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Background and aims Food structure is determined by its composition and the interaction between the compositional or structural elements. Both food structure and the texture perception of foods undergo dynamic changes during different phases of oral processing. During oral processing, both rheological and tribological properties of foods are relevant for sensory perception. The general aim of this thesis was to understand the relationship between the structural properties, rheological and tribological properties during food breakdown, and the sensory perception of foods. More specifically, this thesis aimed to link the properties of food particles in liquid and semi-solid matrices to the tribological and rheological properties, and in this way, understand the sensory perception of these systems. Methods Fat droplets and micro-particle fat replacers based on protein and starch were investigated. These particles varied in size, morphology, deformability and stability, as well as their interaction with the surrounding matrix. These particles were dispersed in liquid or semi-solid gel phases, forming the food model systems under consideration. The friction and microstructural evolution of food model systems under shear was determined using a mouth-mimicking tribometer connected to a confocal laser scanning microscopy. The viscosities of liquid systems were analyzed using a rheometer, and the large deformation properties of semi-solid gel systems were determined during uniaxial compression tests. The sensory perception of the food model systems were measured using quantitative descriptive analysis. The release and deposition of fat droplets on the tongue were determined using in vivo fluorescence. Results Food structural elements could be manipulated to control the tribological properties of food model systems. Morphology, size, and deformability of food particles determine the lubrication behavior of the food systems. Spherical particles with micrometer size were able to reduce friction through a ball bearing mechanism, while irregularly shaped particles increased friction by increasing apparent surface asperity contacts. Deformable particles could flatten the surface by filling asperities, thus reduced friction. Coalescence of unstable droplets could plate-out on the surface and form film patches, thus reduced friction. Other structural elements, such as emulsifiers and sticky molecules, also influenced tribological properties of the systems. Interactions between the food structural elements could influence the rheological properties of liquid and semi-solid food systems. These properties as well as tribological properties were inter-related and all of them affect sensory perception. The inter-relations between physical and sensory properties of food systems were influenced by oral processing, such as oral processing duration and temperature. Furthermore, several fat reduction and replacement strategies were suggested, including increasing the availability of fat that is in contact with oral surfaces, improving the lubrication by ball bearing of particles, and reducing perception of negative attributes such as roughness. Conclusions This thesis showed the importance of food particle properties in both the tribological properties and sensory perception of foods, and emphasized the different lubrication mechanisms of different structure elements and their relation to perception. The differences in behavior of food particles between liquid and semi-solid gel systems were highlighted. These findings would enable a better understanding of relationship between food structure and their physical and sensory properties, and this would allow designing or modifying food products with targeted texture and sensory perception.

Background and aims Food structure is determined by its composition and the interaction between the compositional or structural elements. Both food structure and the texture perception of foods undergo dynamic changes during different phases of oral processing. During oral processing, both rheological and tribological properties of foods are relevant for sensory perception. The general aim of this thesis was to understand the relationship between the structural properties, rheological and tribological properties during food breakdown, and the sensory perception of foods. More specifically, this thesis aimed to link the properties of food particles in liquid and semi-solid matrices to the tribological and rheological properties, and in this way, understand the sensory perception of these systems. Methods Fat droplets and micro-particle fat replacers based on protein and starch were investigated. These particles varied in size, morphology, deformability and stability, as well as their interaction with the surrounding matrix. These particles were dispersed in liquid or semi-solid gel phases, forming the food model systems under consideration. The friction and microstructural evolution of food model systems under shear was determined using a mouth-mimicking tribometer connected to a confocal laser scanning microscopy. The viscosities of liquid systems were analyzed using a rheometer, and the large deformation properties of semi-solid gel systems were determined during uniaxial compression tests. The sensory perception of the food model systems were measured using quantitative descriptive analysis. The release and deposition of fat droplets on the tongue were determined using in vivo fluorescence. Results Food structural elements could be manipulated to control the tribological properties of food model systems. Morphology, size, and deformability of food particles determine the lubrication behavior of the food systems. Spherical particles with micrometer size were able to reduce friction through a ball bearing mechanism, while irregularly shaped particles increased friction by increasing apparent surface asperity contacts. Deformable particles could flatten the surface by filling asperities, thus reduced friction. Coalescence of unstable droplets could plate-out on the surface and form film patches, thus reduced friction. Other structural elements, such as emulsifiers and sticky molecules, also influenced tribological properties of the systems. Interactions between the food structural elements could influence the rheological properties of liquid and semi-solid food systems. These properties as well as tribological properties were inter-related and all of them affect sensory perception. The inter-relations between physical and sensory properties of food systems were influenced by oral processing, such as oral processing duration and temperature. Furthermore, several fat reduction and replacement strategies were suggested, including increasing the availability of fat that is in contact with oral surfaces, improving the lubrication by ball bearing of particles, and reducing perception of negative attributes such as roughness. Conclusions This thesis showed the importance of food particle properties in both the tribological properties and sensory perception of foods, and emphasized the different lubrication mechanisms of different structure elements and their relation to perception. The differences in behavior of food particles between liquid and semi-solid gel systems were highlighted. These findings would enable a better understanding of relationship between food structure and their physical and sensory properties, and this would allow designing or modifying food products with targeted texture and sensory perception.

