Characterization of different double-emulsion formulations based on food-grade emulsifiers and stabilizers

This study focused on the preparation and characterization of water-in-oil-in-water (W1/O/W2)-type double emulsions designed by food-grade emulsifiers and stabilizers. The primary objective of this study was to compare different emulsion formulations in terms of droplet size, rheology, and stability and to reduce the amount of polyglycerol poliricinoleate (PGPR). To achieve these goals, PGPR and a PGPR–lecithin blend were utilized in the formation of the primary phase (W1/O), while varying concentrations of guar gum (GG) and gum tragacanth (GT) incorporated in the secondary water phase (W2). Shear thinning behavior was observed for all emulsion formulations. Sauter mean diameters of the emulsions prepared with PGPR as a hydrophobic emulsifier ranged between 30?µm and 75?µm, while those prepared with the PGPR–lecithin blend varied between 25?µm and 85?µm based on the first day’s measurements. In emulsions with the PGPR–lecithin blend, the smallest droplet size was obtained when the GG–GT blend was incorporated in the external aqueous phase. Moreover, GG–GT blends had high consistency coefficients and high apparent viscosity values. It was also observed that PGPR–lecithin containing emulsions were more stable.     

The effects of emulsifier type,phase ratio,and homogenization methods on stability of the double emulsion

The double emulsion technology has a potential effect on the development of diversity and quality of functional foods by means of decreasing oil or salt concentration, encapsulating and controlling release of valuable components. In this study, it was aimed to formulate stable double emulsions to be used in food systems. W1/O ratios of primary emulsions, stabilized by polyglycerol polyricinoleate (PGPR), were designed as 2:8 and 4:6, and (W1/O)/W2 ratios of the double emulsions were used as 2:8 and 4:6. W/O/W phase ratios, homogenization methods applied to primary emulsion (high-speed homogenization, ultrasonic homogenization), and emulsifier types used in W2 phase [sodium caseinate (SC), xanthan gum, lecithin-whey protein concentrate] were used as independent variables. Particle size and distributions, stability, encapsulation efficiency (EE), rheological properties, long-term stability, and morphological properties of the double emulsions were investigated.

The double emulsions prepared with SC and (W1/O)/W2 ratio of 4:6, were found to have the higher stability values, higher apparent viscosity, and lower particle size. High-speed homogenization applied to primary emulsion reduced particle size of the double emulsion and increased apparent viscosity, but did not affect stability and EE of the double emulsions, significantly.     

Polyols,High Pressure,and Refractive Indices Equalization for Improved Stability of W/O Emulsions for Food Applications

Mixtures of polyols (glycerol, propylene glycol, glucose) and water were emulsified in oil (isopropyl myristate (IPM), medium chain triglycerides (MCT), long chain triglycerides (LCT), and d-limonene) under elevated pressures and homogenization, in the presence of polyglycerol polyricinoleate (PGPR), glycerol monooleate (GMO), and their mixture as emulsifiers to form water-in-oil emulsions. High pressures was applied to: a) the emulsion, b) the aqueous phase and c) the oil phase in the presence of the emulsifiers (PGPR and GMO). Under optimal pressure (2000 atms) applied to the ready-made emulsion or to the aqueous phase prior to its emulsification, and with optimal composition (30wt% polyol in the aqueous phase and MCT as the oil phase), the aqueous droplets were stable for months and submicron in size (0.1 μm). Moreover, due to equalization of the oil and the aqueous phases refractive indices, the emulsions were almost transparent. Pressure and polyols have synergistic effects on the emulsions stability. During preparation, surface tensions and interfacial tensions were dramatically reduced until an optimal water/polyols ratio was achieved, which allows rupturing of the droplets to submicronal size (0.1 μm) without recoalescence and fast diffusion to the interface. These unique W/O emulsions are suitable for preparing W/O/W double emulsions for sustained release of active materials for food applications.     

