Comparison of ultracentrifugal stability parameters with long-term shelf stability of emulsions

The validity of prediction of shelf stability from ultracentrifugal parameters determined on newly prepared Nujol-in-water emulsions stabilized with sodium dodecylsulfate (0.2 to 0.4%), cetylpyridiniumchloride (0.1 to 0.2%), Triton X-100 (0.08 to 0.4%), or Tween 20 (0.08 to 0.4%) was tested by allowing samples to age for periods up to 3 yr. They were then reexamined visually, and an empirical rating scheme devised for describing their stability semiquantitatively. In some cases it was also possible to redetermine the ultracentrifugal parameters on the aged emulsions. None of the ultracentrifugal parameters of the fresh emulsions predicted the order of actual shelf stability correctly in all cases. Possible reasons for the discrepancies are discussed.     

Oxidative stability of sunflower oil bodies

This study investigates the oxidative stability of sunflower oil body suspensions (10 wt‐% lipid). Two washed suspensions of oil bodies were evaluated over 8 days at three temperatures (5, 25 and 45 °C) against three comparable sunflower oil emulsions stabilized with dodecyltrimethylammonium bromide (DTAB), polyoxyethylene‐sorbitan monolaurate (Tween 20) and sodium dodecyl sulfate (SDS) (17 mM). The development of oxidation was monitored by measuring the presence of lipid hydroperoxides and the formation of hexanal. Lipid hydroperoxide concentrations in the DTAB, SDS and Tween 20 emulsions were consistently higher than in the oil body suspensions; furthermore, hexanal formation was not detected in the oil body emulsions, whereas hexanal was present in the headspace of the formulated emulsions. The reasons for the extended resistance to oxidation of the oil body suspensions are hypothesized to be due to the presence of residual seed proteins in the continuous phase and the presence of a strongly stabilized lipid‐water interface.     

Edible oil-in-water emulsions stabilized by hydrophile–lipophile balanced sucrose ester

Conventional emulsions are mostly stabilized by surfactants and for stabilization of oil-in-water emulsions the surfactants should be hydrophilic or with HLB numbers larger than seven. In this work, we report that edible oil-in-water emulsions can also be stabilized by surfactants with an HLB value close to seven. With edible sucrose ester C-1807 (HLB no. = 7) as emulsifier and three edible oils (canola oil, olive oil, soybean oil), edible oil-in-water emulsions can be stabilized by C-1807 at concentrations beyond its critical aggregation concentration (CAC). Although monomeric C-1807 behaves as an inferior emulsifier, they assemble to form multilamellar vesicles in water at concentrations higher than the CAC giving a viscoelastic/gel-like aqueous phase which is partly responsible for emulsion stabilization. Specifically, at 2 wt%, high internal phase emulsions (HIPEs) with ϕ_o = 0.75 can be obtained, which are stable against cooling–heating cycles between 5 and 30°C during storage. The vesicles disperse in the aqueous lamellae surrounding the oil droplets, which together with the viscoelastic/gel-like continuous phase prevents them from flocculation and coalescence.     

Water-in-triglyceride oil emulsions. Effect of fat crystals on stability

The influence of low concentrations (0.1-5%) of fat crystals on the stability of water-in-soybean oil emulsions was examined by light scattering and sedimentation experiments. Both the initial flocculation/coalescence rate and long-term stability against water separation were determined. The initial flocculation/coalescence rate increased upon addition of small amounts of fat crystals. When the crystal concentration was increased above a critical concentration (specific to a system), a decrease in the flocculation/coalescence rate occurred. The increased flocculation/coalescence rate is likely the effect of bridging of water droplets by fat crystals. Fat crystal wetting by water is an important criterion for this phenomenon to occur. Emulsion stabilization for crystal concentrations above critical is caused by a mechanical screening of water droplets. The presence of considerable amounts of crystals in oil also lowered the density difference between droplet and medium, and enhanced viscosity. The degree of increase in viscosity depended upon the emulsifier. Both a decrease in density difference and an increase in viscosity play a role in hindering flocculation/coalescence of droplets. In long-term studies of water separation, all concentrations of fat crystals stabilized the water-in-oil emulsions. The droplet size of these emulsions increased until the critical droplet size was approached where the screening effect of crystals on the droplets no longer stabilized the emulsions. The stabilizing effect for emulsions with monoolein was continuously improved by increasing the amount of crystals up to 5%. For lecithin-stabilized emulsions, an optimal effect was achieved for fact crystal concentrations of 1–2%.     

