Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

There are concerns about using synthetic phenolic antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) as food additives because negative effects to human health have been reported. thus, a replacement of these synthetics by antioxidant extractions from various foods has been proposed. By the generation of more than eight thousand different phenolics, fruits and vegetables are the prime sources of natural antioxidants. The consumption of fruits and vegetables has been strongly linked with several health benefits, a result of their medicinal properties and high nutritional value. Antioxidants control and reduce the oxidative damage in foods by delaying or inhibiting oxidation caused by reactive oxygen species (ROHs); ultimately increasing the shelf-life and quality of these foods.Beta-carotene, ascorbic acid, and many phenolics play dynamic roles in delaying aging, reducing inflammations, and preventing certain cancers. Increasing the consumption of fruits and vegetables has been recommended by many agencies and health care systems. In order to extract, measure, and identify bioactive compounds from a wide variety of fruits and vegetables, researchers use many different techniques and methods. Ultrasonic assisted technique (UAE) is known to be one of the easiest extraction techniques because it uses common laboratory equipment such as ultrasonic baths and probes. In this technique, a smashed sample is mixed with the suitable solvent and placed into the ultrasonic bath while temperature and extraction time are controlled. Five experiments were conducted to study the effects of different ultrasonic parameters on the polyphenol and antioxidant content and antimicrobial activity of extracts from plants grown in southern Illinois. In the first experiment, ultrasonic treatments at different frequencies,temperatures, power levels, and exposure times were compared for their effects on the yield of total phenolics, total flavonoids and antioxidant activities of spinach extracts. The best conditions for extraction judged by yields were an ultrasonic frequency of 37 kHz, extraction time of 30 min, reaction temperature of 400C, and ultrasonic power of 50%. The mean yield (mg/100g), total phenolics (mg gallic acid equivalence/ g DW), flavonoids (mg/g DW), % DPPH free radical scavenging activity, and % ferric reducing antioxidant power were all high (64.88±21.84, 33.96±11.30, 27.37±11.85 , 64.18±16.69 and 70.25 ±9.68). In the second experiment, the study was designed to optimize ultrasonic-assisted extraction of lutein and β-carotene from spinach. Further, the identities and purity of the natural products in the TLC spots were assayed using matrix-assisted laser desorption/ionization time-off-light mass spectrometry (MALDI-TOF MS) analysis. The optimal UAE settings for output of lutein and β-carotene simultaneously from spinach extracts were an extraction temperature of 40 °C, extraction power of 40% (28 W/cm3) and extraction time of 16 min. UAE assisted extraction of carotenes from spinach can provide a source of lutein and β-carotene for the dietary supplement industry. In the third study, investigations of the effects of extraction parameters for UAE on antioxidant activity of peach and pumpkin extracts; and studying the chemical structures of samples before and after processing by Fourier transformed infrared spectroscopy were made. The optimal conditions for peach extracts were an extraction temperature of 41.53 ̊C, power of 43.99 % and time of 27.86 min for total phenolics. The optimal conditions for extractions of total phenolics from pumpkins were inferred to be a temperature of 41.45 ̊C, a power of 44.60 % and a time of 25.67 min. In the fourth study, TLC followed by Quantity-OneTM (Biorad) image analysis was used as a simple and rapid method for identification and quantification of compounds in complex mixtures. The results were consistent under optimal conditions among the experimental values and their predicted values. The MALDI-TOF MS technique was also applied for result confirmation. In the last experiments, UAE and Box-Wilson design were applied to optimize the extraction of antimicrobial activities from spinach extracts and to test their antimicrobial activities on both Gram-negative and Gram-positive bacteria. The spinach extracts exhibited antimicrobial activities against both bacterial pathogens with MICs in the 60-100 mg.ml-1 range. SEM showed that cells of the treated bacterial strains were damaged and showed structural defects compared to the controls. RAPD analysis of genomic DNA showed that the number and sizes of amplicons were decreased for the treated pathogens compared with non-treated strains.

