Master of Science / Department of Grain Science and Industry / Yong Cheng Shi / Waxy wheat starch (WWS) containing little or no amylose has unique properties for food and industrial uses. Hydroxypropylation, a widely used means for modifying starches, could enhance functionalities of starch by substituting hydroxyl groups in starch. There are limited numbers of literatures regarding hydroxypropylation of WWS. WWS hydroxypropylated with 3.0-9.0% propylene oxide (PO) were prepared and compared to hydroxypropylated normal wheat starch (NWS) and hydroxypropylated waxy maize starch (WMS). The molar substitution (MS) of the resulting hydroxypropylated NWS, WWS and WMS was 0.055-0.151, 0.048-0.133, and 0.049-0.139, respectively. Gelatinization temperatures and enthalpy of hydroxypropylated starches were significantly lower than those of their unmodified counterparts and the extent of decrease was positively correlated to the MS. Differential scanning colorimetry (DSC) results showed that hydroxypropylation reduced the retrogradation of the starches during the storage after gelatinization but there were differences between the starches. For the same level of PO reaction (3 and 5% PO), hydroxypropylated WWS retrogradated less than hydroxypropylated WMS, suggesting that for the same level of cold storage stability, less PO is needed for WWS. After reacted with 6% PO, MS was 0.092 and 0.094, respectively, for WWS and WMS, and no retrogradation was observed for those hydroxypropylated starches, indicating that at MS ~0.094, hydroxypropyl groups prevents amylopectin chains from re-associating and forming crystalline structures. In contrast, a higher level of PO (9%) was needed to react with NWS to achieve the hydroxypropylated starch with an MS of 0.151 that gave no retrogradation. Consistent with microscopic observation results, Micro-Visco-Amylograph (MVA) analysis showed hydroxypropylated starches developed viscosity at lower temperatures and had improved hot and cold viscosities. The specific characteristics of hydroxypropylated starches are related to the degree of hydroxypropylation. Therefore, it is critical to determine the level of hydroxypropylation in modified starches. 1H NMR is a simple and rapid means of determining hydroxypropyl (HP) group in modified starches. In this study, a method to prepare a HP starch for NMR analysis was improved. The optimum parameters proposed to hydrolyze HP starches were 10% starch solid content, 3.5% (wt.%) DCl in D2O as the solvent, sodium acetate as an internal standard, heating at 90oC for 1 h. Optionally, 6% (v/v) trifluoroacetic acid-d as the water-peak shifting reagent. Six hydroxypropylated starch samples and two commercial cross-linked and hydroxypropylated starch samples were hydrolyzed with this modified method before 1H NMR analysis, and the results of HP group content in the samples were in agreement with the results from an enzyme-catalyzed method, which indicate that the improved acid hydrolysis method is applicable for both hydroxypropylated starch and cross-linked and hydroxypropylated starch.

RESUMEN El objetivo de esta tesis fue la obtención y caracterización de films biodegradables con características antimicrobianas y/o antioxidantes a partir de quitosano (CH). Para modular sus propiedades y mejorar su funcionalidad, se estudió la combinación con otras matrices poliméricas: almidón de trigo (WS), polivinil alcohol (PVA) y ácido poliláctico (PLA). Además se incorporaron aceites esenciales (EO) de tomillo (Th) o albahaca (B), ¿-tocoferol (Tp) y ácido cítrico (CA). Se evaluó el efecto del tratamiento de homogenización de las dispersiones formadoras de films (FFD) en films de quitosano con EO en diferentes proporciones. La microfluidización dio lugar a una reducción en el tamaño de gota, a una mayor carga superficial de las mismas y una menor viscosidad de las dispersiones. Además, intensificó todos los efectos provocados por la incorporación de EO sobre las propiedades mecánicas de los films debido a potenciación de las interacciones con el polímero. A baja proporción de EO, la microfluidización mejoró las propiedades de barrera al vapor de agua de los films, pero no tuvo un impacto