Phase Transitions in Emulsions Formed by Aqueous Emulsifier and its Action on Improving Mobility in Oil Recovery

Transition from oil-in-water (O/W) emulsions to water-in-oil (W/O) emulsions and its action on enhanced oil recovery was investigated by viscosity, morphology, and simulated flooding experiments. This transition can be realized by increasing the volume ratio of oil to water or decreasing the emulsifier concentration. At a mass concentration of 0.3 wt%, the self-developed emulsifier FJ-1 mainly forms O/W emulsions at a volume ratio (oil to water) of 1:1. The emulsions behave as O/W emulsions with a low viscosity when the volume ratio of oil to water is below 2:1. Above 2:1, increasing volume ratio leads to the O/W emulsions transferring into W/O emulsions with high viscosity. For example, at a volume fraction of 4:1, the viscosity of W/O emulsions reaches 229.1 mPa · s, and separated water can hardly be detected. Transition from O/W emulsions to W/O emulsions with high viscosity can also be realized by decreasing the concentration of emulsifier to 0.05 wt% or lower at a volume ratio of 1:1. These may be the critical factors leading to transition from O/W emulsions to W/O emulsions at core conditions. Simulated flooding experiments show that emulsifier fluids can act as an in situ mobility improver and make an improvement of oil recovery even by 20.4%. The results indicate that the water-in-crude-oil emulsions possess great potential in enhancing oil recovery.     

Stability of W/O Emulsions Encapsulating Polysaccharides

In the frame of formulation of W/O emulsions entrapping polysaccharides devoted to agricultural applications, the aim of this work was to study the stability over time of these emulsions, stabilized with either soybean lecithin or polyglycerol polyricinoleate (PGPR) as emulsifiers. Emulsifiers were dissolved in oil phase, and polysaccharides (carboxymethycellulose (CMC), guar, xanthan) in ultrapure water. Emulsions stability was studied through natural aging tests and accelerated aging tests, using bottle tests, microscopy and calorimetry. Experiments showed that PGPR was more efficient than lecithin to stabilize emulsions containing the polysaccharides studied, and that emulsions prepared with CMC showed the best stability.     

Ethanol-in-oil emulsion (E/O) stabilized by polyglycerol polyricinoleate: A potential delivery system for ethanolic extract

This study evaluated how variations in polyglycerol polyricinoleate (PGPR) concentration and ethanol dispersed phase content affect the stability of ethanol-in-oil (E/O) emulsions. Results indicate that the stable 10?wt% E/O emulsions can be produced using 2?wt% PGPR. Increasing the ethanol dispersed phased content at constant PGPR concentration caused instability in emulsion. These emulsions remained stable to droplet flocculation and coalescence in the presence of Centella asiatica ethanol extract. PGPR does not greatly decrease the interfacial tension of the ethanol–oil interface. However, it adsorbed at the interface and stabilized the ethanol droplets in the emulsion via steric mechanism.     

Preparation,Mass Diffusion,and Biocompatibility Analysis of Porous-Channel Controlled Calcium-Alginate-Gelatin Hybrid Microbeads for In Vitro Culture of NSCs

The Ca-alginate/gelatin (CAG) microbeads were prepared and evaluated through assays for their mechanical strength, permeability, and the feasibility as a cell carrier for in vitro culture of neural stem cells. The effects of different concentrations of sodium alginate, gelatin, and calcium chloride on the mechanical strength of CAG microbeads were determined using a self-made puncture force tester. Following this, the microbeads were immersed in DMEM media for a specified period to test its decay resistance. A diffusion model including a calculation formula of diffusion coefficient was built to investigate the diffusion of glucose and bovine serum albumin (BSA) through the wall of the microbeads. Furthermore, the feasibility of the microbeads for in vitro culture was identified using neural stem cells from Kunming mouse. Through a systematic approach and comprehensive analysis, the optimal gelatin conditions for microbead preparation were determined; the final combination of parameters of 1.5 % (wt%) sodium alginate (SA), 0.5 % (wt%) gelatin, and 4 % (wt%) CaCl₂ were the best conditions for NSC cultures. This experiment demonstrated that CAG microbeads had good cytocompatibility that made it suitable for the culture and successfully maintained stemness of neural stem cells.     

