A utilização de subprodutos provenientes da indústria de alimentos tem como objetivo agregar valor aos mesmos propiciando o desenvolvimento de novas propostas para o uso de tecnologias ainda não consolidadas pela indústria. No caso do beneficiamento de arroz polido, além da extração das proteínas dos grãos quebrados, uma nova proposta seria a extração do amido presente nestes grãos. Neste contexto, os objetivos deste trabalho são testar um método alternativo para a separação do amido do restante dos componentes do grão de arroz, o método Al-Hakkak, utilizar a microfiltração para a etapa de concentração/purificação do amido obtido e, ainda, determinar e comparar a composição e as propriedades da farinha e do amido obtido em cada etapa do processo. Foi verificado que as características da solução de amido obtida pós extração têm influência na formação do fouling, reduzindo o fluxo de permeado e contribuindo para o aumento das resistências. O percentual médio de fouling observado foi de 38%; deve-se à resistência por polarização por concentração cerca de 75% da resistência total do sistema. Já o declínio do fluxo de permeado é controlado pelo mecanismo de formação de torta. O método Al-Hakkak de extração de amido foi capaz de reduzir os teores de proteínas, lipídeos e fibra alimentar em aproximadamente 52%, 94% e 82%, respectivamente. O teor de amido diminuiu com a extração, mas aumentou durante o processo de concentração pelo PSM, resultando em percentuais que variaram de 91,59 a 93,67%. Através das imagens obtidas por MEV foi possível visualizar que não houve alteração da estrutura dos grânulos de amido, além disto, se confirmou o formato poliédrico e o tamanho dos grânulos de 3 a 6 μm. O tamanho dos grânulos também foi confirmado pela análise granulométrica. O poder de inchamento (PI) e a solubilidade (IS) dos grânulos das amostras aumentaram com o acréscimo da temperatura. As temperaturas de gelatinização (Tg) apresentaram valores variando de 71,3 a 74,4°C. / The use of by-products from the food industry aims to add value to the same stimulating the development of new proposals for using technologies not yet consolidated the industry. For the improvement of polished rice, besides the extraction of proteins from broken grains a new proposal would be the extraction of the starch present in these grains. In this context, the objectives of this study are to test an alternative method for the separation of starch from the rest of the components of the rice grain, the Al-Hakkak method using microfiltration to stage concentration/purification of starch obtained, and also determine and compare the composition and properties of flour and starch obtained at each step of the process. It was found that the characteristics of the starch solution obtained after extraction influence the formation of fouling, reducing the permeate flux and contributing to the growing resistance. The average percentage of fouling observed was 38% and is due to the concentration polarization resistance by about 75 % of the total resistance of the system. Since the decline of permeate flux is controlled by mecanism of cake block. The Al-Hakkak method for starch extraction was able to reduce the levels of proteins, lipids and dietary fiber, in approximately 52%, 94% and 82%, respectively. The amount of starch decreased after the Al-Hakkak process but increased during the concentration process by PMS, resulting in a percentage ranging from 91.59 to 93.67%. Through the images obtained by SEM was possible to see that there was no change in the structure of starch granules, moreover, confirmed the polyhedral shape and size of granules 3-6 μm. The size of the granules was also confirmed by particle size analysis. The swelling power (PI) and solubility (S) of the granules of the samples increased with increasing temperature. The gelatinization temperatures (Tg) had values ranging from 71.3 to 74.4°C.

