A study of oil-in-water emulsions stabilized by whey proteins

Like many other emulsifiers, whey protein concentrates stabilize oil-in-water emulsions. However, the emulsifying capacity of whey proteins is affected by several factors, e. g., type of homogenizer, degree of homogenization, protein concentration, oil volume fraction, pH and ionic strength of the aqueous phase. For the present study, oilin-water emulsions were made by homogenizing known amounts of whey protein concentrate with a vegetable oil (i. e. grapeseed oil) at different pH. The emulsifying properties of whey proteins are expressed as a function of the particle size and size distribution of oil droplets as measured by light scattering, and of the surface charge density derived from the electrophoretic mobility.The whey protein concentrate was shown to have an isoelectric point at pH 4.4. Near this pH value, the oil-in-water emulsions exhibited poor stability as expected from the low surface coverage.     

Ostwald ripening of oil-in-water emulsions stabilized by phenoxy-substituted dextrans

The stability of oil-in-water emulsions prepared using dextran, a natural polysaccharide, hydrophobically substituted with phenoxy groups, was studied. The evolution of the emulsion droplet size was investigated as a function of polymer concentration (Cp=0.2 to 1% w/w in a water phase) and the degree of phenoxy substitution (tau=4.2 to 15.7%). For the highest tau values, emulsions, which presented submicrometer droplets, were stable over more than 4 months at room temperature. The most substituted polymers clearly showed a better efficiency to lower the surface tension at the oil/water interface. DexP did not induce real viscosification of the continuous phase. The linearity of the particle volume variation with time, and the invariability of the volume distribution function, proved that Ostwald ripening was the main destabilization mechanism of the phenoxy dextran emulsions. The nature of the oil dispersed phase drastically affected the behavior of emulsions. While the emulsions prepared with n-dodecane presented a particle growth with time, only few size variations occurred when n-hexadecane was used. Furthermore, small ratios of n-hexadecane in n-dodecane phase reduced the particle growth due to the lower solubility and lower diffusion coefficient in water of n-hexadecane, which acted as a ripening inhibitor.     

Yield stress and viscoelastic properties of high internal phase ratio emulsions

 The rheology of high internal phase ratio oil-in-water emulsions was investigated using a controlled-stress rheometer. The dispersed-phase (oil) concentration was varied from 71.24 to 89.61% by volume. Three different types of rheological experiments were conducted for each emulsion, namely: steady shear, oscillatory shear, and creep/recovery experiments. All the emulsions investigated in this study possess a yield stress. The yield-stress values obtained from different rheological experiments for the same emulsion show good agreement with each other. The yield-stress value increases exponentially with an increase in the dispersed-phase concentration. The yield-stress data of this study can be described quite well with the Princen and Kiss equation for high internal phase ratio emulsions provided that the thickness of the interdroplet films is taken into account. For any given emulsion, the storage modulus, measured in the linear viscoelastic region, is found to be constant, independent of the frequency, indicating a solid-like behaviour. The value of the storage modulus increases with an increase in the dispersed-phase concentration. The storage modulus data are interpreted in terms of the Princen and Kiss equation. Received: 23 October 1998 Accepted in revised form: 18 February 1999     

Rheology of high internal phase emulsions

The mechanical dispersion technology used in this study employs rotor-stator mixers that produce water-continuous high internal phase emulsions (HIPEs) with narrow drop size distributions and small drop sizes, even when the internal phase (oil) viscosity is quite high. Analysis of these HIPEs reveals trends that are consistent with formation by a capillary instability mechanism in which a shear deformation produces highly elongated drops that rupture to form uniform, small droplets. In the search for a predictive tool to aid in the manufacture and use of HIPEs, rheology data for these shear-thinning HIPEs have been compared to data for models in the literature. Existing models do not correctly account for the effect of a high internal phase viscosity on the rheological properties of the HIPE. Another shortcoming is failure to correctly address the shear-thinning exponent. Whereas internal phase viscosity does not seem to affect the shear-thinning exponent, the surfactant apparently plays an important role, possibly through its modification of the interfacial tension and continuous phase rheology.     

