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.     

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.     

黄原胶对酪蛋白酸钠乳状液稳定性的影响

研究了一定pH条件下,黄原胶浓度及剪切稀化效应对酪蛋白酸钠乳状液稳定性的影响。结果表明,在酸性条件下,黄原胶无法抑制酪蛋白的变性沉淀,乳液在制备之初,即产生严重絮凝。在中性和弱碱性条件下,黄原胶在一定浓度范围内,诱发了乳状液的排斥絮凝;体系的pH显著影响了乳状液的稳定性,pH6条件下,较低的黄原胶浓度(0.2wt%)便可赋予乳状液良好的稳定性。均质过程大大降低了黄原胶的粘度,导致乳状液的稳定性下降,与添加未经均质处理的黄原胶相比,添加量增大近一倍,才能获得稳定的乳状液。     

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.     

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.     

单硬脂酸甘油酯对酪蛋白再制稀奶油乳化稳定性的影响

分析单硬脂酸甘油酯（glycerin monostearate，GMS）对胶束酪蛋白（micellar casein，MCN）再制稀奶油（recombined dairy creams，RDCs）、酪蛋白酸钙（calcium caseinate，CaC）-RDCs及酪蛋白酸钠（sodium caseinate，NaC）-RDCs乳化稳定性的影响。结果表明：GMS可通过与酪蛋白共同吸附在油水界面上使RDCs的脂肪球分散程度改变，因而乳化稳定性也相应改变。对于MCN-RDCs，GMS可显著增加RDCs的相分离时间，其中2.5% MCN-RDCs的乳化稳定性最大，相分离时间从474 s显著增加至4 622 s。CaC-RDCs中，蛋白添加量为0.5%～2.0%时，GMS的添加使CaC-RDCs的相分离时间由167～483 s增加至177～517 s；而2.5% CaC-RDCs的相分离时间有所下降。NaC-RDCs中，GMS的添加使0.5% NaC-RDCs的相分离时间由1 245 s增加至1 460 s；NaC-RDCs添加量大于1.0%时，相分离时间有不同程度下降。可见，GMS可增加MCN-RDCs的乳化稳定性；而其对CaC-RDCs和NaC-RDCs乳化稳定性的影响与蛋白含量有关，当CaC和NaC添加量分别为0.5%～2.0%、0.5%时，GMS才可增加RDCs体系的乳化稳定性。     

Effects of emulsifier type on physical and oxidative stabilities of algae oil-in-water emulsions

Algae oil-in-water emulsions were prepared using sodium caseinate (SC, 0.5%), whey protein concentrate (WPC, 0.5%), and a mixture of TWEEN80 (T80, 0.5%), and SPAN80 (SP80, 0.6%), and their emulsification and oxidative stabilities during storage were compared. Oil droplet sizes of SC- and T80+SP80-emulsions were smaller than that of WPC-emulsion. Serum layer appeared in all emulsions from day 15, and serum layer thicknesses were higher in WPC-emulsion than SC- and T80+SP80-emulsions, but an excess layer oil was observed only at the top of T80+SP80-emulsion until day 36. According to conjugated dienes, aldehydes, hydroperoxide and TBARS values, the oxidative stability of SC-emulsion was better than those of WPC- and T80+SP80-emulsions. This trend was also observed in fatty acid profiles of the emulsions showing the largest DHA reduction and palmitic acid increase in T80+SP80-emulsion, followed by WPC- and SC-emulsions. In present study, sodium caseinate formed stable algae oil-in-water emulsions with excellent antioxidative activity.     

Comparison of the Emulsifying Properties of Fish Gelatin and Commercial Milk Proteins

ABSTRACT: We have compared the flocculation, coalescence, and creaming properties of oil-in-water emulsions prepared with fish gelatin as sole emulsifying agent with those of emulsions prepared with sodium caseinate and whey protein. Two milk protein samples were selected from 9 commercial protein samples screened in a preliminary study. Emulsions of 20 vol% n -tetradecane or triglyceride oil were made at pH 6.8 and at different protein/oil ratios. Changes in droplet-size distribution were determined after storage and centrifugation and after treatment with excess surfactant. We have demonstrated the superior emulsifying properties of sodium caseinate, the susceptibility of whey protein emulsions to increasing flocculation on storage, and the coalescence of gelatin emulsions following centrifugation.     

