Study of commodity properties of food emulsions Part 1. The effect of dispersion medium composition on kinetic stability of O/W emulsions containing proteins,acidic polysaccharides and calcium salts

The effect of concentrations of acidic polysaccharide and calcium ions on the kinetic stability, viscosity and dispersity of protein-containing O/W emulsions is studied. Variation of kinetic stability of the emulsions studied is independent of dispersion composition. In a wide range of calcium acetate concentrations a correlation is observed between kinetic stability and viscosity of emulsions at sodium alginate concentration in the dispersion medium ≤ 0.3%. The transition zone between liquid solution and gel is widened in the presence of sodium caseinate. Maximum kinetic stability is reached at calcium acetate: sodium alginate concentrations of 1.0-1.2 and ～ 6.0, corresponding to optimum conditions for formation of homogeneous crosslinked structures of calcium alginate and calcium caseinate.     

Oil-in-water emulsions stabilized by sodium caseinate: Influence of pH,high-pressure homogenization and locust bean gum addition

The effect of pH, addition of a thickening agent (locust bean gum) or high-pressure homogenization on the stability of oil-in-water emulsions added by sodium caseinate (Na-CN) was evaluated. For this purpose, emulsions were characterized by visual analysis, microstructure and rheological measurements. Most of the systems were not stable, showing phase separation a few minutes after emulsion preparation. However, creaming behavior was largely affected by the pH, homogenization pressure or locust bean gum (LBG) concentration. The most stable systems were obtained for emulsions homogenized at high pressure, containing an increased amount of LBG or with pH values close to the isoelectric point (pI) of sodium caseinate, which was attributed to the size reduction of the droplets, the higher viscosity of continuous phase and the emulsion gelation (elastic network formation), respectively. All the studied mechanisms were efficient to decrease the molecular mobility, which slowed down the phase separation of the emulsions. In addition, the use of sodium caseinate was also essential to stabilize the emulsions, since it promoted the electrostatic repulsive interactions between droplets.     

Interfacial composition and stability of emulsions made with mixtures of commercial sodium caseinate and whey protein concentrate

The interfacial composition and the stability of oil-in-water emulsion droplets (30% soya oil, pH 7.0) made with mixtures of sodium caseinate and whey protein concentrate (WPC) (1:1 by protein weight) at various total protein concentrations were examined. The average volume-surface diameter (d₃₂) and the total surface protein concentration of emulsion droplets were similar to those of emulsions made with both sodium caseinate alone and WPC alone. Whey proteins were adsorbed in preference to caseins at low protein concentrations (<3%), whereas caseins were adsorbed in preference to whey proteins at high protein concentrations. The creaming stability of the emulsions decreased markedly as the total protein concentration of the system was increased above 2% (sodium caseinate >1%). This was attributed to depletion flocculation caused by the sodium caseinate in these emulsions. Whey proteins did not retard this instability in the emulsions made with mixtures of sodium caseinate and WPC.     

Influence of xanthan gum on the formation and stability of sodium caseinate oil-in-water emulsions

Studies have been made of the changes in droplet sizes, surface coverage and creaming stability of emulsions formed with 30% (w/w) soya oil, and aqueous solution containing 1 or 3% (w/w) sodium caseinate and varying concentrations of xanthan gum. Addition of xanthan prior to homogenization had no significant effect on average emulsion droplet size and surface protein concentration in all emulsions studied. However, addition of low levels of xanthan (≤0.2 wt%) caused flocculation of droplets that resulted in a large decrease in creaming stability and visual phase separation. At higher xanthan concentrations, the creaming stability improved, apparently due to the formation of network of flocculated droplets. It was found that emulsions formed with 3% sodium caseinate in the absence of xanthan showed extensive flocculation that resulted in very low creaming stability. The presence of xanthan in these emulsions increased the creaming stability, although the emulsion droplets were still flocculated. It appears that creaming stability of emulsions made with mixtures of sodium caseinate and xanthan was more closely related to the structure and rheology of the emulsion itself rather than to the rheology of the aqueous phase.     

