Water/Oil Emulsions Prepared by the Membrane Emulsification Method and Their Stability

We developed and tested a simple method to measure dispersed droplet size of W/O emulsions. Then, using a microporous glass membrane treated with oil phase, we produced a W/O emulsion with high water content (40% w/w) at a high emulsification rate by the membrane emulsification method, and assessed its stability. In comparison with emulsions by the stirring methods, variations in dispersed droplet size and viscosity of emulsions by membrane method were small and the emulsions were more stable. Droplet size was not related to the stability of the W/O emulsion prepared by membrane emulsification.     

Production of O/W Emulsions Containing Astaxanthin by Repeated Premix Membrane Emulsification

ABSTRACT: Oil-in-Water (O/W) emulsions are mainly produced by application of high mechanical stress or by membrane emulsification processes at low pressures. Advantages such as narrower droplet size distribution and lower operating costs make membrane emulsification processes more suitable for producing astaxanthin-loaded O/W emulsions. The characteristics of 1 of these membrane emulsification methods, called repeated premix membrane emulsification, are studied in this work. In this emulsification process, a pre-emulsion is repeatedly pushed through a hydrophilic or hydrophobic membrane. In this research, ahydrophilic membrane was used because the objective was to obtain an O/W emulsion. Pre-emulsions were produced by dispersing palm oil containing dissolved astaxanthin in water. The oil droplets were stabilized with a combination of 2 emulsifiers. Each O /W emulsion passed the membrane 3 times underpressures and disperse phase fractions of 5 to 15 bar and from 10 wt% to 40 wt%, respectively. To investigate the production of O/W emulsions by repeated premix membrane emulsification, mean Sauter diameters and fluxes were measured. To find the optimal ranges of pressure and dispersed phase fraction, a "2-level factorial design with central composite and stars points" experimental design was applied.     

Preparation of Monodisperse Food-Grade Oleuropein-Loaded W/O/W Emulsions Using Microchannel Emulsification and Evaluation of Their Storage Stability

W/O/W emulsion is an emerging system in developing new functional and low-calorie food products. The aim of this study is to produce food-grade monodisperse water-in-oil-in-water (W/O/W) emulsions loaded with a hydrophilic bioactive oleuropein. W/O/W emulsions were prepared via high-pressure homogenization and subsequent microchannel (MC) emulsification. The internal aqueous phase was a 5-mM sodium phosphate buffer containing d(+)-glucose (5 wt.%) and oleuropein (0.1–0.7 wt.%). The oil phase consisted of soybean oil and tetraglycerin monolaurate condensed ricinoleic acid esters (TGCR; 3–8 wt.%). The external aqueous phase was a 5-mM sodium phosphate buffer containing d(+)-glucose (5 wt.%) and decaglycerol monolaurate (1 wt.%). Oleuropein-loaded submicron W/O emulsions with average droplet diameters as small as 0.15 μm and monomodal droplet size distributions were prepared by high-pressure homogenization when applying high TGCR concentrations of 5–8 wt.% and low oleuropein concentrations of 0.1–0.3 wt.%. Monodisperse oleuropein-loaded W/O/W emulsions with average W/O droplet diameters of around 27 μm and coefficients of variation of below 5 % were successfully prepared when using a silicon MC array plate with wide channels of 5-μm depth and 18-μm width. The monodisperse W/O/W emulsions prepared at high TGCR concentrations and low oleuropein concentrations were the most stable during 40 days of storage. The adsorption behavior of oleuropein at the internal aqueous–oil interface was relevant to W/O/W emulsions microstructure and stability. The results are believed to provide useful information for successfully preparing stable monodisperse W/O/W emulsions loaded with hydrophilic functional compounds. The surface activity of the loaded material seems to be a key parameter in optimizing the formulation of W/O/W food emulsion.     