Aeration of food is considered to be a good method to create a texture and mouthfeel of food products that is liked by the consumer. However, traditional foams are not stable for a prolonged time. Microbubbles are air bubbles covered with a shell that slows down disproportionation significantly and arrests coalescence. Protein stabilized microbubbles are seen as a promising new food ingredient for encapsulation, to replace fat, to create new textures, and to improve sensorial properties of foods. In order to explore the possible functionalities of microbubbles in food systems, a good understanding is required regarding the formation of protein stabilized microbubbles as well as their stability in environments and at conditions encountered in food products. The aim of this research was to investigate the key parameters for applications of microbubbles in food systems. In Chapter 1 an introduction to this topic is given. In Chapter 2, the effect of the microbubble preparation parameters on the microbubble characteristics, like the microbubble yield, size and stability, was investigated. The protein Bovine Serum Albumin (BSA) and the method sonication was used to manufacture the microbubbles. The manufactured number and stability of microbubbles was highest when they were prepared at a pH around 5 to 6, just above the isoelectric point, and at an ionic strength of 1.0 M. This can be related to the protein coverage at the air/water interface of air bubbles formed during sonication. At a pH close to the isoelectric point the BSA molecules is in its native configuration. Also the repulsion between the proteins is minimized at these pH values and ionic strength. Both the native configuration and the limited repulsion between the proteins result in an optimal protein coverage during the first part of sonication. Also a high protein concentration contributes to a higher surface coverage. The surface coverage is proportional to the protein concentration up to a concentration of 7.5% after which an increase in protein concentration did not lead to a substantial increase in the number of microbubble . In the second part of sonication the protein layer around the air bubble becomes thicker and stronger by heat induced protein-protein interactions. We found that and at a preheating temperature of 55-60°C, about 5 °C below the BSA denaturation temperature, and a final solution temperature of 60-65°C most microbubbles were obtained, while at higher temperatures mainly protein aggregates and (almost) no microbubbles are formed. This suggests that at temperature of around 60°C to 65°C protein aggregated mostly at the air-water interface creating a multi-layered shell, while at higher temperature, they also aggregated in bulk. These aggregates cannot form microbubbles. We found that optimal preparation parameters strongly depend on the protein batch. We hypothesize that the differences in microbubble formation between the protein batches is due to (small) differences in the protein molecular and denaturation properties that determine the temperature at which the molecules start to interact at the air-water interface. Microbubbles made with different protein concentration and preheating temperatures shrunk in time to a radius between 300 nm and 350 nm, after which the size remained constant during further storage. We argue that the driving force for the shrinkage was the Laplace pressure, resulting in an air flux from the bubbles to the solution. We argue that the constant final size can be explained by a thickening of the microbubble shell as a result of the microbubble shrinkage, thereby withstanding the Laplace pressure. In Chapter 3 and Chapter 4, microbubble stability at environments and conditions representative for food products were studies. In Chapter 3 we investigated the stability upon addition of surfactants and acid, When surfactants or acid were added, the microbubbles disappeared in three subsequent steps. The release of air from the microbubble can be well described with the two-parameter Weibull process. This suggests two processes are responsible for the release of air: 1) a shell-weakening process and 2) a random fracture of the weakened shell. After the air has been released from the microbubble the third process is identified in the microbubble disintegration: 3) the shell disintegrated completely into nanometer-sized particles. The probability of fracture was exponentially proportional to the concentration of acid and surfactant, meaning that a lower average breaking time and a higher decay rate were observed at higher surfactant or acid concentrations. For different surfactants, different decay rates were found. The disintegration of the shell into monomeric proteins upon addition of acid or surfactants shows that the interactions in the shell are non-covalent and most probably hydrophobic. After surfactant addition, there was a significant time gap between complete microbubble decay (release of air) and complete shell disintegration, while after acid addition the time at which the complete disintegration of the shell was observed coincided with the time of complete microbubble decay. In Chapter 4 the stability of the microbubbles upon pressure treatment, upon fast cooling after heating and at different storage temperatures was studied. The microbubble stability significantly decreased when microbubbles were pressurized above 1 bar overpressure for 15 seconds or heated above 50°C for 2 minutes. Above those pressures the microbubbles became unstable by buckling. Buckling occurred above a critical pressure. This critical pressure is determined by the shell elastic modulus, the thickness of the shell, and the size of the microbubble. Addition of crosslinkers like glutaraldehyde and tannic acid increased the shell elastic modulus. It was shown that microbubbles were stable against all tested temperatures (up to 120°C) and overpressures (4.7 bar) after they were reinforced by crosslinkers. From the average breaking time at different storage temperatures, we deduced that the activation energy to rupture molecular bonds in the microbubbles shell is 27 kT. In Chapter 5, we investigated the effect of microbubbles on the rheological, tribological sensorial properties of model food systems and we compared this effect to the effect on food systems with emulsion droplets and without an added colloid. We investigated the effect in three model food systems, namely fluids with and without added thickener and a mixed gelatine-agar gel. In a sensory test panellists were asked whether they could discriminate between samples containing microbubbles, emulsion droplets or no added colloid. Emulsions could be sensorially well distinguished from the other two samples, while the microbubble dispersion could not be discriminated from the protein solution. Thus, we concluded that at a volume fraction of 5% of these BSA covered microbubbles were not comparable to oil-in-water emulsions. The good discrimination of emulsion might be ascribed to the fact that emulsion had a lower friction force (measured at shear rates form 10 mm/s to 80 mm/s) than that microbubbles dispersions and protein solutions. Upon mixing emulsions and microbubble dispersions the friction value approximated that of emulsions. This effect was already noticed at only 1.25% (v/v) oil, indicating that microbubbles had not a significant contributions to the friction of these samples. Also microbubble dispersions with and without protein aggregates were compared. The microbubble dispersions with and without thickener containing protein aggregates had a higher viscosity than the those samples without protein aggregates. Protein aggregates in the gelled microbubble sample yielded a higher Young’s modulus and fracture stress. The differences between the gelled samples could be well perceived by the panellists. We attribute this mainly to the fracture properties of the gel. In general we concluded that microbubbles, given their size of ~ 1 mm and volume fraction of 5%, did not contribute to a specific mouthfeel. Finally in Chapter 6, the results presented in the previous chapters are discussed and put in perspective of the general knowledge on microbubbles production, stability, and applications in food. We described the main mechanisms leading to microbubble formation and stability. We showed that the production parameters significantly influence the interactions in the microbubble shell, and the those interactions highly determine the stability of the microbubbles under several conditions. We reported about limitations of sonication as a method to produce microbubbles suitable for food applications and we provided some ways to overcome these limitations. The use of microbubbles in food systems has been explored and we clearly see possible applications for microbubbles in food. We reported about directions for possible further research. In this work we made significant progress in understanding the interactions in the microbubble shell and their relation to microbubble stability. We also advanced in comprehension towards possible applications of microbubbles in food.