A utilização de subprodutos provenientes da indústria de alimentos tem como objetivo agregar valor aos mesmos propiciando o desenvolvimento de novas propostas para o uso de tecnologias ainda não consolidadas pela indústria. No caso do beneficiamento de arroz polido, além da extração das proteínas dos grãos quebrados, uma nova proposta seria a extração do amido presente nestes grãos. Neste contexto, os objetivos deste trabalho são testar um método alternativo para a separação do amido do restante dos componentes do grão de arroz, o método Al-Hakkak, utilizar a microfiltração para a etapa de concentração/purificação do amido obtido e, ainda, determinar e comparar a composição e as propriedades da farinha e do amido obtido em cada etapa do processo. Foi verificado que as características da solução de amido obtida pós extração têm influência na formação do fouling, reduzindo o fluxo de permeado e contribuindo para o aumento das resistências. O percentual médio de fouling observado foi de 38%; deve-se à resistência por polarização por concentração cerca de 75% da resistência total do sistema. Já o declínio do fluxo de permeado é controlado pelo mecanismo de formação de torta. O método Al-Hakkak de extração de amido foi capaz de reduzir os teores de proteínas, lipídeos e fibra alimentar em aproximadamente 52%, 94% e 82%, respectivamente. O teor de amido diminuiu com a extração, mas aumentou durante o processo de concentração pelo PSM, resultando em percentuais que variaram de 91,59 a 93,67%. Através das imagens obtidas por MEV foi possível visualizar que não houve alteração da estrutura dos grânulos de amido, além disto, se confirmou o formato poliédrico e o tamanho dos grânulos de 3 a 6 μm. O tamanho dos grânulos também foi confirmado pela análise granulométrica. O poder de inchamento (PI) e a solubilidade (IS) dos grânulos das amostras aumentaram com o acréscimo da temperatura. As temperaturas de gelatinização (Tg) apresentaram valores variando de 71,3 a 74,4°C. / The use of by-products from the food industry aims to add value to the same stimulating the development of new proposals for using technologies not yet consolidated the industry. For the improvement of polished rice, besides the extraction of proteins from broken grains a new proposal would be the extraction of the starch present in these grains. In this context, the objectives of this study are to test an alternative method for the separation of starch from the rest of the components of the rice grain, the Al-Hakkak method using microfiltration to stage concentration/purification of starch obtained, and also determine and compare the composition and properties of flour and starch obtained at each step of the process. It was found that the characteristics of the starch solution obtained after extraction influence the formation of fouling, reducing the permeate flux and contributing to the growing resistance. The average percentage of fouling observed was 38% and is due to the concentration polarization resistance by about 75 % of the total resistance of the system. Since the decline of permeate flux is controlled by mecanism of cake block. The Al-Hakkak method for starch extraction was able to reduce the levels of proteins, lipids and dietary fiber, in approximately 52%, 94% and 82%, respectively. The amount of starch decreased after the Al-Hakkak process but increased during the concentration process by PMS, resulting in a percentage ranging from 91.59 to 93.67%. Through the images obtained by SEM was possible to see that there was no change in the structure of starch granules, moreover, confirmed the polyhedral shape and size of granules 3-6 μm. The size of the granules was also confirmed by particle size analysis. The swelling power (PI) and solubility (S) of the granules of the samples increased with increasing temperature. The gelatinization temperatures (Tg) had values ranging from 71.3 to 74.4°C.

A utilização de subprodutos provenientes da indústria de alimentos tem como objetivo agregar valor aos mesmos propiciando o desenvolvimento de novas propostas para o uso de tecnologias ainda não consolidadas pela indústria. No caso do beneficiamento de arroz polido, além da extração das proteínas dos grãos quebrados, uma nova proposta seria a extração do amido presente nestes grãos. Neste contexto, os objetivos deste trabalho são testar um método alternativo para a separação do amido do restante dos componentes do grão de arroz, o método Al-Hakkak, utilizar a microfiltração para a etapa de concentração/purificação do amido obtido e, ainda, determinar e comparar a composição e as propriedades da farinha e do amido obtido em cada etapa do processo. Foi verificado que as características da solução de amido obtida pós extração têm influência na formação do fouling, reduzindo o fluxo de permeado e contribuindo para o aumento das resistências. O percentual médio de fouling observado foi de 38%; deve-se à resistência por polarização por concentração cerca de 75% da resistência total do sistema. Já o declínio do fluxo de permeado é controlado pelo mecanismo de formação de torta. O método Al-Hakkak de extração de amido foi capaz de reduzir os teores de proteínas, lipídeos e fibra alimentar em aproximadamente 52%, 94% e 82%, respectivamente. O teor de amido diminuiu com a extração, mas aumentou durante o processo de concentração pelo PSM, resultando em percentuais que variaram de 91,59 a 93,67%. Através das imagens obtidas por MEV foi possível visualizar que não houve alteração da estrutura dos grânulos de amido, além disto, se confirmou o formato poliédrico e o tamanho dos grânulos de 3 a 6 μm. O tamanho dos grânulos também foi confirmado pela análise granulométrica. O poder de inchamento (PI) e a solubilidade (IS) dos grânulos das amostras aumentaram com o acréscimo da temperatura. As temperaturas de gelatinização (Tg) apresentaram valores variando de 71,3 a 74,4°C. / The use of by-products from the food industry aims to add value to the same stimulating the development of new proposals for using technologies not yet consolidated the industry. For the improvement of polished rice, besides the extraction of proteins from broken grains a new proposal would be the extraction of the starch present in these grains. In this context, the objectives of this study are to test an alternative method for the separation of starch from the rest of the components of the rice grain, the Al-Hakkak method using microfiltration to stage concentration/purification of starch obtained, and also determine and compare the composition and properties of flour and starch obtained at each step of the process. It was found that the characteristics of the starch solution obtained after extraction influence the formation of fouling, reducing the permeate flux and contributing to the growing resistance. The average percentage of fouling observed was 38% and is due to the concentration polarization resistance by about 75 % of the total resistance of the system. Since the decline of permeate flux is controlled by mecanism of cake block. The Al-Hakkak method for starch extraction was able to reduce the levels of proteins, lipids and dietary fiber, in approximately 52%, 94% and 82%, respectively. The amount of starch decreased after the Al-Hakkak process but increased during the concentration process by PMS, resulting in a percentage ranging from 91.59 to 93.67%. Through the images obtained by SEM was possible to see that there was no change in the structure of starch granules, moreover, confirmed the polyhedral shape and size of granules 3-6 μm. The size of the granules was also confirmed by particle size analysis. The swelling power (PI) and solubility (S) of the granules of the samples increased with increasing temperature. The gelatinization temperatures (Tg) had values ranging from 71.3 to 74.4°C.

