Antioxidant properties of caseins and whey proteins in model oil-in-water emulsions

The oxidative stabilities of both wheyproteinisolate (WPI)- and sodiumcaseinate-stabilized linoleic acid emulsions with different droplet sizes, protein concentrations and protein concentrations in the continuous phase were examined by determining lipid hydroperoxide and hexanal in the headspace. Emulsions with small droplet size had greater oxidative stability than emulsions with large droplet size in both WPI and sodiumcaseinate-stabilized emulsions. Lipid oxidation was in general lowered by an increase in the protein concentration. At high protein concentrations, the antioxidative effect of the protein in the emulsions appeared to offset the effects of emulsion droplet size and protein type. Replacing the unadsorbed protein in the continuous phase with water markedly decreased the oxidative stability of the emulsions. In contrast, the oxidative stability of the emulsions increased with increasing protein concentration in the continuous phase. This suggests that the antioxidative mechanism of protein in the interfacial region, such as binding trace metal ions from the lipid phase and free-radical-scavenging activity, may involve a dynamic exchange process with protein molecules from the continuous phase.     

Interaction between Emulsion Droplets and Escherichia coli Cells

ABSTRACT Oil‐in‐water emulsions (20% n‐hexadecane, v/v) were stabilized by dodecyltrimethylammonium bromide (DTAB), Tween 20, or sodium dodecyl sulfate (SDS). Particle size distribution and creaming stability were measured before and after adding Escherichia coli cells to emulsions. Both E. coli strains promoted droplet flocculation, coalescence, and creaming in DTAB emulsions, although JM109 cells (surface charge = ‐35 mV) caused faster creaming than E21 cells (surface charge = ‐5 mV). Addition of bacterial cells to SDS emulsions promoted some flocculation and coalescence, but creaming stability was unaffected. Droplet aggregation and accelerated creaming were not observed in emulsions prepared with Tween 20. Surface charges of bacterial cells and emulsion droplets played a key role in emulsion stability.     

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.     

Droplet characterization and stability of soybean oil/palm kernel olein O/W emulsions with the presence of selected polysaccharides

Droplet characteristics, flow properties and stability of egg yolk-stabilized oil-in-water (O/W) emulsions as affected by the presence of xanthan gum (XG), carboxymethyl cellulose (CMC), guar gum (GG), locust bean gum (LBG) and gum Arabic (AG) were studied. The dispersed phase (40%) of the emulsions was based on soybean oil/palm kernel olein blend (70:30) that partially crystallized during extended storage at 5 °C. In freshly prepared emulsions, the presence of XG, CMC, GG and LBG had significantly decreased the droplet mean diameters. XG, LBG, GG and CMC emulsions exhibited a shear-thinning behavior but AG emulsion exhibited a Bingham plastic behavior and control (without gum) emulsion almost exhibited a Newtonian behavior. Both control and AG emulsions exhibited a severe phase separation after storage (30 days, 5 °C). The microstructure of stored XG emulsion showed the presence of partially coalesced droplets, explaining a large increase in its droplet mean diameters. Increases in droplet mean diameters and decreases in flow properties found for stored GG and LBG emulsions were attributed to droplet coalescence. Nevertheless, the occurrence of droplet coalescence in these emulsions was considered to be small as no free oil could be separated under centrifugation force. Increases in flow properties and excellent stability towards phase separation found for stored CMC emulsion suggested that CMC could retard partial coalescence. Thus, the results support the ability of CMC, GG and LBG in reducing partial coalescence either by providing a sufficiently thick continuous phase or by acting as a protective coating for oil droplets.     

Stability of oil: Water emulsions of amaranth proteins. Effect of hydrolysis and pH

In this contribution we have determined the effect of limited enzymatic hydrolysis on the emulsifying capacity of amaranth proteins. The action of enzyme (alcalase and trypsin) and the pH of the continuous phase of the oil/water emulsion (pH 2.0, 6.3 and 8.0) were the variables analyzed. The results obtained show that amaranth protein isolates, AI, contain proteins species capable of forming and stabilizing emulsions, mainly at acidic pH (2.0) and to a lesser extent at pH 8.0. While the emulsions obtained are sensitive to creaming and flocculation, they do not undergo destabilization by coalescence. The emulsions prepared from proteins subjected to low grade trypsin hydrolysis (TH2.2) are sensitive to creaming - flocculation, whereas alcalase-hydrolyzed proteins (AH1.7 and AH9.5) exhibited a significant destabilization by creaming, flocculation and coalescence, mainly at pH 6.3. The effect of the pH of the aqueous phase was determining on the emulsion stability beside the structural and physicochemical characteristics of protein species utilized as tensioactive. At acidic pH (pH 2.0) the unfolding and charge of polypeptides and the capacity of form a viscoelastic film at the interface were essential while at alkaline pH (pH 8.0) the balance among high and low molecular mass protein species and flexibility of the molecule fixed the emulsions properties.     