Influence of Emulsification Technique and Wall Composition on Physicochemical Properties and Oxidative Stability of Fish Oil Microcapsules Produced by Spray Drying

Encapsulation of fish oil is an effective way to protect it against oxidation and masking its fishy odor. One of the possible ways to produce fish oil microcapsules is to produce an oil-in-water (O/W) emulsion followed by spray drying. This study compares the production of the O/W emulsion by mechanical homogenization (rotor–stator) with membrane emulsification and examines the effect of the type and amount of wall material added before drying. The membrane emulsification process selected for the emulsion production is premix membrane emulsification (ME), which consists of the production of a coarse emulsion by mechanical means followed by droplet breakup when the coarse emulsion is forced through a membrane. The emulsions produced had an oil load of 10 and 20 % and were stabilized using whey protein (isolate and hydrolyzate at 1 or 10 %) and sodium caseinate with concentrations of 2 and 10 %. Regarding the material used to build the microcapsule wall, whey protein, maltodextrin, or combinations of them were used at three different oil/wall ratios (1:1, 1:2, 1:3). The results clearly show that premix ME is a suitable technology for producing O/W emulsions stabilized with proteins, which have a smaller droplet size and are more monodisperse than those produced by rotor–stator emulsification. However, protein concentrations of 10 % are required to reduce the droplet size down to 2–3 μm. Small and monodisperse emulsions have been found to produce microcapsules with lower surface oil content, which increases oil encapsulation efficiency and presents lower levels of oxidation during storage at 30 °C. Of all the possible combinations studied, the one with the highest oil encapsulation efficiency is the production of a 20 % O/W emulsion stabilized with 10 % sodium caseinate followed by the addition of 50 % maltodextrin and drying.     

Stability and Oil Migration of Oil‐in‐Water Emulsions Emulsified by Phase‐Separating Biopolymer Mixtures

Oil‐in‐water (O/W) emulsions with varying concentration of oil phase, medium‐chain triglyceride (MCT), were prepared using phase‐separating gum arabic (GA)/sugar beet pectin (SBP) mixture as an emulsifier. Stability of the emulsions including emulsion phase separation, droplet size change, and oil migration were investigated by means of visual observation, droplet size analysis, oil partition analysis, backscattering of light, and interfacial tension measurement. It was found that in the emulsions prepared with 4.0% GA/1.0% SBP, when the concentration of MCT was greater than 2.0%, emulsion phase separation was not observed and the emulsions were stable with droplet size unchanged during storage. This result proves the emulsification ability of phase‐separating biopolymer mixtures and their potential usage as emulsifiers to prepare O/W emulsion. However, when the concentration of MCT was equal or less than 2.0%, emulsion phase separation occurred after preparation resulting in an upper SBP‐rich phase and a lower GA‐rich phase. The droplet size increased in the upper phase whereas decreased slightly in the lower phase with time, compared to the freshly prepared emulsions. During storage, the oil droplets exhibited a complex migration process: first moving to the SBP‐rich phase, then to the GA‐rich phase and finally gathering at the interface between the two phases. The mechanisms of the emulsion stability and oil migration in the phase‐separated emulsions were discussed.     

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.     

Effect of xanthan and guar gums on the formation and stability of soy soluble polysaccharide oil-in-water emulsions

The incorporation of relevant amounts of non-adsorbing hydrocolloids to oil-in-water (O/W) emulsions is a suitable alternative to reduce creaming. The effect of incorporating xanthan gum (XG) or guar gum (GG) in soy soluble polysaccharide (SSPS) stabilized oil-in-water (O/W) emulsions was studied. The emulsions contained 6 wt.% of SSPS, 20 wt.% Perilla seed oil (PSO), an omega-3 vegetable oil, and variable amounts of XG or GG ranging from 0.03 to 0.3 wt.%. The presence of minute amounts of XG or GG in fresh emulsions significantly decreased the emulsion droplet size (EDS) although such low concentrations did not provide enough continuous phase viscosity to arrest creaming. Emulsion microstructure indicated the presence of flocculation even at high concentrations of XG or GG caused by a depletion mechanism. All emulsions with XG or GG exhibited pseudoplastic behavior while the control emulsions showed an almost Newtonian behavior. Emulsion droplet polydispersion generally decreased with increase in the continuous phase viscosity indicating the importance of continuous phase viscosity in the dissipation of shear energy throughout the emulsion during homogenization. The characteristics of the emulsions were closely related to the rheological changes of the continuous phase.     