<div>Starch pasting behavior greatly influences the texture of a variety of food products such as canned soup, sauces, baby foods, batter mixes etc. The annual consumption of starch in the U.S. is 3 million metric tons. It is important to characterize the relationship between the structure, composition and architecture of the starch granules with its pasting behavior in order to arrive at a rational methodology to design modified starch of desirable digestion rate and texture. </div><div> In this research, polymer solution theory was applied to predict the evolution of average granule size of starch at different heating temperatures in terms of its molecular weight, second virial coefficient extent of cross-link and electrostatic interaction within a granule. Evolution of granule size distribution of normal maize starch (NMS) and NMS crosslinked to different extents with sodium trimetaphosphate, waxy rice starch, normal rice starch and normal potato starch when subjected to heating at a rate of 15 C/min to 65, 70, 75, 80, 85 and 90 C was characterized using static laser light scattering. As expected, granule swelling was more pronounced at higher temperatures and resulted in a shift of granule size distribution to larger sizes. Most of the swelling occurred within the first 10 min of heating except for potato starch. Novation 1600 (Modified Potato Starch) is also found to shift to larger sizes at longer holding times and higher temperatures, but this shift is found to be gradual and for penpure 80, even at 60 C, the size distribution shifts to smaller sizes at longer holding times indicating breakup of the granule. </div><div> The structure of normal maize starch was characterized by cryo scanning electron microscopy. The number of crosslinks in the starch network was inferred from equilibrium swelling. This is related to peak viscosity and zeta potential of granule for NMS and its crosslinked starches. Chemical potential profile as well as the temperature profile within the granule at different times were predicted which were then employed to evaluate the granule size at different times. The proposed model is able to describe the swelling behavior of different varieties of starch and also the effect of crosslinking. </div><div> The viscoelasticity for different starch types, heating rates, and heating temperatures were characterized. A methodology to predict the storage modulus of starch paste due to granule swelling, given the physical properties of the starch granule is presented. In high-volume fraction regime, classical model for foam rheology enabled calculation of limiting storage modulus for different starches. By scaling the storage modulus with limiting storage modulus, the storage modulus of a wide range of starches forms a master curve. This master curve when employed along with the swelling model resulted in the successful prediction of development of texture for different types of starches. </div><div> In low-volume fraction regime (below 65%), Stokesian dynamics simulations are used to predict the viscoelasticity of polystyrene micro particles and fractionated starch suspension and compared with experiments. Predicted values of storage modulus from stokesian dynamics simulation at 4 HZ for different volume fractions of monodispersed polystyrene spheres of two different sizes namely 25 and 116 micrometer compared well with experimental values. Stokesian dynamics also describes the storage modulus of fractionated starch granules for volume fractions between 0.4 - 0.5</div><div> The average granule size of starch in presence of sucrose was initially increasing and then decreasing with maximum swelling at 5% and 10% sucrose concentration for NMS and WRS. The average granules size continuously increases for WMS and decreases for NRS with increase in sucrose concentration. The Gelatinization Temperature increases with increase in sucrose concentration for all starches. Enthalpy of Gelatinization increases with increase in sucrose concentration for Normal starches where as there is no effect of sucrose concentration for waxy starches. Flory Huggins starch-sucrose interaction parameter was characterized which is used to predict the equilibrium swelling power using a mathematical model proposed to quantitatively describe the equilibrium swelling in the presence of solute (sucrose) based on Flory Huggins polymer solution theory to develop rational guidelines for identification of sugar substitute with desirable functional properties. The model predictions of equilibrium swelling power agrees with experimental results.</div>