Preparation of highly monodisperse W/O emulsions with hydrophobically modified SPG membranes

Experimental investigations on the hydrophobic modification of SPG membranes and the preparation of monodisperse W/O (water-in-oil) emulsions using the modified membranes were carried out. Effects of the osmotic pressure of disperse phase, the average pore size of membranes, emulsifier concentrations in continuous phase and the transmembrane pressure on the average size, size distribution and size dispersion coefficient of emulsions were systematically studied. The stability of W/O emulsions was also investigated. The results showed that SPG membranes took on excellent hydrophobicity through the modification by silane coupler reagent (octyltriethoxysilane) or by silicone resin (polymethylsilsesquioxane). Monodisperse W/O emulsions with size dispersion coefficient of about 0.25, which meant high monodispersity, were successfully prepared by using the hydrophobically modified SPG membranes with average pore sizes of 1.8, 2.0, 2.5, 4.8 and 11.1 microm. When the osmotic pressure was lower than 0.855 MPa, the average size of emulsions was gradually increased while the size dispersion coefficient delta gradually decreased with the osmotic pressure; when the osmotic pressure was higher than 0.855 MPa, both the coefficients kept unvarying. When kerosene was saturated with disperse phase in advance, the average size of emulsions became larger and the monodispersity of emulsions was slightly better than that prepared using unsaturated kerosene. The smaller the pore size of SPG membranes was, the better the monodispersity of the W/O emulsions. The average size and size dispersion coefficient delta were nearly independent on the emulsifier concentrations when the PGPR concentration was in the range from 0.5 to 5.0 wt%, whereas both of them slightly increased as the PGPR concentration was below 0.5 wt%. The effect of the transmembrane pressure on size distributions was slight. Both the average size and size dispersion coefficient delta slightly increased to some extent with the increase of the transmembrane pressure in the experimental range. The stability of the W/O emulsions was dependent on the storage time. The mean size of W/O emulsions decreased gradually with the increase of storage time at the first 35 days, and then kept constant; while the size dispersion coefficient of W/O emulsions was nearly not changed.     

Application of the fractional factorial design in multiple W/O/W emulsions

In presented research, multiple W/O/W emulsions were developed by using experimental design method. A 24-1 fractional factorial design was performed by varying the following input parameters: primary polymeric emulsifier (PEG 30-dipolyhydroxystearate) concentration (0.8% and 2.4%), secondary polymeric emulsifier (Poloxamer 407) concentration (0.8% and 1.2%), electrolyte magnesium sulfate heptahydrate (0.08% and 0.4%) and electrolyte sodium chloride (0.08% and 0.4%). Multiple emulsions were prepared by a two-step emulsification process. Obtained emulsions were characterized with rheological measurements, conductivity and centrifugation tests. Factorial analysis revealed that the concentration of the primary emulsifier was the predominant factor influencing the phase separation, conductivity and maximal apparent viscosity. Additionally, electrolyte magnesium sulfate heptahydrate was more efficient in stabilizing these systems, compared to sodium chloride. The applied fractional factorial design method enabled determination of the optimal concentrations of the primary and secondary emulsifier, as well as the concentration of electrolytes, in order to obtain W/O/W emulsions with desired maximal apparent viscosities, low values of conductivity and without phase separation after centrifugation.     

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.     