Improvement of stability of oil-in-water emulsions containing caseinate-coated droplets by addition of sodium alginate

ABSTRACT:  The potential of sodium alginate for improving the stability of emulsions containing caseinate-coated droplets was investigated. One wt% corn oil-in-water emulsions containing anionic caseinate-coated droplets (0.15 wt% sodium caseinate) and anionic sodium alginate (0 to 1 wt%) were prepared at pH 7. The pH of these emulsions was then adjusted to 3.5, so that the anionic alginate molecules adsorbed to the cationic caseinate-coated droplets. Extensive droplet aggregation occurred when there was insufficient alginate to completely saturate the droplet surfaces due to bridging flocculation, and when the nonadsorbed alginate concentration was high enough to induce depletion flocculation. Emulsions with relatively small particle sizes could be formed over a range of alginate concentrations (0.1 to 0.4 wt%). The influence of pHs (3 to 7) and sodium chloride (0 to 500 mM) on the properties of primary (0 wt% alginate) and secondary (0.15 wt% alginate) emulsions was studied. Alginate adsorbed to the droplet surfaces at pHs 3, 4, and 5, but not at pHs 6 and 7, due to electrostatic attraction between anionic groups on the alginate and cationic groups on the adsorbed caseinate. Secondary emulsions had better stability than primary emulsions at pH values near caseinate's isoelectric point (pHs 4 and 5). In addition, secondary emulsions were stable up to higher ionic strengths (< 300 mM) than primary emulsions (<50 mM). The controlled electrostatic deposition method utilized in this study could be used to extend the range of application of dairy protein emulsifiers in the food industry.     

Effect of Aqueous Phase Composition on Stability of Sodium Caseinate/Sunflower oil Emulsions

The aim of the present work was to investigate the effect of aqueous phase composition on the stability of emulsions formulated with 10 wt% sunflower oil as fat phase. Aqueous phase was formulated with 0.5, 2, or 5 wt% sodium caseinate, or sodium caseinate with the addition of two different hydrocolloids, xanthan gum or locust bean gum, both at 0.3 or 0.5 wt% level or sodium caseinate or with addition of 20 wt% sucrose. Emulsions were processed by Ultra-Turrax and then further homogenized by ultrasound. Creaming and flocculation kinetics were quantified by analyzing the samples with a Turbiscan MA 2000. Emulsions were also analyzed for particle size distribution, microstructure, viscosity, and dynamic surface properties. The most stable systems of all selected in the present work were the 0.3 or 0.5 wt% XG or 0.5 wt% LBG/0.5 wt% NaCas coarse emulsion and the 20 wt% sucrose/5 wt% NaCas fine emulsion. Surprisingly, coarse emulsions with the lower concentration of NaCas, which had greater D _4,3, were more stable than fine emulsions when the aqueous phase contained XG or LBG. In these conditions, the overall effect was less negative bulk interactions between hydrocolloids and sodium caseinate, which led to stability. Sugar interacted in a positive way, both in bulk and at the interface sites, producing more stable systems for small-droplet high-protein-concentration emulsions. This study shows the relevance of components interactions in microstructure and stability of caseinate emulsions.     

Textural properties of a model aqueous phase in low fat products. Part 2: Alginate/caseinate blends and three-component systems

Summary The second paper in this series completes the investigation of the textural properties of alginate, starch and caseinate preparations. Thus mixtures of alginate and caseinate show liquid-like properties up to 200 p.p.m. Ca²⁺. At higher levels of the counterion, alginate gels form a continuous matrix which supports the liquid-like caseinate inclusions. Caseinate acts mainly as a sequestrant for calcium ions. In the absence of added counterions, the ternary system is characterized by a weak starchy network which supports the liquid alginate and caseinate phases. Addition of Ca²⁺ produces a plethora of textures governed mainly by the alginate phase and the sequestering influence of caseinate. Intelligent manipulation of polymeric composition and levels of calcium resulted in binary systems of caseinate/starch, alginate/starch and caseinate/alginate capable of reproducing the texture of ternary mixtures, thus offering attractive alternatives to the commercial aqueous phases. In conclusion, it is demonstrated that basic understanding of ingredients and their properties in mixtures leads to purposeful formulation of products.     