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O crescente interesse científico relacionado ao estudo das propriedades dos grãos de arroz vermelho (Oryza glaberrima) e preto (Oryza sativa) está atrelado ao elevado teor nutricional desses grãos. Quando submetidos ao processo de beneficiamento, eles geram subprodutos, entre os quais a quirera e o farelo, ricos em amido e compostos fenólicos, respectivamente. Uma vez consideradas as diferenças varietais dos grãos e o potencial uso dos seus subprodutos, os objetivos deste trabalho foram, primeiramente, determinar a composição química e o perfil de compostos bioativos desses grãos e, sequencialmente, avaliar sua atividade antioxidante por meio da análise do efeito protetor de células SH- SY5Y. Posteriormente, esses grãos e seus subprodutos foram utilizados como material para o desenvolvimento de filmes biodegradáveis. A identificação e quantificação de compostos fenólicos foi avaliada em extratos da fração farelo de ambos os grãos, por ser essa a fração que contém sua maior concentração. Os resultados evidenciaram que o ácido ferúlico foi o principal composto fenólico encontrado em ambas as amostras. Enquanto no farelo de arroz preto a cianidina-3-glicosídeo foi a antocianina majoritária, no farelo de arroz vermelho foi identificada a presença de proantocianidinas Com relação à atividade antioxidante, o ensaio realizado em cultura de células SH-SY5Y, demonstrou que os extratos de ambos os farelos de arroz, nas duas concentrações testadas (10 and 50 μg/mL), apresentam um efeito protetor contra as espécies reativas geradas pelo H2O2 (ensaio DCFH-DA) e, esse resultado foi relacionado à presença de compostos bioativos, especialmente ácidos fenólicos e antocianinas. Devido às propriedades físico-químicas e antioxidantes, amido e farinha de arroz vermelho foram utilizados para o desenvolvimento de filmes biodegradáveis. Foram desenvolvidas formulações contendo diferentes proporções de farinha e amido (10:0, 9:1, 7:3, 5:5 e 0:10, p/p). A incorporação de amido nos filmes de farinha promoveu melhora das propriedades mecânicas e estruturais e, redução da permeabilidade ao vapor de água. Baseado na excelente atividade de sequestro do radical DPPH. e no menor custo de produção, a formulação 9:1 foi escolhida para ser aplicada na forma de sachê para análise da estabilidade de óleo de girassol armazenado sob condições de oxidação acelerada. Os resultados demonstraram que os filmes foram eficazes como embalagem protetora impedindo a formação de produtos de degradação primários (peróxidos e dienos conjugados) e secundários (trienos conjugados) durante o armazenamento. A partir dos resultados obtidos neste trabalho, fica evidenciada a possibilidade de utilização dos grãos de arroz vermelho e preto e seus subprodutos como matérias-primas promissoras para o desenvolvimento de embalagens biodegradáveis fonte de compostos antioxidantes. / The increase scientific interest related to the study of the properties of red (Oryza glaberrima) and black rice (Oryza sativa) grains is related to the high nutritional content of these grains. When submitted to the polishing process, they generate by-products, among them broken grains and bran, rich in starch and phenolic compounds, respectively. Once considered varietal differences of the grains, and the potential use of their by-products, the goals of this work were, firstly, to determine the chemical composition and the bioactive compounds profile of these grains and, sequentially evaluate their antioxidant activity by analyzing the protective effect of SH-SY5Y cells. Subsequently, these grains and their by-products were used as material for the development of biodegradable films. The identification and quantification of phenolic compounds was evaluated in extracts of the bran fraction of both grains, since this is the fraction that contains the highest concentration of them. The results showed that ferulic acid was the main phenolic compound found in both samples. While in the black rice bran cyanidin-3-glycoside was the major anthocyanin, in the red rice bran the presence of proanthocyanidins was identified. In relation to the antioxidant activity, the SHSY5Y cell culture assay showed that the extracts from both rice bran, at both concentrations tested (10 and 50 μg/ mL), had a protective effect against the reactive species generated by H2O2 (DCFH-DA assay) and this result was related to the presence of bioactive compounds, especially phenolic acids and anthocyanins. Due to the physicochemical and antioxidant properties, starch and red rice flour were used for the development of biodegradable films Formulations containing different ratios of flour and starch (10:0, 9:1, 7:3, 5:5 and 0:10, w/w) were developed. The incorporation of starch in the flour films promoted improved mechanical and structural properties, and reduced permeability to water vapor. Based on excellent scavenging activity of DPPH radical and lowest production cost, the 9: 1 formulation was chosen to be applied in the form of sachets to analyze the stability of sunflower oil stored under accelerated oxidation conditions. The results demonstrated that the films were effective as protective packaging preventing the formation of primary degradation products (peroxides and conjugated dienes) and secondary (conjugated trienes) during the storage. Based on the results obtained in this work, it was confirmed the possibility of using red and black rice grains and their by-products as promising raw materials for the development of biodegradable packaging source of antioxidant compounds.

