The physico-chemical characteristics of soymilk particles and the gelation properties of soymilk were investigated as a function of soymilk protein concentration, by preparing soymilk samples from different water-to-bean ratios. Particles from different soymilk protein concentrations showed similar protein composition and surface hydrophobicity, but different -potential, size and protein content. The particle voluminosity was derived using a relation between the effective refractive index of soymilk and the turbidity parameter determined experimentally. For the first time, experimental data was compared to theoretical models, drawing general conclusions about colloidal properties of soymilk particles. Protein concentration and the rate of acidification did not have a significant effect on the acid-induced gelation of soymilk. Results demonstrated that decreased charge is a prerequisite for particle aggregation, which is driven by hydrogen bridging. This thesis provides soymilk processors with general principles on the colloidal behaviour of soymilk, valuable information for new product development and better process design. / Soybean Growers of Ontario, Natural Sciences and Engineering Research Council of Canada

Globular proteins are important ingredients in many food formulations because of their nutritional value and their various functional properties such as gel formation. Proteins form gels by polymerization into a three-dimensional matrix. The rheological properties of the resulting viscoelastic solids can be obtained by Instron measurements. In the present work, gels were obtained by heating solutions of bovine serum albumin (BSA) in D$ sb2$O and egg albumin in H$ sb2$O under different conditions (i.e., pH, salt concentration, protein concentration, time of heating and temperature), and their gel strengths were measured by a compression test (Universal Testing Machine LRX). The Fourier transform infrared (FTIR) spectra of the same gel samples were recorded in order to investigate the changes in protein structure at the molecular level accompanying gel formation. Intermolecular $ beta$-sheet formation was found to increase as gel formation progresses at the expense of intramolecular $ beta$-sheet and $ alpha$-helix structures. For BSA, maximum gel strength was obtained around pH 7. The addition of salt had little effect on the gel strength while increase in protein concentration, time of heating and temperature increased the gel strength. The rate of denaturation of BSA and ovalbumin and of mixtures of these proteins in the ratios 9:1, 1:1, and 1:9 was also investigated by measuring the peak height of an aggregation band at 1618 cm$ sp{-1}$; some inhibitory effects of BSA on ovalbumin aggregation were observed. Correlations between the measured gel strengths and the amide I band profile in the FTIR spectra were examined using partial-least-squares (PLS) regression. These studies reveal that gel strengths of a particular protein gel could be adequately predicted from their infrared spectra without the need to carry out the rheological compression measurements.

Variable-temperature Fourier transform infrared spectroscopy can be employed to monitor the denaturation and aggregation of proteins during heat treatment. Information on the changes that occur in protein secondary structure upon heating is provided by detailed examination of the amide I band, as different protein conformations have characteristic amide I frequencies. The objectives of the present study were: (i) to study the changes in protein structure that occur during gelation of whey protein isolate (WPI) and (ii) to correlate the changes in protein structure observed under different physico-chemical conditions to rheological properties of WPI gels prepared under the same conditions. / The FTIR spectra of D2O solutions of WPI at different pHs, ranging from 3 to 10, were recorded as the temperature of the solution was increased from room temperature to 95°C in 5°C increments. In all the solutions studied, the formation of two new bands at 1618--1623 cm -1 and 1678--1684 cm-1 was observed upon heating; these bands are characteristic of aggregate formation and have been previously assigned to antiparallel beta-sheet structure. As the pH increased from 3 to 10, the aggregation temperature of WPI decreased from 85°C to 65°C. / The rheological properties of WPI gels were studied by employing an Instron Universal Testing Machine. The Instron measurements demonstrated that protein concentration, heating temperature, and heating and cooling time are directly related to gel strength. The changes in gel strength as a function of cooling time (for gels prepared by heating at 75°C for 45 min) were correlated to FTIR spectral data for WPI solutions subjected to the same treatment.