Wet-spun porous fibers from high internal phase emulsions: Continuous preparation and high stretchability

Although high internal phase emulsion (HIPE)-templating is promising to prepare macroporous materials (polyHIPEs) with controllable shapes and tuneable property, fibrous polyHIPEs with stretchability and their continuous preparation are still challenging. Here, we report the fabrication of polyHIPE fibers in a continuous manner through wet spinning of HIPEs. The successful fabrication of polyHIPE fibers depends on HIPE dispersed phase fractions, ammonia-catalyzed interfacial reaction and wet spinning. Dry polyHIPE fibers exhibit tunable diameters, hierarchically porous structures, high stability to temperature and to various solutions, and high stretchability (with a high tensile strain of 155%), which is hard to achieve for polyHIPEs. The polyHIPE fibers show enhanced uptakes to both water (14.4 ml g⁻¹) and organic solvents (up to 26.3 ml g⁻¹), and the amphiphilic swelling is rare for polyHIPEs. Moreover, the dry polyHIPE fibers show good thermal insulation, similar to that of cotton. Simple wet spinning, combining with HIPEs with tuneable composition, is promising for preparing various polyHIPE fibers for various potential applications.     

Influence of droplet characteristics on the formation of oil-in-water emulsions stabilized by surfactant-chitosan layers

The objective of this study was to establish the optimum conditions for preparing stable oil-in-water emulsions containing droplets surrounded by surfactant-chitosan layers. A primary emulsion containing small droplets (d32 approximately = 0.3 microm) was prepared by homogenizing 20 wt% corn oil with 80 wt% emulsifier solution (20 mM SDS, 100 mM acetate buffer, pH 3) using a high-pressure valve homogenizer. The primary emulsion was diluted with chitosan solutions to produce secondary emulsions with a range of oil and chitosan concentrations (0.5-10 wt% corn oil, 0-1 wt% chitosan, pH 3). The secondary emulsions were sonicated to help disrupt any droplet aggregates formed during the mixing process. The electrical charge, particle size, and amount of free chitosan in the emulsions were then measured. The droplet charge changed from negative to positive as the amount of chitosan in the emulsions was increased, reaching a relatively constant value (approximately +50 mV) above a critical chitosan concentration (C(Sat)), which indicated that saturation of the droplet surfaces with chitosan occurred. Extremely large droplet aggregates were formed at chitosan concentrations below C(Sat), but stable emulsions could be formed above C(Sat) provided the droplet concentration was not high enough for depletion flocculation to occur. Interestingly, we found that stable multilayer emulsions could also be formed by mixing chitosan with an emulsion stabilized by a nonionic surfactant (Tween 20) due to the fact the initial droplets had some negative charge. The information obtained from this study is useful for preparing emulsions stabilized by multilayer interfacial layers.     

Influence of pH on the stability of oil-in-water emulsions stabilized by a splittable surfactant

A laboratory study was conducted to evaluate the effect of pH on the stability of oil-in-water emulsions stabilized by a commercial splittable surfactant Triton SP-190 by comparison with the results obtained by a common surfactant Triton X-100. The emulsion stability was explored by measuring the volume of oil phase separated and the size of the dispersed droplets. It was found that the addition of inorganic acids did not significantly affect the stability of emulsions stabilized by Triton X-100, but had a profound influence on the stability of emulsions stabilized by Triton SP-190. Moreover, the droplet size of a Triton X-100-stabilized emulsion and its dynamic interfacial activity were insensitive to acids. However, at lower pH the droplet size of the emulsions stabilized by Triton SP-190 was considerably increased. From the dynamic interfacial tension measurements the dynamic interfacial activity of Triton SP-190 at the oil/water interface was found to be strongly inhibited by the addition of acids, resulting in a slower decreasing rate of dynamic interfacial tension. The results demonstrate that the dramatic destabilization of Triton SP-190-stabilized emulsions could be realized by the use of acids, which evidently changed the interfacial properties of the surfactant and resulted in a higher coalescence rate of oil droplets.     

