Antioxidant and emulsifying properties of potato protein hydrolysate in soybean oil-in-water emulsions

The efficacy of a previously developed antioxidative potato protein hydrolysate (PPH) for the stabilisation of oil droplets and inhibition of lipid oxidation in soybean oil-in-water (O/W) emulsions was investigated. Emulsions (10% lipid, pH 7.0) with PPH-coated oil droplets were less stable than those produced with Tween 20 (P < 0.05). However, the presence of PPH, whether added before or after homogenisation with Tween 20, retarded emulsion oxidation, showing reduced formation of peroxides up to 53.4% and malonaldehyde-equivalent substances up to 70.8% after 7-d storage at 37 °C (P < 0.05), when compared with PPH-free emulsions. In the emulsions stabilised by PPH + Tween 20, 8–15% of PPH was distributed at the interface. Adjustment of the pH from 3 to 7 markedly increased ζ-potential of such emulsions (P < 0.05). Inhibition of lipid oxidation by PPH in soybean O/W emulsions can be attributed to both chemical and physical (shielding) actions.     

Protein-stabilized emulsions containing beta-carotene produced by premix membrane emulsification

Protein-stabilized O/W emulsions containing beta-carotene were produced by premix membrane emulsification (ME) using polymeric microfiltration membranes. Bovine serum albumin (BSA) and a whey protein concentrate (WPC) were used as protein emulsifiers while a nonionic small-molecule surfactant, Tween 20, was used both as a control and co-emulsifier. Membrane fouling caused by WPC reduced more significantly transmembrane flux than that by BSA. Mixtures of WPC or BSA with Tween 20 reduced protein membrane fouling and, simultaneously, decreased the mean droplet size. WPC/Tween 20 mixtures enable to produce emulsions with low polydispersion (span < 1) but with a significant membrane fouling while BSA/Tween 20 mixtures led to higher transmembrane fluxes although polydisperse emulsions (span = 7). During storage at 22 and 35 °C, the chemical degradation rate of emulsions with WPC/Tween 20 was slower than those with BSA/Tween 20 whereas Tween 20-stabilized emulsions led to the highest rate of beta-carotene reduction during storage at 35 °C.     

Effects of enzymatically modified starch on the encapsulation efficiency and stability of water-in-oil-in-water emulsions

The present study was performed to investigate the possibility of using 4-α-glucanotransferase (4αGTase)-treated starch in W/O/W emulsions to increase their encapsulation efficiency (EE) and stability. Emulsions were prepared using soybean oil, polyglycerol polyricinoleate (PGPR), 4αGTase-treated starch and Tween 20. The mean diameter of W/O/W droplets ranged from 4 to 10 μm depending on the sonication time. When the dye was loaded in the internal water phase, the emulsion prepared by sonication for 1 and 2 min showed a high EE of the dye (>90%). The W/O/W emulsion prepared by sonication for 3 min showed an EE of <90%, but this EE was improved by adding 4αGTase-treated starch to the internal water phase. 4αGTase-treated starch was added to the internal water phase of W/O/W emulsions prepared with a low concentration of PGPR, and the PGPR concentration required to maintain an EE >90% was reduced. W/O/W emulsions containing 4αGTase-treated starch also showed better stability against heating and shearing stresses. These results indicated that 4αGTase-treated starch could be used in the preparation of W/O/W emulsions, which would allow the formulation of W/O/W emulsions with a reduced surfactant concentration.     

Stability and characterisation of phospholipid-based curcumin-encapsulated microemulsions

The ternary phase diagram of a curcumin-encapsulated O/W microemulsion system using food-acceptable components, lecithin and Tween 80 as the surfactants and ethyl oleate as the oil phase, was constructed. The stability and characterisation of curcumin in microemulsion were investigated. The results indicated that a composition of curcumin microemulsion (DI water: surfactants (the mole ratio of lecithin/Tween 80 was 0.3): EO = 10:1.7:0.4 in wt ratio) was stable for 2 months with an average diameter of 71.8 ± 2.45 nm, as detected by UV–Vis spectra and diameter distributions. The microemulsion possesses an ability to be diluted with aqueous buffer without destroying its structure for 48 h. A skin permeation study for testing the penetration effect of various curcumin loading in the microemulsions with different particle diameters was also performed and discussed in this contribution.     