Properties of palm-oil-in-water emulsions: Effect of mixed emulsifiers

Palm-oil-in-water emulsions were prepared with mixtures of Tween 40 and Span 40 in various proportions. Stability and droplet-size distribution of the emulsions were monitored. Interfacial tensions of the palm oil/water interface were also determined in the presence of these emulsifier mixtures. Emulsifying efficiency of the emulsifier mixtures was assessed. No synergistic effect of Tween 40 (sorbitan monopalmitate with 18–22 moles of ethylene oxide) and Span 40 (sorbitan monopalmitate) was found on interfacial tension. Tween 40 alone (hydrophilic-lipophilic balance value 15.6) at 1.0% w/w gave palm oil emulsions that were stable for more than 30 d at 60°C. Emulsifier mixtures of Tween 40 and Span 40 with hydrophilic-lipophilic balance values in the range of 8.0–8.6 produced stable emulsions only at much higher emulsifier-mixture concentrations. The inherent nature of the oil and the accompanying natural surface-active materials present in the oil can influence the prevailing conditions at the oil/water interface and alter composition of the interfacial film and hence its stability.     

Effect of cefoperazone sodium on the physicochemical properties of surfactants

The effects of cefoperazone sodium (CS), a pharmaceutical compound, on the critical micelle concentration (CMC) of surfactants with different charges [cetyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and Triton X-100], the cloud point of Triton X-100, and the Krafft temperatures of SDS and CTAB were studied. The interaction of CS with differently charged surfactants was determined by ultraviolet and fluorescence spectrophotometry. The results show that with increasing CS concentration, the Krafft temperature increases and the CMC decreases in the SDS/H₂O system, whereas the opposite results are obtained in the CTAB/H₂O system. Both the cloud point and the CMC of Triton X-100 increase with the addition of CS. The above results are attributed to the different micellar interactions between CS and surfactants with different charges.     

Emulsifier type,metal chelation and pH affect oxidative stability of n‐3‐enriched emulsions

Recent research has shown that the oxidative stability of oil‐in‐water emulsions is affected by the type of surfactant used as emulsifier. The aim of this study was to evaluate the effect of real food emulsifiers as well as metal chelation by EDTA and pH on the oxidative stability of a 10% n‐3‐enriched oil‐in‐water emulsion. The selected food emulsifiers were Tween 80, Citrem, sodium caseinate and lecithin. Lipid oxidation was evaluated by determination of peroxide values and secondary volatile oxidation products. Moreover, the zeta potential and the droplet sizes were determined. Tween resulted in the least oxidatively stable emulsions, followed by Citrem. When iron was present, caseinate‐stabilized emulsions oxidized slower than lecithin emulsions at pH 3, whereas the opposite was the case at pH 7. Oxidation generally progressed faster at pH 3 than at pH 7, irrespective of the addition of iron. EDTA generally reduced oxidation, as evaluated by volatiles formation in all emulsions, irrespective of pH and emulsifier type, except in the lecithin and caseinate emulsions where a pro‐oxidative effect was observed for some volatiles. The different effects of the emulsifier types could be related to their ability to chelate iron, scavenge free radicals, interfere with interactions between the lipid hydroperoxides and iron as well as to form a physical barrier around the oil droplets.     

不同表面活性剂对单相微乳液特性的影响

表面活性剂是影响微乳液特性的关键因素之一。本文选取聚氧乙烯脱水山梨醇单油酸酯（Tween 80）、烷基糖苷1214（APG 1214）、十二烷基苯磺酸钠（SDBS）、脂肪醇聚氧乙烯醚硫酸钠（AES）、十二烷基硫酸钠（SDS）和95%纯度鼠李糖脂（R-95%）这6种表面活性剂,通过对其乳化性能和临界胶束浓度进行筛选,结合其形成微乳液的拟三元相图、粒径分布和界面张力分析其特性,并提出微乳液增溶油能力和增溶油成本。研究表明：APG 1214、SDBS、Tween 80乳化性能好、临界胶束浓度低具有更易形成微乳液的优势;5种表面活性剂（Tween 80、SDBS、APG 1214、SDS、AES）均可与正丁醇、水和3号白油自发形成单相微乳液,单相区面积大小为AES型>SDS型>APG 1214型>Tween 80型>SDBS型,最大增溶油能力大小为SDS型>AES型>APG 1214型>Tween 80型>SDBS型,最低增溶油成本大小为AES型相似文献   