significativo en la permeabilidad al oxígeno. Los films ejercieron un papel protector frente a la oxidación en grasa de cerdo. La presencia de EO en los films, a pesar de aumentar la permeabilidad al oxígeno, dio lugar a una menor velocidad de oxidación de las muestras (especialmente a alta humedad relativa), probablemente por el efecto antioxidante de los componentes de los EO. Los films de quitosano se mostraron efectivos en el control del deterioro microbiano cuando se aplicaron en carne de cerdo picada, pero la incorporación de los EO no mejoró su actividad antimicrobiana. Se incorporó CH en films de WS en diferentes proporciones. La adición de CH en cantidades crecientes dio lugar a un aumento en la viscosidad y estabilidad de las FFD. Ambos polímeros mostraron un alto grado de compatibilidad lo que dio lugar a una microestructura homogénea. El aumento de la proporción de CH dio lugar a films con mejores propiedades mecánicas ya que el CH pareció inhibir la retrogradación del almidón. Los films WS:CH dieron lugar a una reducción de la carga microbiana cuando se aplicaron en muestras de carne de cerdo picada. Se incorporaron diferentes antioxidantes (aceite esencial de tomillo y albahaca, ácido cítrico y ¿-tocoferol) en films mezcla de WS (80%) y CH (20%). Los films presentaron una microestructura heterogénea por la inmiscibilidad de componentes, principalmente el film con ¿-tocoferol que presentó separación de fases. Esto llevó asociado una superficie más rugosa, con menor brillo y, en el caso del ¿-tocoferol, un color más amarillo. No obstante la incorporación de antioxidantes conllevó un aumento de la transparencia y una disminución de la permeabilidad al oxígeno. El CA provocó un aumento en el módulo de elasticidad y un descenso de la extensibilidad de los films. La incorporación de CH en matrices de PVA dio lugar a films altamente homogéneos, debido a la compatibilidad de ambos polímeros. Se obtuvieron films más resistentes y rígidos, pero menos extensibles. Se observó una reducción del grado de cristalinidad y un aumento de la estabilidad térmica, además de una reducción de la trasmisión de la luz UV. Así mismo, cuando se aplicaron a muestras de carne de cerdo picada presentaron una acción antimicrobiana. La incorporación de CH en una matriz de PLA mediante extrusión no afectó al comportamiento térmico del PLA ni a su grado de cristalinidad. Ambos polímeros se mostraron incompatibles. La reducción del tamaño de las partículas de CH minimizó el impacto negativo sobre las propiedades mecánicas y de barrera al vapor de agua. En su aplicación a muestras de carne de cerdo picada, la presencia de CH mejoró las propiedades antimicrobianas de los films. / Bonilla Lagos, MJ. (2013). Desarrollo de films y recubrimientos comestibles bio-activos como soporte de agentes antioxidantes y antimicrobianos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/28370 / TESIS

Made available in DSpace on 2017-07-21T18:53:03Z (GMT). No. of bitstreams: 1 Juliane Alves Souza.pdf: 2088285 bytes, checksum: 7df534f70b74bb908ee007c98dc1179a (MD5) Previous issue date: 2014-12-12 / Cereals have an important role in human nutrition. Wheat is one of the most cultivated and consumed cereals in the world being used in the preparation of the enormous diversity of products. The wheat flour fortification with iron and folic acid is obligatory in Brazil in according with current legislation. Starch is a reserve polysaccharide of vegetable consisting essentially of amylose and amylopectin. It is a matter abundant and replaceable material being the main source of carbohydrate in diet human. Starches in their native form have limited features for industrial use so it is important modification aiming to acquire improved stability, rheological properties, paste, gel texture, water retention, among others. The chemical modification, still very used, is not considered as safe a one way of modification, so the physical modification is well regarded by food industry. Heat Moisture Treatment (HMT) in starch is considered a natural method and is conducted with a moisture content of 30% and a maximum temperature of 120 ° C. Were studied native wheat and modified starches with