Development of a new reflectance technique to investigate the mechanism of emulsification

A new reflectance technique has been developed to measure the droplet size evolution during the process of emulsification in real-time. This has been used to investigate the dynamic behaviour of 50% oil-in-water emulsions. The performed experiments were designed in order to investigate the occurring droplet break-up and droplet coalescence phenomena individually, by carefully creating processing conditions where each of those events is dominant. The effect of emulsifier (Tween 20) concentration and different hydrodynamic conditions on the droplet break-up and coalescence phenomena and the emulsion droplet size evolution during processing were all investigated. The concentration of Tween 20 was shown to be a key parameter affecting the droplet size of the emulsion at the early stages of processing (within the first 3 min). However, during the later stages of processing, hydrodynamic conditions have a more pronounced effect on determining the final droplet size. Unlike droplet break-up, droplet coalescence rate decreases by intensifying the hydrodynamic conditions of the process as a consequence of the high capillary pressure of the smaller droplets being produced.     

Influence of emulsifier type on freeze-thaw stability of hydrogenated palm oil-in-water emulsions

The influence of emulsifier type (Tween 20, whey protein isolate, casein) on the physical properties of 20 wt% hydrogenated palm oil-in-water emulsions after crystallization of (i) the oil phase only or (ii) both the oil and water phases has been examined. Emulsion stability was assessed by differential scanning calorimetry measurements of fat destabilization after cool–heat cycles, and by measurements of mean particle size, oiling off, and gravitational separation after isothermal storage (−20 to 37 °C). Tween 20-stabilized emulsions showed appreciable fat destabilization at temperatures where the oil phase was partially crystalline, which was attributed to partial coalescence. Protein-stabilized emulsions were stable under these conditions, which was mainly attributed to the relatively thick interfacial membranes surrounding the droplets. When both oil and water phases crystallized, there was complete destabilization of Tween 20- and casein-stabilized emulsions, and extensive destabilization of whey protein-stabilized emulsions, which was attributed to ice crystallization. The results of this study could facilitate the development of frozen food products with improved properties.     

Flocculation and coalescence in water-in-oil emulsions stabilized by paraffin wax crystals

Water-in-mineral oil emulsions were prepared with small amounts of paraffin wax (0–2% w/w) added to the continuous phase, either by addition of pre-crystallized wax to the emulsion prior to emulsification or via subsequent quench-cooling of wax crystals in situ. Stability of the emulsions was examined using pulsed NMR droplet-size analysis, sedimentation and microscopy. Both pre and post-crystallized wax decreased the degree of droplet coalescence, however, emulsions made with post-crystallized wax were more stable over a 10-day period. Microscopy showed that visible crystals were strictly associated with droplets and droplet clusters indicating an affinity of the crystals to the interface. The incorporation of as little as 0.125% wax resulted in a notable decrease in emulsion sedimentation. After 24 days of storage, samples prepared with post-crystallized wax showed no sedimentation or flocculation, unlike pre-crystallized samples which were still somewhat destabilized despite the presence of as much as 2% wax. From these findings, rapid crystallization of wax in the continuous phase of a water-in-oil emulsion following emulsification is an effective means of enhancing long-term stability.     

Structure and stability of heat-treated concentrated dairy-protein-stabilised oil-in-water emulsions: A stability map characterisation approach

Emulsion instabilities such as depletion flocculation, coalescence, aggregation and heat-induced protein aggregation may be detrimental to the production of sterilised food emulsions. The type and the amount of protein present in the continuous phase and at the oil–water interface are crucial in the design of emulsions with appropriate stability. In this study, four oil-in-water model emulsion systems (pH 6.8–7.0) were formulated, characterised and categorised according to the potential interactions between protein-coated or surfactant-coated emulsion droplets and non-adsorbed proteins present in the continuous phase. The heat stability, the creaming behaviour and the flow behaviour of the model emulsions were influenced by both the emulsifier type and the type of protein in the continuous phase. The results suggest that this stability map approach of predicting droplet–droplet, droplet–protein and protein–protein interactions will be useful for the future design of heat-stable emulsion-based beverages with good creaming stability at high protein concentrations.     