Controlled release formulations deliver an active ingredient over an extended period of time. It is an ideal dosage form for an active ingredient with a short elimination half-life. An active ingredient with a short elimination half-life would be released in small portions over an extended period of time and thus less frequent administration is necessary and this improve patient compliance. Other advantages of these formulations include: decreased side effects, constant drug levels in the blood, improvement in treatment efficiency and reduction in cost of administration. Controlled release beads are formulated in such a way that the active ingredient is embedded in a matrix of insoluble substance like chitosan; the dissolving drug then has to find its way through the pores of the matrix into the surrounding medium. The chitosan matrix swells to form a gel, the drug then has to first dissolve in the matrix and diffuse through the outer surface into the surrounding medium. Chitosan is a biocompatible, biodegradable polymer of natural origin. It has mucoadhesive properties as well as the ability to manipulate the tight junctions in the epithelium membrane and these properties have qualified chitosan as an effective drug carrier in controlled release dosage forms. The effect of a modern controlled release polymer namely Kollidon® SR in combination with chitosan on drug release was investigated. Ketoprofen was chosen as model drug. Ketoprofen is an anti-inflammatory drug that causes gastrointestinal side effects in conventional dosage forms. Ketoprofen has a short elimination half-life of 2.05 ± 0.58 h and this characteristic makes it an ideal candidate for use in a controlled release formulation. The aim of this study was to achieve controlled release and minimize gastrointestinal effects of ketoprofen with chitosan particles. Kollidon® SR was used as polymer because it exhibits pH independent release characteristics and previous studies have shown potential for this combination. Chitosan beads and chitosan-Kollidon® SR beads, as well as chitosan granules and chitosan-Kollidon® SR granules, were prepared and investigated as potential controlled release formulations. Chitosan beads were prepared through the inotropic gelation method using tripolyphosphate as a cross linking agent. Granules were prepared through wet granulation using 2% v/v acetic acid as the granulating fluid or by dissolving ketoprofen in ethanol and Kollidon® SR in 2-pyrrolidinone and using the solution as granulating fluid. Kollidon® SR was added in concentrations of 0.25, 0.5 and 1% (w/v) in the bead formulations and concentrations of 1, 5 and 10% (w/w) in the granule formulations. The beads and granules were characterised by evaluating the following properties: morphology, drug loading and drug release. Additionally swelling and friability tests were also conducted on the bead formulations. The cross linking times of the bead formulations were varied to investigate the effect of cross linking time on the characteristics of the beads. Chitosan-Kollidon® SR beads showed promising results for controlled release formulations and ketoprofen were released over an extended period of time. Drug loading of the plain chitosan beads was 74.65 ± 0.71% and it was noted that the inclusion of Kollidon® SR in the beads resulted in an increase in drug loading and the formulation containing 1% (w/v) Kollidon® SR, cross linked for 30 minutes had a drug loading of 77.38 ± 0.01%. Drug loading of the beads that were cross linked for a longer time were slightly lower which is an indication that some of the drug might have leached out during cross linking. The degree of swelling was promising with some beads swelling to a degree of 2.5 in phosphate buffer solution pH 5.6. Granules had a drug loading between 81.73 ± 1.53% and 93.30 ± 0.50%. Ketoprofen release from the beads and the granules in PBS pH 7.40 at 37 °C over a period of 6 hours were investigated. The bead formulations were more effective in achieving controlled release and it was noted that the bead formulations that was cross linked for a longer period was more efficient in achieving controlled release. The granules did not form a matrix and were not effective in achieving controlled release. Controlled release of ketoprofen were achieved and the results show potential for chitosan-Kollidon® SR formulations in the future. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2008.

Defatted soybean was subjected to isolation procedures as follows: NaOH extraction/acid precipitation (NaOH-IE); water extraction/acid precipitation (H2O-IE); NaOH extraction/cryoprecipitation (NaOH-CP) and citric acid extraction/cryoprecipitation (CA-CP). NaOH-CP and CA-CP each resulted in precipitation of one protein mainly consisting of glycinin and beta-conglycinin, respectively. The proteins were subjected to polyacrylamide gel electrophoresis (PAGE), SDS-PAGE, size exclusion-chromatography (SEC) and differential scanning calorimetry (DSC) for characterization. PAGE, SDS-PAGE, SEC and DSC confirmed the homogeneity of NaOH-CP. The gelation properties and structural characteristics of NaOH-CP were investigated; the minimum protein concentration required for formation of a thermally-induced gel from NaOH-CP was 8%. With cold-set gelation, in the presence of 30 mM CaCl2, the minimum protein concentration required for formation of a self-supporting gel was 4%. At 100 mM CaCl 2, cold-set gelation of 10% protein concentration gave gel of strength 7.4 N compared to the 7.8 N gel strength obtained with thermally-induced gel at 16% protein concentration. The effects of heating on the NaOH-CP structure, in the presence of varying concentrations of NaCl and reducing agents, were examined by Fourier transform infrared (FTIR) spectroscopy and DSC. FTIR spectroscopy revealed that at 25°C the NaOH-CP protein showed four bands at 1633, 1650, 1667, and 1689 cm-1. At 85°C, the temperature associated with gelation, the four bands decreased in intensity with the simultaneous increase in the intensity of a band at 1644 cm-1 as result of the protein unfolding, furthermore two new bands at 1616 and 1685 cm -1 appeared. The latter two bands are attributed to intermolecular mu-sheet formed during gelation. The NaOH-CP did not exhibit any aggregation band between 25--100°C in the presence of NaCl. The DSC studies revealed that the protein denatured at approximately 102°