Effect of Nanoparticle Hydrophobicity on Stability of Highly Concentrated Emulsions

The effect of hydrophobicity index (HI) of fumed nanosilica specimens on stability of water-in-oil (W/O) highly concentrated emulsions (HCE with ? = 90 vol%) with an overcooled dispersed phase was studied. A series of five silica with HI in the 0.60–1.34 range and HI > 3 were used separately and in combination with a low molecular weight traditional surfactant, Sorbitan MonoOleate (SMO). First, it was shown that SMO alone can stabilize W/O HCE whereas only silica nanoparticles with intermediate HI in the range 0.97 ≤ HI ≤ 1.34 could form W/O emulsions only up to 77–79 vol%. Then, on the contrary to SMO-based emulsions, Pickering emulsions are unstable under shearing. When mixed (silica plus SMO) emulsifier systems were used, firstly a thermodynamic consideration revealed that only SMO is likely to adsorb at the W/O interface and controls the emulsifying process by the decrease in the interfacial tension. Then, interestingly, all different kinds of emulsion stability investigated in this study demonstrate a breaking point (BP) at HI = 0.97. Below the BP the emulsions were found to be very unstable on shelf as well as under shear. Above the BP, a clear synergy between colloidal silica and SMO surfactant has been found.      

Effect of Emulsification Method on the Properties of Lecithin‐ and PGPR‐Stabilized Water‐in‐Oil‐Emulsions

Water‐in‐oil (w/o) emulsions were prepared with phosphatidylcholine‐depleted lecithin or polyglycerol polyricinoleate (PGPR) as emulsifying agents. The effect of different laboratory emulsification devices and the effect of sodium chloride on particle size distribution, coalescence stability, and water droplet sedimentation were investigated. The properties of lecithin‐stabilized w/o emulsions were found to depend more strongly on the emulsifying method than those prepared with PGPR. The rotor‐stator system was not suitable for preparing stable w/o emulsions with lecithin. Whereas the addition of salt was essential to achieve coalescence‐stable emulsions prepared with PGPR, the presence of NaCl favored the coalescence of water droplets and phase separation in emulsions containing lecithin.     

Oxidative stability and effect of stress factors on flaxseed oil-in-water emulsions stabilized by sodium caseinate–sodium alginate–chitosan interfacial membrane

The susceptibility of heart healthy ω-3 fatty acids to lipid oxidation has hindered its incorporation into healthful foods and beverages. In this study, plant-based flaxseed oil rich in ω-3 fatty acids were dispersed into primary, secondary and tertiary emulsion system. A primary emulsion containing sodium caseinate-stabilized cationic droplets was prepared by homogenizing flaxseed oil as oil phase and sodium caseinate solution as the aqueous phase in an ultrasonicator. A secondary emulsion comprising of sodium caseinate–sodium alginate anionic droplets were produced by diluting appropriate primary emulsion with alginate solution. Further, a tertiary emulsion composed of sodium caseinate–sodium alginate–chitosan-coated cationic droplets was produced by diluting secondary emulsion with chitosan solution. The resistance of primary, secondary and tertiary emulsions with the same lipid concentration to destabilization by thermal treatment (30–90 °C for 30 min), sodium chloride addition (≤70 mM NaCl) and oxidative degradation (hydroperoxide concentration and TBARS) was determined. The results showed that secondary emulsions could resist variation in environmental stresses of salt and heat as well as protect the oil phase from decomposition better than primary and tertiary emulsions. Interfacial engineering could be used to design emulsion system with desirable characteristics.     

Cinnamoyl Alginate Microspheres: Effect of UV-Treatment on Release of FITC-Dextran

Cinnamoyl alginate microspheres were prepared using the water droplets of W/O emulsions as a template. Cinnamoyl alginates having variable content of the cinnamoyl group were prepared by a condensation reaction. The photo-dimerization degree of the cinnamoyl group increased as the molar ratio of pyranose unit/cinnamoyl group increased from 1:0.043 to 1:0.18. The air/water interfacial activity of cinnamoyl alginate also increased with increasing the molar ratio. Aqueous solution of cinnamoyl alginate was dispersed in mineral oil to obtain W/O emulsion. UV light (254 nm, 6 W) was irradiated to the emulsion to dimerize the cinnamoyl groups, and CaCl₂ was added to the emulsion to cross-link the cinnamoyl alginate. The surface of UV-treated microspheres was rougher than that of UV-untreated microspheres, possibly due to the photo-dimerization-induced tension on the alginate chains. The release degrees for 24 hours of fluorescein isothiocyanate-dextran (FITC-dextran; MW 4000) from UV-treated microspheres were markedly higher than those from UV-untreated ones. This is possibly due to the intramolecular dimerization of cinnamoyl group. The UV irradiation-induced percentage increase in the maximum release degree was greater as the content of cinnamoyl group was higher.     