Protection of Lactobacillus acidophilus from the low pH of a model gastric juice by incorporation in a W/O/W emulsion

The protective effect of a W/O/W emulsion for Lactobacillus acidophilus from a model gastric juice was investigated in order to develop a method for utilizing the advantages of the probiotics. The bacteria were included in the inner-phase solution of the W/O/W emulsion, and a method for counting the viable-bacteria included in the W/O/W emulsion was developed. The relative viability of the bacteria included in the W/O/W emulsion was 49% at 2 h in the model gastric juice, whereas the viability of the bacteria directly dispersed in the juice declined to 1.3% even at 0.67 h. The relative viabilities of the encapsulated bacteria in the model gastric juice at 2 h were 0.12 and 1.10 for the emulsions having the median diameters of 11.9 and 25.4 μm, prepared with inner-phase volume ratios at 0.03 and 0.45, respectively. The relative viabilities of the bacteria in the W/O/W emulsions with the median diameters of 11 and 27 μm, prepared at the homogenization speed of 2.2×10⁴ and 9.8×10³ rpm, were 0.4 and 0.8, respectively. These results suggested that both the inner-phase volume ratio and the median diameter of oil droplet affected the relative viability of the included bacteria.     

Synergistic effects of polyglycerol ester of polyricinoleic acid and sodium caseinate on the stabilisation of water–oil–water emulsions

The inherent thermodynamic instability of water–oil–water (W/O/W) emulsions has restrictions for their application in food systems. The objective of this study was to develop a food grade W/O/W emulsions with high yield and stability using minimal concentrations of surfactants. Emulsions were prepared using soybean oil, polyglycerol ester of polyricinoleic acid (PGPR) alone or in combination with sodium caseinate (NaCN) as emulsifier(s) for primary water-in-oil (W/O) emulsions and NaCN as the sole emulsifier for secondary W/O/W emulsions. Increasing the concentration of PGPR (0.5–8%w/v) had no effect on the droplet sizes of the resulting W/O/W emulsions. However, significant increases in droplet sizes of W/O/W emulsions were observed when the concentration of NaCN in external phase was reduced from 0.5 to 0.03% (w/v) (p<0.05). Percentage yields of emulsions (using a water-soluble dye) improved when PGPR concentration in the inner phase was increased from 0.5 to 8% (w/v). A stable W/O/W emulsion with a yield >90% could be prepared with 4% (w/v) PGPR alone as primary hydrophobic emulsifier and 0.5% (w/v) NaCN as external hydrophilic emulsifier. The concentration of PGPR in the inner phase could be reduced to 2% (w/v) without affecting the yield and stability of the W/O/W emulsion by partially replacing PGPR with 0.5% (w/v) NaCN, which was added to the aqueous phase of the primary W/O emulsion. The results indicate that a possible synergistic effect may exist between PGPR and NaCN, thus allowing formulation of double emulsions with reduced surfactant concentration.     

Effect of protein oxidation on kinetics of droplets stability probed by microrheology in O/W and W/O emulsions of whey protein concentrate

Whey protein concentrate (WPC) was oxidized by peroxyl radicals derived from 2,2′-azobis (2-amidinopropane) dihydrochloride (AAPH) and the kinetics of droplet stability in O/W and W/O emulsions stabilized by oxidized WPC were evaluated by studying the micro-rheology. Degrees of protein oxidation were indicated by carbonyl concentration and emulsion types were distinguished by fluorescence microscopy. Oxidation resulted in free sulfhydryl groups degradation and surface hydrophobicity decrease. Moderate protein oxidation promoted to form diminutive droplets, which aggregated quickly to gel-network structure and decreased the motion rate of droplets, leading to the increased elasticity and viscosity, which led to better stability. Over-oxidation underwent severe droplet aggregation and sediment with increased motion rate, which resulted in instability of emulsions. The W/O emulsions of oxidized WPC were more inclined to block the motion of droplets and form a stable structure with higher viscosity, compared with the O/W emulsions.     