Effect of glycation on sodium caseinate-stabilized emulsions obtained by ultrasound

This work explores the potential of high-intensity ultrasound to produce fine-dispersion, long-time-stable, oil-in-water emulsions prepared with native and glycated bovine sodium caseinate (SC). Regardless the ultrasound amplitude and time assayed, the sonicated emulsions of native SC at 0.5 mg/mL had much higher emulsifying activity indexes compared with those emulsions formed by Ultra-Turrax (IKA Werke GmbH & Co., Staufen, Germany) homogenization. Nevertheless, the native SC emulsions were very unstable despite the optimization of parameters such as protein concentration, amplitude of ultrasound wave, and sonication time by using a Box-Behnken design. Early glycation of SC with either galactose, lactose, or 10 kDa dextran substantially improved both emulsifying activity and the stability, whereas at advanced stages of glycation, SC emulsions showed notably reduced emulsifying properties, likely because extensive glycation of SC promoted its polymerization mainly through covalent cross-linking, as was demonstrated by particle size measurements. The increase in particle diameter of glycoconjugates likely affected the diffusion of SC from bulk to the oil-water interface and slowed the reorientation process of the protein at the interface. These findings show that the combined effect of early-stage glycation of SC and high-intensity ultrasound as an emergent technique to form emulsions has the potential to provide improved emulsions that could be used in several food applications.     

Sodium caseinate/carboxymethylcellulose interactions at oil–water interface: Relationship to emulsion stability

The effect of carboxymethylcellulose (CMC) on the properties of oil-in-water emulsions prepared with sodium caseinate (CN) was studied at different pHs (4–7). At pH 7, the surface protein coverage increased gradually with increasing CMC concentration, followed by a preferential adsorption of β-casein. While at pH 4, a sharp decrease in surface protein coverage was noted between 0 and 0.3 wt.% CMC, and no obvious difference in protein composition was observed. ζ-Potential measurements indicated that CMC adsorbed onto the CN-coated droplets at pH 4–5, but not at pH 6–7. As a result, the excess of non-adsorbed CMC induced depletion flocculation in the neutral emulsions. However, the acidic emulsions containing high levels of CMC (>0.3 wt.%) remained stable after 60 days of storage due to the formation of multilayer structures. At pH 4, CMC desorbed from the droplet surfaces at high NaCl concentrations, leading to lower emulsion stability.     

Effect of added calcium chloride on the physicochemical and rheological properties of aqueous mixtures of sodium caseinate/sodium alginate and respective oil-in-water emulsions

Changes induced by addition of calcium chloride in particle size distribution and electrokinetic potential were determined in sodium caseinate/sodium alginate mixtures dissolved in water or acetate buffer at ambient temperature. Rheological properties of aqueous mixtures and respective oil-in-water emulsions (30% oil w/w) were evaluated using a low-stress rheometer. Stability and particle diameter of emulsions were measured. Caseinate and alginate solutions were negatively charged and showed negative electrokinetic potential; however values of mixtures were between those of the values for the individual hydrocolloids. When calcium ions were added the electrokinetic potential diminished while the negative charge was preserved. Aqueous mixtures of caseinate and alginate showed average particles size between of those of caseinate or alginate samples. We observed low viscosity values and Newtonian behavior for both caseinate (1 and 2%) and alginate (0.1%). Addition of 5 mM CaCl₂ to alginate solutions induced shear-thinning behavior as well as the development of viscoelasticity. Both the viscosity and the elastic modulus of these polysaccharide solutions were attenuated by the presence of protein or dispersed oil in mixtures or emulsions, respectively. High average particle diameter of emulsions prepared was obtained (close to 10 μm), however, stability of emulsions was possible only with the addition of CaCl₂ to the mixtures, in both water and acetate buffer. In these cases elastic behavior predominated to viscosity in the formation of emulsions, confirming the prevalence of aqueous phase rheology on emulsions.     