A review of: “Nineteenth Century Attitudes: Men of Science (Chemists and Chemistry Series,Vol. 13)”. Sydney Ross. Kluwer Academic Publishers; Dordrecht, 1991. pp. xi+235. $69.00.

Abstract

The potential of polytetrafluoroethylene (PTFE) membranes as water‐in‐oil (W/O) emulsification devices was investigated to obtain uniformly sized droplets and to convert them into microcapsules and polymer particles via subsequent treatments. Uniform W/O emulsion droplets have not been achieved using glass membranes unless the membrane was rendered hydrophobic by treatment with silanes. If a PTFE membrane is capable of providing uniform droplets for a W/O emulsion, a coordinated membrane emulsification system can be established since glass membranes have been so successful for O/W (oil‐in‐water) emulsification. In order to examine the feasibility of PTFE membrane emulsification, O/W and W/O emulsion characteristics prepared using PTFE membranes were compared with those prepared by the conventional SPG (Shirasu porous glass) membrane emulsification method. A 3 wt.% sodium chloride solution was dispersed in kerosene using a low HLB surfactant. Effects of the membrane pore size, permeation pressure, and the type of emulsifiers and concentration on the droplet size and on the size distribution (CV, coefficient of variation) were investigated. The CV of the droplets was fairly low, and the average droplet size was correlated with the critical permeation pressure of the dispersed phase, revealing that the PTFE membrane could be used as a one‐pass membrane emulsification device. Low CV values were maintained with a Span 85 (HLB = 1.8) concentration, 0.2–5.0 wt.% and a range of HLB from 1.8–5.0. For a brief demonstration of practical applications, nylon‐6,10 microcapsules prepared by interfacial polycondensation and poly(acrylamide) hydrogels from inverse suspension polymerization are illustrated.     

Dynamic Stability of Heavy Crude Oil-in-Water Emulsions

The transport of heavy oil as concentrated oil-in-water (O/W) emulsions is one of the most promising pipeline techniques, and how to ensure a steady flow is the key to the successful application of this technology. Most of the previous studies focused on the static stability of the emulsions. However, the stability changes constantly with time and external shearing in the transportation. In this paper, a stable O/W emulsion was prepared for its dynamic stability to be tested by three methods of small-scale flow loop, rheology and stirring, respectively. The results indicated that the O/W emulsion with 30 vol.% water and 0.2 wt.% OP-10 could well satisfy the transport requirement. A critical temperature existed to make the rheological property of the emulsion rapidly deteriorate. For low-Reynolds-number turbulent pipe flow, an appropriate increase of temperatures and shear rates was conducive to the flocculation-dissociation balance of the internal phase, which could effectively reduce the apparent viscosity of the emulsion and the flow frictional resistance. High flow rate of O/W emulsions could be transported at relatively low temperatures to ensure great dynamic stability, and low flow rate of that could be done at relatively high temperatures to obtain low apparent viscosity.     

Synthesis and surface properties of self-crosslinking core–shell acrylic copolymer emulsions containing fluorine/silicone in the shell