Aeration of food is considered to be a good method to create a texture and mouthfeel of food products that is liked by the consumer. However, traditional foams are not stable for a prolonged time. Microbubbles are air bubbles covered with a shell that slows down disproportionation significantly and arrests coalescence. Protein stabilized microbubbles are seen as a promising new food ingredient for encapsulation, to replace fat, to create new textures, and to improve sensorial properties of foods. In order to explore the possible functionalities of microbubbles in food systems, a good understanding is required regarding the formation of protein stabilized microbubbles as well as their stability in environments and at conditions encountered in food products. The aim of this research was to investigate the key parameters for applications of microbubbles in food systems. In Chapter 1 an introduction to this topic is given. In Chapter 2, the effect of the microbubble preparation parameters on the microbubble characteristics, like the microbubble yield, size and stability, was investigated. The protein Bovine Serum Albumin (BSA) and the method sonication was used to manufacture the microbubbles. The manufactured number and stability of microbubbles was highest when they were prepared at a pH around 5 to 6, just above the isoelectric point, and at an ionic strength of 1.0 M. This can be related to the protein coverage at the air/water interface of air bubbles formed during sonication. At a pH close to the isoelectric point the BSA molecules is in its native configuration. Also the repulsion between the proteins is minimized at these pH values and ionic strength. Both the native configuration and the limited repulsion between the proteins result in an optimal protein coverage during the first part of sonication. Also a high protein concentration contributes to a higher surface coverage. The surface coverage is proportional to the protein concentration up to a concentration of 7.5% after which an increase in protein concentration did not lead to a substantial increase in the number of microbubble . In the second part of sonication the protein layer around the air bubble becomes thicker and stronger by heat induced protein-protein interactions. We found that and at a preheating temperature of 55-60°C, about 5 °C below the BSA denaturation temperature, and a final solution temperature of 60-65°C most microbubbles were obtained, while at higher temperatures mainly protein aggregates and (almost) no microbubbles are formed. This suggests that at temperature of around 60°C to 65°C protein aggregated mostly at the air-water interface creating a multi-layered shell, while at higher temperature, they also aggregated in bulk. These aggregates cannot form microbubbles. We found that optimal preparation parameters strongly depend on the protein batch. We hypothesize that the differences in microbubble formation between the protein batches is due to (small) differences in the protein molecular and denaturation properties that determine the temperature at which the molecules start to interact at the air-water interface. Microbubbles made with different protein concentration and preheating temperatures shrunk in time to a radius between 300 nm and 350 nm, after which the size remained constant during further storage. We argue that the driving force for the shrinkage was the Laplace pressure, resulting in an air flux from the bubbles to the solution. We argue that the constant final size can be explained by a thickening of the microbubble shell as a result of the microbubble shrinkage, thereby withstanding the Laplace pressure. In Chapter 3 and Chapter 4, microbubble stability at environments and conditions representative for food products were studies. In Chapter 3 we investigated the stability upon addition of surfactants and acid, When surfactants or acid were added, the microbubbles disappeared in three subsequent steps. The release of air from the microbubble can be well described with the two-parameter Weibull process. This suggests two processes are responsible for the release of air: 1) a shell-weakening process and 2) a random fracture of the weakened shell. After the air has been released from the microbubble the third process is identified in the microbubble disintegration: 3) the shell disintegrated completely into nanometer-sized particles. The probability of fracture was exponentially proportional to the concentration of acid and surfactant, meaning that a lower average breaking time and a higher decay rate were observed at higher surfactant or acid concentrations. For different surfactants, different decay rates were found. The disintegration of the shell into monomeric proteins upon addition of acid or surfactants shows that the interactions in the shell are non-covalent and most probably hydrophobic. After surfactant addition, there was a significant time gap between complete microbubble decay (release of air) and complete shell disintegration, while after acid addition the time at which the complete disintegration of the shell was observed coincided with the time of complete microbubble decay. In Chapter 4 the stability of the microbubbles upon pressure treatment, upon fast cooling after heating and at different storage temperatures was studied. The microbubble stability significantly decreased when microbubbles were pressurized above 1 bar overpressure for 15 seconds or heated above 50°C for 2 minutes. Above those pressures the microbubbles became unstable by buckling. Buckling occurred above a critical pressure. This critical pressure is determined by the shell elastic modulus, the thickness of the shell, and the size of the microbubble. Addition of crosslinkers like glutaraldehyde and tannic acid increased the shell elastic modulus. It was shown that microbubbles were stable against all tested temperatures (up to 120°C) and overpressures (4.7 bar) after they were reinforced by crosslinkers. From the average breaking time at different storage temperatures, we deduced that the activation energy to rupture molecular bonds in the microbubbles shell is 27 kT. In Chapter 5, we investigated the effect of microbubbles on the rheological, tribological sensorial properties of model food systems and we compared this effect to the effect on food systems with emulsion droplets and without an added colloid. We investigated the effect in three model food systems, namely fluids with and without added thickener and a mixed gelatine-agar gel. In a sensory test panellists were asked whether they could discriminate between samples containing microbubbles, emulsion droplets or no added colloid. Emulsions could be sensorially well distinguished from the other two samples, while the microbubble dispersion could not be discriminated from the protein solution. Thus, we concluded that at a volume fraction of 5% of these BSA covered microbubbles were not comparable to oil-in-water emulsions. The good discrimination of emulsion might be ascribed to the fact that emulsion had a lower friction force (measured at shear rates form 10 mm/s to 80 mm/s) than that microbubbles dispersions and protein solutions. Upon mixing emulsions and microbubble dispersions the friction value approximated that of emulsions. This effect was already noticed at only 1.25% (v/v) oil, indicating that microbubbles had not a significant contributions to the friction of these samples. Also microbubble dispersions with and without protein aggregates were compared. The microbubble dispersions with and without thickener containing protein aggregates had a higher viscosity than the those samples without protein aggregates. Protein aggregates in the gelled microbubble sample yielded a higher Young’s modulus and fracture stress. The differences between the gelled samples could be well perceived by the panellists. We attribute this mainly to the fracture properties of the gel. In general we concluded that microbubbles, given their size of ~ 1 mm and volume fraction of 5%, did not contribute to a specific mouthfeel. Finally in Chapter 6, the results presented in the previous chapters are discussed and put in perspective of the general knowledge on microbubbles production, stability, and applications in food. We described the main mechanisms leading to microbubble formation and stability. We showed that the production parameters significantly influence the interactions in the microbubble shell, and the those interactions highly determine the stability of the microbubbles under several conditions. We reported about limitations of sonication as a method to produce microbubbles suitable for food applications and we provided some ways to overcome these limitations. The use of microbubbles in food systems has been explored and we clearly see possible applications for microbubbles in food. We reported about directions for possible further research. In this work we made significant progress in understanding the interactions in the microbubble shell and their relation to microbubble stability. We also advanced in comprehension towards possible applications of microbubbles in food.

