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1.
Cosmetic oil-in-water emulsions with a stearyl phosphate emulsifier are examined by means of static and dynamic 31P nuclear magnetic resonance (NMR) techniques to characterize the molecular properties of the emulsifier in situ. The interfacially bound emulsifier can be deteced by high-resolution NMR spectroscopy, whereas the excess emulsifier exists as a solid lipid phase not detectable by this technique. The emulsions and the emulsifier raw material, consisting of monostearyl phosphate as well as distearly phosphate, are examined by solid state cross polarization magic angle spinning NMR spectroscopy to prove the existence of solid emulsifier phases in the emulsions. By applying dynamic 31P NMR methods to the interfacially bound emulsifier, information about the molecular dynamics at the interface is obtained. The results of the T 1 and T 2 relaxation time measurements indicate a restricted motion of the molecules that is dependent on the oil droplet size in the emulsions. This is verified by 31P NMR pulsed gradient spin echo self-diffusion measurements on emulsions with different droplet sizes. Only about 5 wt% of the total emulsifier used is bound at the interface; the excess forms solid lipid phases. The coverage of the interface seems to be independent of the emulsifier concentration. Only the monoester of the emulsifier raw material shows interfacial activity. Its mobility indicates the two-dimensional environment of the molecules on the surface of the oil droplets.  相似文献   

2.
The effect of the molecular environment on the physical and oxidative properties of homogenized or microfluidized fish oil-in-water emulsions (5% w/w tuna oil in pH 7 phosphate buffer) stabilized by whey protein isolate (WPI, 1 or 5% w/w) or lecithin (2.5% w/w) was examined. Laser light-scattering measurements showed that WPI-stabilized emulsions had smaller particle sizes than lecithin-stabilized emulsions, and that higher pressures reduced the particle size. WPI afforded more protection against oil oxidation than did lecithin, as evidenced by the lower headspace propanal of emulsions as measured by GC-headspace analysis, despite the larger interface in WPI-stabilized emulsions. Reducing the concentration of WPI in emulsions from 5 to 1% decreased the oxidative stability of WPI-stabilized emulsions. The 1H NMR transverse relaxation times (T 2) of FA chains in emulsion droplets stabilized by the same surfactants made by homogenization or microfluidization were different and not always related to particle size. The higher mobility (i.e., longer T 2) of the unsaturated parts of the FA chains within an oil droplet, compared with the saturated parts, suggests that the unsaturated components tended to stay in the core of the oil droplets. This experimental result supports the hypothesis reported in other literature that the more unsaturated FA are buried in the oil core of oil-in-water emulsions. The lack of a universal correlation between particle size and oxidation suggests that the mobility of particles in an emulsion has an influence on the rate of oxidation.  相似文献   

3.
The effects of droplet size and emulsifiers on oxidative stability of polyunsaturated TAG in oil-in-water (o/w) emulsions with droplet sizes of 0.806±0.0690, 3.28±0.0660, or 10.7±0.106 μm (mean ± SD) were investigated. Hydroperoxide contents in the emulsion with a mean droplet size of 0.831 μm were significantly lower than those in the emulsion with a mean droplet size of 12.8 μm for up to 120 h of oxidation time. Residual oxygen contents in the headspace air of the vials containing an o/w emulsion with a mean droplet size of 0.831 μm were lower compared with those of the emulsion with a mean droplet size of 12.8 μm. Hexanal developed from soybean oil TAG o/w emulsions with smaller droplet size showed significantly lower residual oxygen contents than those of the larger droplet size emulsions. Consequently, oxidative stability of TAG in o/w emulsions could be controlled by the size of oil droplet even though the origins of TAG were different. Spin-spin relaxation time of protons of acyl residues on TAG in o/w emulsions measured by 1H NMR suggested that motional frequency of some acyl residues was shorter in o/w emulsions with a smaller droplet size. The effect of the wedge associated with hydrophobic acyl residues of emulsifiers was proposed as a possible mechanism to explain differences in oxidative stability between o/w emulsions with different droplet sizes.  相似文献   