The fundamentals of the photopolymerization process are not well understood. As a result, issues affecting the cure speed and overall quality of the final product (shape, size, and surface finish) of photopolymerization impose significant limitations on applications that require fast processing and high spatial resolution. To address this issue, microrheology was employed to perform in-situ monitoring of the liquid-to-gel transition during free-radical photopolymerization. Photosensitive acrylate and hydrogel resins were exposed to ultraviolet light, while the Brownian motion of micrometer sized, inert fluorescent tracer particles was tracked via optical videomicroscopy. Statistical analysis of particle motion yielded the rheological properties of the embedding medium as a function of time and location, thereby relating UV exposure to the progress of polymerization and gelation. The microrheological setup enabled a detailed study of three-dimensional gelation profiles; other experimental parameters that were initially varied include photoinitiator concentration, monomer composition, and light intensity. Significant changes in gelation time were observed with varying UV intensity and UV penetration depth into the sample. In addition, oxygen inhibition was found to significantly impact the cure speed of monomeric resins. The preliminary results were used to test the accuracy of the energy threshold model, which is often used to empirically predict the outcome of photopolymerization reactions. By using lithographic masks to generate well-defined UV illumination patterns with characteristic dimensions of tens of micrometers, it could be shown unambiguously that the diffusion of oxygen, an inhibitor, plays a critical role in the polymerization reaction. The experiments are in excellent agreement with a simple two-step model of oxygen consumption followed by polymerization. The use of high-speed electronic shutters in the UV light path enabled us to control the illumination time of the samples with high precision. Microrheological analysis could be used to reconstruct three-dimensional profiles of partially polymerized samples. Traditional photorheometry is not capable of resolving the evolution of sample rheology with such spatial resolution. In addition, experiments with pulsed illumination were used to quantify the role of dark reactions due to residual free radicals after termination of UV illumination.

Nanomaterials are currently attracting billions of dollars in research funding and are entering such diverse fields as the computing, communications, life science and energy sectors. The growing popularity of nanomaterials demands a comprehensive understanding of the means by which such materials can be produced including the effects of physical and chemical factors. One method of forming inorganic nanomaterials is the sol-gel process; a low temperature process combining the benefits of glass and plastics technology. Whilst the research community has ascertained that gravity is important and appears to affect the sol-gel process, no coherent picture of the role of gravity on the sol-gel process has been proposed. The flexibility of the sol-gel process, and the promise it holds for creating products as diverse as hydrogen fuel cell membranes through to protective coatings for space vehicles, make it an important area of study. This thesis addressed a fundamental gap in the scientific knowledge concerned with the sol-gel process: how and why does gravity affect the sol-gel process? The nanomaterial chosen for study was a xerogel, a dense compound with a high surface area which finds applications in high temperature ceramics, energy saving coatings, molecular filtration and thin film sensors. The xerogel was produced from an acid catalysed sol. 2ml samples of the sol were subjected to reduced, normal and high gravity levels, and the resultant xerogels were characterised through liquid and solid state NMR and nitrogen adsorption/desorption techniques. Viscosity and pH measurements were also recorded. Reduced gravity conditions were provided by NASA’s KC-135 aircraft which is capable of creating a 25 second window of 1x10−2 gravities. A centrifuge was utilised to simulate increased gravity environments and xerogels were formed between 2 and 70 gravities. Analysis of the results led to two major contributions to this field of scientific endeavour. It was concluded that (1) gravity affected the reaction pathways of the sol-gel process and (2) gravity directly altered the molecular structure of xerogels The second contribution was determined through the NMR studies, where it was shown that a reduction in gravity resulted in a molecular structure composed of extended branches of cyclic compounds. Due to a decrease in convection in reduced gravity the molecular structure of the sample was dominated by cyclisation. In terrestrial and high gravity the molecular structure grew through both bimolecularisation and cyclisation reactions. Thus the gravity level also determined the reaction pathway available within the sol by creating a more or less convective environment. This created a structure composed of cyclics (rings) and chains. As gelation and drying of the sol occurred there was a loss in Q4 group amount. Chains, having a higher energy configuration than rings, underwent repolymerisation. Short chains formed which reacted end-to-end to form small, stable rings. The rings packed together more closely within the liquid sol and delayed the formation of a spanning cluster. The greater the gravity level, the greater the extent of bimolecularisation reactions contributing to chain formation, in turn allowing a greater degree of repolymerisation of the molecular structure. Thus gel times increased as the gravity level increased. Again gravity directly affected the reaction pathway of the sol-gel process. In reduced gravity the sol gelled very quickly due to the formation of a cyclic structure which was not capable of repolymerisation. The final contribution of this thesis was the proposal of a mechanistic model. The model depicted the ffect of gravity on the formation of the molecular structure of a xerogel.