Alginate‐Based Emulsion Template Containing High Oil Loading Stabilized by Nonionic Surfactants

Oil‐in‐water (O/W) emulsion‐gel systems containing high oil payloads are of increasing interest for food applications because of the reduction in encapsulation cost, consumption frequency or volume of food products. This study shows a facile approach to prepare stable alginate‐based O/W emulsions at high oil loading using a mixture of nonionic surfactants (Tween 80 and Span 20) as a template to form gelled‐emulsions. The synergistic effects of alginate and surfactants on the O/W emulsion properties were evaluated in terms of oil droplet size and emulsion stability. At 2% (w/v) of alginate and 1% (w/v) of surfactants, the size distribution of oil droplets was narrow and monomodal, even at an oil loading of 70% (v/v). The emulsions formed were stable against phase separation. The oil droplet size could be further reduced to below 1 μm using a high‐shear homogenizer. The emulsions formed could be easily molded and gelled into solids of different shapes via ionic gelation. The findings of this study create possible avenues for applications in food industries.     

Dispersion Stability of O/W Emulsions with Different Oil Contents Under Various Freezing and Thawing Conditions

Freezing and thawing of oil‐in‐water (O/W) emulsion‐type foods bring about oil–water separation and deterioration; hence, the effects of freezing and thawing conditions on the destabilization of O/W emulsions were examined. The freezing rate and thawing temperature hardly affected the stability of the O/W emulsion. O/W emulsions having different oil fractions were stored at temperatures ranging from –30 to –20 °C and then thawed. The stability after thawing depended on the storage temperature, irrespective of the oil fraction of the emulsion. A good correlation was found between the time at which the stability began to decrease and the time taken for the oil to crystalize. These results indicated that the dominant cause for the destabilization of the O/W emulsion during freezing and thawing is the crystallization of the oil phase and that the effects of the freezing and thawing rates on the stability are insignificant.     

Surface-active solid lipid nanoparticles as Pickering stabilizers for oil-in-water emulsions

Oil-in-water (O/W) emulsions solely stabilized by surface-active solid lipid nanoparticles (SLNs) were developed. The SLNs were generated by quench-cooling hot O/W nanoemulsions consisting of 7.5% glyceryl stearyl citrate (GSC) dispersed in water. Their initial volume-weighted mean particle diameter (～152 nm) and zeta potential (ca.-49 mV) remained unchanged for 24 weeks. O/W emulsions (oil phase volume fraction: 0.2) containing 7.5% (w/w) GSC SLNs in the aqueous phase were kinetically-stable for 12 weeks and did not visually phase-separate over 24 weeks. The O/W emulsions generated with solid-state GSC SLNs had a volume-weighted mean oil droplet diameter of ～459 nm and a zeta potential of ca.-43 mV. Emulsion microstructure evaluated with TEM revealed dispersed oil droplets sparsely covered with adsorbed Pickering-type SLNs as well aggregated SLNs present in the continuous phase. Gradual emulsion destabilization resulted from GSC SLN dissolution during the experimental timeframe. Overall, surface-active SLNs developed via nanoemulsions effectively kinetically stabilized O/W emulsions.     