4.
《分离科学与技术》2012,47(7):1884-1895
Abstract

Droplet size is a key factor in the treatment of oil‐in‐water (O/W) emulsions, because of its influence on emulsion properties. The addition of a coagulant salt generally causes emulsion destabilization, increasing the droplet size, and enhancing coalescence between oil droplets, which helps its further treatment. The influence of CaCl2 addition on droplet size distribution of a commercial O/W emulsion used in machining processes was studied in order to facilitate oil removal and to improve its further treatment by centrifugation, ultrafiltration (UF) and vacuum evaporation. The critical coagulation concentration (CCC) was observed at a CaCl2 concentration of 0.05 M. The quality of the final aqueous effluent, expressed as its chemical oxygen demand (COD) value, was compared for all treatments. The highest COD values were obtained for centrifugation, while the COD of the UF permeate was approximately constant for all UF trials. The best effluent quality was obtained by vacuum evaporation. A combination of these techniques should be appropriate for most industrial treatments of O/W emulsions, depending on the subsequent use of the resulting aqueous effluent.  相似文献   

5.
Oil-in-water emulsions stabilized with methylcellulose (MC) varied in stability depending on the composition of the fat phase. When droplets were composed entirely of liquid oil, MC was able to form a continuous, protective film around the droplets. Therefore, when two liquid oil droplets were brought into contact, they underwent extreme shape deformation but did not coalesce, even when excess force was used. Subsequently, interfacial crystals extending into the aqueous phase from palm kernel oil droplets were aimed into an entirely liquid oil droplet. The MC-coated droplet would deform wherever the crystal contacted; however, the protruding crystals could not penetrate into the liquid oil droplet. Conversely, when the target droplet was composed of a small amount of solid fat that resulted in localized crystalline regions and the interfacial crystals of the second droplet were aimed at this region, they then easily pierced the droplet. This demonstrates that MC is an excellent stabilizer for liquid oil droplets but internal lipid crystals within fat globules can alter MC surface conformation to allow for crystal penetration and arrested coalescence.  相似文献   

6.
Linseed contains high levels of polyunsaturated fatty acids (PUFA), such as α-linolenic acid (> 50% ALA-18:3), that are naturally protected against thermal oxidation by their encapsulation within linseed oil bodies (OB) by multiple components including antioxidant proteins and mucilage emulsifying agents. Linseed OB emulsions (LSE) can be produced by grinding linseed seeds, adding water, adjusting pH, and sonication. This is a process that can encapsulate externally added PUFA to minimize their thermal oxidation, as it does for the intrinsic ALA PUFA. Fish oil (FO) encapsulation into this LSE platform to form linseed fish oil emulsions (LSFE) offers the possibility of a nutritive delivery system of the biologically essential FO PUFA eicosapentaenoic acid and docosahexaenoic acid. In this study, 1H low-field nuclear magnetic resonance (LF-NMR) is used to characterize LSE's and LSFE's chemical and structural properties as well as their stability and changes under thermal oxidation (55 °C for 96 hours). 1H LF-NMR data processing was developed to generate one-dimensional (1D) T1 (spin–lattice), 1D T2 (spin–spin), and 2D (T1 vs. T2) relaxation time spectra that can characterize OB emulsions and monitor their time domain fingerprints (spectrum peaks) of chemical and structural changes during the oxidation process. The 1H LF-NMR analysis were further supported and correlated with conventional peroxide value test, self-diffusion, droplet size distribution, zeta potential estimation of surface stability, and gas chromatography–mass spectrometry analysis of fatty acid profile changes under thermal oxidation conditions. The 1D and 2D LF-NMR relaxation spectra showed that the LSE and LSFE did not suffer intense oxidation process, due to PUFA assembly in OB oxidative protection. These results were further confirmed by the supportive analytical methodologies. The results of this study demonstrate the efficacy of 1H LF-NMR methodology to monitor PUFA's rich oil and emulsion thermal oxidation.  相似文献   