A lifestyle that combines poor food choices with very low or no physical activity can result in the development of diseases such as obesity, and this is affecting a growing number of children. One of the most effective strategies to fight obesity combines physical activity and the consumption of low energy-dense foods, such as vegetables. Vegetables are known to have health benefits but are often non-appealing to children/adolescents due to their bitterness, undesired texture, and their low satiating capacity. One of the possible solutions to increase vegetable intake by children is to incorporate vegetables in a food matrix they like. Several studies have shown that pasta is very much appreciated by children, making it an ideal candidate for the development of vegetable-enriched foods. In this work, dried broccoli powder (BP) was used to enrich pasta-like products. We have investigated aspects that are important to sensorial properties and aspects related to possible health benefits. One aspect relevant to sensorial properties is rheology. The rheology of sweet potato starch (SPS) dough was drastically affected by high volume fractions of BP. This was caused by the swelling of the broccoli powder, up to a maximum of 7.6 times their original volume. In order to control this high swelling capacity of the particles two approaches were followed and both resulted in the prevention of particle swelling. The first was the use of hydrocolloids with high water binding capacity (e.g. xanthan gum) and the second was the use of a different matrix (durum wheat semolina (DWS)). DWS pasta did not show to be greatly affected by the incorporation of high amounts of broccoli powder. The acceptability of pasta products was assessed using a test panel. The results showed that all samples tested (0 – 30%BP) were acceptable, where 30% BP turned out to be on the limit of acceptability. Glucosinolates (GLs) are phytochemicals that are associated with the health benefits of broccoli. An increasing volume fraction of broccoli powder resulted in an increasing content of glucosinolates in dried cooked pasta. At volume fractions higher than 20% BP this effect levels off. From this work, we can conclude that as much as 20% BP can be added to DWS pasta to improve nutritional properties (in terms of GLs) while maintaining acceptable sensorial properties.

The mechanical properties of food play an important role during manufacturing, storage, handling, and last but not least, during consumption. For an adequate understanding of the mechanical properties of liquid, liquid-like, soft solid, and solid foods, a basic understanding of relevant aspects of rheology and fracture mechanics is essential. Focusing on basic principles, Rheology and Fracture Mechanics of Foods examines how rheological and fracture behavior in food relates to product structure. Divided into three parts, the book reviews basic concepts and emphasizes aspects relevant for studying food products, raw materials, and intermediate products. It then introduces measuring methods and the equipment used for studying mechanical properties of food products, highlighting tests that deliver reproducible and interpretable data. The final part investigates the relation between rheological and fracture behavior of matter and physical structure at the relevant molecular, mesoscopic, and macroscopic length scales. In addition to the basics of rheology and fracture mechanics, the book explores the relationship between measured mechanical properties and the structure of the different types of food and how they may determine texture perception

A lifestyle that combines poor food choices with very low or no physical activity can result in the development of diseases such as obesity, and this is affecting a growing number of children. One of the most effective strategies to fight obesity combines physical activity and the consumption of low energy-dense foods, such as vegetables. Vegetables are known to have health benefits but are often non-appealing to children/adolescents due to their bitterness, undesired texture, and their low satiating capacity. One of the possible solutions to increase vegetable intake by children is to incorporate vegetables in a food matrix they like. Several studies have shown that pasta is very much appreciated by children, making it an ideal candidate for the development of vegetable-enriched foods. In this work, dried broccoli powder (BP) was used to enrich pasta-like products. We have investigated aspects that are important to sensorial properties and aspects related to possible health benefits. One aspect relevant to sensorial properties is rheology. The rheology of sweet potato starch (SPS) dough was drastically affected by high volume fractions of BP. This was caused by the swelling of the broccoli powder, up to a maximum of 7.6 times their original volume. In order to control this high swelling capacity of the particles two approaches were followed and both resulted in the prevention of particle swelling. The first was the use of hydrocolloids with high water binding capacity (e.g. xanthan gum) and the second was the use of a different matrix (durum wheat semolina (DWS)). DWS pasta did not show to be greatly affected by the incorporation of high amounts of broccoli powder. The acceptability of pasta products was assessed using a test panel. The results showed that all samples tested (0 – 30%BP) were acceptable, where 30% BP turned out to be on the limit of acceptability. Glucosinolates (GLs) are phytochemicals that are associated with the health benefits of broccoli. An increasing volume fraction of broccoli powder resulted in an increasing content of glucosinolates in dried cooked pasta. At volume fractions higher than 20% BP this effect levels off. From this work, we can conclude that as much as 20% BP can be added to DWS pasta to improve nutritional properties (in terms of GLs) while maintaining acceptable sensorial properties.

Increased protein consumption gives rise to various health benefits. High-protein intake can lead to muscle development, body weight control and suppression of sarcopenia progression. However, increasing the protein content in food products leads to textural changes over time. These changes result in product hardening over time and several negative sensorial attributes such as rubbery and dry mouth feel. This thesis describes the role of structuring to control the rheological and mechanical properties of high-protein model foods. By altering the internal structure of the model systems, textural properties of the model systems at initial stage (fresh products) can be improved. Content of this thesis can be distinguished into four parts. The first part reviews existing studies related to high-protein foods. The effects of ingredients and processing were evaluated with respect to food products having a high protein content. Some studies indicated typical problems occurring in products or model systems with an increased protein content such as product hardening over time. Ingredients that might be added to ameliorate product properties were plasticizers, peptides made from whey proteins, disulphide reducing agents, and components that block the free thiol groups in proteins. This part provides guidelines for structuring high-protein foods aimed at avoiding or reducing the unfavourable changes in properties over time. Concentrated proteins in their native (unmodified) form can be replaced by protein domains or structural elements with altered properties. These domains or elements mitigate the changes in product structure, resulting in a product that is softer than the one made from native proteins only. The second part focuses on the structural elements made from whey protein isolate (WPI), namely WPI aggregates and WPI microparticles. WPI aggregates were formed by different heating conditions at neutral pH. Generally, a higher concentration and a higher temperature resulted in bigger and less dense aggregates. A higher temperature also resulted in a higher reactivity (a larger number of available thiol groups). Heating an aggregate suspension led to a weaker gel than a gel made from native protein at similar. This result was hypothesized to originate from the lower number of contact points formed with larger aggregates. It was concluded that the most pronounced weakening effect could be obtained with aggregates that are large, dense, and non-reactive. That is why WPI microparticles were created. The particles were formed by gelling a concentrated WPI solution, and subsequent drying the gel and milling it into small particles. Partial replacement of native WPI with WPI microparticles resulted in a weaker gel than a gel made from native WPI only at the same total protein concentration. This result was attributed to the inability of the microparticles to form a gel. However, the weakening effect of these particles in the model system was limited due to water redistribution and the good bonding between the particles and the protein continuous phase. The third part describes how the properties of high-protein gels containing WPI microparticles change over time. A high-protein gel made from native WPI was used as a reference. The firmness and fracture stress of the gel made from WPI only increased during the first few days and then stabilized. The gel consisting of WPI microparticles in WPI or in a mixture of locust bean gum (LBG)–xanthan gum (XG) tended to harden for a longer period. Most likely, water redistribution is responsible for this observation.

