Swelling of high acyl gellan gum hydrogel: Characterization of network strengthening and slower release.

This study examined the mechanism of swelling for high acyl (HA) gellan gum and the impacts on the hydrogel mechanical properties and the release of a model drug (glucose). Controlling the material properties and the release of entrapped drugs during use in aqueous environments, such as the stomach or bodily fluids, are crucial in designing functional applications. Swelling of HA gellan gum was controlled by varying the osmotic environment with salts and solvents, and effects on the gel network were characterized by uniaxial compression tests, DSC, and rheology. Low ionic strength solutions caused the greatest degree of swelling (up to 400 %) and corresponded to a more brittle gel with a greater modulus and greater network enthalpy. Swelling slowed the release of glucose by decreasing the diffusion flux. The osmotic environment was found to produce different functional properties, and it is crucial to consider these changes in the design of formulations.

Temperature influences on network formation of low DE maltodextrin gels.

Gelation of maltodextrin (DE 2) was examined over a range of temperatures to understand the behaviour within mixed-gel systems. Maltodextrin solutions were prepared at 95 °C and held at temperatures between 5 °C and 60 °C for four days. Bulk gel properties and the underlying microstructure were analysed using fracture strength, proton relaxation time, and differential scanning calorimetry (DSC). Holding at lower temperatures led to a greater gel strength with a brittle and crumbly texture. Analysis of the microstructure showed that gelation at 10 °C versus 60 °C produced a greater number of aggregates (melting enthalpy 14.5 J/g versus 3.4 J/g) and structuring of a higher melting entropy (45 mJ/g K versus 10 mJ/g K). A thermal hysteresis with signs of structure corresponding to both holding temperatures was also measured. Elevated temperature was hypothesized to decrease the amount of smaller molecular weight chains participating in aggregation by shifting from the helix to coil form.

The hydrophobic modification of kappa carrageenan microgel particles for the stabilisation of foams.

HYPOTHESIS: Polysaccharides such as kappa carrageenan are often utilised in fat replacement techniques in the food industry. However, the structural role they can provide within a product is limited by their hydrophilic nature. Hydrophilic particles can be surface-activated by hydrophobic modification e.g. in-situ interaction with a surfactant. This can drastically improve foam stability by providing a structural barrier around bubble interfaces offering protection against disproportionation and coalescence. Hence, it should be possible to bind negatively charged kappa carrageenan particles with a cationic surfactant through electrostatic interaction, in order to alter their surface properties. EXPERIMENTS: Lauric arginate was mixed with kappa carrageenan microgel particles at various concentrations and the potential electrostatic interaction was studied using zeta potential, turbidity and rheological measurements. Mixtures were then aerated and foaming properties explored, in particular the location of the particles. FINDINGS: Lauric arginate was successfully bound to kappa carrageenan microgel particles. Consequently, particles were surface-activated and adsorbed at the air/water interface, as shown by optical and confocal microscopy. Foam half-life peaked at an intermediate surfactant concentration, where there was sufficient surfactant to coat particle surfaces but the concentration was low enough to prevent the formation of large aggregates unable to adsorb at the a/w interfaces.

Fabrication, characterisation and stability of oil-in-water emulsions stabilised by solid lipid particles: the role of particle characteristics and emulsion microstructure upon Pickering functionality.

The quest to identify and use bio-based particles with a Pickering stabilisation potential for food applications has lately been particularly substantial and includes, among other candidates, lipid-based particles. The present study investigates the ability of solid lipid particles to stabilise oil-in-water (o/w) emulsions against coalescence. Results obtained showed that emulsion stability could be achieved when low amounts (0.8 wt/wt%) of a surface active species (e.g. Tween 80 or NaCas) were used in particles' fabrication. Triple staining of the o/w emulsions enabled the visualisation of emulsion droplets' surface via confocal microscopy. This revealed an interfacial location of the lipid particles, hence confirming stabilisation via a Pickering mechanism. Emulsion droplet size was controlled by varying several formulation parameters, such as the type of the lipid and surface active component, the processing route and the polarity of the dispersed phase. Differential scanning calorimetry (DSC) was employed as the analytical tool to quantify the amount of crystalline material available to stabilise the emulsion droplets at different intervals during the experimental timeframe. Dissolution of lipid particles in the oil phase was observed and evolved distinctly between a wax and a triglyceride, and in the presence of a non-ionic surfactant and a protein. Yet, this behaviour did not result in emulsion destabilisation. Moreover, emulsion's thermal stability was found to be determined by the behaviour of lipid particles under temperature effects.

Functional food microstructures for macronutrient release and delivery.