STABILITY OF OIL-IN-WATER EMULSIONS. 2. Effects of Oil Phase Volume, Stability Test, Viscosity, Type of Oil and Protein Additive

SUMMARY –Stability of oil-in-water emulsions stabilized in sodium caseinate, gelatin and soy sodium proteinate was found to be increased by either an increase in the aqueous phase protein concentration (0.5–2.5%) or oil phase volume (20–50%). Both factors were significantly interrelated. Emulsions stabilized by soy sodium proteinate were generally higher in stability as compared to those stabilized by gelatin or sodium caseinate. With emulsions containing gelatin, greater stability occurred when the stability testing temperature was increased from 37–70°C and when the time interval was decreased from 24 hr to 90 min. Maximum relative viscosities of emulsions stabilized by gelatin and sodium caseinate were 2.0 and 2.5, respectively. Emulsions stabilized by soy sodium proteinate were quite viscous, with relative viscosity from 1.5–30 depending on both protein concentration and oil phase volume. Interchanging the emulsified oil among corn, soybean, safflower and peanut oils did not alter emulsion stability when examined at three concentrations of soy sodium proteinate. Changing the oil to olive oil significantly increased emulsion stability at each soy sodium proteinate level with oil phase volumes of 30, 40 and 50%.     

Oil-in-Water Emulsions Stabilized by Sodium Caseinate or Whey Protein Isolate as influenced by Glycerol Monostearate

Competitive adsorption between glycerol monostearate (GMS) and whey protein isolate (WPI) or sodium caseinate was studied in oil-in-water emulsions (20 wt % soya oil, deionized water, pH 7). Addition of GMS resulted in partial displacement of WPI or sodium caseinate from the emulsion interface. SDS-PAGE showed that GMS altered the adsorbed layer composition in sodium caseinate stabilized emulsions containing < 1.0 wt % protein. Predominance of β-casein at the interface in the absence of surfactant was reduced in the presence of GMS. The distribution of α-lactalbumin and β-lactoglobulin between the aqueous bulk phase and the fat surface in emulsions stabilized with WPI was independent of the concentration of added protein or surfactant.     

Production and stabilization of a flaxseed oil multi-layer emulsion containing sodium caseinate and pectin

The purpose of this research is the evaluation of a flaxseed oil-in-water emulsion, stabilized by a multi-layer structure consisting of sodium caseinate (Na-caseinate) and pectin to provide a basis for the combination of these materials for future studies. In the first step, the o/w emulsion (10 g oil, 90 g aqueous phase, and a pH 6.8) with varying concentration of Na-caseinate was investigated. Second, the pectin solution (0.05–1.5 g/100 g solution) was added to the primary emulsions and the pH was adjusted to 3.0. The emulsions were characterized by mean particle size (dynamic light scattering and static light scattering techniques), ζ-potential, turbidity value, creaming index, and the visualization of the microstructure. A clear separation of the oil phase at low protein contents and destabilizing by depletion flocculation at high protein content were observed. Extensive droplet flocculation and coalescence were determined until the pectin concentration reached 0.5 g/100 g solution for the secondary emulsion. After 7 days of storage, a 1.5 g/100 g solution pectin content had good stability with a relatively small size distribution, high turbidity value, and no cream phase separation.     

Stabilization of multilayered emulsions by sodium caseinate and κ-carrageenan

The influence of the κ-carrageenan concentration and pH on the properties of oil-in-water multilayered emulsions was studied. Multilayered emulsions were prepared by the mixture of a primary emulsion stabilized by 0.5% (w/v) sodium caseinate (Na-CN) with κ-carrageenan solutions with different concentrations (0.05–1% w/v). The emulsions were evaluated at pH 7 and 3.5. At pH 7, there was little adsorption of κ-carrageenan onto the droplet surface and a depletion flocculation was observed when the polysaccharide concentration exceeded 0.5% (w/v). At pH 3.5, a mixed κ-carrageenan–Na-CN second layer was formed around the protein-covered droplets and the emulsions showed bridging flocculation at lower polysaccharide concentrations (0.05–0.25% w/v). Stable emulsions could be formed with the highest κ-carrageenan concentration (1% w/v) at both pH values (7.0 and 3.5). Thus, stable emulsions were successfully produced using protein–polysaccharide interfacial complexes, and the oil droplet diameter, zeta potential and rheological properties of these emulsions were not affected by changes in the pH.     