Oxidative stability of oil-in-water emulsions stabilised with protein or surfactant emulsifiers in various oxidation conditions

Many studies have investigated the effect of emulsifiers on the oxidative stability of oil-in-water (O/W) emulsions. A better oxidative stability of surfactant-stabilised O/W emulsions as compared to protein-stabilised emulsions has been recently shown in conditions when the major part of the emulsifier is adsorbed at the oil-water interface and oxidation is induced by iron−ethylenediaminetetraacetic acid (EDTA) complex. In this work, the contribution of the interfacial layer to the oxidation of emulsified lipids is investigated under various incubation conditions, involving different oxidation mechanisms. O/W emulsions were formulated at pH 6.7 with limited amounts of emulsifiers in the aqueous phase. Emulsions were incubated either at 33 °C without initiator at 25 °C in the presence of iron/ascorbate, metmyoglobin or 2,2′-azobis(2-amidinopropane)-dihydrochloride (AAPH). Oxygen uptake and volatile compound formation confirmed that protein-stabilised emulsions are less oxidatively stable than Tween 20-stabilised ones. This work also shows complex oxidative interrelationships between oxidation initiator and certain proteins, such as β-casein and bovine serum albumin.     

Flaxseed oil – Whey protein isolate emulsions: Effect of high pressure homogenization

The effect of high-pressure homogenization (20–100 MPa) and the number of homogenization cycles (1–7) on the stability of flaxseed oil - whey protein isolate emulsions was evaluated. All the emulsions were stable to creaming for at least 9 d of storage. An increase in homogenization pressure from 20 to 80 MPa and number of passes through the homogenizer up to 3, decreased the mean droplet size of the O/W emulsions despite the higher polydispersity. Emulsions homogenized at lower pressures (20 MPa) showed a monomodal distribution of the particles, whereas, an increase in pressure to 80 MPa led to a bimodal distribution, indicating droplets coalescence. High-pressure homogenization (80 MPa) and an increase in the number of homogenization cycles, led to the formation of high molecular weight aggregates (>200 kDa), which favored an increase in viscosity of the emulsions. The increase in homogenization pressure also increased the formation of primary oxidation products, which could be explained by the increase in temperature and in the surface area of the droplets.     

Catastrophic inversion and rheological behavior in soy lecithin and Tween 80 based food emulsions

Emulsions inversion occurs in many industrial processes and may be influenced by the formulation conditions, composition and emulsification protocols. In this work, the influence of emulsifiers and stirring on catastrophic inversion (O/W to W/O) was evaluated. Emulsions were prepared with different stirring rates, using soy lecithin and Tween 80, at 2 and 5 wt%. The aqueous phase was distilled water with 1 wt% NaCl and the oil phase was soy oil. These emulsions were analyzed by conductivity, stability, microscopy and rheology assays. The most stable emulsions presented inversion with a smaller amount of the external phase. Rheological analysis showed that, with a higher concentration of emulsifier, it is better to use Tween 80 when lower viscosity is desired, while soy lecithin is more appropriate for higher viscosity products. The oscillatory tests showed that while the emulsions prepared using Tween 80 exhibited concentrated solution behavior, those prepared with soy lecithin exhibited strong gel behavior.     

Emulsifying properties of collagen fibers: Effect of pH,protein concentration and homogenization pressure

The emulsifying properties of collagen fibers were evaluated in oil-in-water (O/W) emulsions produced under different conditions of pH, protein content and type of emulsification device (rotor–stator and high-pressure homogenizer). The stability, microstructure and rheology of the O/W emulsions were measured. The phase separation and droplet size of the emulsions prepared using the rotor–stator device (primary emulsion) decreased with protein concentration and reduction in pH, allowing the production of electrostatically stable emulsions at pH 3.5. In contrast, emulsions at higher pH values (4.5, 5.5 and 7.5) showed a microscopic three-dimensional network responsible for their stability at protein contents higher than 1.0% (w/w). The emulsions at pH 3.5 homogenized by high pressure (up to 100 MPa) showed a decrease in surface mean diameter (d₃₂) with increasing pressure and the number of passes through the homogenizer. These emulsions showed droplets with lower dispersion and d₃₂ between 1.00 and 4.05 μm, six times lower than values observed for primary emulsions. The emulsions presented shear-thinning behavior and lower consistency index and viscosity at higher homogenization pressures. In addition, the emulsions showed a less structured gel-like behavior with increase in homogenization pressure and number of passes, since the pressure disrupted the collagen fiber structure and the oil droplets. The results of this work showed that the collagen fiber has a good potential for use as an emulsifier in the food industry, mainly in acid products.     