Effects of Acidity, Temperature and Emulsifier Concentration on the Distribution of Caffeic Acid in Stripped Corn and Olive Oil-in-Water Emulsions

We evaluated the effects of oil type, oil to water ratio, emulsifier concentration, acidity, and temperature on the distribution of caffeic acid, CA, in emulsions composed of stripped olive and corn oils, acidic water, and Tween 20. CA mainly distributes between the water and interfacial regions because it is sparingly soluble in oils, as demonstrated by auxiliary partitioning experiments in the absence of an emulsifier. The distributions of CA were determined in the intact emulsions from values of the partition constant between the water-interfacial region, P _W ^I , determined under different experimental conditions. At any given pH, CA is mostly located in the interfacial region of the emulsion,  %CA_I > 50 % at the lowest emulsifier volume fraction, Φ_I = 0.005, and its percentage increasing upon increasing Φ_I with  %CA_I > 90 % at Φ_I = 0.04. At any given Φ_I,  %CA_I decreases substantially with increasing pH because of the ionization of the CA. Our results indicate that the main parameters affecting the distribution of CA are Φ_I and the acidity, while the nature of the oil, the oil to water ratio and temperature have only minor effects. Results should aid the understanding of how environmental conditions affect the distribution of phenolic acids in emulsions.     

Adsorption of nonionic surfactants at fluid-fluid interfaces: Importance in the coalescence of bubbles and drops

Major industrial applications of surfactants are related to the stability of emulsions and foams, which is directly dependent on the rate of coalescence of drops and bubbles. Surfactant molecules adsorb at the liquid-liquid and gas-liquid interfaces and prevent the drops and bubbles from coalescing with one another. Therefore, it is important to correlate the adsorption of surfactant with the time required for coalescence. In this work, we have studied the adsorption of three nonionic surfactants, Tween 20, Triton X-100 and Span 80 at air-water and water-toluene interfaces. The variation of surface and interfacial tension with the concentration of surfactant was studied and the data were fitted using a surface equation of state derived from the Langmuir adsorption isotherm. We have studied binary coalescence of water drops in toluene in presence of these three surfactants. Coalescence of air bubbles at flat air-water interface was studied in presence of the water-soluble surfactants, Tween 20 and Triton X-100. A stochastic model for coalescence was used to fit the coalescence time distributions. The significance of the model parameters was discussed.     

白油W/O/W型多重乳状液的稳定性研究

以多重乳状液相对体积为衡量标准,用显微镜直接观察,探讨了乳化剂的HLB值、质量分数、亲油亲水乳化剂体积比及油水的相比等对白油W/O/W型多重乳状液体系稳定性的影响。结果表明单一乳化剂体系中适宜的制备条件:乳液中乳化剂质量分数为12.2%,V(Span80)/V(Tween80)=7.5;适合多重乳液稳定的油水相比为:第一相体积比为2.5,第二相体积比为0.2。复合乳化剂体系中适宜的制备条件:第一相乳化剂的HLB值为6.5,V(复合乳化剂)/V(Tween80)=27.5,乳液中乳化剂质量分数为9.5%。     

Characterization of enzymatically prepared biosurfactants

Various fatty monoesters of sugars and sugar alcohols were prepared enzymatically in organic solvent. Water produced during esterification was removed by refluxing through a dessicant under reduced pressure. Surface properties of these esters such as surface and interfacial tensions and their ability to stabilize emulsions at 30°C were evaluated: oleate esters of glucose, fructose, and sorbitol show similar behavior in reduction of surface and interfacial tensions, and values for the critical micelle concentration are about 8·10⁻⁵ M. It was also observed with sorbitol esters that the shorter the alkyl chain, the higher the critical micelle concentration. Generally, emulsions prepared with the emulsifier dissolved in the water or in the oil phase lead to oil-in-water or water-in-oil emulsions, respectively. Sorbitol monolaurate significantly increased the stability of oil-in-water emulsions, with only 5% separation of the phases after 48h at 30°C, compared to 10% for chemically prepared sorbitan monolaurate under the same conditions. Sorbitol monoerucate was very efficient in stabilizing water-in-oil emulsions, with only 1% separation of the phases.     