Interfacial adsorption and shear flow properties of gum arabic-sodium caseinate mixtures

This work discusses rheological and physicochemical properties of sodium caseinate and gum arabic, in aqueous media (25 °C). All the systems showed low viscosity values and Newtonian behaviour in the shear rate range studied. From particle size distribution, a limited thermodynamic compatibility was observed since hydrocolloids mixtures showed particles size between the values from the systems alone. Interfacial tension measurements at equilibrium at the air-water interface, revealed that the binding affinity of arabic to the air water interface is very low compared to that of caseinate. The adsorption critical concentration could be deduced as a function of aqueous solutions composition. In competitive adsorption experiments involving simultaneous adsorption of the hydrocolloids from a bulk mixture, sodium caseinate displaced gum arabic from the interface at both polysaccharide concentrations, changing the adsorption critical concentration.     

Influence of EDTA and citrate on thermal stability of whey protein stabilized oil-in-water emulsions containing calcium chloride

The influence of calcium ions and chelating agents on the thermal stability of model nutritional beverages was examined. Oil-in-water emulsions (6.94% (w/v) soybean oil, 0.35% (w/v) WPI, 0.02% (w/v) sodium azide, 20 mM Tris buffer, 0–10 mM CaCl₂, and 0–40 mM EDTA or citrate, pH 7.0) were stored at temperatures between 30 and 120 °C for 15 min. The particle size, particle charge, creaming stability, rheology, and free-calcium concentration of the emulsions were then measured. In the absence of chelating agents, appreciable droplet aggregation occurred in emulsions held at temperatures from 80 to 120 °C, which led to increased emulsion particle diameter, shear-thinning behavior, apparent viscosity, and creaming instability. Addition of chelating agents to the emulsions prior to heating decreased, but did not prevent, droplet aggregation in the emulsions. EDTA was more effective than citrate in decreasing droplet aggregation. Heat treatment increased the amount of chelating agents required to prevent droplet aggregation in the emulsions. Free-calcium concentration and droplet surface potential was independent of heat-treatment temperature, indicating that the performance of the chelating agents in binding calcium ions was not affected by the heat treatment. It was suggested that increased hydrophobic attractive interactions between the droplets occurred during heating, which induced droplet aggregation.     

Physical properties of edible films made from mixtures of sodium caseinate and WPI

The physical properties of thin films (25–30 μm) made from mixtures of sodium caseinate (NaCas) and whey protein isolate (WPI) were investigated. Films were formed by mixing solutions of NaCas (2.5% w/w protein), plasticised with glycerol (NaCas–gly) at a glycerol:protein ratio of 0.32, with WPI solutions (2.3% w/w protein), plasticised (WPI-gly) at a glycerol:protein ratio 0.37. Tensile and water barrier properties of films formed from mixtures of NaCas–gly and WPI-gly were similar to films containing NaCas–gly only. Films containing only WPI-gly had higher maximum load and elastic modulus values than the mixed films. Increasing the NaCas–gly content of the films from 25 to 100% greatly increased solubility. This increased film solubility may increase the number of food applications for protein-based films.     

Characterization and improvement of rheological properties of sodium caseinate glycated with galactose, lactose and dextran