7.
Membrane emulsification has the potential to revolutionize the energy-efficient production of uniform emulsions and dispersions, relevant to diverse fields from pharmaceutical active ingredient controlled release particles to Fast Moving Consumer Goods. A novel highly robust single-pass continuous phase crossflow system has been developed providing dispersed phase concentrations up to 40% vol/vol and dispersed phase fluxes up to 5,730 L m−2 hr−1, from a single 100 mm long membrane tube. Extensive results of two oil-in-water systems (vegetable oil and PolyCaproLactone dissolved in DiChloroMethane) and one water-in-oil system (sodium silicate solution) are reported, using hydrophilic and hydrophobic membranes respectively. Mathematical models are validated enabling comprehensive engineering analysis of processes including predicted droplet size, membrane pressure drops, and energy requirement for dispersion production. Surfactant depletion, pore utilization, and droplet interaction at the membrane surface were investigated to provide a comprehensive analysis of the capabilities of novel annular-flow membrane emulsification for high throughput emulsion generation.  相似文献   

8.
Our objective was to study the influence of droplet composition on the rate of lipid oxidation in emulsions. A series of oil-in-water emulsions stabilized by a nonionic surfactant (Tween 20) was studied. These emulsions had the same total oil concentration (5 wt%) and initial droplet diameter (0.3 μm), but contained droplets with different ratios of ethyl linoleate (substrate) andn-tetradecane (inert diluent). Lipid oxidation was measured as a function of time by three different methods: gas-chromatographic determination of residual substrate; ultraviolet-visible spectrophotometric determination of conjugated dienes; and measurement of aqueous thiobarbituric acid-reactive substances. All three methods showed similar trends for emulsions of similar composition. The progress of lipid oxidation in the emulsions was dependent on the concentration of ethyl linoleate in the emulsion droplets. At low concentrations (1% oil as substrate), oxidation proceeded at a relatively slow and constant rate. At intermediate concentrations (20%), the oxidation rate was rapid initially and then slowed down with time. At high concentrations (100%), the oxidation rate was slow at first, and then increased with time. An explanation of our results is proposed in terms of the distribution of substrate molecules between the droplet interior and interface, and the ingress of aqueous radicals into the emulsion droplets.  相似文献   

9.
Water‐in‐oil (W/O, 30:70) emulsions were prepared with phosphatidylcholine‐depleted lecithin [PC/(PI,PE) = 0.16] or polyglycerol polyricinoleate (PGPR) as emulsifying agents by means of pressure homogenization. The effect of lipid type (medium‐chain triacylglycerols, sunflower, olive, butter oil, or MCT‐oil/vegetable fat blends) was investigated in relation to particle size distribution, coalescence stability and the sedimentation of the water droplets. A significant correlation (p <0.05) was observed between the interfacial pressure caused by the addition of lecithin to the pure lipids and the specific surface area of the emulsion droplets (rs = 0.700), and between the viscosity of the lipids used as the continuous phase (reflecting the fatty acid composition) and the specific surface area of the emulsion droplets (rs = 0.8459) on the other hand. Blends of vegetable fat and MCT‐oil led to reduced coalescence stability due to the attachment of fat crystals to the emulsion droplets. Lecithin‐stabilized W/O emulsions showed significantly higher viscosities compared to those stabilized with PGPR. It was possible to adjust the rheological properties of lecithin‐stabilized emulsions by varying the lipid phase.  相似文献   

10.
Water-in-soybean oil-in-water (W/O/W) emulsions with an internal water phase content of 10–30% (vol/vol) were prepared by a two-step emulsification method using microfluidization and straight-through microchannel (MC) emulsification. A straight-through MC is a silicon array of micrometer-sized through-holes running through the plate. Microfluidization produced water-in-oil (W/O) emulsions with submicron water droplets of 0.15–0.26 μm in average diameter (d av,w/o) and 42–53% in CV (CVw/o) using tetraglycerin monolaurate condensed ricinoleic acid esters (TGCR) and polyglycerin polycondensed ricinoleic acid esters (PGPR) as surfactants dissolved in the oil phase. The d av,w/o and viscosity of the W/O emulsions increased with an increase in internal water phase content. Straight-through MC emulsification was performed using the W/O emulsions as the to-be-dispersed phase and polyoxyethylene (20) sorbitan monooleate (Tween® 80) as a surfactant dissolved in the external water phase. Monodisperse W/O/W emulsions with d av,w/o/w of 39.0–41.0 μm and CVw/o/w below 5% were successfully formed from a straight-through MC with an oblong section (42.8×13.3 μm), using the TGCR-containing systems. The d av,w/o/w of the monodisperse W/O/W emulsions decreased as the internal water phase content increased because of the increase in viscosity of the to-be-dispersed phase. Little leakage of the internal water droplets and no droplet coalescence or droplet break-down were observed during straight-through MC emulsification.  相似文献   