There is a need to understand the role of fat, protein and carbohydrate in human health, and also how foods containing and/or structured using these macronutrients can be designed so that they can have a positive impact on health. This may include a reduction in fat, salt or sugar, the protection and targeted release of micronutrients or active ingredients from/to particular parts of the digestive system, improvement of gastrointestinal health or satiety enhancing properties. Such foods can be designed with various macro- and microstructures that will impact on macronutrient release and delivery. These include simple and double emulsions, the use of Pickering particles and shells, nanoparticles, liposomes, gelled networks, fluid gels and gel particles, foams, self-assembled structures, and encapsulated systems. In order to design foods that deliver these benefits understanding of how these structures behave in the gastrointestinal tract is also required, which should involve utilising both in vitro and in vivo studies. This review aims to draw together research in these areas, by focusing on the current state of the art, but also exciting possibilities for future research and food development.

Physical and material properties of an emulsion-based lipstick produced via a continuous process.

OBJECTIVES: Water-in-oil emulsions in lipsticks could have the potential to improve moisturizing properties and deliver hydrophilic molecules to the lips. The aim of this work was to investigate the effect of a continuous process (scraped surface heat exchanger (SSHE) and pin stirrer (PS)) on the physical and material properties of an emulsion-based lipstick by altering the processing conditions of both the SSHE and PS. METHODS: Emulsion formation was achieved using a SSHE and PS. Emulsions were analysed using nuclear magnetic resonance restricted diffusion (droplet size), texture analysis and rheology (mechanical properties). RESULTS: Results showed that a higher impeller rotational velocity (IRV) (1500 r.p.m.) and a lower exit temperature (52°C) produce the smallest droplets (~ 4 µm), due to greater disruptive forces and a higher viscosity of the continuous phase. The addition of a PS reduces the droplet size (14-6 µm) if the SSHE has a low IRV (500 r.p.m.), due to greater droplet disruption as the emulsion passes through the PS unit. Results also show that if the jacket temperature of a SSHE is 65°C, so that crystallization occurs in both process and post-production, droplets can be integrated into the network resulting in a stiffer wax network (G' - 0.12, in comparison to 0.02 MPa). This is due to small crystals creating a shell around water droplets which can form connections with the continuous network forming a structured network. The addition of a pin stirrer can disrupt a formed network reducing the stiffness of the emulsion (0.3-0.05 MPa). CONCLUSION: This work suggests the potential use of a continuous process in producing an emulsion-based lipstick, particularly when wax crystals are produced in the process. Future work should consider the moisturizing or lubricating properties of wax continuous emulsions and the release of hydrophilic compounds from the aqueous phase.

Fat crystallisation at oil-water interfaces.

This review focuses on recent advances in the understanding of lipid crystallisation at or in the vicinity of an interface in emulsified systems and the consequences regarding stability, structure and thermal behaviour. Amphiphilic molecules such as emulsifiers are preferably adsorbed at the interface. Such molecules are known for their ability to interact with triglycerides under certain conditions. In the same manner that inorganic crystals grown on an organic matrix see their nucleation, morphology and structure controlled by the underlying matrix, recent studies report a templating effect linked to the presence of emulsifiers at the oil/water interface. Emulsifiers affect fat crystallisation and fat crystal behaviour in numerous ways, acting as impurities seeding nucleation and, in some cases, retarding or enhancing polymorphic transitions towards more stable forms. This understanding is of crucial importance for the design of stable structures within emulsions, regardless of whether the system is oil or water continuous. In this paper, crystallisation mechanisms are briefly described, as well as recent technical advances that allow the study of crystallisation and crystal forms. Indeed, the study of the interface and of its effect on lipid crystallisation in emulsions has been limited for a long time by the lack of in-situ investigative techniques. This review also highlights reported interfacial effects in food and pharmaceutical emulsion systems. These effects are strongly linked to the presence of emulsifiers at the interface and their effects on crystallisation kinetics, and crystal morphology and stability.

Interfacial behaviour of sodium stearoyllactylate (SSL) as an oil-in-water pickering emulsion stabiliser.