Effects of pH and salt concentration on oil-in-water emulsions stabilized solely by nanocomposite microgel particles

Aqueous dispersions of lightly cross-linked poly(4-vinylpyridine)/silica nanocomposite microgel particles are used as a sole emulsifier of methyl myristate and water (1:1 by volume) at various pH values and salt concentrations at 20 degrees C. These particles become swollen at low pH with the hydrodynamic diameter increasing from 250 nm at pH 8.8 to 630 nm at pH 2.7. For batch emulsions prepared at pH 3.4, oil-in-water (o/w) emulsions are formed that are stable to coalescence but exhibit creaming. Below pH 3.3, however, these emulsions are very unstable to coalescence and rapid phase separation occurs just after homogenization (pH-dependent). The pH for 50% ionization of the pyridine groups in the particles in the bulk (pK(a)) was determined to be 3.4 by acid titration measurements of the aqueous dispersion. Thus, the charged swollen particles no longer adsorb at the oil-water interface. For continuous emulsions (prepared at high pH with the pH then decreased abruptly or progressively), demulsification takes place rapidly below pH 3.3, implying that particles adsorbed at the oil-water interface can become charged (protonated) and detached from the interface in situ (pH-responsive). Furthermore, at a fixed pH of 4.0, addition of sodium chloride to the aqueous dispersion increases the degree of ionization of the particles and batch emulsions are significantly unstable to coalescence at a salt concentration of 0.24 mol kg(-1). The degree of ionization of such microgel particles is a critical factor in controlling the coalescence stability of o/w emulsions stabilized by them.     

Tough interconnected polymerized medium and high internal phase emulsions reinforced by silica particles

Emulsion templating using high internal phase emulsions is an effective route to prepare low density and high porosity macroporous polymers known as polymerized high internal phase emulsions (polyHIPEs). Conventional polyHIPEs, synthesized from surfactant stabilized w/o emulsions have low permeabilities and poor mechanical properties. We present interconnected open macroporous low density nanocomposites produced by polymerizing the continuous phase of emulsion templates, which contained styrene, polyethyleneglycoldimethacrylate, and silylated silica particles. Polyethyleneglycoldimethacrylate and the silylated silica particles acted as crosslinker. The functionalized silica particles were incorporated into the polymer, which resulted in a significant improvement of the mechanical properties of the polyHIPEs without affecting the interconnected and permeable pore structures. The polyHIPEs contained up to 60 wt % silylated silica particles. Young's modulus of the reinforced macroporous polymers increased up to 600% compared with nonreinforced macroporous polymers. The mechanical performance was further increased by increasing the foam density of the macroporous nanocomposites from around 200 to 370 g/cm³ by raising the organic phase volume of the emulsion templates from 20 to 40 vol %. The macroporous polymers synthesized from less concentrated emulsions also possessed interconnected open porous although less permeable structures. The polyHIPE nanocomposites have a permeability of about 200 mD, whereas the polyMIPE nanocomposites still have permeabilities of around 50 mD. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1979–1989, 2010     

One-pot preparation of mono-dispersed and physiologically stabilized gold colloid

We have developed a rapid and simple method for the preparation of nearly mono-dispersed gold colloids with a fairly high concentration above 10 mM using hydroxylamine as the reducing agents, in the presence of α-methoxy-ω-mercaptoethyl-poly(ethylene glycol)(MeO-PEG-SH). It was found that a hydroxylamine acted not only as a reducing agent, but also as a nucleation agent under alkaline reaction conditions. Though the colloid concentration was fairly high, the dispersion stability was remarkably improved even in a high ionic strength in the range greater than 1 M NaCl, in which conventional citrate gold colloids immediately flocculate and precipitate. The obtained colloid was successfully re-dispersed in aqueous media after lyophilization. In addition, the prepared gold colloid reduced a protein adsorption significantly on its surface. Concerning these results, the obtained colloidal dispersion may be suitable for biological applications, since a regionally concentrated colloidal dispersion with dispersion stability is required for bio-labeling and bio-imaging systems.Electronic Supplementary Material Supplementary material is available for this article at     