The aim of this work was to investigate the effect of non-enzymatic glycosylation with galactose, lactose, and 10 kDa dextran on the rheological properties of sodium caseinate. To promote the formation of covalent complexes, the reaction was done in solid state (a_w = 0.67), pH 7.0 (0.1 M sodium phosphate buffer), and temperature set at 50 and 60 °C. The progress of Maillard reaction was indirectly traced by measuring the formation of the Amadori compound, through furosine (2-furoylmethyl-lysine) analysis, and brown polymers, and the resulting glycoconjugates were characterized by LC/ESI-MS and SEC. Results showed a higher reactivity of galactose than lactose and dextran to form the glycoconjugates, due to its smaller molecular weight. Glycation with galactose and lactose increased the viscosity of caseinate and also altered its flow characteristics from Newtonian to shear-thinning. Oscillatory testing showed a higher elastic modulus (G′) in glycoconjugates when compared to non-glycated caseinate, especially with galactose, where a gel-like behaviour was observed after long incubation times. Glycation with dextran did not produce substantial improvements in the rheological properties of caseinate, probably due to the limited extent of the reaction. Our results show that by controlling the rate and extent of the Maillard reaction is a technologically feasible operation to improve the viscosity and gelling properties of sodium caseinate-based ingredients.     

Double emulsion (W/O/W) gel stabilised by polyglycerol polyricinoleate and calcium caseinate as mangiferin carrier: insights on formulation and stability properties

Mangiferin (MGF) is a phenolic compound isolated from mango, but its poor solubility significantly limits its use. In this study, MGF was embedded into the inner aqueous phase of W₁/O/W₂ emulsions. Firstly, the dissolution method of MGF was determined. MGF remained stable in solution with pH 13 at 30 min, and its solubility reached 10 mg mL⁻¹. When the pH of MGF solutions was adjusted from pH 13 to pH 6, MGF did not immediately crystallise, providing sufficient time to construct the MGF-loaded W₁/O/W₂ emulsions. Subsequently, the MGF-loaded W₁/O/W₂ emulsions were constructed using polyglycerol polyricinoleate (PGPR) and calcium caseinate (CAS). The formation and stability of the W₁/O/W₂ emulsions were investigated. The MGF-loaded W₁/O/W₂ emulsions stabilised with 1% PGPR and 1% – 3% CAS exhibited a low viscosity, limited loading capacity, and poor stability. Conversely, the MGF-loaded W₁/O/W₂ emulsions stabilised by 3%PGPR–3%CAS exhibited optimal loading capacity (encapsulation efficiency = 95.31% and loading efficiency = 0.91%) and stability, which was attributed to the fact that high viscosity and gel state retarded the migration of inner aqueous phase. These results indicated that the W₁/O/W₂ emulsions stabilised by PGPR and CAS may be a potential alternative for encapsulating mangiferin.     

Temperature-dependent complexation between sodium caseinate and gum arabic

Complex formation between sodium caseinate and gum arabic as a function of temperature was investigated using dynamic light scattering, fluorescence and NMR. At neutral pH, the turbidity and the particle size increased when sodium caseinate and gum arabic mixtures were heated in situ at temperatures above a critical temperature. The increases in turbidity and particle size were reversible. This effect was considered to be due to hydrophobic interactions, leading to the formation of a complex between sodium caseinate and gum arabic. ¹H NMR spectroscopy showed that ANS, which bound to caseinate at low temperatures in caseinate solution or a caseinate-gum arabic mixture, was released at high temperatures upon formation of a caseinate or caseinate-gum arabic complex. This supported changes observed in the fluorescence of 8-anilino-1-naphthalene sulfonate upon binding to caseinate, which decreased at high temperatures for caseinate alone or when sodium caseinate was mixed with gum arabic. Light-scattering (turbidity) and dynamic light-scattering studies show that the temperature-dependent complexation between sodium caseinate and gum arabic was sensitive to the mass ratio of protein to gum arabic (greater complexation at a 1:5 ratio than a 1:1 ratio) and the pH (maximum complexation at pH 6.5).     

Calcium-Induced Destabilization of Oil-in-Water Emulsions Stabilized by Caseinate or by β-Lactoglobulin

The stability to aggregation of 20% soya oil-in-water emulsions stabilized by 0.3 to 2% sodium caseinate or β-lactoglobulin in the presence of calcium chloride solutions was studied using light scattering and electron microscopy. Stability increased with the amount of protein in the emulsion, and decreased with the concentration of added calcium. Growth of particle size with concentration of Ca²⁺ was more in emulsions containing lower concentrations of protein. Sodium chloride at 50 and 100 mM stabilized both systems to the presence of calcium ions. Microstructure and light scattering showed caseinate emulsions formed clusters even at low concentrations of Ca²⁺ while β-lactoglobulin emulsions formed extensive strands.     