The ability of a food ingredient, sodium stearoyllactylate (SSL), to stabilise oil-in-water (O/W) emulsions against coalescence was investigated, and closely linked to its capacity to act as a Pickering stabiliser. Results showed that emulsion stability could be achieved with a relatively low SSL concentration (≥0.1 wt%), and cryogenic-scanning electron microscopy (cryo-SEM) visualisation of emulsion structure revealed the presence of colloidal SSL aggregates adsorbed at the oil-water interface. Surface properties of SSL could be modified by altering the size of these aggregates in water; a faster decrease in surface tension was observed when SSL dispersions were subjected to high pressure homogenisation (HPH). The rate of SSL adsorption at the sunflower oil-water interface also increased after HPH, and a higher interfacial tension (IFT) was observed with increasing SSL concentration. Differential scanning calorimetry (DSC) enabled a comparison of the thermal behaviour of SSL in aqueous dispersions with SSL-stabilised O/W emulsions. SSL melting enthalpy depended on emulsion interfacial area and the corresponding DSC data was used to determine the amount of SSL adsorbed at the oil-water interface. An idealised theoretical interfacial coverage calculation based on Pickering emulsion theory was in general agreement with the mass of SSL adsorbed as predicted by DSC.

Effect of emulsifier type and concentration, aqueous phase volume and wax ratio on physical, material and mechanical properties of water in oil lipsticks.

OBJECTIVES: Water-in-oil emulsions in lipsticks could have the potential to improve moisturizing properties and deliver hydrophilic molecules to the lips. The aims of this work were (i) to investigate the effect of emulsifier type (polymer vs. monomer, and saturated vs. unsaturated chain) and concentration on droplet size and (ii) to investigate the effect of wax ratio (carnauba wax, microcrystalline wax, paraffin wax and performalene) and aqueous phase volume on material properties (Young's modulus, point of fracture, elastic modulus and viscous modulus). METHODS: Emulsion formation was achieved using a high shear mixer. RESULTS: Results showed that the saturated nature of the emulsifier had very little effect on droplet size, neither did the use of an emulsifier with a larger head group (droplet size ~18-25 µm). Polyglycerol polyricinoleate (PGPR) resulted in emulsions with the smallest droplets (~3-5 µm), as expected from previous studies that show that it produces a thick elastic interface. The results also showed that both Young's modulus and point of fracture increase with increasing percentage of carnauba wax (following a power law dependency of 3), but decrease with increasing percentage of microcrystalline wax, suggesting that the carnauba wax is included in the overall wax network formed by the saturated components, whereas the microcrystalline wax forms irregular crystals that disrupt the overall wax crystal network. Young's modulus, elastic modulus and viscous modulus all decrease with increasing aqueous phase volume in the emulsions, although the slope of the decrease in elastic and viscous moduli is dependent on the addition of solid wax, as a result of strengthening the network. CONCLUSIONS: This work suggests the potential use for emulsions in lipstick applications, particularly when PGPR is used as an emulsifier, and with the addition of solid wax, as it increases network strength.

Boundary lubrication by sodium salts: a Hofmeister series effect.

Boundary lubrication plays an important role in the function of sliding surfaces in contact. Of particular interest in this study, boundary regime tribology is relevant for understanding textural attributes perceived during oral consumption of food, where the tongue squeezes and slides against the hard palate. This work investigates aqueous lubrication of a sliding/rolling ball-on-disc contact by sodium anions of the Hofmeister series in both water and guar gum solutions. Low concentrations (0.001 M) of strongly kosmotropic salts provide reduced friction coefficients in both systems (water and guar gum solutions), although a different mechanism prevails in each. Surface-bound hydrated ions are responsible in the case of water, and salt-promoted adsorption of hydrated-polymer chains dominate with guar gum. In each system, friction decreases in accordance with the Hofmeister series: iodide, nitrate, bromide, chloride, fluoride, phosphate and citrate. The addition of salt has little impact on solution of bulk viscosity, and so this work demonstrates that significant boundary lubrication can be provided without surface modification and with lubricants of viscosity similar to that of water.

Competitive adsorption of surfactants and hydrophilic silica particles at the oil-water interface: interfacial tension and contact angle studies.

The effect of surfactants' type and concentration on the interfacial tension and contact angle in the presence of hydrophilic silica particles was investigated. Silica particles have been shown to have an antagonistic effect on interfacial tension and contact angle in the presence of both W/O and O/W surfactants. Silica particles, combined with W/O surfactant, have no effect on interfacial tension, which is only dictated by the surfactant concentration, while they strongly affect interfacial tension when combined with O/W surfactants. At low O/W surfactant, both particles and surfactant are adsorbed at the interface, modifying the interface structure. At higher concentration, interfacial tension is only dictated by the surfactant. By increasing the surfactant concentration, the contact angle that a drop of aqueous phase assumes on a glass substrate placed in oil media decreases or increases depending on whether the surfactant is of W/O or O/W type, respectively. This is due to the modification of the wettability of the glass by the oil or water induced by the surfactants. Regardless of the surfactant's type, the contact angle profile was dictated by both particles and surfactant at low surfactant concentration, whereas it is dictated by the surfactant only at high concentration.