Increased protein consumption gives rise to various health benefits. High-protein intake can lead to muscle development, body weight control and suppression of sarcopenia progression. However, increasing the protein content in food products leads to textural changes over time. These changes result in product hardening over time and several negative sensorial attributes such as rubbery and dry mouth feel. This thesis describes the role of structuring to control the rheological and mechanical properties of high-protein model foods. By altering the internal structure of the model systems, textural properties of the model systems at initial stage (fresh products) can be improved. Content of this thesis can be distinguished into four parts. The first part reviews existing studies related to high-protein foods. The effects of ingredients and processing were evaluated with respect to food products having a high protein content. Some studies indicated typical problems occurring in products or model systems with an increased protein content such as product hardening over time. Ingredients that might be added to ameliorate product properties were plasticizers, peptides made from whey proteins, disulphide reducing agents, and components that block the free thiol groups in proteins. This part provides guidelines for structuring high-protein foods aimed at avoiding or reducing the unfavourable changes in properties over time. Concentrated proteins in their native (unmodified) form can be replaced by protein domains or structural elements with altered properties. These domains or elements mitigate the changes in product structure, resulting in a product that is softer than the one made from native proteins only. The second part focuses on the structural elements made from whey protein isolate (WPI), namely WPI aggregates and WPI microparticles. WPI aggregates were formed by different heating conditions at neutral pH. Generally, a higher concentration and a higher temperature resulted in bigger and less dense aggregates. A higher temperature also resulted in a higher reactivity (a larger number of available thiol groups). Heating an aggregate suspension led to a weaker gel than a gel made from native protein at similar. This result was hypothesized to originate from the lower number of contact points formed with larger aggregates. It was concluded that the most pronounced weakening effect could be obtained with aggregates that are large, dense, and non-reactive. That is why WPI microparticles were created. The particles were formed by gelling a concentrated WPI solution, and subsequent drying the gel and milling it into small particles. Partial replacement of native WPI with WPI microparticles resulted in a weaker gel than a gel made from native WPI only at the same total protein concentration. This result was attributed to the inability of the microparticles to form a gel. However, the weakening effect of these particles in the model system was limited due to water redistribution and the good bonding between the particles and the protein continuous phase. The third part describes how the properties of high-protein gels containing WPI microparticles change over time. A high-protein gel made from native WPI was used as a reference. The firmness and fracture stress of the gel made from WPI only increased during the first few days and then stabilized. The gel consisting of WPI microparticles in WPI or in a mixture of locust bean gum (LBG)–xanthan gum (XG) tended to harden for a longer period. Most likely, water redistribution is responsible for this observation.

cum laude graduation (with distinction)

cum laude graduation (with distinction)

When we eat a food product, we perceive its sensory properties and subconsciously decide whether we like the food. Next to properties of flavor and taste, we perceive textural properties. How thick, rough and creamy the food is perceived depends on the structure and properties of the food product in the mouth. This thesis explores which properties of semisolid foods (mayonnaise, Dutch custard) are important for the perception of creaminess and other textural properties as well as how we can instrumentally measure these properties.

When we eat a food product, we perceive its sensory properties and subconsciously decide whether we like the food. Next to properties of flavor and taste, we perceive textural properties. How thick, rough and creamy the food is perceived depends on the structure and properties of the food product in the mouth. This thesis explores which properties of semisolid foods (mayonnaise, Dutch custard) are important for the perception of creaminess and other textural properties as well as how we can instrumentally measure these properties.

Both health and sustainability are drivers for the increased interest in the creation of novel foods comprising a high protein content. The key challenge is the formation of an attractive, stable and palatable food texture, which is mainly determined by the food structure. In this research, new processing routes based on flow are explored to create innovative protein-rich structures (exceeding 10%), and in parallel, insight is gained in the relevant mechanisms of structure formation. Dense dispersions of sodium caseinate and calcium caseinate, which are derived from milk, were mixed in a conventional mixer and sheared in an in house developed shear cell device. After mixing dense (sodium or calcium) caseinate dispersions, homogenous structures were obtained of which the properties were determined by the dispersed phase added, in this case palm fat. Shearing of dense calcium caseinate dispersions in combination with solidification using the enzyme transglutaminase resulted in completely different structures; highly fibrous structures were produced, which may serve as a basis for the creation of meat analogs. In contrast, after treating dense sodium caseinate dispersions using this novel structuring process, homogenous structures were obtained. It appeared that the intrinsic properties of protein dispersions are important for the formation of fibrous structures using well-defined flow. Based on the differences in performance between the two types of caseinates, tools and parameters can be derived to optimize and control the formation of fibrous products. In conclusion, the development of equipment that is dedicated to structure food ingredients is promising for the creation of novel foods on the one hand, and for gaining scientific understanding of structure formation on the other hand.