Stable emulsions of a core–shell acrylic copolymer (non-crosslinkable V0, and crosslinkable V2, V4, V6, and V8, where the numbers indicate the wt% of crosslinking agent based on the total acrylate monomer content) containing butyl acrylate (BA, 45 wt%), glycidyl methacrylate (GMA, 45 wt%), heptadecafluorodecyl methacrylate (PFA, 10 wt%), and various contents of crosslinking agent (vinyltriethoxysilane, VTES) were synthesized using a three-stage seeded emulsion polymerization process with a small amount of surfactant. The average particle size and viscosity of emulsions increased significantly with increasing VTES content. This study examined the effects of the VTES content on the surface/mechanical properties of self-crosslinked copolymer film samples containing a fixed acrylate monomer content to find the optimum VTES content. XPS showed that the film–air surface of the copolymer samples had a higher fluorine/silicone content than the film–dish interface. The tensile strength/modulus, thermal stability, and two Tgs (α and β Tgs) of the film samples increased significantly with increasing VTES content. The contact angle of the film samples increased with increasing VTES content up to approximately 6 wt%, and then decreased slightly. The optimum VTES content was approximately 6 wt% based on the total acrylate monomer content to obtain a high water/oil repellent coating material (V6) with the highest water/methylene iodide-contact angles (118.2°/81.8°) and lowest surface energy (18.4 mN/m).     

Behavior and Stability of Naphthenic Acid/Naphthenate Stabilized Emulsions. Mixed C80-Tetraacid and Stearic Acid Stabilization

Previous studies have focused on monomeric naphthenic acids and their ability to stabilize emulsions, but little has been reported on C80-tetraacids and their ability to function as an emulsifier. In this article, we report on the chemistry of the C80-tetraacids as an emulsion stabilizer and also on the role this acid has in mixed monoacid-tetraacid systems. The study focuses on the type of emulsion formed and the stability of these emulsions with respect to water cut, pH, salinity of the water phase, and type of counterion. Interfacial behavior and the electrostatic properties of the emulsion were studied in order to determine which of the acids were present at the interface and which of the acids gave the largest contribution to the emulsion stability. It was found that C80-tetraacids form only O/W emulsion under the conditions studied. Addition of monoacid to the system did not change the type of emulsion formed. Highest stability was seen for emulsions containing both monoacid and tetraacids. When adding NaCl a phase inversion from O/W to W/O emulsion appeared around a concentration of 2 wt% of NaCl.     

Fat crystals: A tool to inhibit molecular transport in W/O/W double emulsions

Water-in-oil-in-water (W/O/W) double emulsions are a promising technology for encapsulation applications of water soluble compounds with respect to functional food systems. Yet molecular transport through the oil phase is a well-known problem for liquid oil-based double emulsions. The influence of network crystallization in the oil phase of W/O/W globules was evaluated by NMR and laser light scattering experiments on both a liquid oil-based double emulsion and a solid fat-based double emulsion. Water transport was assessed by low-resolution NMR diffusometry and by an osmotically induced swelling or shrinking experiment, whereas manganese ion permeation was followed by means of T₂-relaxometry. The solid fat-based W/O/W globules contained a crystal network with about 80% solid fat. This W/O/W emulsion showed a reduced molecular water exchange and a slower manganese ion influx in the considered time frame, whereas its globule size remained stable under the applied osmotic gradients. The reduced permeability of the oil phase is assumed to be caused by the increased tortuosity of the diffusive path imposed by the crystal network. This solid network also provided mechanical strength to the W/O/W globules to counteract the applied osmotic forces.     

Oil and Water Separation Using a Glass Microfiber Coalescing Bed

A vertical sleeve separator using glass microfiber with a mean diameter of 4 µm as coalescence medium was explored to remove oil from the oil-in-water (O/W) emulsions. The artificial emulsions were prepared by mixing diesel oil and water to obtain oil droplets with a mean diameter about 7 µm. A series of experiments were performed to investigate the effect of such parameters as bed porosity (0.850–0.925), bed height (2.0–20.0 mm), flow velocity (1.0–20.0 mL/s), and influent oil concentration (200.0–3000.0 mg/L) on the effluent oil concentration and oil removal efficiency. The obtained effluent oil concentration was from 4.98 to 53.04 mg/L, and the oil removal efficiency was 96.4–99.8%. In addition, the article identifies the interaction between bed porosity and height, explains the mutual influences between the emulsion velocity and concentration, and quantitatively derives the appropriate ranges of bed characteristics and operating conditions.