Glycerol thermal processing (GTP) is studied as a novel biomass pretreatment method in this research with the purposes to facilitate biopolymer fractionation and biomass saccharification. This approach is performed by treating sweet gum particles on polymer processing equipment at high temperatures and short times in the presence of anhydrous glycerol. Nine severity conditions are studied to assess the impact of time and temperature during the processing on biopolymer structure and conversion. The GTP pretreatment results in the disruption of cell wall networks by increasing the removal of side-chain sugars and lignin-carbohydrate linkages based on severity conditions. After pretreatment, 41% of the lignin and 68% of the xylan is recovered in a dry powdered form by subsequent extractions without additional catalysts, leaving a relatively pure cellulose fraction, 84% glucan, as found in chemical pulps. Lignin structural analysis indicated GTP processing resulted in extensive degradation of B-aryl ether bonds through the C-y elimination, followed by abundant phenolic hydroxyl liberation. At the same time, condensation occurred in the GTP lignin, providing relatively high molecular weight, near to that of the enzymatic mild acidolysis lignin. Better thermal stability was observed for this GTP lignin. In addition to lignin, xylan was successfully isolated as another polymer stream after GTP pretreatment. The recovered water insoluble xylan (WIX) was predominant alkali soluble fraction with a maximum purity of 84% and comparable molecular weight to xylan isolated from non-pretreated fibers. Additionally, the narrow molecular weight distribution of recovered WIX, was arisen from the pre-extraction of low molecular weight water-soluble xylan. Additionally, a 20-fold increase of the ultimate enzymatic saccharification for GTP pretreated biomass was observed even with significant amounts of lignin and xylan remaining on the non-extracted fiber. The shear and heat processing caused a disintegrated cell wall structure with formation of biomass debris and release of cellulose fibrils, enhancing surface area and most likely porosity. These structural changes were responsible for the improved biomass digestibility. Additionally, no significant inhibitory compounds for saccharification are produced during GTP processing, even at high temperatures. While lignin extraction did not promote improvement in hydrolysis rates, further xylan extraction greatly increases the initial enzymatic hydrolysis rate and final level of saccharification. The serial of studies fully demonstrate glycerol thermal processing as a novel pretreatment method to enhance biomass saccharification for biofuel production, as well as facilitate biopolymer fractionation. Moreover, the study shows the impact of thermally introduced structural changes to wood biopolymers when heated in anhydrous environments in the presence of hydrogen bonding solvent. / Ph. D.

No description available.

O principal objetivo do trabalho foi desenvolver uma ferramenta de simulação, para servir de base para o projeto e dimensionamento de processos contínuos de pasteurização de alimentos líquidos em trocadores de calor a placas, possibilitando minimizar perdas de qualidade sensorial e nutricional, bem como gastos desnecessários com aquecimento e resfriamento, decorrentes do sobreprocessamento, tendo o controle sobre o histórico de temperatura. Foi desenvolvida uma modelagem matemática para o processo contínuo de pasteurização HTST (High Temperature Short Time) de leite em trocador de calor a placas com três seções, para determinação da distribuição de temperatura ao longo do processo e avaliação do impacto sobre o leite. Foram desenvolvidos três modelos e seus resultados confrontados com os dados experimentais, realizados com água e leite. Os três modelos forneceram resultados similares e próximos ao comportamento experimental. O cálculo de letalidade permitiu detectar sobreprocessamento no processo estudado. Ensaios com indicador enzimático (fosfatase alcalina em tampão fosfato) foram realizados para quantificar o impacto do processo sobre o produto e comparar com a letalidade calculada pelos modelos. / The aim of this work was to develop a simulation tool to be used in the design of continuous pasteurization of liquid foods using plate heat exchangers, enabling to minimize the nutritional and sensorial losses as well as unnecessary costs during heating and cooling, caused by the overprocessing. The control is made by the temperature profile. A mathematical model was developed for continuous milk HTST (High Temperature Short Time) pasteurization with a three section plate heat exchanger to determine the temperature profile and to evaluate the process impact on the product. Three models were tested and the simulation results compared with the experimental data using water and milk. The results of the three models were similar among them and close to the experimental behavior. Calculating the lethality of the process showed it was overprocessing the product. Tests using enzymatic indicator (alkaline phosphatase in phosphate buffer) were held to quantify the impact of the process on the product and compare to the lethality calculated using the models.