11.
Interfacial properties are of critical importance to various separation applications. In heavy oil recovery, for example, a low oil–water interfacial tension (IFT) benefits the separation of heavy oil from their host rocks, which becomes problematic in the later stage of oil–water separation. CO2-responsive surfactants were investigated to enhance the overall heavy oil recovery by switching their interfacial activity to the desired state in each stage. The surfactants at interfacially active state greatly enhanced the separation of heavy oil from hosting solids, as demonstrated by measuring contact angle and oil liberation using a custom-designed on-line visualization system. Meanwhile, the resulting heavy oil-in-water emulsions could also be easily demulsified by the bubbling of CO2 gas, which switched off the interfacial activity of the surfactants. Furthermore, CO2-responsive surfactants could be partially recycled in process water to improve sustainability, making CO2-responsive surfactants to be promising chemical aids in heavy oil production and many other vital industries.  相似文献   

12.
The details of the interfacial changes occurring during digestion of an oil-in-water emulsion stabilized with soy protein isolate (SPI) and the impact of the changes on lipolysis and subsequent release of β-carotene (BC) were studied using a two-step in vitro digestion model with varying composition containing bile salts (BS), colipase (COL), phospholipids (PL), and phospholipase A2 (PLA2). The hydrolysis of the interfacial layer by pepsin resulted in significant changes in the emulsion droplet size distribution. The introduction of bio-surfactants (BS and PL), in combination with the release of lipid digestion products in the duodenal stage, resulted in re-emulsification of the oil droplets. During this stage a significant increase in the negative charge of the oil droplets from −40 to −70 mV, was also observed, indicating significant changes in interfacial composition. The activity of the pancreatic triglyceride lipase (PTL), as monitored by the liberation of free fatty acids, was largely governed by the composition of digestive fluids. In the presence of BS alone, lipid hydrolysis reached 66.1 ± 3.4%, while addition of PL inhibited lipolysis. Inclusion of PLA2 was found to increase the rate of lipolysis markedly, and the introduction of COL, along with BS, significantly increased the efficiency of the lipolysis such that a maximum lipid hydrolysis of 81.2 ± 1.2% was reached with about 50% transfer of BC to the mixed micelles.  相似文献   

13.
The measurement of electrochemical impedance spectroscopy used in situ is a suitable technique for the characterization of oil and water-in-oil emulsions. Nyquist diagrams for dehydrated oils are characterized by the formation of one semi-circle. The equivalent circuit proposed for the dehydrated oil is a resistance and capacitor (ROCO) in parallel. The resistance and conductivity of the oil calculated by impedance were 2.96 Gohm and 486 nS m?1, respectively. Nyquist diagrams for the system composed of water emulsions in oil are mainly characterized by two semi-circles with different relaxation for oil and water-in-oil emulsions. The equivalent circuit is formed by RO and CPEO in parallel and in series with the arrangement of RW/O and CPEW/O in parallel, where RO and CPEO represents the oil, and RW/O and CPEW/O represents water-in-oil emulsions. The resistance of oil (RO) and water-in-oil (RW/O) emulsions increase with the increasing amount of water in the preparation. The increase in resistance shows that the emulsions become more stable with the addition of water. This result is consistent with the formation of rigid films on water–oil interfaces. The impedance measurements were applied to the analysis of the demulsification of the water-in-oil emulsions under an electrostatic field.  相似文献   