Effect of hydrocolloid type and concentration on flow behaviour and sensory properties of milk beverages model systems

Formulation of low-calorie flavoured milk beverages involves the use of hydrocolloids to obtain an acceptable mouthfeel. Sodium alginate and κ-carrageenan are the most commonly used. In this paper, the rheological behaviour of model solutions containing either of these two hydrocolloids, with or without the addition of sucrose, in water or milk, has been studied. All solutions fitted well to the Ostwald de Waele model. The analyses of variance showed that in κ-carrageenan solutions, the effect of the medium–hydrocolloid interaction on both flow index (n) and apparent viscosity at 1 s⁻¹ (η₁) was significant. Milk-based solutions were more pseudoplastic and more viscous than the aqueous solutions, due to the well known κ-carrageenan–casein molecular interaction. In alginate solutions, the medium–hydrocolloid interaction was also significant but the differences in both n and η₁ values were of less entity. Sensory viscosity differences of more viscous chocolate milk model systems were well explained by apparent viscosity values at low shear rate (10 s⁻¹), while for less viscous samples apparent viscosity at higher shear rate (300 s⁻¹) values were appropriate. At similar viscosity, κ-carrageenan systems showed better flavour-releasing properties than alginate.     

Influence of calcium on tensile, optical and water vapour permeability properties of sodium caseinate edible films

The influence of calcium on sodium caseinate edible films with and without lipid addition (oleic acid (OA)–beeswax (BW) mixtures) was investigated through the analysis of tensile, optical and water vapour barrier properties. Calcium was added by substitution of sodium caseinate by calcium caseinate. Calcium caseinate films have less transparency and more rigidity but they have lower water vapour permeability values than sodium caseinate films. The effect of substitution was different for films with and without lipids. Calcium caseinate increased tensile strength and decreased elongation of films, depending on the level of substitution and lipid presence. Among control films (without lipid), water vapour permeability was reduced when calcium caseinate was present, reaching values of 3.9 (±0.2) g mm kPa⁻¹ h⁻¹ m⁻². Nevertheless, in the films containing lipids, this reduction was inhibited when the level of sodium caseinate substitution exceeded 50%. Film transparency and gloss was reduced by calcium caseinate and lipid presence, although pure calcium caseinate films were glossier. When taking all the studied variables into account, the films prepared with 2:1 NaCas:CaCas ratio and 70:30 OA:BW ratio showed the most adequate properties.     

Stability of protein‐stabilised β‐carotene nanodispersions against heating,salts and pH

BACKGROUND: Milk proteins are used in a wide range of formulated food emulsions. The stability of food emulsions depends on their ingredients and processing conditions. In this work, β‐carotene nanodispersions were prepared with selected milk‐protein products using solvent‐displacement method. The objective of this work was to evaluate the stability of these nanodispersions against heating, salts and pH. RESULTS: Sodium caseinate (SC)‐stabilised nanodispersions possessed the smallest mean particle size of 17 nm, while those prepared with whey‐protein products resulted in larger mean particle sizes (45–127 nm). Formation of large particles (mean particle size of 300 nm) started after 1 h of heating at 60 °C in nanodispersions prepared with SC. More drastic particle size changes were observed in nanodispersions prepared with whey protein concentrate and whey protein isolate. The SC‐stabilised nanodispersions were fairly stable against Na⁺ ions at concentrations below 100 mmol L^?1, but drastic aggregation occurred in ≥ 50 mmol L^?1 CaCl₂ solutions. Aggregation was also observed in whey protein‐stabilised nanodispersions after the addition of NaCl and CaCl₂ solutions. All sample exhibited the smallest mean particle size at neutral pH, but large aggregates were formed at both ends of extreme pH and at pH around the isoelectric point of the proteins. CONCLUSION: The nanodispersions prepared with SC were generally more stable against thermal processing, ionic strength and pH, compared to those prepared with whey proteins. The stable β‐carotene nanodispersions showed a good potential for industrial applications. Copyright © 2008 Society of Chemical Industry     