A demanda por produtos industrializados que apresentem máxima preservação de suas características naturais têm crescido e feito as indústrias alimentícias re-analisarem seus processos para atingirem essa necessidade do mercado. A abordagem convencional conservadora, utilizada para o dimensionamento do processamento térmico de alimentos, pode levar ao sobre-processamento especialmente no regime laminar, devido às significativas distribuições de temperatura e tempos de residência existentes. Um modelo matemático, composto por equações diferenciais de massa e energia foi elaborado, considerando o processamento térmico de um fluido não-newtoniano, sob regime laminar, escoando em um trocador de calor bitubular. No modelo, se levou em conta as dispersões efetivas de massa e energia associadas com o escoamento laminar não ideal, as trocas de calor com o ambiente, a letalidade que ocorre no aquecimento e resfriamento e o perfil de velocidade. O modelo foi testado por meio de simulações do estudo de caso do processamento térmico de suco de graviola (fluido pseudoplástico) considerando a destruição de bolores e leveduras. Objetivou-se nas simulações avaliar o efeito de distintas considerações do modelo nas variáveis consideradas. Os resultados indicaram que as etapas de aquecimento e resfriamento contribuíram de forma significativa na letalidade do processo, assim como as considerações quanto às dispersões de massa e energia. Como exemplo, as letalidades, considerando a abordagem convencional (tubo de retenção isotérmico com velocidade máxima) e o modelo completo (com todas as considerações) apresentaram valores de 1,46 e 5,74, respectivamente. A flexibilidade do modelo elaborado, assim como os tempos computacionais pequenos necessários para obter os resultados são as principais vantagens do uso do mesmo. Acredita-se que o modelo elaborado pode contribuir de forma importante para o correto dimensionamento e avaliação de processos térmicos em indústrias de alimentos, permitindo que a demanda dos consumidores seja atendida. / The demand for industrialized food with maximum retention of sensorial and nutritional attributes has grown and made the food industries rethink operational conditions to meet this market expectation. The classic conservative approach, used for the design of thermal food processing can lead to over-processing specially in laminar regime, due to the existing significant temperature and residence time distributions. A mathematical model, comprising differential equations for mass and heat transfer was elaborated, considering the thermal processing of a non-Newtonian liquid, under laminar flow in a double-pipe heat exchanger. In the model, it was taken into account the effective mass and energy dispersions associated with the non-ideal laminar flow, the heat exchange with the ambient, the contribution from heating and cooling sections in the lethality and the velocity profile. The model was tested through simulations of a study case of soursop juice processing (pseudoplastic fluid) regarding the destruction of yeast and molds. The objective of the simulations was to evaluate the effect of distinct model assumptions on the variables. The results indicated that the heating and cooling sections and the assumptions regarding the effective mass and energy dispersions had an important contribution to the processing lethality. As an example, the lethality, regarding the conventional approach (isothermal holding tube at the maximum velocity) and the complete model (with all the assumptions) were 1.46 and 5.74, respectively. The model flexibility and the small computational time needed for the results to the obtained are the main advantages of its use. It is expected that the developed model can be an important contribution to the correct design and evaluation of thermal processing in food industries, allowing the consumer demands to the reached.