Impact of iron encapsulation within the interior aqueous phase of water-in-oil-in-water emulsions on lipid oxidation

Iron (Fe³⁺) was encapsulated within the internal aqueous phase of water-in-oil-in-water (W/O/W) emulsions, and then the impact of this iron on the oxidative stability of fish oil droplets was examined. There was no significant change in lipid droplet diameter in the W/O/W emulsions during 7 days storage, suggesting that the emulsions were stable to lipid droplet flocculation and coalescence, and internal water diffusion/expulsion. The initial iron encapsulation (4 mg/100 g emulsion) within the internal aqueous phase of the water-in-oil (W/O) emulsions was high (>99.75%), although, a small amount leaked out over 7 days storage (≈10 μg/100 g emulsion). When W/O/W emulsions were mixed with fish oil droplets the thiobarbituric acid-reactive substances (TBARS) formed decreased (compared to fish oil droplets alone) by an amount that depended on iron concentration and location, i.e., no added iron < iron in external aqueous phase < iron in internal aqueous phase. These differences were attributed to the impact of W/O droplets on the concentration and location of iron and lipid oxidation reaction products within the system.     

Effects of water-soluble soybean polysaccharide on rheological properties,stability and lipid digestibility of oil-in-water emulsion during in vitro gastrointestinal digestion

Water-soluble soybean polysaccharide (SSPS) is a naturally occurring emulsifier. SSPS was used as the sole emulsifier to stabilize an oil-in-water (O/W) emulsion. The effects were investigated of different SSPS concentrations (3–20% (w/w)) on the lipid digestibility, rheological properties and stability of O/W emulsions during in vitro digestion model. The droplet size of the emulsions tended to increase during the oral phase because the emulsions were unstable and droplets coalesced, except with a SSPS concentration of 20% (w/w). The presence of SSPS markedly reduced the free fatty acid (FFA) content after its stabilized O/W emulsion passed through in vitro gastrointestinal digestion. The amount of FFA significantly decreased as the concentration of SSPS increased due to SSPS stabilization film on oil droplet surface and high viscous system. SSPS may be an attractive alternative ingredient to control the lipid digestibility of emulsions for various food products.     

大豆可溶性多糖与Fe2+对O/W乳状液物理稳定性及流变特性的影响

研究大豆可溶性多糖(soybean soluble polysaccharides,SSPS)及不同浓度的Fe2+对大豆分离蛋白(soy isolated protein,SPI)稳定的O/W乳状液的物理稳定性和流变特性的影响。通过测定14 d内添加SSPS和不同浓度的Fe2+的乳状液的稳定动力学指数(turbiscan stability index,TSI)、稳态流变、粒径大小及分布和Zeta-电位,确定其物理稳定性。结果表明,与SPI乳状液相比,添加SSPS后,SSPS-SPI乳状液的TSI显著降低(p<0.05),液滴的表面积平均直径(d_3,2)和体积平均直径(d_4,3)增加,粘度系数增加,Zeta-电位绝对值降低,表明SSPS增加了SPI乳状液的粘度,提高了乳状液的物理稳定性;添加0.1 mmol/L Fe2+后,乳状液的TSI最低,液滴的d_3,2和d_4,3分别为0.686、2.136 μm,为最小粒径,粘度增加,稳定性较好;随着Fe2+浓度的增加,乳状液的TSI显著增加(p<0.05),粒径增大,分布范围变宽,表明0.2~0.5 mmol/L的Fe2+降低了乳状液的物理稳定性。总之,SSPS和0.1 mmol/L Fe2+的添加,提高了SPI稳定的O/W乳状液的物理稳定性。     

Rheological and microstructural characterization of WPI-stabilized O/W emulsions exhibiting time-dependent flow behavior

The rheological behavior of oil-in-water (O/W) emulsions stabilized by whey protein isolate (WPI) and its relationship with the microstructural changes caused by shearing was studied. O/W emulsions (50, 55, and 60 g oil/100 g) were made using ultrasound and their rheological properties were determined by: flow curve test, constant shear rate test, and hysteresis loop test. Microstructural changes were evaluated in terms of droplet size and droplet size distribution. Emulsions containing 50 and 55 g oil/100 g showed a Newtonian behavior, whereas those with 60 g oil/100 g exhibited shear-thinning behavior. Under constant deformation, the apparent viscosity of the emulsions decreased with time. The hysteresis loop test revealed that increasing oil content increased the degree of thixotropy of the emulsions. Moreover, before and after the constant deformation test droplet size distributions did not show differences, indicating that the decrease in the apparent viscosity may be promoted by breakdown and further deformation and/or reorganization of oil droplets flocs. In turn, experimental data obtained from the constant shear rate test was fitted to a structural kinetic model. The rate constant values showed no particular trend with oil content and shear rate, implying that probably wall slip occurred at high shear rates and high oil contents.     