Influence of droplet size on the efficacy of oil-in-water emulsions loaded with phenolic antimicrobials

In this study we investigated the effect of droplet size on the antimicrobial activity of emulsions containing two essential oil compounds that are known for their antimicrobial effectiveness: carvacrol and eugenol. Coarse emulsions were prepared by blending a triacylglyceride (Miglyol 812N) containing various concentrations of carvacrol or eugenol (5, 15, 30, 50 wt%) at an oil droplet mass fraction of 10 wt% with an aqueous phase containing 2 wt% Tween 80(?). Premixes were then further dispersed using a high shear blender, a high pressure homogenizer at different pressures or an ultrasonicator to produce droplets with a variety of mean diameters. Microscopy and light scattering storage stability studies over 10 days indicated that manufactured emulsions were stable, i.e. that no aggregation, creaming or other destabilization mechanisms occurred and droplet size distributions remained unchanged. The antimicrobial activity of emulsions was assessed against two model microorganisms, the Gram negative Escherichia coli C 600 and the Gram positive Listeria innocua, by determining growth over time behavior. The analysis yielded the unexpected result that emulsions with larger droplet sizes were more effective at inhibiting growth and inactivating cells than smaller ones. For example, emulsions with a mean oil droplet size of 3000 nm at a concentration of 800 ppm carvacrol completely inhibited L. innocua, while for 80 nm emulsions, only a delay of growth could be observed. Measurements of the concentration of the antimicrobial compounds in the aqueous phase indicated that concentrations of eugenol and carvacrol decreased with decreasing oil droplet sizes. Determination of interfacial tension further showed that eugenol and carvacrol are preferentially located in the oil-water interfaces. Theoretical calculations of Tween 80(?) concentrations needed to saturate interfaces suggested that in small emulsions for the given formulation less Tween 80(?) micelles are present in the aqueous phase. We therefore attribute the fact that antimicrobial nanoemulsions are less active than macroemulsions due to an increased sequestering of antimicrobials in emulsion interfaces and a decreased solubilization in excess Tween 80(?) micelles.     

Depletion flocculation and thermodynamic incompatibility in whey protein stabilised O/W emulsions

The stability of whey protein stabilised emulsions, containing methylcellulose added after emulsification in their bulk phase, was investigated. The phase diagram of the ternary system whey proteins/methylcellulose/water was first established and used to identify the conditions permitting polymer phase separation within the emulsion bulk phase. Emulsions containing a whey protein and methylcellulose concentration in the bulk phase below and above the phase separation threshold could therefore be prepared. Below the phase separation threshold, the creaming rate of the oil droplets was faster than the one predicted by the Stokes equation, due to methylcellulose-induced depletion flocculation. Above the phase separation threshold, the destabilisation of the emulsion involved different mechanisms, depending on the emulsifier adsorbed at the O/W interface. In the case of Tween 40 stabilised droplets, depletion flocculation led to a complete creaming of the fat globules while phase separation led to the formation of two polymer-rich phases, namely a protein-rich phase at the bottom of the tube and a methylcellulose-rich phase above. In the case of whey protein stabilised droplets, phase separation between bulk whey proteins and methylcellulose occurred, and the fat globules were entrapped in the protein-rich phase. These results permitted to describe the destabilisation mechanisms of both Tween 40 and whey protein stabilised emulsions in the presence of unadsorbed polysaccharide. They could be used to better understand the destabilisation processes arising in food emulsions, especially in those emulsions containing whey proteins, small surfactant molecules and polysaccharides.     

基于食品级胶体颗粒稳定Pickering乳液的研究进展

Pickering乳液是一种以固体颗粒为乳化剂制成的乳液。与常规乳液相比,Pickering乳液具有潜在的优越性,其良好的物理稳定性可有效防止液滴聚结。本文主要综述了影响Pickering乳液稳定性的各类因素以及稳定Pickering乳液的各类食品级胶体颗粒。Pickering颗粒的高密度可以帮助调整高糖高密度的连续相和低密度芳香油之间的密度差异,保证体系的稳定,Pickering乳液还可以在乳液形成之后发生改性,为乳液带来更多功能。Pickering乳液是食品乳液工程研究中一种有前途的研究物质,对食品乳液的研发和加工将有其独特的推动作用。     