Phase inversion temperatures of triton X-100/1-butanol/hydrocarbon/water systems

The formation of a water-in-oil (w/o) microemulsion in Triton X-100/1-butanol/alkane/water systems was investigated at 25.0±0.1°C. Phase inversion temperatures in hydrocarbon-water microemulsions stabilized with Triton X-100 were determined for different hydrocarbons. It was found that the more soluble the alkane (oil), functioning as a nonionic emulsifier, the lower was the phase inversion temperature, above which oil-in-water type microemulsions invert to w/o type. The effect of the presence of cosurfactant was studied. No phase inversion was observed in the absence of cosurfactant. The effect on phase inversion temperature of decreasing or increasing the temperature was evaluated. By definition, phase inversion was not affected by different temperatures.     

Oxidation of linoleic acid in emulsions: Effect of substrate, emulsifier, and sugar concentration

Linoleic acid oxidation in oil-in-water emulsions stabilized by a nonionic surfactant (Tween-20) was studied. The emulsion composition was varied at a constant oil droplet size. Lipid oxidation was measured as a function of time in the presence of a catalyst (FeSO₄ corbic acid) by two methods: gas chromatographic determination of residual substrate and ultraviolet-visible spectrophotometric determination of conjugated dienes. Rate of oxidation was influenced by the emulsion composition (relative concentrations of substrate and emulsifier) and especially by the partition of the emulsifier between the interface and water phase. Concentrations of emulsifier exceeding the critical micelle concentration protected the fatty acid against oxidation. Excess surfactant formed micelles and mixed micelles with linoleic acid, which retarded oxidation by diluting the substrate or perhaps by replacing linoleic acid at the interface, making it less accessible to radical attack. The addition of sucrose also had a protective effect, but only up to a certain concentration, indicating the effect may involve factors other than viscosity.     

Oxidation and Colloidal Stability of Oil-in-Water Emulsion as Affected by Pigmented Rice Hull Extracts

Extracts from the hull of pigmented rice were prepared using a mixture of methanol–water (1:1, 2:1, and 3:1, v/v) for different extraction times (0–180 min). Total phenolic content (TPC) of the extracts increased with increasing concentration of methanol and extraction time (P < 0.05). A positive correlation between TPC and antioxidant activities, i.e., DPPH and ABTS radical scavenging activities and reducing power, was observed. The extracts prepared using methanol–water at the ratio of 3:1 for 180 min at 50 °C, referred as rice hull phenolic extract (RHPE), showed the highest TPC and free radical scavenging abilities and reducing power (P < 0.05). When the effects of RHPE on physicochemical stability of the emulsions stabilized by different emulsifiers, i.e., Tween 20 and bovine serum albumin (BSA), were examined, the collapse of emulsion was retarded when RHPE was applied in BSA‐based emulsions, whereas a negative effect was noticeable in Tween 20‐based counterpart. Lower oxidative degree was found for BSA stabilized emulsions, compared to Tween 20 containing system. RHPE (1–3 %) markedly improved the oxidative stability, particularly for BSA stabilized emulsions. Therefore, RHPE could be employed along with the selected protein to increase physicochemical stability of emulsion.     

Relationship between foaming properties and solution properties of protein/nonionic surfactant mixtures

The foaming properties of bovine serum albumin (BSA), in the absence and presence of Triton X-100 (TX-100), have been investigated using shaking tests. The results showed that increases in the TX-100 bulk concentration rapidly reduced both foam height and foam stability at TX-100 concentrations below about 0.25 mM, but increased foam height and foam stability at TX-100 concentration above 0.3 mM. The interaction between BSA and TX-100 has been studied using fluorescence spectroscopy. The surfactant appeared to bind to BSA with a low molar ratio (about one surfactant molecule per protein molecule) at concentrations below the critical micelle concentration (CMC); the binding became weaker at concentrations above the CMC. It was confirmed that protein-protein or protein-surfactant interactions had significant influence upon foaming properties of mixed protein/surfactant system.     

一种测定乳状液稳定性的简便有效的新方法

An innovational test method was developed on the basis of redefinition of the emulsion stability. The stability was characterized by relative volume percentage of disperse phase demulsified thoroughly from the top part and the bottom part of an emulsion sample, each weighting the same amount, after being settled for a given time at constant temperature. Three series of emulsions were prepared and tested successfully, which were emulsions of paraffin oil and water stabilized with polyoxyethylene lauryl ether series (AEO3 and AEO9) at various HLBs,and emulsions of rapeseed oil and water stablized with sorbitan monoleate (Span80) and each of polyoxyethylene(20) sorbitan carboxylic esters (Tween20, Tween40, Tween60, Tween80 and Tween85) at different HLBs. It proved that this method is especially workable while the boundaries are opaque in a wide range of HLBs and is capable of offering an accurate optimum HLB.     