负载葡萄皮粉花色苷提取物的W/O/W型复乳制备及其体外消化评价

以葡萄皮花色苷(ACNs)提取物为内水相(W1),玉米油为油相,乳清蛋白(WPI)溶液为外水相(W2)制备水包油包水(W/O/W)型复乳。复乳的包埋率高达(93.19±2.78)%,平均粒径为(287.90±3.12)nm。经口腔消化后,乳液未发现有明显变化;模拟胃部消化后,乳液液滴相互融合形成具有双层结构的较大微粒,其平均粒径(d>600 nm)显著增加(P<0.05)。经模拟肠道消化后,微粒成为空油滴,其平均粒径为(387.53±15.96)nm,此时抗氧化活性最高。研究结果表明,W/O/W型复乳在口腔和胃部能有效保护ACNs,实现靶向性肠道输送。负载ACNs的复乳系统在食品工业中有很大的应用潜力。     

Cross-linking proteins by laccase: Effects on the droplet size and rheology of emulsions stabilized by sodium caseinate

The aim of this work was to evaluate the influence of laccase and ferulic acid on the characteristics of oil-in-water emulsions stabilized by sodium caseinate at different pH (3, 5 and 7). Emulsions were prepared by high pressure homogenization of soybean oil with sodium caseinate solution containing varied concentrations of laccase (0, 1 and 5 mg/mL) and ferulic acid (5 and 10 mM). Laccase treatment and pH exerted a strong influence on the properties with a consequent effect on stability, structure and rheology of emulsions stabilized by Na-caseinate. At pH 7, O/W emulsions were kinetically stable due to the negative protein charge which enabled electrostatic repulsion between oil droplets resulting in an emulsion with small droplet size, low viscosity, pseudoplasticity and viscoelastic properties. The laccase treatment led to emulsions showing shear-thinning behavior as a result of a more structured system. O/W emulsions at pH 5 and 3 showed phase separation due to the proximity to protein pI, but the laccase treatment improved their stability of emulsions especially at pH 3. At pH 3, the addition of ferulic acid and laccase produced emulsions with larger droplet size but with narrower droplet size distribution, increased viscosity, pseudoplasticity and viscoelastic properties (gel-like behavior). Comparing laccase treatments, the combined addition of laccase and ferulic acid generally produced emulsions with lower stability (pH 5), larger droplet size (pH 3, 5 and 7) and higher pseudoplasticity (pH 5 and 7) than emulsion with only ferulic acid. The results suggested that the cross-linking of proteins by laccase and ferulic acid improved protein emulsifying properties by changing functional mechanisms of the protein on emulsion structure and rheology, showing that sodium caseinate can be successfully used in acid products when treated with laccase.     

Effect of heat treatment on the properties of soy protein‐stabilised emulsions

The effect of heat treatment on the properties of soy protein‐stabilised emulsions was investigated. Emulsions were prepared with unheated and heat‐treated soy protein (NSP and HSP) dispersions. Heating on soy protein dispersions at 95 °C for 30 min resulted in smaller average oil droplet size, lower tendency for oil droplet flocculation, higher protein adsorption and lower viscosity. The properties of emulsions were significantly influenced by the protein concentration. The sodium dodecyl sulphate–polyacrylamide gel electrophoresis (SDS–PAGE) profiles showed that the heat treatment on soy protein dispersions increased the protein adsorption at O/W interface. The viscosity of all samples at low shear rate was inversely proportional to the d₃₂, suggesting a positive relation to the total interfacial area per unit volume. Emulsions showed shear‐thinning behaviour. The relaxation time was found to increase with aqueous phase viscosity determined by the Cross viscosity model.