Comparison of droplet flocculation in hexadecane oil-in-water emulsions stabilized by beta-lactoglobulin at pH 3 and 7

The influence of surface and thermal denaturation of adsorbed beta-lactoglobulin (beta-Lg) on the flocculation of hydrocarbon oil droplets was measured at pH 3 and compared with that at pH 7. Oil-in-water emulsions (5 wt % n-hexadecane, 0.5 wt % beta-Lg, pH 3.0) were prepared that contained different levels of salt (0-150 mM NaCl) added immediately after homogenization. The mean particle diameter (d43) and particle size distribution of diluted emulsions were measured by laser diffraction when they were either (i) stored at 30 degrees C for 48 h or (ii) subjected to different thermal treatments (30-95 degrees C for 20 min). In the absence of salt, little droplet flocculation was observed at pH 3 or 7 because of the strong electrostatic repulsion between the droplets. In the presence of 150 mM NaCl, a progressive increase in mean particle size with time was observed in pH 7 emulsions during storage at 30 degrees C, but no significant change in mean particle diameter with time (d43 approximately 1.4 +/- 0.2 microm) was observed in the pH 3 emulsions. Droplet aggregation became more extensive in pH 7 emulsions containing salt (added before thermal processing) when they were heated above 70 degrees C, which was attributed to thermal denaturation of adsorbed beta-Lg leading to interdroplet disulfide bond formation. In contrast, the mean particle size decreased and the creaming stability improved when pH 3 emulsions were heated above 70 degrees C. These results suggest that the droplets in the pH 3 emulsions were weakly flocculated at temperatures below the thermal denaturation temperature of beta-Lg (T < 70 degrees C) but that flocs did not form so readily above this temperature, which was attributed to a reduction in droplet surface hydrophobicity due to protein conformational changes. The most likely explanation for the difference in behavior of the emulsions is that disulfide bond formation occurs much more readily at pH 7 than at pH 3.     

Influence of environmental stresses on stability of oil-in-water emulsions containing droplets stabilized by beta-lactoglobulin-iota-carrageenan membranes

An oil-in-water emulsion (5 wt% corn oil, 0.5 wt% beta-lactoglobulin (beta-Lg), 0.1 wt% iota-carrageenan, 5 mM phosphate buffer, pH 6.0) containing anionic droplets stabilized by interfacial membranes comprising of beta-lactoglobulin and iota-carrageenan was produced using a two-stage process. A primary emulsion containing anionic beta-Lg coated droplets was prepared by homogenizing oil and emulsifier solution together using a high-pressure valve homogenizer. A secondary emulsion containing beta-Lg-iota-carrageenan coated droplets was formed by mixing the primary emulsion with an aqueous iota-carrageenan solution. The stability of primary and secondary emulsions to sodium chloride (0-500 mM), calcium chloride (0-12 mM), and thermal processing (30-90 degrees C) were analyzed using zeta-potential, particle size and creaming stability measurements. The secondary emulsion had better stability to droplet aggregation than the primary emulsion at NaCl 相似文献   

Selective retardation of perfume oil evaporation from oil-in-water emulsions stabilized by either surfactant or nanoparticles

We have used dynamic headspace analysis to investigate the evaporation rates of perfume oils from stirred oil-in-water emulsions into a flowing gas stream. We compare the behavior of an oil of low water solubility (limonene) and one of high water solubility (benzyl acetate). It is shown how the evaporation of an oil of low water solubility is selectively retarded and how the retardation effect depends on the oil volume fraction in the emulsion. We compare how the evaporation retardation depends on the nature of the adsorbed film stabilizing the emulsion. Surfactant films are less effective than adsorbed films of nanoparticles, and the retardation can be further enhanced by compression of the adsorbed nanoparticle films by preshrinking the emulsion drops.     

Recent advances in separation applications of polymerized high internal phase emulsions

Polymerized high internal phase emulsions as highly porous adsorption materials have received increasing attention and wide applications in separation science in recent years due to their remarkable merits such as highly interconnected porosity, high permeability, good thermal and chemical stability, and tailorable chemistry. In this review, we attempt to introduce some strategies to utilize polymerized high internal phase emulsions for separation science, and highlight the recent advances made in the applications of polymerized high internal phase emulsions for diverse separation of small organic molecules, carbon dioxide, metal ions, proteins, and other interesting targets. Potential challenges and future perspectives for polymerized high internal phase emulsion research in the field of separation science are also speculated at the end of this review.     