Os trocadores de calor tubulares são muito utilizados para o processamento térmico de alimentos líquidos viscosos por possuírem um maior diâmetro hidráulico em comparação aos trocadores de calor a placas. O cálculo da letalidade neste tipo de trocador está diretamente relacionado ao perfil de velocidade e à distribuição do tempo de residência (DTR). Para escoamento laminar de fluidos viscosos, Newtonianos e não-Newtonianos, geralmente adota-se um perfil de velocidade laminar e de lei de potência, respectivamente. No entanto, algumas características do equipamento como irregularidades na tubulação, a corrugação do tubo ou as curvas podem modificar o perfil de velocidade ideal. Esse desvio da idealidade pode ser caracterizado através da determinação experimental da distribuição do tempo de residência do processo. Este trabalho teve como objetivo a determinação experimental da DTR de fluidos viscosos em um equipamento bitubular de processamento térmico e o ajuste do perfil de velocidade associado. Modelos clássicos de DTR foram ajustados aos dados, assim como foram propostos e testados novos modelos generalizados de DTR, a fim de caracterizar o escoamento laminar não ideal em tubos. A determinação da DTR experimental foi realizada para vazões entre 10 e 50 L/h utilizando água, solução de carboximeticelulose 1,0% (pseudoplástico) e mistura glicerina/água 80%. Os dados de DTR foram obtidos através de duas técnicas: condutimétrica e colorimétrica. A primeira técnica baseia-se na injeção de solução saturada de cloreto de sódio e detecção online por um condutivímetro, porém, não apresentou resultados satisfatórios mostrando que o método não é adequado para fluidos viscosos. Já a segunda técnica utilizada se baseia na injeção de corante e posterior detecção em espectrofotômetro. Os modelos que melhor se ajustaram aos dados experimentais para os três fluidos estudados foram os modelos generalizados y-laminar e exponencial. A letalidade foi calculada a partir da distribuição de temperatura no trocador de calor em estado estacionário e do tempo médio de residência obtido experimentalmente e permitiu detectar o sobreprocessamento no processo estudado. / Tubular heat exchangers are widely used for thermal processing of viscous liquid foods because they have larger hydraulic diameters than the plate heat exchangers. The calculation of lethality in this type of exchanger is directly related to velocity profile and the residence time distribution (RTD). For the laminar flow of viscous fluids, Newtonian and non-Newtonian, generally laminar and power law velocity profiles are used, respectively. However, some features of the equipment as irregularities in the pipe, the corrugation of the pipe or the presence of curves can change the ideal velocity profile. This ideality deviation can be characterized through the experimental determination of the residence time distribution of the process. The aim of this work was the experimental determination of the RTD of a viscous fluid in a bitubular thermal processing equipment and the determination of the associated velocity profile. Classic models of RTD were fitted to the data, as well as were proposed and tested new generalized models of RTD, in order to characterize the non ideal laminar flow in tubes. The experimental determination of RTD was performed to volumetric flow rates between 10 and 50 L/h using water, carboximeticelulose solution 1,0% (pseudoplastic) and glycerin/water mixture 80%. The RTD data were obtained through two techniques: conductimetric and colorimetric. The first technique is based on injection of saturated solution of sodium chloride and online detection with a conductivimeter however, unsatisfactory results showed that the method was not suitable for viscous fluids. The second technique is based on the injection of dye and subsequent detection with a spectrophotometer. The best fitted models to the experimental data for the three studied fluids were: ylaminar and exponential generalized models. The lethality was calculated from the temperature distribution in the heat exchanger at steady state and average residence time obtained experimentally and allowed the evaluation of the overprocessing of this process.