The overall aim of this thesis is to determine if the interactions between normal and waxy rice starch and milk proteins from four milk protein ingredients, namely skim milk powder (SMP), milk protein concentrate (MPC), sodium caseinate (NaCAS) and whey protein isolate (WPI) do occur, and to identify the mechanisms underlying these interactions. Different milk protein ingredients at various concentrations (0 to 10%, w/w) affected markedly and differently the pasting behaviour of 10% (w/w) rice starches. SMP delayed the pasting of both rice starches by increasing the onset temperature (Tonset) and the peak viscosity temperature (Tpeak) of pasting. This was mainly due to the presence of lactose and ions, which was further supported by the investigation of the effects of UFSMP (a solution of salts and lactose present in SMP at their proper concentration) and lactose. The addition of NaCAS also delayed the pasting of rice starch; Tpeak in the case of both starches was increased. For normal rice starch paste, MPC and WPI decreased the Tpeak. MPC had no affect on Tpeak of waxy rice starch paste. The qualitative viscoelastic behaviour of rice starch/milk protein ingredient gels obtained from the above pastes was dominated by the continuous phase made of the starch molecules. There was evidence, as indicated by confocal microscopy, of phase separation between the milk proteins of SMP and MPC and the two starches. The phase separation was not observed in the addition of either NaCAS or WPI. Studies on the thermal behaviour of rice starch/milk protein ingredient mixtures by differential scanning calorimetry (DSC) showed that SMP, similarly to UFSMP, delayed the gelatinization of both starches. NaCAS also delayed the gelatinisation of both starches but had a greater effect on waxy than normal rice starch. The addition of NaCAS did not affect Tonset but increased Tpeak for normal rice starch, whereas the gelatinisation temperature of waxy rice starch was highly affected by the addition of NaCAS with both Tonset and Tpeak shifted to higher temperatures. MPC had no affect on the gelatinization temperature of normal rice starch, whereas the gelatinization temperature of waxy rice starch was increased by the addition of MPC. The addition of WPI to both rice starches showed two thermal transitions. The first of these was due to the gelatinisation of the starches and the second to the denaturation of ß-lactoglobulin (ß-lg). The addition of WPI to normal rice starch showed that the thermal behaviour of normal starch and protein were independent from each other. In contrast, the thermal behaviour of waxy rice starch was modified by the addition of WPI; both Tonset and Tpeak were increased. SMP decreased the Tonset of swelling, swelling ratio and the amount of starch leaching from both starches. These observed changes were due to the presence of lactose and ions in SMP. NaCAS slightly increased Tonset of swelling but the amount of starch leaching was reduced for both rice starches. The rigidity of both starches tended to increase in the presence of NaCAS. MPC and WPI affected the swelling behaviour of normal and waxy rice starch differently. A dramatic increase in the swelling of normal rice starch/MPC or WPI mixtures was observed, whereas this trend was not evident for waxy rice starch/ MPC or WPI mixtures. The difference in the water holding ability and gelatinization peak temperatures of the two starches over the temperature range at which whey proteins denature and form gels are believed to be responsible for the observed differences. The results from confocal microscopy showed that milk proteins, such as a-casein, ß- casein, ß-lg and a-lactalbumin (a-la), were adsorbed onto the granule surface of both normal and waxy rice starch. The mechanism for this adsorption is the hydrophilic interactions; hydrogen bonds between hydroxyl group from terminated glucan molecule that protrude around starch granule surface-hydroxyl; amino, or other electron-donation or electron-accepting groups of the added proteins. Using sodium dodecyl sulfatepolyacrylamide gel electrophoresis (SDS-PAGE) it was found that for SMP and MPC the adsorbed as- to ß-casein ratio on both starches was similar to the as-casein to ß- casein ratio in the casein micelle at low SMP and MPC concentrations. But at high concentrations of SMP or MPC, this ratio decreased indicating that more ß-casein was adsorbed preferentially to as-casein. In the case of NaCAS, as-casein was adsorbed preferentially to ß-casein. Moreover, there was evidence of multilayer adsorption of ascasein into the surface of rice starch granules. Compared to the other milk protein ingredients, very small amounts of the ß-lg and a-la from WPI were adsorbed onto starch granules. However, the adsorbed amounts of ß-lg and a-la from WPI continuously increased with increasing WPI concentration, suggesting that these two proteins, particularly ß-lg, adsorbed in multilayers too.