Design and application of water-in-oil emulsions for use in lipstick formulations.

The addition of water to lipsticks in the form of a water-in-oil emulsion is an attractive opportunity for cosmetics manufacturers to deliver hydrophilic molecules to the consumers, as well as improving the moisturizing properties. In this work, the effect of the emulsifier type and water content on the structural properties of the designed products was investigated. It has been shown that PGPR leads to smaller droplets than the other emulsifiers tested. This was attributed to the ability of PGPR to form elastic interfaces that slow the coalescence between droplets during the process. It was also observed that crystals of wax tend to form structures at the interface upon cooling that prevent coalescence during storage. These structures also prevent leakage of water into the continuous phase. No effect of the water content on the melting properties of the emulsions was observed. Upon addition of more than 10% water, softening of the material was measured, due to the overall decrease in solid content. Addition of crystalline material (hard paraffin) was successfully used to reinstate the material properties.

O/W emulsions stabilised by both low molecular weight surfactants and colloidal particles: The effect of surfactant type and concentration.

The stability against coalescence of O/W emulsions in the presence of both surfactants and colloidal particles was investigated. In particular the effect of the surfactant type and concentration in these emulsifier mixtures on the O/W emulsions' stability was studied. Two types of surfactants were selected; those that have the ability to stabilise O/W emulsions on their own (O/W surfactants) and those that cannot (W/O surfactants). Tween 60 and Sodium Caseinate were selected as the O/W surfactants and lecithin as the W/O surfactant. Oil-in-water emulsions prepared with both particles and any of the three surfactants were stable against coalescence but, depending on the type of surfactant, the behaviour of the systems was found to depend on surfactant concentration. The droplet sizes of emulsions stabilised by mixed emulsifier systems containing low concentrations of O/W surfactants (Tween 60 or Sodium Caseinate) were smaller than those solely stabilised by either the surfactant or particles alone. At intermediate O/W surfactants concentrations, the droplet sizes of the emulsions increased. Further increases in the O/W surfactants' concentration, resulted in the complete removal of particles from the interface with the system now behaving as a surfactant-only stabilised emulsion. The behaviour of emulsions stabilised by emulsifier mixtures containing W/O surfactants was not dependent on the concentration of surfactant: no removal of particles was observed.

Mass transfer and nutrient absorption in a simulated model of small intestine.

There is an increasing need to understand how food formulations behave in vivo from both food and pharma industries. A number of models have been proposed for the stomach, but few are available for the other parts of the gastrointestinal tract. An experimental rig that simulates the segmentation motion occurring in the small intestine has been developed. The objective of developing such an experimental apparatus was to study mass transport phenomena occurring in the lumen and their potential effect on the concentration of species available for absorption. When segmentation motion was applied the mass transfer coefficient in the lumen side was increased up to a factor of 7. The viscosity of the lumen, as influenced by guar gum concentration, had a profound effect on the mass transfer coefficient. The experimental model was also used to demonstrate that glucose available for absorption, resulting from starch hydrolysis, can be significantly reduced by altering the lumen viscosity. Results suggest that absorption of nutrients could be controlled by mass transfer. Practical Application: To address health-related diseases such as obesity, novel foods that provide advanced functions are required. To achieve the full potential offered by the latest developments in the field of food material science, a fundamental understanding of the behavior of food structures in vivo is required. Using the developed gut model we have demonstrated that absorption of nutrients can be controlled by mass transfer limitations.

Mixed-emulsifier stabilised emulsions: Investigation of the effect of monoolein and hydrophilic silica particle mixtures on the stability against coalescence.

The stability against coalescence of vegetable oil-in-water "food grade" emulsions in the presence of both surfactant (monoolein) and colloidal particles (hydrophilic silica) has been studied and compared to the stability of systems where only the low molecular weight surfactant or the colloidal particles act as the emulsifier. No attempt was made to stop the emulsions from creaming and the data presented for coalescence stability is for droplets in the creamed layer. These are severe conditions as the contact time between droplets in such closed packed conditions is very high or even infinite. These mixed emulsifier systems were found to induce long-term emulsion stability against coalescence via a synergistic "two-part" mechanism in which both the surfactant and colloidal particles components have specific functions. The role of the surfactant is to initially "delay" the re-coalescence phenomena and induce further droplet break-up during emulsification by rapidly covering the new (naked) interface and reducing interfacial tension in order to allow the time for the silica particles to assemble at the oil/water interface and provide long-term stability. This dual manner by which mixed-emulsifier systems induced stability was found to depend on the concentrations of both monoolein and silica particles.