Microstructural design to reduce lipid oxidation in oil-inwater emulsions

The influence of emulsifier type (Tween 20 and sodium caseinate (CAS)) and oil phase volume fraction (5% and 30%) on emulsion oxidative stability was investigated. The primary and secondary lipid oxidation products of emulsions stored at 40 °C were measured over 7 days. The results indicated that the oxidative stability of samples stabilised with CAS was significantly higher compared with emulsions stabilised with Tween 20. We propose that this is due to iron binding ability of CAS. Moreover, the impacts of Pickering emulsions (Silica particles) on lipid oxidation were studied and compared with Tween 20 stabilised emulsions. The results showed that silica particles could increase the oxidative stability of 20% sunflower oil-in-water emulsions by acting as a physical barrier between pro-oxidants located in continuous phase and hydroperxide at droplet interface.     

Physicochemical properties of a dressing-type o/w emulsion as influenced by orange pulp fiber incorporation

A low-in-oil dressing-type o/w emulsion incorporating a rich-in-fiber orange pulp commercial product, either in crude form or following comminution, was prepared and the rheological properties and physicochemical stability of the emulsion were studied. Interactions between the adsorbed at the droplet surfaces yolk proteins and the pulp surface constituents, possibly electrostatic in nature, resulted in extensive droplet aggregation. This was reflected in the dramatic increase of emulsion rheological parameter values, derived by applying the power or the Casson equation to shear stress-rate of shear data. Pulp incorporation resulted in an improvement of emulsion stability against creaming while the stability against droplet coalescence was only marginally affected. In addition, the rheological parameter values of the fortified with pulp emulsion exhibited an appreciable increase with storage, especially in the case of emulsions incorporating the crude pulp. These findings are combined with oil droplet or pulp particle size and ζ-potential data to probe the emulsion structure and explain its behavior during aging.     

The influence of different stabilizers and salt addition on the stability of model emulsions containing olive or sesame oil

Stabilizers are widely used in low-fat emulsion production. However, food industry pays attention to ingredients, such as resistant starch (RS) that also present substantial benefits to human health. Low-fat model emulsions of either olive or sesame oil that also contained xanthan gum (XG), whey protein concentrate (WPC), and undigested (resistant) starch (RS) were produced and stored at 5 °C. Salt was added in selected samples. A multiple light scattering technique was applied for investigating destabilization phenomena. Microscopic observations and droplet size measurements took place. Rheological properties performing a heating–cooling cycle experiment (5–25–5 °C) were measured. Olive oil emulsions presented the greatest stability and the lowest droplet size. RS plays the role of solid particle stabilizer, mainly entrapped in the matrix of the continuous phase. By salt addition stability was significantly improved, whereas droplet size was decreased. Those samples had a more pronounced elastic character and significantly greater viscosity values than their counterparts without salt.     

Heat stability of oil-in-water emulsions formed with intact or hydrolysed whey proteins: influence of polysaccharides

The heat stability of emulsions (4 wt% corn oil) formed with whey protein isolate (WPI) or extensively hydrolysed whey protein (WPH) products and containing xanthan gum or guar gum was examined after a retort treatment at 121 °C for 16 min. At neutral pH and low ionic strength, emulsions stabilized with both 0.5 and 4 wt% WPI (intact whey protein) were stable against retorting. The amount of β-lactoglobulin (β-lg) at the droplet surface increased during retorting, especially in the emulsion containing 4 wt% protein, whereas the amount of adsorbed α-lactalbumin (α-la) decreased markedly. Addition of xanthan gum or guar gum caused depletion flocculation of the emulsion droplets, but this flocculation did not lead to their aggregation during heating. In contrast, the droplet size of emulsions formed with WPH increased during heat treatment, indicating that coalescence had occurred. The coalescence during heating was enhanced considerably with increasing concentration of polysaccharide in the emulsions, up to 0.12% and 0.2% for xanthan gum and guar gum, respectively; whey peptides in the WPH emulsions formed weaker and looser, mobile interfacial structures than those formed with intact whey proteins. Consequently, the lack of electrostatic and steric repulsion resulted in the coalescence of flocculated droplets during retort treatment. At higher levels of xanthan gum or guar gum addition, the extent of coalescence decreased gradually, apparently because of the high viscosity of the aqueous phase.     