Nanoemulsion- and emulsion-based delivery systems for curcumin: Encapsulation and release properties

Curcumin has been reported to have many biological activities, but its application as a functional ingredient is currently limited because of its poor water-solubility and bioaccessibility. This study investigated the impact of different lipid-based formulations on curcumin encapsulation and bioaccessibility. Oil-in-water nanoemulsions (r < 100 nm), or conventional emulsions (r > 100 nm), were prepared with different lipids: long, medium, and short chain triacylglycerols (LCT, MCT and SCT, respectively). An in vitro model simulating small intestine digestion conditions characterised rate and extent of lipid phase digestion. A centrifugation method determined fraction of curcumin released into mixed micelles after digestion (bioaccessibility). Initial digestion rate decreased in the order SCT > MCT > LCT, while final digestion extent decreased in the order MCT > SCT > LCT. The bioaccessibility of curcumin decreased in the order MCT > LCT ? SCT and appeared to be slightly higher in conventional emulsions than in nanoemulsions.     

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.     

Rheological properties of corn oil emulsions stabilized by commercial micellar casein and high pressure homogenization

The rheological behavior of corn oil emulsions prepared by high pressure homogenization (HPH) was investigated. Coarse emulsions of corn oil (10-30 g oil/100 g emulsion) in casein dispersions containing 0.5-3.5 g micellar casein/100 g casein dispersion in an oil-free basis were homogenized at 0-300 MPa. Flow behavior under continuous increasing (0-150 s⁻¹) or decreasing (150-0 s⁻¹) shear rate was tested. Emulsions that showed macroscopic change in consistency were tested for viscoelasticity (G′). Homogenization of emulsions with low oil concentration (10 g/100 g) resulted in Newtonian behavior for all treatment pressures. The rheological behavior of emulsions with higher oil concentration (30 g/100 g) was dependent on casein concentration in the aqueous phase and varied from Newtonian to shear thinning. Homogenization pressures between 20 and 100 MPa induced the formation of a gel-like structure possibly through pressure-induced interactions between caseins surrounding adjacent droplets.     

Physical characteristics of submicron emulsions upon partial displacement of whey protein by a small molecular weight surfactant and pectin addition

O/W emulsions (6 wt.% olive oil) were prepared at pH 3.3 using different WPI:Tween 20 weight ratios (1:0, 3:1, 1:1, 1:3, 0:1) at 1 wt.% total concentration. The emulsion droplet size was found to decrease with an increase in Tween 20. A minimum droplet size of d_3,2 300 nm was found for Tween systems alone, similar to that found (360 nm) for a 1:1 WPI:Tween 20 combination (p < 0.05). This specific composition showed a value for the interfacial tension close to that of Tween 20 alone. However, the emulsions presented low stability regardless of the WPI:Tween 20 ratio. To increase their stability, pectin was added, in various concentrations (0.2, 0.4 and 0.6 wt.%), using the Layer by Layer technique. In the presence of pectin, the ζ-potential of the oil droplets became negative; indicating that negatively charged pectin was absorbed onto the positively-charged droplet surface forming a secondary layer. The additional layer resulted in a wide range of emulsion stability. For all pectin concentrations, the 1:1 ratio of WPI:Tween 20 showed the highest stability. In most emulsions, extensive aggregation of oil droplets was observed, and their viscosity increased. Insufficient amounts of pectin to form the secondary layers led to bridging flocculation phenomena of oppositely charged pectin and proteins, leading to aggregation of the oil droplets. The higher the concentration of pectin, the greater the stability of the emulsion due to higher viscosity. All in all, the addition of a second layer consisting of pectin can be used to increase the stability of an emulsion containing emulsion droplets in the sub-micron range.     

Modified starch granules as particle-stabilizers of oil-in-water emulsions

Oil-in-water (O/W) emulsions of 20 vol% n-tetradecane have been prepared using food-compatible hydrophobic starch particulates as the primary emulsifier. As such, the systems appear to be Pickering emulsions. The starch particulates were generated from chemically cross-linked granules that do not swell on prolonged contact with water and which were made partially hydrophobic by reaction with octenyl succinic anhydride. The degree of substitution was of the order of 0.03. The size of the modified starch particulates was reduced by freezer-milling before preparing the emulsions via a jet homogenizer. Conventional light transmission microscopy, confocal laser scanning microscopy, scanning electron microscopy, multi-angle light scattering and laser Doppler light scattering all suggested that a wide range of starch particle sizes was produced. Some particles were considerably smaller than the original starch granule sizes, but a large proportion appeared to be above several microns in size. The emulsion droplets produced using 1–3 wt.% of starch as emulsifier were quite large (from approximately 1 to 20 μm in diameter), i.e., of the same order of size as a large proportion of the starch particulates. Consequently, the emulsions creamed readily, but they were extremely stable to coalescence with no significant change in the emulsion droplet-size distributions appearing for over 3 months. Further tests on the surface tensions of the homogenized and non-homogenized starch dispersions themselves confirmed the supposition that the O/W emulsions were stabilized by starch particulates and not starch molecules.     