14.
Oxidation of methyl linoleate in O/W emulsions having droplets of median diameters ranging from 17 nm to 8.0 μm was carried out at 40°C. The oxidation process was analyzed on the basis of a kinetic equation of the autocatalytic type. The induction period was found to be shorter and the oxidation rate constant lower for emulsions with smaller oil droplets. The stoichiometry between methyl linoleate and oxygen was observed to be independent of both the size of oil droplet and the type of the surfactant and was found to be unity during the early stage of the oxidation. However, more oxgen was consumed in the oxidation of the methyl linoleate in the later half of the oxidation process.  相似文献   

15.
The flow regimes of multiple emulsions in the continuous Couette‐Taylor flow (CTF) contactor and characterization of the dispersion state are reported. The proposed method of multiple emulsion preparation is a one‐step procedure on the contrary to the classical two‐step procedure. The effect of operating parameters in the CTF contactor on multiple emulsion appearance, structure (drop size and packing), and rheological behavior is discussed. The key factors affecting multiple emulsion preparation in the CTF apparatus were the phases ratio, the rotational flow, and an annular gap width. The influence of an axial flow was more significant in the range of small rotational rates. The operating conditions were optimized to find the best characteristic multiple emulsions (largest interfacial area). The paper presents the same exemplary data of using W1/O/W2 emulsions as emulsion liquid membranes (ELMs) in the extraction process and O1/W/O2 for control active agent (drug) release.  相似文献   

16.
Aroma compounds partition between the different phases of a food emulsion and the headspace but only those in the headspace are perceived. Phase transitions in the lipid droplets profoundly affect the position of the partitioning equilibria and hence headspace aroma concentration. The release of four volatile aroma compounds (ethyl butanoate, pentanoate, heptanoate and octanoate) from eicosane, hydrogenated palm fat or Salatrim® emulsions stabilized with sodium caseinate were investigated as a function of fat crystallization, particle size and droplet concentration. For all compounds, the headspace aroma concentration in equilibrium with solid droplet emulsions was significantly higher than that in equilibrium with liquid droplet emulsions. The partitioning of volatile aroma compounds from emulsion does not depend on the type of liquid lipid, however, the interactions between solid lipid droplets and aroma compounds are significantly influenced by the nature of the crystalline fat. Notably, partitioning into the headspace was much lower for solid triglyceride droplet emulsions than for solid alkane emulsions. It was proposed that both residual liquid lipid in solid triglycerides and aroma co-crystallization with solid lipid could be responsible for higher aroma absorption by solid triglycerides.  相似文献   

17.
《Ceramics International》2022,48(13):18753-18764
A novel Al2O3 ceramic membrane modified by cobweb-bridged WO3 nanowires was successfully fabricated for oil/water emulsions separation. Freeze-casting was employed to obtain directional gradient Al2O3 porous ceramics at first. Then, the cobweb-bridged WO3 nanowires were successfully introduced into the separation layer by in-situ hydrothermal synthesis to construct the WO3 nanowires/Al2O3 membrane. Results showed that WO3 nanowires increased the surface roughness from 45.9 nm to 54.8 nm, the instantaneous water contact angle (WCA) and underwater oil contact angle (UOCA) reached the optimum values of 8.5° and 157.8°, respectively. Construction of cobweb-bridged WO3 nanowires not only achieved a high separating efficiency of oil/water emulsions up to 92.35%, but also maintained high permeation fluxes at around 1600 L/m2·h·bar. After 10 cycles, the separation efficiency of the membrane remained above 90%. Moreover, the WO3 nanowires/Al2O3 membrane still maintained underwater superoleophobicity after being immersed in strongly acidic, alkaline, and saline solutions, showing a high UOCA above 150° for all tested oil. The WO3 nanowires/Al2O3 membrane is promising in oil/water emulsions separation application for its high separation efficiency, durability, and excellent chemical stability.  相似文献   

