Surfactant Concentration,Antioxidants, and Chelators Influencing Oxidative Stability of Water‐in‐Walnut Oil Emulsions

Effects of surfactant concentration, antioxidants with different polarities, and chelator type on the oxidative stability of water‐in‐stripped walnut oil (W/O) emulsions stabilized by polyglycerol polyricinoleate (PGPR) were evaluated. The formation of primary oxidation products (lipid hydroperoxides) and secondary oxidation products (hexanal) decreased with increasing PGPR concentrations (0.3–1.0 wt% of emulsions). Excess surfactant might solubilize lipid hydroperoxides out of the oil–water interface, resulting in the decreased lipid oxidation rates in W/O emulsions. At concentrations of 10–1000 μM, the polar Trolox demonstrated concentration‐dependent antioxidant activity according to both hydroperoxide and hexanal formation. The antioxidant efficiency of the non‐polar α‐tocopherol was slightly reduced at the higher range of 500–1000 μM based on hydroperoxide formation. Both ethylenediaminetetraacetic acid (EDTA) and deferoxamine (DFO) at concentrations of 5–100 μM reduced the rates of lipid oxidation at varying degrees, indicating that endogenous transition metals may promote lipid oxidation in W/O emulsions. EDTA was a stronger inhibitor of lipid oxidation than DFO. These results suggest that the oxidative stability of W/O emulsions could be improved by the appropriate choice of surfactant concentration, antioxidants, and chelators.     

Antioxidant activity of phenolic compounds in sunflower oil‐in‐water emulsions containing sodium caseinate and lactose

The aim of this work was to study the evolution of oxidation and the efficiency of phenolic antioxidants in sunflower oil‐in‐water emulsions containing sodium caseinate and lactose (Cas‐Lac) or stabilized by Tween‐20 (T‐20). Two groups of phenolic antioxidants which are structurally similar were tested, i.e. (1) α‐tocopherol and its water‐soluble analogue, Trolox; and (2) gallic acid and its ester derivatives propyl gallate and dodecyl gallate. Emulsion samples were oxidized at 40 °C and the progress of oxidation was followed through quantitation of oxidized triacylglycerol monomers, dimers and oligomers. Results showed that Cas‐Lac emulsions were more stable to oxidation than T‐20 emulsions. In both types of emulsions, the most protective antioxidants were the compounds of lower polarity, namely, α‐tocopherol and dodecyl gallate. It was also found that substantial amounts of α‐tocopherol coexisted with significant polymerization, which was indicative of the heterogeneity of oxidation, i.e. differences of oxidation rate in oil droplets.     

Do antioxidants improve the oxidative stability of oil-in-water emulsions?

Oil-in-water emulsions were prepared with 30% stripped sunflower oil, stabilized by 20 g/L BSA and homogenized under high pressure to obtain a mean droplet size near 0.5 μm. The emulsions were shown to be physically stable during storage in a shaker at 47°C for 5 d. Such a medium was suitable to test the efficiency of different types of antioxidants. Oxidation of control emulsions appeared rapidly without a lag phase, and the contents of conjugated dienes and hexanal reached a plateau after around 20 h. In the presence of EDTA, the oxidation was strongly inhibited, suggesting that some metallic ions present in the oil or the protein solution act as inducers. Ascorbic acid and ascorbyl palmitate were inactive. Isoeugenol was found to be a powerful antioxidant, better than eugenol, α-tocopherol, and Trolox.     

Effect of the initial concentration of emulsifying agents on the ultracentrifugal stability of oil-in-water emulsions

The rate of loss of oil from 50% Nujol-50% water emulsions stabilized with varying concentrations of Tween 20 or Triton X-100, and from 50% olive oil-50% water emulsions stabilized with sodium dodecyl sulfate (SDS), was determined by ultracentrifugation at 39,460 rpm. In all cases the ultracentrifugal stability increased with increasing initial concentration of emulsifier, although, unlike the behavior of Nujol-water-SDS emulsions, the rate of separation of oil decreased with time. The quantity of olive oil separated after a given time of centrifugation decreased linearly with increasing concentration of SDS, reaching zero at a concentration of SDS somewhat below the critical micelle concentration, and at adsorption of SDS corresponding to only about half the saturation capacity. The ultracentrifugal stability of Nujol emulsions with Tween 20 or Triton X-100 continued to increase slowly with increasing concentration of emulsifier, even at concentrations far greater than the critical micelle concentration.     

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.     

Droplet composition affects the rate of oxidation of emulsified ethyl linoleate

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.     

Effect of different antioxidants on lycopene degradation in oil‐in‐water emulsions

There is interest in incorporating lycopene into foods because it is a natural pigment and can also play a role in preventing disease. Therefore, the effect of the addition of various antioxidants in lycopene containing oil‐in‐water emulsions stabilized with Tween 20 at acidic pH was studied in order to determine protection systems against lycopene oxidation. In this model, EDTA showed pro‐oxidant activity while other chelators like citric acid and tripolyphosphate showed no effect. The free radical scavengers, propyl gallate (PG), gallic acid (GA), and α‐tocopherol all had the ability to decrease lycopene oxidation with α‐tocopherol being the most effective. The combination of 1 µM α‐tocopherol and 10 µM GA was more effective than the individual antioxidants. Addition of ascorbic acid to the combination of α‐tocopherol and GA system accelerated lycopene loss. These results suggest that by the proper selection of free radical scavenging antioxidants, lycopene stability in oil‐in‐water emulsions could be significantly improved. Practical applications: Evidence that dietary lycopene decreases the risk for a number of health conditions has generated new opportunities for addition of lycopene to functional foods. A successful strategy to deliver lycopene into foods is by means of oil‐in‐water emulsions. However, lycopene may decompose thus causing nutritional loss and color fading. In order to prevent this, the effectiveness of various antioxidants and their combinations in Tween 20 stabilized oil‐in‐water emulsions was studied. Overall, lycopene oxidation in oil‐in‐water emulsions could be significantly reduced by the proper selection of free radical scavengers. This fact is of interest to food industry for increasing the shelf‐life of lycopene containing functional foods where the lycopene is dispersed in the food in the form of an oil‐in‐water emulsion.     