Interfacial tension in aqueous biopolymer-surfactant mixtures.

The current study offers a first insight into the interfacial properties of pullulan-sodium dodecyl sulphate (SDS) aqueous two-phase systems (ATPS) in the presence of sodium chloride (NaCl). The effect of composition on the interfacial tension (sigma) in these ATPS was investigated over a wide range of pullulan, SDS and NaCl concentrations. An increase in the interfacial tension was observed with increasing pullulan and SDS concentrations and a small increase was also observed as the NaCl concentration was increased. In both cases the interfacial tension increases were closely related to the phase behaviour of these systems; as a consequence of increasing the pullulan, SDS and/or NaCl concentrations, the system moves further away from the critical point. In all systems interfacial tensions (of the order of muN/m) were comparable with those reported for polymer-polymer ATPS. Interfacial tensions sigma can be well correlated with the difference in pullulan and SDS concentrations between the phases (DeltaC pul and DeltaC SDS) and also the tie-line length (TLL); all yield straight lines on a log-log scale.

Micellar casein gelation at high sucrose content.

This article investigates the effect of sucrose addition on the formation of casein gels by acidification and/or renneting of pure micellar casein. Gelation kinetics and gel properties were followed by rheological methods, and microscopy and syneresis measurements were used to obtain a more complete characterization of the structures formed. Sucrose content has been identified as a key parameter for controlling the kinetics of aggregation and the strength of the final gels. Results have shown that the effect of sucrose on gelation can vary such that effects can be completely reversed depending on the gelation route used. During acid gelation, addition of up to 30% (wt/wt) sucrose causes gels to form more rapidly and at higher pH values, and to have higher viscoelastic moduli and a more homogeneous microstructure than those without sucrose. By contrast, gels formed by renneting in the presence of sucrose are weaker and have longer gelation times. It is proposed that sucrose reduces solvent quality and causes the collapse of the "hairy" kappa-casein brush on the surface of the casein micelles. This may explain why sucrose increases the possibility of gel formation during acidification and reduces the degree of kappa-casein hydrolysis during renneting.

Interfacial tension in phase-separated gelatin/dextran aqueous mixtures.

The effect of solute concentrations on interfacial tension was investigated in phase-separated mixtures of dextran and gelatin over a range of concentrations that covered different tie-lines and different positions on one tie-line. The investigations were carried out using equilibrated gelatin-rich and dextran-rich phases in a computer-controlled Couette device at 40 degrees C (above the gelation point of gelatin) and interfacial tensions were measured using the retracting drop method. The results show that the interfacial tension can be related to the length of the tie-line or to the difference in the concentration of dextran (or gelatin) in the separated phases. Interfacial tension increases as either of these parameters increases. For concentrations lying on any single tie-line, the interfacial tension is constant and independent of the concentration of biopolymers. Also, the addition of small amounts of low molecular weight dextran to a dextran-rich phase does not significantly affect the interfacial tension between the gelatine-rich and dextran-rich phases. Experimental results were also compared with theoretical predictions of the interfacial tension using a Flory-Huggins based analysis of the measured tie-line data. Reasonable agreement was found between predicted and measured values, indicating that this approach captures the basic physics of the system.

Gelation of casein-whey mixtures: effects of heating whey proteins alone or in the presence of casein micelles.

The aim of the present work was to investigate the role of whey protein denaturation on the acid induced gelation of casein. This was studied by determining the effect of whey protein denaturation both in the presence and absence of casein micelles. The study showed that milk gelation kinetics and gel properties are greatly influenced by the heat treatment sequence. When the whey proteins are denatured separately and subsequently added to casein micelles, acid-induced gelation occurs more rapidly and leads to gels with a more particulated microstructure than gels made from co-heated systems. The gels resulting from heat-treatment of a mixture of pre-denatured whey protein with casein micelles are heterogeneous in nature due to particulates formed from casein micelles which are complexed with denatured whey proteins and also from separate whey protein aggregates. Whey proteins thus offer an opportunity not only to control casein gelation but also to control the level of syneresis, which can occur.

Simulation of endo-PG digest patterns and implications for the determination of pectin fine structure.

Novel stepwise approaches to the calculation of enzyme digest patterns are described and used in the validation of a computer simulation. Results obtained using the simulation show that, while a previously proposed model of endo-PG action captures some of the salient features of this enzymes behaviour, it is not sufficient to successfully predict experimental digest patterns from pectic substrates. Subsequently, it has been shown that a modified model incorporating existing information regarding subsite architecture and speculative site tolerances for esterified residues, goes someway towards improving the situation.