Thesis (M.Sc. (Tech.))--University of Waikato, 2006. / Title from PDF cover (viewed March 5, 2008). Includes bibliographical references (p. 107-110)

Orientador: Aulus Cavalieri Carciofi / Coorientador: Thaila Cristina Putarov / Banca: Alexandre de Mello Kessçer / Banca: Jane Maria Bertocco Ezequiel / Resumo: O uso generalizado da tecnologia de extrusão em alimentos para cães deve-se ao fato desta promover mudanças físicas e químicas no ingrediente tornando possível seu uso na alimentação animal. Estas mudanças ocorrem principalmente devido a aplicação de energia térmica especifica (ETE) e energia mecânica especifica (EME) aplicada ao processo de extrusão. Diversos estudos evidenciam o uso e a quantidade de EME para o adequado processamento de alimentos, contudo, ainda se desconhecem as diferenças nutricionais e a influência na macroestrutura dos kibbles resultantes do cozimento por ETE em relação a aqueles obtidos pela aplicação de EME. Desta forma, os objetivos deste estudo foram avaliar a aplicação de seis quantidades de energia térmica específica (ETE) no pré-condicionador, em dois sistemas de extrusão, sobre os parâmetros de processo, a gelatinização do amido, a macroestrutura dos kibbles, a digestibilidade in vitro e in vivo de alimento para cães e produtos da fermentação microbiana no cólon. O estudo foi dividido em dois experimentos. O primeiro experimento avaliou o efeito da aplicação de ETE em dois sistemas de extrusão sobre os parâmetros de processo e a partir destes resultados, as dietas que apresentaram maior variação em relação ao cozimento do amido foram utilizadas para o segundo experimento que avaliou a digestibilidade, produtos da fermentação e palatabilidade de rações para cães. Uma dieta padrão para cães adultos em manutenção foi formulada de acordo com as reco... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: - The generalized use of extrusion in pet food is due to the modification of the physical and chemical characteristics of the ingredient, which make possible its use in animal food. These changes occur mainly due to the application of specific thermal energy (STE) and specific mechanical energy (SME) to the extrusion process. Several studies demonstrate the suitable use and quantity of SME for proper pet food processing, however, there are no information about the STE application to the conditioner on the nutritional differences and its influences on the macrostructure of kibbles of dog food. Thus, the objectives of this study were to evaluate the application of six amounts of specific thermal energy (STE) in the preconditioner, in two extrusion systems, on the process parameters, starch gelatinization, macrostructure of kibbles, in vitro and in vivo digestibility and fermentation products of dog food. The study was divided in two experiments. The first experiment evaluated the effect of STE application in two extrusion systems on process parameters and from these results, the diets with higher amplitude of starch cooking were used for the second experiment, which evaluated the digestibility, fermentation products and palatability of dog food. A standard diet for adult dogs in maintenance was formulated according to the nutritional recommendations of the Fédération Européenne de I'industrie des Aliments pour Animaux familiers (FEDIAF, 2014). The diets were produced in the extruder Wenger X-20 (extruder A) and extruder Manzoni Mex-250 (extruder B) by the modulation of water and steam addition to reach the desired temperatures which correspond to application of six STE (temperatures: 45°C, 55°C, 65°C, 75°C, 85°C, 95°C). For the first experiment, a completely randomized design in a ... ((Complete abstract click electronic access below) / Mestre