Utilization of layer-by-layer interfacial deposition technique to improve freeze–thaw stability of oil-in-water emulsions

The freeze–thaw stability of 5 wt% hydrogenated palm oil-in-water emulsions (pH 3) containing droplets stabilized by sodium dodecyl sulfate (SDS)–chitosan–pectin membranes was studied. The multilayered interfacial membranes were created using an electrostatic layer-by-layer deposition method. The ζ-potential, mean particle diameter, fat destabilization, apparent viscosity and microstructure of the emulsions were used to examine the influence of freezing on their stability. Emulsions containing oil droplets stabilized only by SDS were highly unstable to droplet coalescence when either the oil phase became partially crystallized or the water phase crystallized. Emulsions containing oil droplets stabilized by SDS–chitosan membranes were stable to droplet coalescence, but unstable to droplet flocculation. Emulsions containing droplets stabilized by SDS–chitosan–pectin membranes were stable to both droplet coalescence and flocculation. The interfacial engineering technology utilized in this study could lead to the creation of food emulsions with improved stability to freeze–thaw cycling.     

Effect of salt content on the rheological properties of salad dressing-type emulsions stabilized by emulsifier blends

The effects that salt content and composition of emulsifier blends exert on the rheological properties of salad dressing-type emulsions were studied. Binary blends of egg yolk and different types of amphiphilic molecules (Tween 20, sucrose laurate and pea protein), in several proportions, were used to stabilize emulsions. Salt concentration was ranged from 0 to 2.3% w/w. Steady-state flow tests and small-amplitude oscillatory shear measurements within the linear viscoelastic region were carried out. Rheological tests were complemented with droplet size distribution measurements. Rheological properties and physical stability of the emulsions studied were significantly influenced by salt content and the nature of binary emulsifier blends. In general, the values of rheological parameters studied increased with salt content. However, salt affects in much higher extent the properties of emulsions stabilized by high proportions of egg yolk or pea protein in the emulsifier blend, rather than those mainly stabilized by non-ionic low-molecular-weight surfactants, which are less sensitive to changes in the ionic strength. In this sense, the increase observed in the values of viscosity and linear viscoelastic functions of emulsions is more important when a protein is predominant in the emulsifier blend. This effect was explained on the basis of a more apparent increasing interdroplet interactions and viscosity of the continuous medium, both of them induced by salt addition, which lead to the consecution of an extensively flocculated state and improved creaming stability. On the contrary, different blends of pea protein and egg yolk showed a quite similar evolution of the rheological parameters with salt concentration.     

Emulsifying characterization of hens egg yolk proteins in oil-in-water emulsions

Emulsifying properties of egg yolk as a function of pH and oil volume were studied. Egg yolk proteins formed larger emulsion particles at pH 3 and the mean droplet size of the emulsions was decreased with increasing pH. A linear relationship between turbidity and mean droplet size of egg yolk emulsions could not be obtained. This may be due to the floculation of the emulsions. Egg yolk proteins formed thicker multilayers at low oil volume, however total protein adsorption ratio against original proteins was 55–65%, independent to protein and oil concentration. Electrophoretic analysis of the egg yolk emulsion revealed that the main components to adsorb at the interface was glanular lipovitellins, even though its emulsifying property was lower than that of plasma because of poor solubility at low ionic strength (0.1 M NaCl) at pH 7. These results indicate that the main contributor for egg yolk emulsion is granules and it can affect the emulsifying properties of egg yolk at different pH values.     

Effect of emulsifiers and fat crystals on shear induced droplet break-up,coalescence and phase inversion

We have investigated the breakup and coalescence of food grade emulsions under dynamic conditions with a range of emulsifiers. Not unexpectedly, breakup of the emulsions varied with applied shear. The coalescence rate for an emulsifier free system with purified sunflower oil after the imposed shear was reduced, was measured at 1.2 × 10⁻² s⁻¹, which is similar to reported values for non-food systems but could be totally arrested by the use of Tween 80, other surfactants such as gelatin and Tween 20 were also used. Phase inversion of 40% tripalmatin with either Tween 20 or monopalmatin, which is an important industrial process, was shown not to occur in the absence of crystals. By adjusting the emulsifier concentration and hence the movement of the crystals we have shown that the crystallisation of triglycerides controls the process dynamics and ultimately the phase inversion temperature. Both of the former effects also help describe the need for an excessive amount of emulsifier when forming food grade nano-emulsions. Thus, we show that with a myritol emulsion with either Tween 20 or Tween 80, it is the back reaction of nano-emulsion coalescence that determines the final droplet size and not the initial energy input from the emulsification process.