubility increased with increasing of the treatment temperature and time, and after 1 h at 50ºC the modified starch became totally soluble to 95ºC. The average size of the cassava starch granules decreased with increasing of the treatment time and temperature from 25.2 µm to 20.0 µm after 12 hours of treatment at 50ºC. The milling decreased the average size of the native starch granules and those submitted to milder treatments (1 h at 30 or 40oC), while the average size of the starch granules treated for 12 h, independent of temperature, kept unchanged. From scanning electron microscopy, the native cassava starch granules presented round shape and smooth surface. After acid-ethanol treatment at 50oC for 1h, before and after milling, the granules displayed rough and exfoliated surfaces suggesting erosion with solubilization of the outer layer of the granules. Some granules treated at 50oC during 12 h showed deformed surfaces suggesting partial gelatinization of the starch that was more intense after milling. Relative crystalline index (CI) of the starches, determined from X-ray diffraction, increased with increasing of the treatment time and temperature, while the amylose content, intrinsic viscosity and pasting viscosities decreased... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2017-07-21T18:53:06Z (GMT). No. of bitstreams: 1 Simone Rosa da Silveira Lazzarotto.pdf: 1687996 bytes, checksum: 6af491e1aaa6d51c6be5d21a623c4dc9 (MD5) Previous issue date: 2016-03-04 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Starch is the main constituent of many plants, widely used in paper, textile, pharmaceutical and food industries. The Araucaria angustifolia, a Brazilian native conifer, there is seeds known as "pinhões" with high starch content. The aim of this study was to modify the “pinhão” starches with different concentrations of potassium permanganate (KMnO4) solutions. The samples were characterized by Thermogravimetry (TG-DTA), Differential Scanning Calorimetry (DSC), Viscoamilografic Analysis (RVA), X-Ray Diffraction, Scanning Electron Microscopy (SEM) and colorimetry. In the TG-DTA curves with synthetic air were observed three mass loss in the samples. In this analysis were changes in the peak temperature and the intensity of thermal events of samples, where in the sample (3) of the “pinhão” starch treated with a concentration of 0.005 mol L-1 KMnO4 were more evident due to consecutive reactions. In the same analysis, but in nitrogen atmosphere, the samples showed two endothermic events of masses losses and only the sample (3) had a last exothermic event of mass loss indicative of the largest oxygen index. The DSC analyzes showed a reduction in gelatinization enthalpy values of all treated samples. These same samples showed less retrogradation tendency (setback) and lower viscosity compared with the native sample in the pasta property analysis (RVA). The X-ray diffraction of the native and treated samples showed similar profiles to the starches A - type pattern. The micrography obtained by SEM showed no significant changes regarding to the diameter and starches granules shape after modification. Through reflectance spectroscopy was showed color change for modified starch samples due to darkening caused by KMnO4.These results showed that the properties of the “pinhão” starches were changed by oxidative action of KMnO4 and future applications will be studied. / O amido é o principal constituinte de diversas plantas, amplamente utilizado em indústrias de papel, têxtil, farmacêutica, e alimentos. A Araucaria angustifolia, uma conífera nativa brasileira, possui sementes conhecidas como “pinhões” com alto teor amiláceo. O objetivo deste estudo foi modificar amidos de pinhão com soluções de diferentes concentrações de permanganato de potássio (KMnO4). As amostras foram caracterizadas por Termogravimetria (TG-DTA), Calorimetria Exploratória Diferencial (DSC), Análise Viscoamilográfica (RVA), Difratometria de Raios X, Microscopia Eletrônica de Varredura (MEV) e colorimetria. Nas curvas TG-DTA com ar sintético foram observadas três perdas de massas nas amostras. Nesta análise houve alterações nas temperaturas de pico e nas intensidades dos eventos térmicos das amostras, sendo que na amostra (3) de amido de pinhão tratado com a concentração de 0,005 mol L-1 de KMnO4, foram mais evidentes devido às reações consecutivas. Na mesma análise realizada em atmosfera de nitrogênio as amostras apresentaram dois eventos endotérmicos de perdas de massas e apenas a amostra (3) apresentou um último evento de perda de massas exotérmico indicativo do maior índice de oxigênio. Nas análises de DSC observou-se uma redução nos valores de entalpia de gelatinização das amostras tratadas. Estas mesmas amostras apresentaram menor tendência a retrogradação (setback) e menor viscosidade, em comparação com a amostra nativa nas análises de propriedade de pasta (RVA). Os difratogramas de raios X das amostras nativa e tratadas mostraram perfis semelhantes ao padrão tipo “A” de amidos. As micrografias obtidas no MEV indicaram que não houve mudanças significativas no diâmetro e na forma dos grânulos de amido após a modificação. Através da espectroscopia de reflectancia foi observada alteração de cor para as amostras de amido modificadas devido ao escurecimento provocado pelo KMnO4. Estes resultados demonstram que as propriedades dos amidos de pinhão foram alteradas pela ação oxidativa do KMnO4 e futuras aplicações poderão ser estudadas.