Rheology and microstructure of myofibrillar protein-plant lipid composite gels: Effect of emulsion droplet size and membrane type

Composite gels were prepared from 2% myofibrillar protein (MP) with 10% imbedded pre-emulsified plant oils (olive and peanut) of various particle sizes at 0.6 M NaCl, pH 6.2. Dynamic rheological testing upon temperature sweeping (20-70 °C at 2 °C/min) showed substantial increases in G′ (elastic modulus) of MP sols/gels with the addition of emulsions, and the G′ increases were inversely related to the emulsion droplet size. Furthermore, gels containing emulsified olive oil had a greater (P < 0.05) hardness than those containing emulsified peanut oil. Regardless of oil types, MP-coated oil droplets exhibited stronger reinforcement of MP gels than Tween 80-stablized oil droplets; the latter composite gels had considerable syneresis. Light microscopy with paraffin sectioning revealed a stable gel structure when filled with protein-coated oil droplets, compared to gels with Tween 80-treated emulsions that showed coalesced oil droplets. These results suggest that rheological characteristics, hardness, texture, and water-holding capacity of MP gels were influenced by type of oils, the nature of the interfacial membrane, and the size of emulsion droplets.     

Effects of chlorophyll photosensitisation on the oxidative stability in oil-in-water emulsions

Effects of chlorophyll photosensitisation on the oxidative stability of oil-in-water (O/W) emulsions were determined by analysing headspace oxygen content, lipid hydroperoxides, and headspace volatiles. The roles of transition metals and singlet oxygen were tested by adding ethylenediaminetetraacetic acid (EDTA) and sodium azide, respectively. Emulsions with chlorophylls and visible light irradiation had significantly high lipid hydroperoxides and headspace volatiles and low headspace oxygen content (p < 0.05) after 32 h while samples without light irradiation did not show any significant changes (p > 0.05). Sodium azide did not show clear antioxidant capacities in O/W emulsion systems rather showed prooxidant properties at some concentration. Addition of EDTA, a metal chelator, accelerated the rates of lipid oxidation in a concentration dependent manner. EDTA may enhance the stability of chlorophylls in O/W emulsions and the resulting higher chlorophyll concentrations may generate more singlet oxygen thus accelerating the rates of lipid oxidation.     

Effects of emulsifier charges on the oxidative stability in oil-in-water emulsions under riboflavin photosensitization

The oxidative stability in oil-in-water (O/W) emulsions containing different emulsifier charges was tested under riboflavin photosensitization by analysis of headspace oxygen content and lipid hydroperoxides. Sodium dodecyl sulfate (SDS), Tween 20, and cetyltrimethylammonium bromide (CTAB) were selected as anionic, neutral, and cationic emulsifiers, respectively. The O/W emulsions containing CTAB had lower oxidative stability than those with SDS and Tween 20. The addition of ethylenediaminetetraacetic acid, a well-known metal chelator, increased the oxidative stability in O/W emulsions, irrespective of emulsifier charges. Oxidative stability in Tween 20-stabilized emulsions decreased in FeCl₃ and FeCl₂ concentration-dependent manner. However, oxidative stability in samples containing CTAB increased up to 0.5mM of FeCl₃ and FeCl₂ and then decreased, which implies that CTAB act differently during lipid oxidation compared to SDS and Tween 20.     