Orientadores: Antonio Carlos Bannwart, Vanessa Cristina Bizotto Guersoni / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica e Intituto de Geociências / Made available in DSpace on 2018-08-23T12:53:21Z (GMT). No. of bitstreams: 1 Luthi_IvanaFlores_M.pdf: 8342331 bytes, checksum: f3ec460359159b1e4595a11295e8bb23 (MD5) Previous issue date: 2013 / Resumo: O escoamento de petróleo através de linhas flexíveis submarinas está sujeito a paradas de produção por razões operacionais ou emergenciais. Na produção de óleos parafínicos em águas profundas (baixa temperatura do ambiente marinho, cerca de 4 °C) essas paradas podem causar o resfriamento abaixo do ponto de fluidez desses óleos. Nesta situação, uma estrutura gelificada é formada, composta por cristais de parafinas distribuídos em uma matriz viscosa, a qual bloqueia a linha de produção. A formação deste gel, bem como seu envelhecimento, representa sérios problemas para o processo de repartida, pois a pressão necessária para fazer fluir o óleo gelificado e consequentemente, retomar o escoamento na linha de produção, torna-se maior que a pressão normal de operação da linha. Para melhor compreensão do processo de retomada de escoamento, análises físico-químicas e reológicas, bem como testes de repartida, foram realizadas. Por meio de um reômetro, parâmetros essenciais que descrevem o comportamento reológico de um óleo parafínico cru, como TIAC (Temperatura Inicial de Aparecimento de Cristais), curvas de fluxo, tensão mínima de escoamento e tixotropia, foram caracterizados. Medições de tensão mínima de escoamento podem ser utilizadas para estimar a pressão mínima de repartida. No entanto, como o processo de fluência do gel é dependente do tempo, a tixotropia torna-se relevante e assim, o tempo necessário para desobstruir uma linha bloqueada com óleo gelificado dependerá principalmente da pressão aplicada e da viscosidade aparente, a qual decai com o tempo. Além disso, efeitos de encolhimento térmico e compressibilidade devido ao resfriamento e envelhecimento do óleo parafínico também devem ser considerados. Assim, testes de repartida foram realizados em uma linha horizontal bloqueada com óleo parafínico gelificado. Os resultados analisados foram comparados com as características reológicas estudadas. Dessa forma, foi verificado que o envelhecimento influencia na estruturação da rede de cristais de parafinas formada. A fluência do óleo parafínico é fortemente dependente do tempo. O caráter tixotrópico do óleo parafínico foi revelado mostrando que este fator deve ser considerado nas análises de repartida. Assim, os testes de repartida na linha horizontal confirmaram que o processo de retomada do escoamento em uma linha gelificada possui forte dependência com as complexas propriedades reológicas do gel parafínico, além de uma propagação inicial da pressão durante a repartida. Portanto, quando esses fenômenos não são considerados, custos operacionais desnecessários são envolvidos, visto que pressões superestimadas são utilizadas no dimensionamento do sistema de bombeio / Abstract: Subsea deepwater flowlines transporting crudes are subjected to shutdowns for operational or emergency reasons. In the offshore deepwater production of waxy crudes, the low temperature of the surrounding seawater may lead the oil to cool below its pour point. In this situation, a gelled structure composed of paraffin crystals distributed through a viscous matrix is formed, blocking the flowline. The formation of this gel, as well as its aging, present serious complications for the flow restart process, since the required pumping pressure becomes greater than the normal operating pressure. To better understand the restart process, rheological tests and restart pressure measurements in a pipe were performed for a waxy crude. Using a rheometer, essential parameters that describe the behavior of the waxy crude, such as WAT (Wax Appearance Temperature), flow curves, yield stress and thixotropy were characterized. Yield stress measurements can be used to estimate the minimum pressure required to restart the flow. However, as the yielding process is time-dependent, related phenomena such as thixotropy is relevant for the gel breakup, because the time required to restart a line blocked with gelled waxy oil depends mainly on the applied pressure and apparent viscosity which decreases with time. Furthermore, effects of thermal shrinkage and compressibility due to cooling and aging may also be considered. Thus, start-up tests were also performed in a horizontal pipeline blocked with gelled waxy crude oil. The results were compared to the rheological characteristics determined by rheometery. Thus, it was verified that aging time influences the structure of the wax crystals network formed. The flow of paraffin oils is highly dependent on time. The thixotropic character of paraffin oil was revealed, showing this factor must be considered in the restart analyzes. The restart tests in the horizontal line confirmed that the restart process has close connection with the complex rheological properties of gelled crudes and also, that this process has an initial pressure propagation. Therefore, when these phenomena are not considered, the use of conservative pressure values would lead to pump oversizing and unnecessary operational costs / Mestrado / Explotação / Mestra em Ciências e Engenharia de Petróleo