Production and characterization of oil-in-water emulsions containing droplets stabilized by multilayer membranes consisting of beta-lactoglobulin, iota-carrageenan and gelatin

The influence of environmental conditions (pH, NaCl, CaCl2, and temperature) on the properties and stability of oil-in-water (O/W) emulsions containing oil droplets surrounded by one-, two-, or three-layer interfacial membranes has been investigated. Three oil-in-water emulsions were prepared with the same droplet concentration and buffer (5 wt % corn oil, 5 mM phosphate buffer, pH 6) but with different biopolymers: (i) primary emulsion: 0.5 wt % beta-Lg; (ii) secondary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan; (iii) tertiary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan, 0-2 wt % gelatin. The secondary and tertiary emulsions were prepared by electrostatic deposition of the charged biopolymers onto the surfaces of the oil droplets so as to form two- and three-layer interfacial membranes, respectively. The stability of the emulsions to pH (3-8), sodium chloride (0-500 mM), calcium chloride (0-12 mM), and thermal processing (30-90 degrees C) was determined. We found that multilayer emulsions had better stability to droplet aggregation than single-layer emulsions under certain environmental conditions and that one or more of the biopolymer layers could be made to desorb from the droplet surfaces in response to specific environmental changes (e.g., high salt or high temperature). These results suggest that the interfacial engineering technology used in this study could lead to the creation of food emulsions with improved stability to environmental stresses or to emulsions with triggered release characteristics.     

One-pot three-component synthesis, structure and redox properties of ferrocenyl isoxazoles

A consecutive coupling-cycloaddition sequence of acid chlorides, terminal alkynes, and in situ generated nitrile oxides furnishes ferrocenyl substituted redox active isoxazoles in moderate to good yields. The structure was unambiguously assigned by X-ray structure analyses and the electronic structure was elucidated by computational methods. Redox potentials of all representatives are strongly effected by the electronic nature of the bridging isoxazoloyl moiety.     

Complex layering observed in high internal phase emulsions at a silicon surface by neutron reflectometry

The neutron reflectivity profiles from the interface between silicon and aqueous phase-in-oil high internal phase emulsions of steadily increasing surfactant hydrophilicity, are reported for two isotopic contrasts for each surfactant. Layered models are required to fit the structured reflectivity profiles that demonstrate that the oxidised top layer of the silicon is always covered by a surfactant monolayer. Interposed between the surfactant monolayer and the bulk emulsion is a layer of oil--a geometric effect caused by reorganisation of the aqueous droplets. As the surfactant hydrophilicity increases, alternating aqueous and oil+surfactant layers are inserted between this topmost oil layer and the oxide attached surfactant monolayer. The resulting structures have compositions and layer spacings suggestive of sections from lamellar phases. This increase in layer ordering with increasing surfactant hydrophilicity is expected. The bulk emulsions are observed to exhibit lamellar or sponge phases increasingly as surfactant hydrophilicity increases.     

Synergistic effect of silica nanoparticles and charged surfactants in the formation and stability of submicron oil-in-water emulsions

The influence of hydrophilic silica nanoparticles on the emulsification of a triglyceride oil (Miglyol812) in the presence of charged surfactants (lecithin or oleylamine) and the long term stability of the resultant oil-in-water emulsions are reported. A synergistic effect of nanoparticles and surfactants in improving emulsification and stability to coalescence is evident only when the silica nanoparticles are initially added to the oil phase. When nanoparticles are included from the water phase, no synergistic stabilisation was observed due to electrostatic bridging or unfavourable attachment due to the repulsive electrostatic and hydration forces. Free energies of adsorption for silica nanoparticles at the oil-water interface calculated from experimentally determined interfacial tensions and three phase contact angles can be correlated to long-term emulsion stability only when silica is added from oil phase.