Effect of thermal treatments on the properties of coconut milk emulsions prepared with surface-active stabilizers

Previously we have demonstrated improved stability of coconut milk emulsions homogenized with various surface-active stabilizers, i.e., 1 wt% sodium caseinate, whey protein isolate (WPI), sodium dodecyl sulfate (SDS), or polyoxyethylene sorbitan monolaurate (Tween 20) [Tangsuphoom, N., & Coupland, J. N. (2008). Effect of surface-active stabilizers on the microstructure and stability of coconut milk emulsions. Food Hydrocolloids, 22(7), 1233–1242]. This study examines the changes in bulk and microstructural properties of those emulsions following thermal treatments normally used to preserve coconut milk products (i.e., −20 °C, −10 °C, 5 °C, 70 °C, 90 °C, and 120 °C). Calorimetric methods were used to determine the destabilization of emulsions and the denaturation of coconut and surface-active proteins. Homogenized coconut milk prepared without additives was destabilized by freeze–thaw, (−20 °C and −10 °C) but not by chilling (5 °C). Samples homogenized with proteins were not affected by low temperature treatments while those prepared with surfactants were stable to chilling but partially or fully coalesced following freeze–thaw. Homogenized coconut milk prepared without additives coalesced and flocculated after being heated at 90 °C or 120 °C for 1 h in due to the denaturation and subsequent aggregation of coconut proteins. Samples emulsified with caseinate were not affected by heat treatments while those prepared with WPI showed extensive coalescence and phase separation after being treated at 90 °C or 120 °C. Samples prepared with SDS were stable to heating but those prepared with Tween 20 completely destabilized by heating at 120 °C.     

Effect of chitosan on the stability and properties of modified lecithin stabilized oil-in-water monodisperse emulsion prepared by microchannel emulsification

The effect of chitosan (CHI) on the stability of monodisperse modified lecithin (ML) stabilized soybean oil-in-water (O/W) emulsion was investigated. Monodisperse emulsion droplets with particle size of 24.4 ± 0.7 μm and coefficient of variation below 12% were prepared by microchannel (MC) emulsification using a hydrophilic asymmetric straight-through MC silicon 24 × 24 mm microchip consisting of 23,348 microchannels. The stability of the ML stabilized monodisperse emulsion droplets was investigated as a function of CHI addition at various concentration, pH, ionic strength, thermal treatment and freezing-thawing treatment by means of particle size and ζ-potential measurements as well as microscopic observation. The monodisperse O/W emulsions were diluted with CHI solution at various concentrations to a final droplet concentration of 1 wt% soybean oil, 0.25 wt% ML and 0–0.5 wt% CHI at pH 3. Pronounced droplet aggregation was observed when CHI was present at a concentration range of between 0.01 and 0.04 wt%. Above this concentration range, flocculations were less extensive, indicating some restabilization. ML stabilized emulsions were stable at a wide range of NaCl concentrations (0–1000 mM) and pH (3–8). On the contrary, in the presence of CHI, aggregation of the emulsion droplets was observed when NaCl concentration was above 200 mM and when the pH started to approach the pKa of CHI (i.e. ∼6.2–7.0). Emulsions containing CHI were found to have better stability at high temperature (>70 °C) in comparison to the emulsion stabilized only by ML. With sucrose/sorbitol as cryoprotectant aids, emulsions with the addition of CHI were found to be more resistant to droplet coalescence as compared to those without CHI after freezing at −20 °C for 22 h and thawing at 30 °C for 2 h. The use of CHI may potentially destabilize ML-stabilized O/W emulsions but its stability can be enhanced by selectively choosing the appropriate CHI concentrations and conditions of preparation.     

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.     

Antioxidant capacities of α-tocopherol,trolox, ascorbic acid,and ascorbyl palmitate in riboflavin photosensitized oil-in-water emulsions

Antioxidant capacities of α-tocopherol, trolox, ascorbic acid, and ascorbyl palmitate at 0.01, 0.1, and 1.0 mM in riboflavin photosensitized oil-in-water (O/W) emulsions were determined using headspace oxygen depletion, lipid hydroperoxide, and headspace volatile analyses. After 32 h visible light irradiation, headspace oxygen in O/W emulsions without adding antioxidants, with 1.0 mM α-tocopherol, trolox, ascorbic acid, and ascorbyl palmitate decreased to 18.50%, 18.85%, 16.01%, 17.92%, and 19.88%, respectively, whereas those samples in the dark were 20.74%. Trolox and ascorbic acid acted as prooxidants while their lipophilic counterparts, α-tocopherol and ascorbyl palmitate, respectively showed antioxidant properties. Similar antioxidative or prooxidative properties of the tested compounds can be observed in the results of lipid hydroperoxides and headspace volatiles. However, the prooxidant and antioxidant properties of the tested compounds were not clearly shown at 0.01 and 0.1 mM concentration. Both the type and concentration of antioxidants influenced the antioxidant capacities in riboflavin photosensitized O/W emulsions.