The overall aim of this thesis is to determine if the interactions between normal and waxy rice starch and milk proteins from four milk protein ingredients, namely skim milk powder (SMP), milk protein concentrate (MPC), sodium caseinate (NaCAS) and whey protein isolate (WPI) do occur, and to identify the mechanisms underlying these interactions. Different milk protein ingredients at various concentrations (0 to 10%, w/w) affected markedly and differently the pasting behaviour of 10% (w/w) rice starches. SMP delayed the pasting of both rice starches by increasing the onset temperature (Tonset) and the peak viscosity temperature (Tpeak) of pasting. This was mainly due to the presence of lactose and ions, which was further supported by the investigation of the effects of UFSMP (a solution of salts and lactose present in SMP at their proper concentration) and lactose. The addition of NaCAS also delayed the pasting of rice starch; Tpeak in the case of both starches was increased. For normal rice starch paste, MPC and WPI decreased the Tpeak. MPC had no affect on Tpeak of waxy rice starch paste. The qualitative viscoelastic behaviour of rice starch/milk protein ingredient gels obtained from the above pastes was dominated by the continuous phase made of the starch molecules. There was evidence, as indicated by confocal microscopy, of phase separation between the milk proteins of SMP and MPC and the two starches. The phase separation was not observed in the addition of either NaCAS or WPI. Studies on the thermal behaviour of rice starch/milk protein ingredient mixtures by differential scanning calorimetry (DSC) showed that SMP, similarly to UFSMP, delayed the gelatinization of both starches. NaCAS also delayed the gelatinisation of both starches but had a greater effect on waxy than normal rice starch. The addition of NaCAS did not affect Tonset but increased Tpeak for normal rice starch, whereas the gelatinisation temperature of waxy rice starch was highly affected by the addition of NaCAS with both Tonset and Tpeak shifted to higher temperatures. MPC had no affect on the gelatinization temperature of normal rice starch, whereas the gelatinization temperature of waxy rice starch was increased by the addition of MPC. The addition of WPI to both rice starches showed two thermal transitions. The first of these was due to the gelatinisation of the starches and the second to the denaturation of ß-lactoglobulin (ß-lg). The addition of WPI to normal rice starch showed that the thermal behaviour of normal starch and protein were independent from each other. In contrast, the thermal behaviour of waxy rice starch was modified by the addition of WPI; both Tonset and Tpeak were increased. SMP decreased the Tonset of swelling, swelling ratio and the amount of starch leaching from both starches. These observed changes were due to the presence of lactose and ions in SMP. NaCAS slightly increased Tonset of swelling but the amount of starch leaching was reduced for both rice starches. The rigidity of both starches tended to increase in the presence of NaCAS. MPC and WPI affected the swelling behaviour of normal and waxy rice starch differently. A dramatic increase in the swelling of normal rice starch/MPC or WPI mixtures was observed, whereas this trend was not evident for waxy rice starch/ MPC or WPI mixtures. The difference in the water holding ability and gelatinization peak temperatures of the two starches over the temperature range at which whey proteins denature and form gels are believed to be responsible for the observed differences. The results from confocal microscopy showed that milk proteins, such as a-casein, ß- casein, ß-lg and a-lactalbumin (a-la), were adsorbed onto the granule surface of both normal and waxy rice starch. The mechanism for this adsorption is the hydrophilic interactions; hydrogen bonds between hydroxyl group from terminated glucan molecule that protrude around starch granule surface-hydroxyl; amino, or other electron-donation or electron-accepting groups of the added proteins. Using sodium dodecyl sulfatepolyacrylamide gel electrophoresis (SDS-PAGE) it was found that for SMP and MPC the adsorbed as- to ß-casein ratio on both starches was similar to the as-casein to ß- casein ratio in the casein micelle at low SMP and MPC concentrations. But at high concentrations of SMP or MPC, this ratio decreased indicating that more ß-casein was adsorbed preferentially to as-casein. In the case of NaCAS, as-casein was adsorbed preferentially to ß-casein. Moreover, there was evidence of multilayer adsorption of ascasein into the surface of rice starch granules. Compared to the other milk protein ingredients, very small amounts of the ß-lg and a-la from WPI were adsorbed onto starch granules. However, the adsorbed amounts of ß-lg and a-la from WPI continuously increased with increasing WPI concentration, suggesting that these two proteins, particularly ß-lg, adsorbed in multilayers too.