18.
Double emulsions created by phase inversion can be used for fast liquid–liquid separation; therefore, the coalescence behaviors of these types of multiple emulsions need to be predictable for different physical properties and drop size ratios. The aim of this study is to determine the influence of the effective overall drop diameter and the internal droplet size on the coalescence time and the coalescence behavior. Experimental investigations on the physical stability of single stagnant water-in-oil-in-water (W1/O/W2) double emulsion globules are performed. For this investigation, a formation device to inject one water droplet into an oil drop inside a water bulk phase is developed. The coalescence process of the sole internal water droplet floating on the O/W2 interface with the water bulk phase, often termed droplet expulsion or external coalescence, is recorded with a high speed camera. Based on image analysis, the diameters of the effective overall drop D, containing the oil and entrapped water volume, and the internal water droplet d are determined. Additionally, the coalescence time τ, including the time from the first contact of the internal droplet and the drop-bulk interface to the film rupture is measured. A large increase in coalescence time with increasing water droplet diameters is found. For the investigated paraffin oil–water system and initial drop sizes, partial coalescence occurs. In this case, the diameter ratio of daughter-to-mother droplet ψ is determined.  相似文献   

19.
We have characterized micro-droplet generation using water immiscible hexafluorophosphate ([PF6])- and bis(trifluoromethylsulfonyl)imide ([Tf2N])-based room temperature ionic liquids (RTILs). The interfacial tension between total 7 RTILs and phosphate buffered saline (PBS) was measured using a tensiometer for the first time. PBS is one of the most commonly used buffer solutions in cell-related researches. The measured interfacial tension ranges from 8.51 to 11.62 and from 9.56 to 13.19 for [Tf2N]- and [PF6]-based RTILs, respectively. The RTILs micro-droplets were generated in a microfluidic device. The micro-droplet size and generation frequency were determined based on continuous monitoring of light transmittance at the interface in microchannel. The size of RTIL micro-droplets was inversely proportional to the increase of PBS solution flow rate and RTILs hydrophobicity, while droplet generation frequency was proportional to those changes. The measured size of RTILs droplets ranged from 0.6 to 10.5 nl, and from 1.0 to 17.1 nl for [Tf2N]- and [PF6]-based RTILs, respectively. The measured frequency of generated RTILs droplets ranged from 2.3 to 37.2 droplet/min, and from 2.7 to 17.1 droplet/min for [Tf2N]- and [PF6]-based RTILs, respectively. The capillary numbers were calculated depending on the RTILs, and ranged from 0.51×10-3 to 1.06×10-3 and from 5.00×10-3 to 8.65×10-3, for [Tf2N]- and [PF6]-based RTILs, respectively. The interfacial tension between RTILs and PBS will contribute to developing bioprocesses using immiscible RTILs. Also, the RTILs micro-droplets will enable the high-throughput monitoring of various biological and chemical reactions using RTILs as new reaction media.  相似文献   

20.
Soybean glycinin [11S] was modified by an acidic pH treatment to improve its emulsifying properties. Glycinin was obtained by isoelectric precipitation (11Sn) and then treated with acid (11St). The oil–water interfacial tension and rheology were measured. The rate constants of adsorption (ka) and rearrangement (kr) of proteins at the interface and the dilational (E), elastic (Ed), and viscous modulus (Ev) of the protein interfacial film were determined. Particle size distribution (PSD), interfacial protein concentration (Γ), and the creaming destabilization rate constants ks (for the smaller droplets) and kl (for the larger droplets) were analyzed in oil‐in‐water emulsions (25% v/v of oil and 75% v/v of 1 mg/mL protein solution in 10 mM sodium phosphate buffers, pH 7.0 and 2.5, respectively). Compared to the native protein, the acid treatment caused irreversible denaturation of 11S and significantly increased Г, ka, E, Ed, and Ev (P ≤ 0.05), resulting in a greater rate of protein adsorption to the interface and a stronger interfacial film. PSD showed a bimodal distribution with peaks above and below 4 μm. Smaller droplets moved toward smaller diameters for 11St. It also showed lower values of creaming destabilization constants ks (d ≤ 4 μm) and kl (d ≥ 4 μm) than 11Sn. In conclusion, acid treatment of 11S enhances the creaming stability of its emulsions by improving the interfacial properties and reducing the droplet size.  相似文献   

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