Freeze-thaw stability of oil-in-water emulsions prepared with native and thermally-denatured soybean isolates

Freeze-thaw stability of oil-in-water emulsions prepared with native or thermally-denatured soy isolates (NSI and DSI, respectively) as the sole emulsifier and sunflower oil (? = 0.25) has been examined at various protein concentrations (0.5, 1.0 and 2.0% w/v), comparatively with sodium caseinate (SC). The freeze-thaw stability was assessed by measurements of particle size, oiling off and gravitational separation after isothermal storage at −20 °C for 24 h and further thawing. The oil phase remained in liquid state and the amount of ice formed was similar (>97%) whatever the sample type and protein concentration. At 0.5%, NSI and DSI emulsions where highly unstable, exhibiting a coagulated cream layer with appreciable oiling off (>25%), whereas those prepared with SC were more stable, due to their initial lower flocculation degree (FD %) and particle size. For all emulsions, the increase of protein concentration (0.5–2.0% w/v) improves the freeze-thaw stability as a consequence of a decrease of initial FD %. At 2.0%, where is enough protein to cover the interface, a lower coalescence stability of NSI emulsion respect to those prepared with NSI was observed after freeze-thawing. This result can be attributed to the high tendency to aggregation of native soy globulins at subzero temperatures. Notwithstanding this, unlike the SC emulsions, the formation of new flocs in soy isolates-stabilized emulsions during freeze-thawing cannot be totally controlled.     

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.     

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。     

酒精对酪蛋白酸钠溶液及O/W乳状液的影响

介绍了酒精对酪蛋白酸钠溶液及酪蛋白稳定的O/W乳状液性质的影响 .试验表明酒精在一定程度上可以降低酪蛋白酸钠的溶解度 .界面张力的测定则表明酒精的存在在很大程度上可以降低油—水界面和油—酪蛋白溶液界面的界面张力 .含酒精的乳状液体系的粘度会由于酒精的存在而提高 ,在酒精体积分数达 3 0 %时 ,乳状液体系的粘度会突然大幅度升高 .通过O/W乳状液的分层稳定性测定可发现 ,低浓度的酒精可以提高酪蛋白稳定的乳状液的分层稳定性 ,但酒精质体积分数超过 3 2 %时 ,乳状液的分层稳定性会受到破坏 .含酒精的O/W乳状液体系中油相含量的提高在一定范围内可以提高乳状液的稳定性 ,但高分散相浓度的含酒精的乳状液体系中由于连续相中酒精浓度的提高使乳状液体系稳定性下降 .     

Lipid and water crystallization in protein-stabilised oil-in-water emulsions

Phase and state transitions occurring during freezing and thawing of oil-in-water emulsions with different water phase formulations, interfacial compositions and two lipid types were studied as crucial factors affecting emulsion stability. Emulsions containing 0–40% (w/w) sucrose in the water phase at pH 7, and 10, 20, 30, 40% (w/w) dispersed lipid phase (sunflower oil, SO or hydrogenated palm kernel oil, HPKO) with whey protein isolate, WPI, or sodium caseinate, NaCAS, (protein:lipid = 1:10 and 2:10) as emulsifier were prepared. Phase/state behaviour of the continuous and dispersed phases was determined by differential scanning calorimetry (DSC). Emulsion stability and morphology were derived from DSC data, gravitational separation and particle size analysis during 4 freeze-thaw cycles. Systems were stable when only lipid crystallization occurred. DSC data showed that lipid crystallization prior to water crystallization (i.e. emulsions containing HPKO) caused destabilisation at low sucrose concentrations (0, 2.5 and 5% w/w). Emulsions were stable if the dispersed oil phase crystallized after the dispersing water phase (i.e. emulsions containing SO). A concentration of sucrose ≥10% (w/w) in the aqueous phase gave stable emulsions. At 10:1 lipid to protein ratio, WPI showed better stabilising properties than NaCAS at 2.5 and 5% (w/w) sucrose. Double concentration of WPI (lipid:protein = 10:2) at 0% (w/w) sucrose significantly improved systems stability, whereas no positive effect was observed when the concentration of NaCAS was increased. From morphology study, in addition to lipid destabilisation, thickening and flocculation caused instability of the systems. These were extensive in systems containing WPI and were ascribed to interactions between whey proteins during thermal cycling.