O processamento térmico contínuo usando trocadores de calor é uma forma muito comum de industrialização de alimentos líquidos. Atrelada à inativação de micro-organismos e enzimas pela alta temperatura, está a perda de qualidade do produto; portanto, o estudo e avaliação deste tipo de processo é fundamental para garantir a inocuidade e a melhora da qualidade do produto. Neste trabalho foi desenvolvida a modelagem matemática de um processo térmico contínuo em trocadores bitubulares para determinação da distribuição da temperatura média do produto e da letalidade sobre um atributo de segurança ou qualidade. No modelo, foram considerados os trocadores de aquecimento e de resfriamento, bem como o tubo de retenção. Admitiu-se regime permanente, escoamento pistonado e leva-se em conta a troca de energia com o ambiente. Para a aplicação do modelo, foi adotado um sistema em escala de laboratório com vazão de processamento entre 10 e 50 L/h, trocadores com quatro módulos de troca térmica e área total de 0,13 m² e sistema de indicação e aquisição de dados de temperatura. Como fluidos de trabalho foram usados: mistura de glicerina/água 80 % (Newtoniano) e solução 1 % de carboxi-metil-celulose (CMC, não-Newtoniano). Fluidos e utilidade foram água quente pressurizada e água gelada. Os parâmetros de troca térmica do modelo foram ajustados com sucesso através de ensaios experimentais. Foram ajustados: 1) coeficientes de convecção natural do ar sobre as seções de aquecimento e de resfriamento; 2) parâmetros da correlação de Nusselt x Reynolds para o coeficiente de convecção dos fluidos de trabalho; 3) coeficiente global de troca térmica com o ambiente no tubo de retenção. A validação do modelo ajustado foi realizada através da comparação das distribuições de temperatura experimental com a predição do modelo. A letalidade, levando em conta o tempo espacial no percurso do produto foi calculada e avaliada, indicando importante contribuição da seção de aquecimento e forte influência da elevação de temperatura na entrada do tubo de retenção para compensar as perdas para o ambiente. O modelo proposto mostra-se útil para a avaliação de processos térmicos em sistemas tubulares. / The continuous thermal processing using heat exchangers is a very usual form of industrialization of liquid foods. Linked to the inactivation of microorganisms and enzymes by high temperature is the loss of product quality; thus, the study and evaluation of this type of process is critical to ensure the safety and improve product quality. In this work, it was developed a mathematical model of a continuous process with tubular heat exchangers to determine the distribution of the average temperature of the product and the lethality considering a safety or quality attribute. In the model, are considered the exchangers for heating and cooling and the holding tube. It was assumed steady state plug-flow and it was taken into account the energy exchange with the ambient air. For the application of the model, it was adopted a laboratory system with processing flow rate between 10 and 50 L/h, exchangers with four heat transfer modules and total area of 0.13 m² and a temperature indication and acquisition system. The working fluids used were: a mixture of glycerol/water 80 % (Newtonian) and a 1 % solution of carboxymethylcellulose (CMC, non-Newtonian). Utility fluids were pressurized hot water and cold water. The heat transfer parameters of the model were adjusted successfully using the experimental data. Were adjusted: 1) the coefficients of natural convection of the air over the heating and cooling sections; 2) the parameters of the Nusselt x Reynolds correlation for the convective coefficient of the working fluid; 3) the overall heat exchange coefficient between the product and the ambient air in the holding tube. The validation of the fitted model was performed by comparing the experimental temperature distributions with the prediction from the model. Lethality, taking into account the space-time in the path of the product was calculated and evaluated, indicating a significant contribution of the heating section and a strong influence on the temperature rise in the entrance of the holding tube to compensate for losses to the surroundings. The model proves useful for the evaluation of thermal processes in tubular systems.

<p>Mathematical modeling of heat transfer is a common method utilized in designing thermal processes for food, modeling degradation kinetics of microorganisms and nutrients, designing food processing equipment as well as for process optimization and for ensuring scale-up feasibility of a product. It is essential to have all the necessary components for modeling including the geometry, boundary conditions, initial temperature, and the temperature-dependent thermal properties. Getting temperature-dependent thermal properties of food product is difficult due to the lack of effective and efficient devices or techniques. To show the influence of temperature-dependent thermal properties, retort processing of potato soup was simulated using both temperature-dependent (dynamic) and fixed thermal properties. Three methods, TPCell, Choi-Okos predictive model and