Effect of processing conditions and composition on sodium caseinate emulsions stability

Many food products such as ice cream, yoghurt, and mayonnaise are some examples of emulsion-based food. The physicochemical properties of emulsions play an important role in food systems as they directly contribute to texture, sensory and nutritional properties of food. One of the main properties is stability which refers to the ability of an emulsion to resist physical changes over time. The aim of the present work was to analyze the effect of processing conditions and composition on sodium caseinate (NaCas) emulsions stability. The main destabilization mechanisms were identified and quantified. The relationship between them and the factors that influence them were also investigated. Emulsions stabilized with NaCas were prepared using an ultrasound liquid processor or a high pressure homogenizer. Stability of emulsions was followed by a Turbiscan (TMA 2000) which allows the optical characterization of any type of dispersion. The physical evolution of this process is followed without disturbing the original system and with good accuracy and reproducibility. To further describe systems, droplet size distribution was analyzed with light scattering equipment. The main mechanism of destabilization in a given formulation depended on different factors such as NaCas concentration, droplet size or processing conditions. The rate of destabilization was markedly lower with addition of sugar or a hydrocolloid to the aqueous phase. Xanthan (XG) and locust bean (LBG) gums produced an increase in viscosity of the continuous phase and structural changes in emulsions such as gelation. Sugars interacted with the protein decreasing particle size and increasing emulsion stability. The stability of caseinate emulsions was strongly affected not only by the oil-to-protein ratio but also by processing conditions and composition of aqueous phase. The structure of the protein and the interactions protein–sugar or the presence of a hydrocolloid played a key role in creaming and flocculation processes of these emulsions.     

一种水包油包胶型乳液的制备及其在乳化肠中的应用

以结冷胶和无水氯化钙为内水相凝固剂,酪蛋白酸钠为外水相乳化剂,制备一种水包油包胶（S/O/W）型 乳液。以多重乳液粒径和分布为指标,研究酪蛋白酸钠添加量对S/O/W型多重乳液加工适应性的影响。结果表明： 正交试验得到S/O型单重乳液最佳制备条件为：内水相中结冷胶添加量0.2%、无水氯化钙添加量0.5%;内水相乳化 剂聚甘油蓖麻醇酯添加量2.5%;油相为精炼猪油,油水体积比3∶2;剪切速率17 500 r/min,剪切时间1.5 min。将制 得的S/O型单重乳液与不同添加量酪蛋白酸钠混合制得S/O/W型多重乳液。当酪蛋白酸钠添加量0.1%时,S/O/W型 多重乳液粒径符合加工要求,且贮藏、热处理、剪切稳定性较好。以多重乳液替代猪脂肪制备的低脂乳化肠与高脂 （精炼猪油含量20%）乳化肠外观不存在明显差异;微观结构观察结果表明,多重乳液在乳化肠中包裹良好、分布 均匀。     

Water Vapor Permeability of Caseinate-Based Edible Films as Affected by pH, Calcium Crosslinking and Lipid Content

Edible films were cast from solutions of sodium or calcium caseinate and from emulsions of these proteins with acetylated monoglyceride, beeswax, and stearic acid. The water vapor permeabilities of the films were evaluated at 25°C using the ASTM E96–80 method, modified to calculate the % relative humidity at the film underside. Adjustment to pH 4.6 (isoelectric point), calcium ion crosslinking and combined effects of calcium ascorbate buffer (pH 4.6) reduced water vapor permeability of sodium caseinate films by 36%, 42%, and 43%, respectively. Calcium caseinate-beeswax emulsion films had water vapor permeabilities up to 90% lower than pure sodium caseinate films. Water vapor permeability varied by a factor of two depending on emulsion film orientation, indicating nonisotropic structure.