The overall aim of this thesis is to determine if the interactions between normal and waxy rice starch and milk proteins from four milk protein ingredients, namely skim milk powder (SMP), milk protein concentrate (MPC), sodium caseinate (NaCAS) and whey protein isolate (WPI) do occur, and to identify the mechanisms underlying these interactions. Different milk protein ingredients at various concentrations (0 to 10%, w/w) affected markedly and differently the pasting behaviour of 10% (w/w) rice starches. SMP delayed the pasting of both rice starches by increasing the onset temperature (Tonset) and the peak viscosity temperature (Tpeak) of pasting. This was mainly due to the presence of lactose and ions, which was further supported by the investigation of the effects of UFSMP (a solution of salts and lactose present in SMP at their proper concentration) and lactose. The addition of NaCAS also delayed the pasting of rice starch; Tpeak in the case of both starches was increased. For normal rice starch paste, MPC and WPI decreased the Tpeak. MPC had no affect on Tpeak of waxy rice starch paste. The qualitative viscoelastic behaviour of rice starch/milk protein ingredient gels obtained from the above pastes was dominated by the continuous phase made of the starch molecules. There was evidence, as indicated by confocal microscopy, of phase separation between the milk proteins of SMP and MPC and the two starches. The phase separation was not observed in the addition of either NaCAS or WPI. Studies on the thermal behaviour of rice starch/milk protein ingredient mixtures by differential scanning calorimetry (DSC) showed that SMP, similarly to UFSMP, delayed the gelatinization of both starches. NaCAS also delayed the gelatinisation of both starches but had a greater effect on waxy than normal rice starch. The addition of NaCAS did not affect Tonset but increased Tpeak for normal rice starch, whereas the gelatinisation temperature of waxy rice starch was highly affected by the addition of NaCAS with both Tonset and Tpeak shifted to higher temperatures. MPC had no affect on the gelatinization temperature of normal rice starch, whereas the gelatinization temperature of waxy rice starch was increased by the addition of MPC. The addition of WPI to both rice starches showed two thermal transitions. The first of these was due to the gelatinisation of the starches and the second to the denaturation of ß-lactoglobulin (ß-lg). The addition of WPI to normal rice starch showed that the thermal behaviour of normal starch and protein were independent from each other. In contrast, the thermal behaviour of waxy rice starch was modified by the addition of WPI; both Tonset and Tpeak were increased. SMP decreased the Tonset of swelling, swelling ratio and the amount of starch leaching from both starches. These observed changes were due to the presence of lactose and ions in SMP. NaCAS slightly increased Tonset of swelling but the amount of starch leaching was reduced for both rice starches. The rigidity of both starches tended to increase in the presence of NaCAS. MPC and WPI affected the swelling behaviour of normal and waxy rice starch differently. A dramatic increase in the swelling of normal rice starch/MPC or WPI mixtures was observed, whereas this trend was not evident for waxy rice starch/ MPC or WPI mixtures. The difference in the water holding ability and gelatinization peak temperatures of the two starches over the temperature range at which whey proteins denature and form gels are believed to be responsible for the observed differences. The results from confocal microscopy showed that milk proteins, such as a-casein, ß- casein, ß-lg and a-lactalbumin (a-la), were adsorbed onto the granule surface of both normal and waxy rice starch. The mechanism for this adsorption is the hydrophilic interactions; hydrogen bonds between hydroxyl group from terminated glucan molecule that protrude around starch granule surface-hydroxyl; amino, or other electron-donation or electron-accepting groups of the added proteins. Using sodium dodecyl sulfatepolyacrylamide gel electrophoresis (SDS-PAGE) it was found that for SMP and MPC the adsorbed as- to ß-casein ratio on both starches was similar to the as-casein to ß- casein ratio in the casein micelle at low SMP and MPC concentrations. But at high concentrations of SMP or MPC, this ratio decreased indicating that more ß-casein was adsorbed preferentially to as-casein. In the case of NaCAS, as-casein was adsorbed preferentially to ß-casein. Moreover, there was evidence of multilayer adsorption of ascasein into the surface of rice starch granules. Compared to the other milk protein ingredients, very small amounts of the ß-lg and a-la from WPI were adsorbed onto starch granules. However, the adsorbed amounts of ß-lg and a-la from WPI continuously increased with increasing WPI concentration, suggesting that these two proteins, particularly ß-lg, adsorbed in multilayers too.