KD2 Pro, were used to determine the thermal conductivity at 25°C and 120°C for comparison. The proximate composition of the sample was determined for prediction of thermal properties with the Choi-Okos model. The accuracy of simulation was evaluated based on the temperature at the cold spot and corresponding sterilization value. Results suggested that using temperature-dependent thermal properties in heat transfer modeling increased the accuracy of the simulation. Simulation performed with temperature-dependent properties obtained from TPCell matched very closely with experimental heat penetration data. Additionally, the sensitivity of temperature-dependent thermal properties obtained from TPCell in detecting variation in product formulation was evaluated. Four variations of potato soup were prepared to compare their respective lethality value. Thermal conductivity, specific heat capacity and density of the potato soups were measured, and simulation was performed using the measured thermal properties and a scheduled process as boundary conditions. Thermal properties of food product changed with the formulation which affected the processing time to achieve minimum lethality value. A significant difference in thermal conductivities was seen for these potato soups causing the scheduled process to be only suitable for thermal processing of some formulations while others would be undercooked that could lead to food safety risk. Since the thermal conductivity measurements were sensitive in detecting the difference in the formulation, it can be used as a tool to select a formulation that can best suit the processing conditions of the heat penetration tests. The technique described can be used for any thermal processes in the food industry including pasteurization, retort, and aseptic processing. This application will be beneficial for the industry to pre-screen the iterations and only select formulation that suits the scheduled process for successful heat penetration trials and reduce trial costs.</p>

Neste trabalho foram crescidos filmes finos de oxinitreto de silício (SiOxNy) por processamento térmico rápido (RTP) utilizando um forno térmico convencional adaptado, objetivando fabricar células solares MOS com baixo custo agregado e bom rendimento de conversão de baixas intensidades luminosas em energia elétrica de forma reprodutível. A receita de oxinitretação otimizada foi desenvolvida em ambiente misto de 5N2:1O2 na temperatura de 850°C para tempos de processo, na faixa de 10 a 80s seguido por uma passivação em 2L/min de N2 por 80s. Os dielétricos crescidos foram caracterizados fisicamente quanto à espessura (entre 1,50 e 2,95nm), à microrugosidade (<0,95nmRMS) e à concentração de nitrogênio (1,0-2,1%atm). As características de tunelamento foram investigadas em capacitores MOS e apontaram para a existência de armadilhas interfaciais do tipo K capazes de armazenar cargas positivas. Nas células solares MOS, a corrente de fundo foi característica para todos os processos de oxinitretação empregados (~0,5-2µA/cm2) e apresentaram níveis de resposta à luz incidente na faixa de 1 a 8mA/cm2 compatível com aplicações de conversão de energia em ambientes internos e externos (energy harvesting). A característica densidade de corrente x tensão de porta (JxVG) das células solares apresentou um comportamento aproximadamente linear desde a densidade de corrente de curto-circuito (JSC) até a tensão de curto-circuito (VOC) implicando em potência gerada máximas (PGmáx) de até centenas de µA/cm2 para VG ? VOC/2 para uma ampla faixa de intensidade radiante incidente (11,8 - 105,7mW/cm2) alcançando rendimentos de conversão de até 5,5%. / In this work, silicon oxynitrides (SiOxNy) were grown by means of a homemade Rapid Thermal Processing (RTP). The goal was to manufacture MOS solar cells with a reduced price and reasonable light conversion efficiency for low light intensity. The optimized oxidation recipe consisted of using an environment with gas mixture of 5N2:1O2 at a temperature of 850°C and different processing times in the range of 10 to 80s followed by a passivation step in ultrapure N2 (2L/min) at the same temperature of 850oC for 80s. The oxynitrides were grown with thickness in the range of 1.50 to 2.95nm with surface microroughness lower than 0.95nmRMS and nitrogen concentration in the range of 1.0 to 2.1%atm. The tunneling characteristics were studied with the aid of MOS capacitor and K-type interfacial traps related to Si(p)/Si?N structure were detected positively charged for VG > 0. The background current in the MOS solar cells (~0.5-2µA/cm2) were similar for all samples and the current response to the incident light was in the range of 1 to 8mA/cm2, which is compatible with energy conversion for indoor and outdoor environments (energy harvesting). The current density x gate voltage (JxVG) characteristics of the MOS solar cells presented a nearly linear behavior since the short-circuit current density (JSC) till to the open circuit voltage (VOC) so that the maximum generated power was of hundreds of µA/cm2 for VG ? VOC/2 for a large range of radiant intensities (11.8 - 105.7 mW/cm2) and achieving efficiency conversion up to 5.5%.