presence and absence of folic acid and iron, by HMT at 121 °C for a period of 1 hour. The effects of HMT were studied using the following techniques: thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), x-ray diffraction (DRX), atomic force microscopy (NC-AFM), rapid visco analysis (RVA), the flame atomic absorption spectrometry (FEAA) and reflectance photocolorimetry. From the TG and DTG curves was observed that for the physically treated starches, the values of weight loss for starch in the presence of folic acid iron in the first and third stages decreased and the second increased as increased moisture. The DSC, modified starches, the temperatures at which the event occurred and the enthalpy of gelatinization decreased and the higher the moisture treatment was lower enthalpy. All starches showed bimodal distribution and irregularities in the micro-images of AFM with changes in average diameter and roughness, after physical modification. For all starches DRX peaks did not undergo pronounced displacement, however there was a decrease in crystallinity after modification. All starches showed high paste temperature and low peak viscosity. Was determined absence iron concentration to starch without folic acid and iron and little change for the presence of starch with these nutrients. With respect to color analysis for all samples studied, there was little variation in color between them, with causing a trend mainly to yellow after modification. / Cereais possuem importante papel na alimentação humana. O trigo é um dos cereais mais cultivados e consumidos no mundo sendo utilizado na elaboração de enorme diversidade de produtos. A fortificação da farinha de trigo com ferro e ácido fólico é obrigatória no Brasil de acordo com a legislação vigente. O amido é um polissacarídeo de reserva vegetal constituído basicamente por amilose e amilopectina. É uma matéria prima abundante e renovável sendo a principal fonte de carboidrato na alimentação humana. Amidos na forma nativa possuem características limitadas para uso industrial por isso torna-se importante sua modificação visando adquirir melhor estabilidade, propriedades reológicas, de pasta, textura de géis, retenção de água entre outros. A modificação química, ainda muito utilizada, não é considerada uma forma tão segura de modificação, por isso a modificação física é bem vista pela indústria alimentícia. A modificação por umidade e temperatura controladas (HMT) em amido é considerada um método natural e é conduzida com teor de umidade de até 30% e temperatura máxima de 121 ºC. Foram estudados amidos trigo nativos e modificados, com presença e ausência de ácido fólico e ferro, por HMT a 121°C por um período de 1 hora. Os efeitos do HMT foram estudados utilizando as seguintes técnicas: termogravimetria e termogravimetria derivada (TG/DTG), calorimetria exploratória diferencial (DSC), difração de raios X (DRX), microscopia de força atômica (NC-AFM), análise viscoamilográfica rápida (RVA), espectrometria de absorção atômica com chama (FEAA) e refletância fotocolorimetria. A partir das curvas TG e DTG, observou-se que para os amidos tratados fisicamente, os valores de perda de massa para o amido em presença de ácido fólico e ferro, nas primeiras e terceiras etapas diminuíram e da segunda aumentaram, conforme aumento da umidade. Após a análise de DSC, os amidos modificados, as temperaturas em que ocorreu o evento e o valor da entalpia de gelatinização diminuíram e quanto maior a umidade de tratamento menor foi à entalpia. Os amidos deste estudo apresentaram distribuição bimodal e irregularidades nas microimagens de AFM, com alterações nos diâmetros médios e rugosidade, após a modificação física. Para todos os amidos os picos de DRX não sofreram deslocamento acentuado, porem houve redução da cristalinidade após a modificação. Todos os amidos apresentaram alta temperatura de pasta e baixo pico de viscosidade. Foi determinada ausência de ferro para o amido sem ácido fólico e ferro e pouca alteração para o amido com presença desses nutrientes. Com relação a análise de cor, para todas as amostras estudadas, houve pouca variação de cor entre elas, com tendência ao amarelamento após a modificação.