The overall aim of this thesis is to determine if the interactions between normal and waxy rice starch and milk proteins from four milk protein ingredients, namely skim milk powder (SMP), milk protein concentrate (MPC), sodium caseinate (NaCAS) and whey protein isolate (WPI) do occur, and to identify the mechanisms underlying these interactions. Different milk protein ingredients at various concentrations (0 to 10%, w/w) affected markedly and differently the pasting behaviour of 10% (w/w) rice starches. SMP delayed the pasting of both rice starches by increasing the onset temperature (Tonset) and the peak viscosity temperature (Tpeak) of pasting. This was mainly due to the presence of lactose and ions, which was further supported by the investigation of the effects of UFSMP (a solution of salts and lactose present in SMP at their proper concentration) and lactose. The addition of NaCAS also delayed the pasting of rice starch; Tpeak in the case of both starches was increased. For normal rice starch paste, MPC and WPI decreased the Tpeak. MPC had no affect on Tpeak of waxy rice starch paste. The qualitative viscoelastic behaviour of rice starch/milk protein ingredient gels obtained from the above pastes was dominated by the continuous phase made of the starch molecules. There was evidence, as indicated by confocal microscopy, of phase separation between the milk proteins of SMP and MPC and the two starches. The phase separation was not observed in the addition of either NaCAS or WPI. Studies on the thermal behaviour of rice starch/milk protein ingredient mixtures by differential scanning calorimetry (DSC) showed that SMP, similarly to UFSMP, delayed the gelatinization of both starches. NaCAS also delayed the gelatinisation of both starches but had a greater effect on waxy than normal rice starch. The addition of NaCAS did not affect Tonset but increased Tpeak for normal rice starch, whereas the gelatinisation temperature of waxy rice starch was highly affected by the addition of NaCAS with both Tonset and Tpeak shifted to higher temperatures. MPC had no affect on the gelatinization temperature of normal rice starch, whereas the gelatinization temperature of waxy rice starch was increased by the addition of MPC. The addition of WPI to both rice starches showed two thermal transitions. The first of these was due to the gelatinisation of the starches and the second to the denaturation of ß-lactoglobulin (ß-lg). The addition of WPI to normal rice starch showed that the thermal behaviour of normal starch and protein were independent from each other. In contrast, the thermal behaviour of waxy rice starch was modified by the addition of WPI; both Tonset and Tpeak were increased. SMP decreased the Tonset of swelling, swelling ratio and the amount of starch leaching from both starches. These observed changes were due to the presence of lactose and ions in SMP. NaCAS slightly increased Tonset of swelling but the amount of starch leaching was reduced for both rice starches. The rigidity of both starches tended to increase in the presence of NaCAS. MPC and WPI affected the swelling behaviour of normal and waxy rice starch differently. A dramatic increase in the swelling of normal rice starch/MPC or WPI mixtures was observed, whereas this trend was not evident for waxy rice starch/ MPC or WPI mixtures. The difference in the water holding ability and gelatinization peak temperatures of the two starches over the temperature range at which whey proteins denature and form gels are believed to be responsible for the observed differences. The results from confocal microscopy showed that milk proteins, such as a-casein, ß- casein, ß-lg and a-lactalbumin (a-la), were adsorbed onto the granule surface of both normal and waxy rice starch. The mechanism for this adsorption is the hydrophilic interactions; hydrogen bonds between hydroxyl group from terminated glucan molecule that protrude around starch granule surface-hydroxyl; amino, or other electron-donation or electron-accepting groups of the added proteins. Using sodium dodecyl sulfatepolyacrylamide gel electrophoresis (SDS-PAGE) it was found that for SMP and MPC the adsorbed as- to ß-casein ratio on both starches was similar to the as-casein to ß- casein ratio in the casein micelle at low SMP and MPC concentrations. But at high concentrations of SMP or MPC, this ratio decreased indicating that more ß-casein was adsorbed preferentially to as-casein. In the case of NaCAS, as-casein was adsorbed preferentially to ß-casein. Moreover, there was evidence of multilayer adsorption of ascasein into the surface of rice starch granules. Compared to the other milk protein ingredients, very small amounts of the ß-lg and a-la from WPI were adsorbed onto starch granules. However, the adsorbed amounts of ß-lg and a-la from WPI continuously increased with increasing WPI concentration, suggesting that these two proteins, particularly ß-lg, adsorbed in multilayers too.