Rhamnolipids Obtained from a PHA-Negative Mutant of Pseudomonas aeruginosa 47T2 ΔAD: Composition and Emulsifying Behavior

Pseudomonas aeruginosa 47T2 (NCBIM 40044) synthesizes polyhydroxyalkanoic acids (PHAs) and rhamnolipids (Rhls). The knockout mutant for PHAs biosynthesis, P. aeruginosa 47T2 ΔAD prepared in this study, increased the cellular yield of Rhls production by 28 %. The Rhls mixture (composed up to eight homologs) reduced the water surface tension to 31.67 mN/m with a critical micelle concentration of 105 mg/L. The IC₅₀ (μg/mL) of the neutral red uptake assay and methylthiazol tetrazolium assay ranged between 53.9 and 72 μg/mL, which is similar to that of sodium dodecyl sulfate (SDS). Rhamnolipids had a lower hemolytic effect at 110.8 μg/ml than SDS, a commercial anionic surfactant, at 43.6 μg/mL. This suggests that the Rhls mixture could be used in topical pharmaceutical and cosmetic applications or cleansers as a biosurfactant. The emulsifying properties in water/oil dispersions were determined using ternary phase diagrams at 25 °C. Isopropyl myristate, soybean oil, olive oil and Casablanca oil were used as the oil components. Total emulsions were obtained with most of the oils.     

纳米Fe3O4稳定的Pickering型ASA乳液

利用纳米Fe₃O₄作为稳定剂和乳化剂来制备Pickering型ASA（alkenyl succinic anhydride） 施胶乳液,并研究了固体颗粒浓度、油水比、水分散相pH对乳液类型、稳定性、形态及施胶性能的影响。结果表明,纳米Fe₃O₄能够乳化制备均一稳定的Pickering型ASA乳液。乳液在室温下静置稳定,析出油相体积分数随固体颗粒用量的增加而增大,随油水比的增大而减小。油水比为2：1,水分散相浓度为0.1%（质量分数）时制备的ASA乳液稳定性最佳。固体颗粒部分吸附在油/水界面处,部分分散在分散相中,随分散相中固体颗粒浓度的增加,乳液稳定性变差。乳液静置分层之前,ASA发生部分水解。在放置1 h后用于纸页浆内施胶,随ASA乳液用量的增加,纸页表面接触角逐渐增大,且纸页表面粗糙度下降。在ASA的添加量为1.0%（质量分数）时,纸页表面接触角达到93.5°,纸页表面粗糙度为15.924 μm。     

Preparation and characterization of highly stable monodisperse argan oil‐in‐water emulsions using microchannel emulsification

Argan oil is well known for its nutraceutical properties. Its specific fatty acid composition and antioxidant content contribute to the stability of the oil and to its dietetic and culinary values. There is an increasing interest to use argan oil in cosmetics, pharmaceutics, and food products. However, the formulation of highly stable emulsions with prolonged shelf life is needed. In this study, argan oil‐in‐water (O/W) emulsions were prepared using microchannel (MC) emulsification process, stabilized by different non‐ionic emulsifiers. The effects of processing temperature on droplet size and size distribution were studied. Physical stability of argan O/W emulsions was also investigated by accelerated stability testing and during storage at room temperature (25 ± 2°C). Highly monodisperse argan O/W emulsions were produced at temperatures up to 70°C. The obtained emulsions were physically stable for several months at room temperature. Furthermore, emulsifier type, concentration, and temperature were the major determinants influencing the droplet size and size distribution. The results indicated that a suitable emulsifier should be selected by experimentation, since the interfacial tension and hydrophilic–lipophilic balance values were not suitable to predict the emulsifying efficiency. Practical applications: MC emulsification produces efficiently monodisperse droplets at wide range of temperatures. The findings of this work may be of great interest for both scientific and industrial purposes since highly stable and monodisperse argan oil‐in‐water emulsions were produced which can be incorporated into food, cosmetic, or pharmaceutical formulations.