The general aim of the work described in this thesis was to investigate structure-rheologyrelations for dairy related products, focusing on model systems containing sodium caseinate. The acid inducedgelationof sodium caseinate, of sodium caseinate stabilized emulsions, and the effect of shear on the structure formation was characterized. Special attention was given to the sol-gel transition point, which was defined by a frequency independent loss tangent. It was shown that the sol-gel transition point is completely controlled by the pH and the temperature, independent of the concentration sodium caseinate or the applied shear rate. Considering sodium caseinate solutions, increase of the temperature of acidification caused a decrease of the critical pH forgelationand a more dense gel structure. The formed gels were not in thermodynamicequilibrium,however, due to the slow kinetics of the system they were stable on the time scale of the experiment. At the gel point we have strong indications that the structure can not be characterized by a single fractal dimension. During the acid inducedgelationof sodium caseinate stabilized emulsions a single sol-gel transition was observed. Addition of an excess of sodium caseinate to the emulsion resulted in two sol-gel transitions upon acidification. Application of shear during the acidification of the emulsions showed a decreasing radius of the aggregates formed at thegelpointwith increasing shear rate. The aggregates formed becamemore densedue to the application of shear while the network that was formed by the aggregates became less compact. No shear induced alignment was observed of emulsion droplets dispersed in water or ina sodiumcaseinatesolution, while emulsion droplets dispersed in axanthansolution did align in a shear field. Addition of sodium inhibited the string formation of the emulsion droplets

Both health and sustainability are drivers for the increased interest in the creation of novel foods comprising a high protein content. The key challenge is the formation of an attractive, stable and palatable food texture, which is mainly determined by the food structure. In this research, new processing routes based on flow are explored to create innovative protein-rich structures (exceeding 10%), and in parallel, insight is gained in the relevant mechanisms of structure formation. Dense dispersions of sodium caseinate and calcium caseinate, which are derived from milk, were mixed in a conventional mixer and sheared in an in house developed shear cell device. After mixing dense (sodium or calcium) caseinate dispersions, homogenous structures were obtained of which the properties were determined by the dispersed phase added, in this case palm fat. Shearing of dense calcium caseinate dispersions in combination with solidification using the enzyme transglutaminase resulted in completely different structures; highly fibrous structures were produced, which may serve as a basis for the creation of meat analogs. In contrast, after treating dense sodium caseinate dispersions using this novel structuring process, homogenous structures were obtained. It appeared that the intrinsic properties of protein dispersions are important for the formation of fibrous structures using well-defined flow. Based on the differences in performance between the two types of caseinates, tools and parameters can be derived to optimize and control the formation of fibrous products. In conclusion, the development of equipment that is dedicated to structure food ingredients is promising for the creation of novel foods on the one hand, and for gaining scientific understanding of structure formation on the other hand.

Onderzoek naar de relatie tussen moleculaire structuur van eiwitten en het schuimgedrag van de oplossing

The rheological behaviour of granular sludges (diameter 20–315 μm) originating from different anaerobic reactors was carried out using rotation tests. The sieved granular sludges suspensions display a non-Newtonian rheological behaviour and the limit viscosity was therefore used as a rheological parameter. The values obtained, which depend on the shear rate used, were strongly influenced by the total suspended solids (TSS) content of granular sludge and an exponential relation was found between the TSS and the rheological parameter limit viscosity. The increase of viscosity as a function of TSS content of the granular sludge as well as the increase of granule size underlines the importance of the interaction between granules in the evolution of this rheological parameter. Significant differences in granular sludge limit viscosity were found for granular sludge of different origins. All measurements performed with 10 g.l−1 TSS granular sludge indicate the ability of the chosen rheological parameter to describe different granular sludge quality.

Dit IOP Industriële Eiwitten project is gericht op het leggen van relaties tussen biochemische karakteristieken van tarwegluten en hun reologisch gedrag. Op deze wijze wordt inzicht verkregen in structuurfunctie relaties van tarwegluten, met name gericht op bakkerijtoepassingen. Voor dit onderzoek zijn zes Europese tarwe-variëteiten geselecteerd, die vergelijkbare eiwitgehaltes hebben, maar een groot verschil in bakkwaliteit vertonen. Kwaliteitsverschillen tussen deze variëteiten uiten zich het meest in de benodigde kneedtijd om optimale bakkwaliteit te bereiken. Er zijn duidelijke aanwijzingen dat hieraan een aantal biochemische factoren ten grondslag liggen zoals de hoeveelheid van het glutenine polymeer, de polymerisatie ervan en de mate van fysische interacties tussen de gluten-eiwitten

cum laude graduation (with distinction)

Properties of Fibrillar Protein Assemblies and their Percolating Networks. PhD thesis, Wageningen University, The Netherlands Keywords: bovine serum albumin, complex fluids, excluded volume, fibrils, gels, innovation, b-lactoglobulin, ovalbumin, percolation, proteins, rheology, rheo-optics, self-assembly, structure function relations. Abstract The objective of this thesis was to explore the assembly of food proteins into fibrils, and to describe the resulting percolating systems at rest and under shear flow, in terms of mesoscopic fibril properties. The effect of ionic strength on the percolation concentration for three different food proteins, namely b-lactoglobulin, bovine serum albumin and ovalbumin is described. The dependence of ionic strength on the percolation concentration was explained using an adjusted random contact model, in which the percolation concentration is related to the average number of contacts per particle, and the excluded volume of the rod. Also the contour length, persistence length, and bending rigidity for these three protein assemblies were determined, as well as the phase behaviour of b-lactoglobulin at low pH. A new multistep Ca2+-induced cold gelation process is described to prepare b-lactoglobulin gels at very low protein concentrations (0.07%). The behaviour of fibrillar assemblies of ovalbumin under oscillatory shear, close to the critical percolation concentration, was probed with the use of rheo-optical measurements and Fourier transform rheology. Also the effect of shear flow on the critical percolation concentration for solutions of fibrillar protein assemblies was investigated. Results of viscosity measurements were analysed using percolation theory, where the effect of shear flow was taken into account. The experimental results were compared with our theoretical calculations for the percolation concentration versus shear, based on a random contact model for rodlike particles, making use of a shear dependent excluded volume per fibril. In conclusion conditions leading to gel formation, in terms of mesoscopic fibril properties, under non-flow conditions have been discussed. The observed critical gelation concentration was explained in terms of an excluded volume per fibril (at zero shear). The influence of shear flow on this critical gelation concentration was also described. Here, the critical percolation concentration versus shear flow could again be expressed in terms of an excluded volume per fibril, in this case as a function of shear.

cum laude graduation (with distinction)