Submitted by Gabriela Lopes (gmachadolopesufpel@gmail.com) on 2017-03-14T15:42:14Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-03-17T21:44:15Z (GMT) No. of bitstreams: 2 Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-03-17T21:44:15Z (GMT). No. of bitstreams: 2 Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-11-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A associação entre polímeros naturais e sintéticos para formação de biocompósitos tem sido estudada. A mistura do amido com o poli (óxido de etileno) (PEO) para a formação de biocompósitos é interessante, pois o PEO é biodegradável, apresenta alta viscosidade e biocompatibilidade com matrizes orgânicas. Além disso, o PEO apresenta uma estrutura semicristalina que pode influenciar nas propriedades dos biocompositos. A interação do amido com PEO pode ser influenciada pela estrutura molecular do amido. Com isso, objetivou-se com o presente trabalho desenvolver filmes biocompósitos à base de amidos de trigo nativo, fosfatado ou intercruzado com a adição do PEO. O amido de trigo foi modificado por fosfatação e por ligação cruzada. Os amidos foram avaliados quanto ao teor de fósforo, teor de amilose, poder de intumescimento, solubilidade em água, propriedades térmicas, propriedades de pasta, cristalinidade e morfologia. Os filmes foram elaborados com amido nativo, fosfatado ou de ligação cruzada, e com adição de PEO. Os filmes foram avaliados quanto à morfologia, solubilidade em água, permeabilidade ao vapor de água (PVA), propriedades mecânicas, parâmetros de cor (luminosidade e opacidade), cristalinidade, rugosidade e higroscopicidade. O amido fosfatado, em relação aos demais amidos, apresentou maior teor de fósforo, teor de amilose e maior poder de intumescimento e solubilidade em água. Os filmes, independentemente do tipo de amido, com a adição de PEO quando comparados aos filmes de amidos sem PEO, apresentaram morfologia descontínua, foram mais cristalinos e rugosos e menos hidrofílicos. Os filmes biocompósitos apresentaram características adequadas para aplicação em embalagens flexíveis. / The association between natural and synthetic polymers for the formation of biocomposites has been studied. The mixture of starch with poly (ethylene oxide) (PEO) for the formation of biocomposites is interesting, since the PEO is biodegradable, has high viscosity and biocompatibility with organic matrices. In addition, PEO has a semicrystalline structure that may influence the properties of the biocomposites. The interaction of the starch with PEO can be influenced by the molecular structure of the starch. The aim of this work was to develop biocomposite films based on native wheat starches, phosphated or crosslinked with the addition of PEO. The wheat starch was modified by phosphating and crosslinking. Starches were evaluated for phosphorus content, amylose content, swelling power, water solubility, thermal properties, past properties, crystallinity and morphology. The films were prepared with native, phosphate or crosslinked starch, and with addition of PEO. The films were evaluated for morphology, water solubility, water vapor permeability (WVP), mechanical properties, color parameters (luminosity and opacity), crystallinity, roughness and hygroscopicity. The phosphate starch, in relation to the other starches, presented higher phosphorus content, amylose content, swelling power and water solubility. The films, regardless of the type of starch, with the addition of PEO when compared to the starch films without PEO presented discontinuous morphology, were more crystalline and rough and less hydrophilic. The biocomposite films presented characteristics for possible use in flexible packages.

L'effet des traitements hydrothermiques et l’effet des arômes sur la structure de l'amidon et de ses propriétés physiques ont été étudiés. L’amidon de blé natif a été traité à 2 hydratations différentes (rapports eau-amidon: 50/50 et 80/20 g/g) et à 2 températures (65 et 85 °C) en présence d’ arômes (hexanoate d'éthyle et de 2-hexanone). Les échantillons fraîchement préparés ont été soumis à l’analyse calorimétrique (AED) et au dosage d’ arôme. Aucun complexe d'inclusion entre amidon et arôme n’a pu être détecté par AED cependant le résultat de l'analyse aromatique a prouvé qu'il y avait des interactions arôme-amidon. Les deux composés d’arôme (hexanoate d'éthyle et 2-hexanone) ont interagi avec l'amidon à des teneurs comparables. Les pertes d’arômes ont été trouvées les plus élevées dans les échantillons traités aux plus hautes hydratation et température . La perte d’arôme était principalement liée à l’évaporation lors des traitements hydrothermiques. Après les traitements hydrothermiques, les échantillons ont été lyophilisés ont montré une stabilité d’arôme à la lyophilisation. Les échantillons lyophilisés ont été soumis à diverses études: DSC (Tg), RVA, la taille des granules, XRD, WAXS, SAXS étude et de stockage. Les traitements hydrothermiques ont conduit à des échantillons avec des propriétés différentes. A haute hydratation, la température influence la taille des granules et des propriétés rhéologiques à la cuisson (pasting). Les échantillons chauffés à 65 °C présentaient des tailles de granules significativement plus importantes, une viscosité maximale (en RVA) inférieure à celles des échantillons chauffés à 85 °C mais de significative différence en % de cristallinité. A faible hydratation, la température de chauffage n’avait pas d’influencer significative sur la taille des granules, mais un effet significatif sur les propriétés rhéologiques à la cuisson, le degré de cristallinité et le profil SAXS. Les échantillons chauffés à 65°C avaient une viscosité maximale supérieure , un degré de cristallinité plus élevé et des pics SAXS plus importants qu’après un chauffage à 85 °C. La teneur résiduelle en arôme n'a eu aucune influence significative sur la structure, mais semble affecter les propriétés rhéologiques à la cuisson. En ce qui concerne l'étude à la conservations, les échantillons ont été stockés à 58 et 75% d'humidité relative et étudiés par analyse SPME, par extraction d’arôme et par AED pour un suivide relaxation d’enthalpie après de 2, 4 et 14 semaines de stockage. Les échantillons avaient une plus grande libération de l'arôme à 75% HR et l’hexanoate d’éthyle montré une plus grande libération de 2-hexanone. Les échantillons ont montré une augmentation de relaxation d'enthalpie de lors d'un stockage. / The effect of hydrothermal treatments and flavours addition on starch structure and its physical properties were studied. Native wheat starch was treated at 2 different hydrations (water-starch ratios: 50/50 and 80/20 g w/w) and temperatures (65 and 85 °C) in the presence of flavours (ethyl hexanoate and 2-hexanone). The freshly prepared samples were subjected to DSC and flavour analysis. Flavour inclusion complex could not be detected by DSC, however the result of flavour analysis proved that there were flavours interactions with starch. Both ethyl hexanoate and 2-hexanone interacted with starch at similar rates. The highest flavour loss was found in the samples at high hydration and heated at 85 °C. The loss of flavour was mainly due to vaporisation during hydrothermal treatments. After hydrothermal treatments, the samples subjected to freeze-drying and they showed flavour stability upon freeze-drying. The freeze-dried samples were subjected to various studies: DSC (Tg), RVA, granule size, XRD, WAXS, SAXS and storage study. The hydrothermal treatments resulted in samples with different properties. At high hydration, temperature influenced granule size and pasting properties. The samples heated at 65 °C had significantly greater granule diameter, lower peak viscosity than samples heated at 85 °C and no significantly difference in % crystallinity. At low hydration, heating temperature had no significantly influence on granule diameter but significantly affected pasting properties, % crystallinity and SAXS profile. The samples heated at 65 °C had a greater peak viscosity, % crystallinity and greater peak on SAXS than after a treatment at 85 °C. The residual flavour contenthad no significant influence on structure but affected pasting properties. Regarding storage study, the samples were stored at 58 and 75 % RH and withdrawn for SPME, flavour residual extraction and DSC (enthalpy of relaxation) at 2, 4 and 14 weeks of storage. The samples had greater flavour release at 75% RH and ethyl hexanoate showed greater release than 2-hexanone. The samples showed increasing of enthalpy relaxation upon storage.

This diploma thesis deals with preparation and testing of biodegradable materials for use in the packaging indrustry. The task of this work is to prepare set of laboratory made films based on wheat starch, glycerol, polyvinyl alcohol with the addition of a suitable additive, which has been selected as citric acid. A suitable composition meeting the requirements of the packaging foils has been found. Quaternary blends from all components achieve the best results. It has been found that citric acid can influence the chemical structure and thus affect the mechanical and thermal properities and also the degree of solubility. The films were characterized in terms of mechanical properities by tensile testing and thermal stability by means of thermogravimetric analysis with respect to the phase structure. The structure was characterized by Fourier transform infrared spectroscopy and confocal laser scanning microscopy. The biodegradability of the film was tested by its solubility in aqueous medium.