Properties of Fibrillar Protein Assemblies and their Percolating Networks. PhD thesis, Wageningen University, The Netherlands Keywords: bovine serum albumin, complex fluids, excluded volume, fibrils, gels, innovation, b-lactoglobulin, ovalbumin, percolation, proteins, rheology, rheo-optics, self-assembly, structure function relations. Abstract The objective of this thesis was to explore the assembly of food proteins into fibrils, and to describe the resulting percolating systems at rest and under shear flow, in terms of mesoscopic fibril properties. The effect of ionic strength on the percolation concentration for three different food proteins, namely b-lactoglobulin, bovine serum albumin and ovalbumin is described. The dependence of ionic strength on the percolation concentration was explained using an adjusted random contact model, in which the percolation concentration is related to the average number of contacts per particle, and the excluded volume of the rod. Also the contour length, persistence length, and bending rigidity for these three protein assemblies were determined, as well as the phase behaviour of b-lactoglobulin at low pH. A new multistep Ca2+-induced cold gelation process is described to prepare b-lactoglobulin gels at very low protein concentrations (0.07%). The behaviour of fibrillar assemblies of ovalbumin under oscillatory shear, close to the critical percolation concentration, was probed with the use of rheo-optical measurements and Fourier transform rheology. Also the effect of shear flow on the critical percolation concentration for solutions of fibrillar protein assemblies was investigated. Results of viscosity measurements were analysed using percolation theory, where the effect of shear flow was taken into account. The experimental results were compared with our theoretical calculations for the percolation concentration versus shear, based on a random contact model for rodlike particles, making use of a shear dependent excluded volume per fibril. In conclusion conditions leading to gel formation, in terms of mesoscopic fibril properties, under non-flow conditions have been discussed. The observed critical gelation concentration was explained in terms of an excluded volume per fibril (at zero shear). The influence of shear flow on this critical gelation concentration was also described. Here, the critical percolation concentration versus shear flow could again be expressed in terms of an excluded volume per fibril, in this case as a function of shear.

Keywords: pentosans, gluten yield, gluten properties, glutenin macropolymerThe gluten protein polymeric network plays a pivotal role in determining the end-use quality of wheat in many food products. The properties of this polymeric network are strongly affected by wheat flour composition (protein, starch and pentosans etc.), ingredients (i.e. salt, fat), processing aids (i.e. enzymes) and process parameters (mixing time, mixing water, temperature). Although the content of pentosans, usually divided into water unextractable solids (WUS) and water extractable pentosans (WEP) in wheat flour is low (1-2%w/w), these polymers play an important role in gluten formation and properties. Unravelling the underlying relationships and understanding the effect of pentosans on gluten network formation is, therefore, of extreme importance. The aim of this thesis is to clarify the mechanism of action of pentosans on gluten formation and properties. The study was greatly facilitated by the use of a miniaturized set-up for gluten-starch separation. This allowed us to systematically study the effect of pentosans on gluten formation and properties gluten.The results show that both WUS and WEP affect gluten yield, composition and properties in a similar fashion. Pretreatment of WUS and WEP with xylanase did not remove the negative effect on gluten yield, but addition of xylanase or ferulic acid (FA) during gluten extraction did. Added pentosans hinder gluten agglomeration even if they are only present during the dough dilution phase. This is only partly related to a viscosity effect. FA related interactions are more important here. Both act on the ability of glutenin macropolymer (GMP) particles to form gluten, affecting both gluten yield and gluten rheological properties. We propose that pentosans interfere with gluten formation in both an indirect and a direct way. The indirect effect is related to water availability. The direct effect is related to an interaction between pentosans and gluten in which FA plays an important role.The interference of WUS or WEP with gluten formation caused an incomplete aggregation of gluten protein, which was reflected in a larger average GMP particle size and a smaller tendency of these particles to aggregate. If xylanase or FA were added, aggregation was more complete, which was reflected in a smaller average GMP particle size and a larger tendency of these particles to aggregate. Now, also smaller GMP particles were recovered. The same trend was found with three wheat cultivars of very different qualities. Based on our results, we propose a possible explanation for the effect of pentosans on gluten formation and properties. Both a physical effect and a chemical effect are involved. The physical effect is related to viscosity and likely also depletion attraction between protein particles. The chemical effect is related to FA and 'controls' the tendency of the particles to aggregate and hence also gluten yield. In our explanation pentosans do not so much affect the growth of these particles directly after mixing, but hinder the further agglomeration of especially smaller particles to end up in the gluten. The partial agglomeration of GMP particles will result in turn in GMP with a different GMP particle size distribution and hence in gluten with changed rheological properties.

Keywords: pentosans, gluten yield, gluten properties, glutenin macropolymerThe gluten protein polymeric network plays a pivotal role in determining the end-use quality of wheat in many food products. The properties of this polymeric network are strongly affected by wheat flour composition (protein, starch and pentosans etc.), ingredients (i.e. salt, fat), processing aids (i.e. enzymes) and process parameters (mixing time, mixing water, temperature). Although the content of pentosans, usually divided into water unextractable solids (WUS) and water extractable pentosans (WEP) in wheat flour is low (1-2%w/w), these polymers play an important role in gluten formation and properties. Unravelling the underlying relationships and understanding the effect of pentosans on gluten network formation is, therefore, of extreme importance. The aim of this thesis is to clarify the mechanism of action of pentosans on gluten formation and properties. The study was greatly facilitated by the use of a miniaturized set-up for gluten-starch separation. This allowed us to systematically study the effect of pentosans on gluten formation and properties gluten.The results show that both WUS and WEP affect gluten yield, composition and properties in a similar fashion. Pretreatment of WUS and WEP with xylanase did not remove the negative effect on gluten yield, but addition of xylanase or ferulic acid (FA) during gluten extraction did. Added pentosans hinder gluten agglomeration even if they are only present during the dough dilution phase. This is only partly related to a viscosity effect. FA related interactions are more important here. Both act on the ability of glutenin macropolymer (GMP) particles to form gluten, affecting both gluten yield and gluten rheological properties. We propose that pentosans interfere with gluten formation in both an indirect and a direct way. The indirect effect is related to water availability. The direct effect is related to an interaction between pentosans and gluten in which FA plays an important role.The interference of WUS or WEP with gluten formation caused an incomplete aggregation of gluten protein, which was reflected in a larger average GMP particle size and a smaller tendency of these particles to aggregate. If xylanase or FA were added, aggregation was more complete, which was reflected in a smaller average GMP particle size and a larger tendency of these particles to aggregate. Now, also smaller GMP particles were recovered. The same trend was found with three wheat cultivars of very different qualities. Based on our results, we propose a possible explanation for the effect of pentosans on gluten formation and properties. Both a physical effect and a chemical effect are involved. The physical effect is related to viscosity and likely also depletion attraction between protein particles. The chemical effect is related to FA and 'controls' the tendency of the particles to aggregate and hence also gluten yield. In our explanation pentosans do not so much affect the growth of these particles directly after mixing, but hinder the further agglomeration of especially smaller particles to end up in the gluten. The partial agglomeration of GMP particles will result in turn in GMP with a different GMP particle size distribution and hence in gluten with changed rheological properties.

Keywords: soy protein isolate, glycinin,β-conglycinin, heat denaturation, gelation, network structure, rheology, permeability measurements, microscopy, pH, ionic strength, emulsified oil dropletsThis study was performed to understand the factors determining heat-induced formation and properties of soy protein gels the relations between gel properties and network structure in order to support application of soy proteins in food products. Three soy protein preparations were used: soy protein isolate, which is a mixture of soy proteins, purified glycinin and aβ-conglycinin rich fraction. Glycinin andβ-conglycinin are the main proteins in soybeans. Protein denaturation was studied by differential scanning calorimetry. Rheological properties of the soy protein gels were investigated in small and large deformation tests. Information on coarseness of the network structure was obtained by permeability measurements and confocal scanning laser microscopy.Heat denaturation proved to be a prerequisite for gel formation at all conditions of pH and ionic strength studied.β-Conglycinin gels were formed at temperatures of about 55-70°C and glycinin gels at about 70-95°C. Soy protein isolate gels were formed on heat denaturation ofβ-conglycinin at pH lower than 6 and on heat denaturation of glycinin at pH higher than 6. On further heating at 90 or 95°C, gels became stiffer, which was explained by further incorporation of protein in the network and, at pH 7 and 7.6, by the occurrence of rearrangements in the network structure. Gel stiffening on cooling was thermoreversibel and did not involve covalent bond formation and rearrangements.Gel properties like stiffness, fracture behaviour and water holding capacity strongly depend on conditions during gel formation, such as pH, salt concentration, protein concentration, heating conditions and addition of oil droplets. Also the type of protein, glycinin orβ-conglycinin, and their mixing ratio affect gel properties. The differences in gel properties could, for a large part, be related to differences in the network structure of the gels. The most important structural characteristics are pore size, thickness and curvature of the strands. Another factor determining gel properties is the amount of protein incorporated in the network. At pH > 5, less protein (mainly acidic polypeptides) participated in network formation than at lower pH values.

Keywords: soy protein isolate, glycinin,β-conglycinin, heat denaturation, gelation, network structure, rheology, permeability measurements, microscopy, pH, ionic strength, emulsified oil dropletsThis study was performed to understand the factors determining heat-induced formation and properties of soy protein gels the relations between gel properties and network structure in order to support application of soy proteins in food products. Three soy protein preparations were used: soy protein isolate, which is a mixture of soy proteins, purified glycinin and aβ-conglycinin rich fraction. Glycinin andβ-conglycinin are the main proteins in soybeans. Protein denaturation was studied by differential scanning calorimetry. Rheological properties of the soy protein gels were investigated in small and large deformation tests. Information on coarseness of the network structure was obtained by permeability measurements and confocal scanning laser microscopy.Heat denaturation proved to be a prerequisite for gel formation at all conditions of pH and ionic strength studied.β-Conglycinin gels were formed at temperatures of about 55-70°C and glycinin gels at about 70-95°C. Soy protein isolate gels were formed on heat denaturation ofβ-conglycinin at pH lower than 6 and on heat denaturation of glycinin at pH higher than 6. On further heating at 90 or 95°C, gels became stiffer, which was explained by further incorporation of protein in the network and, at pH 7 and 7.6, by the occurrence of rearrangements in the network structure. Gel stiffening on cooling was thermoreversibel and did not involve covalent bond formation and rearrangements.Gel properties like stiffness, fracture behaviour and water holding capacity strongly depend on conditions during gel formation, such as pH, salt concentration, protein concentration, heating conditions and addition of oil droplets. Also the type of protein, glycinin orβ-conglycinin, and their mixing ratio affect gel properties. The differences in gel properties could, for a large part, be related to differences in the network structure of the gels. The most important structural characteristics are pore size, thickness and curvature of the strands. Another factor determining gel properties is the amount of protein incorporated in the network. At pH > 5, less protein (mainly acidic polypeptides) participated in network formation than at lower pH values.

Onderzoek naar de relatie tussen moleculaire structuur van eiwitten en het schuimgedrag van de oplossing

Dit IOP Industriële Eiwitten project is gericht op het leggen van relaties tussen biochemische karakteristieken van tarwegluten en hun reologisch gedrag. Op deze wijze wordt inzicht verkregen in structuurfunctie relaties van tarwegluten, met name gericht op bakkerijtoepassingen. Voor dit onderzoek zijn zes Europese tarwe-variëteiten geselecteerd, die vergelijkbare eiwitgehaltes hebben, maar een groot verschil in bakkwaliteit vertonen. Kwaliteitsverschillen tussen deze variëteiten uiten zich het meest in de benodigde kneedtijd om optimale bakkwaliteit te bereiken. Er zijn duidelijke aanwijzingen dat hieraan een aantal biochemische factoren ten grondslag liggen zoals de hoeveelheid van het glutenine polymeer, de polymerisatie ervan en de mate van fysische interacties tussen de gluten-eiwitten

Het geven van een gewenste consistentie of van een bepaalde vaste vorm aan eiwitbevattende mengsels komt in het algemeen neer op het doen geleren van het eiwit. De vraag welke soorten reologische eigenschappen dan nodig zijn wordt kort besproken. Daarna komen de drie voornaamste typen eiwitgelen aan de orde, te weten gelatine, deeltjesgelen (bijvoorbeeld van caseïnedeeltjes) en gelen gevormd als gevolg van hittedenaturatie van globulaire eiwitten (bijvoorbeeld van ovalbumine, ß-lactoglobuline, sommige vleeseiwitten). Deze typen verschillen nogal in vormingswijze en in eigenschappen