Antioxidant Activity of Raisin Extracts in Bulk Oil,Oil in Water Emulsion,and Sunflower Butter Model Systems

The antioxidant activities of the raisin extract (RE) in stripped corn oil, stripped corn oil emulsions, and sunflower butter stored at 60 °C for up to 15 days was evaluated. Peroxide values and hexanal content were measured on a half day, 2 or 3 day basis for the emulsion, sunflower butter, and bulk oil, respectively. The RE had the best antioxidant activity in the bulk oil system. Statistical contrasts indicated the oxidation of bulk corn oil treated with RE was significantly (p < 0.001 and p = 0.044) lower than bulk oil and bulk oil treated with tertiary-butylhydroquinone (TBHQ), respectively. No differences (p = 0.15) in hexanal concentrations were observed in stored bulk oils treated with RE and TBHQ. However, both these materials inhibited hexanal formation better (p < 0.001) when compared to the control corn oil. In contrast, 200 μg/g TBHQ had better (p = 0.0004) antioxidant activity than 3,000 μg/g RE in the oil in water(o/w) emulsion. No significant differences (p = 0.1637) in hexanal formation were observed in the emulsions treated with RE and TBHQ. However, the data indicated that the RE treated emulsion did undergo more secondary oxidation than the emulsion treated with TBHQ beyond 110 h. The 3,000 μg/g RE had antioxidant activity in sunflower butter, but was less effective than the 200 μg/g TBHQ and a lower RE concentration (200 μg/g). The observations supported the hypothesis that RE has antioxidant activity in the multiple model systems.     

γ‐ and δ‐tocopherols are more effective than α‐tocopherol on the autoxidation of a 10% rapeseed oil triacylglycerol‐in‐water emulsion with and without a radical initiator

The antioxidative effects of γ‐ and mainly δ‐tocopherol in a multiphase system were hardly considered up to now. The aim of this study was i) to assess the effects and ii) to follow the degradation of α‐, γ‐ and δ‐tocopherol in concentrations of 0.01%, 0.05%, 0.1% and 0.25% during the oxidation of a 10% purified rapeseed oil triacylglycerol‐in‐water emulsion at 40 °C in the dark for 15 wk in a system containing a low oxygen concentration. Oxidation experiments were performed weekly by assessing the formation of hydroperoxides and hexanal, and the stability of the tocopherols was determined using high‐performance liquid chromatography. Storage tests were conducted with and without the addition of 0.01% α, α′‐azoisobutyronitrile (AIBN), which is a known radical initiator. α‐Tocopherol increased the formation of hydroperoxides in both tests as well as the generation of hexanal when the radical initiator was added; furthermore it was the least stable. γ‐Tocopherol delayed the formation of hexanal and prolonged the stability of the emulsion in a dose‐dependant manner. δ‐Tocopherol was the most stable and also the most effective in delaying lipid oxidation in the emulsions. Each concentration that was tested reduced the rate of hydroperoxide and especially hexanal formation. Hexanal was only formed to a slight extent after 15 wk of oxidation in the test with AIBN and the lowest dose of 0.01% δ‐tocopherol. For all tocopherols, strong correlations were found between tocopherol stability and the extent of oxidation. Results suggest that i) mainly δ‐tocopherol, but also γ‐tocopherol even less pronounced, are very good antioxidants in order to stabilize and prolong the shelf life of oil‐in‐water emulsions, ii) the antioxidative effects were intensified with increasing amounts.     

Partition behaviour of antioxidative phenolic compounds in heterophasic systems

Differences in the efficiency of antioxidants in dispersed lipid systems may be related to the differential solubility of the antioxidants within the physically distinct phases of colloidal food systems. This study determined the partitioning of antioxidants in water/oil systems, surfactant solutions (dodecyltrimethylammonium bromide, DTABr, sodium dodecylsulfate, SDS, polyoxyethylenesorbitan monolaurate, Tween 20), and emulsions. There were significant differences in the partition of the antioxidants between oil, water and interfacial phases both as a function of pH and surfactant. The proportions of hydrophilic antioxidants (ferulic acid, caffeic acid, gallic acid, propyl gallate, catechin and Trolox) showed significant decreases in the aqueous phase when lowering the pH from 7.0 to 3.0 in Tween 20 emulsions. DTABr lowered the proportion of all antioxidants in the unbuffered aqueous phase to a higher extent than SDS or Tween 20. Changing the ionic strength (5mM NaCl to 50mM NaCl) did not cause significant differences in water/oil systems. Therefore, the effectiveness of hydrophilic antioxidants in heterophasic systems is influenced by their partition into the different phases of water/oil, surfactant and emulsion systems.     

Effect of classic sterilization on lipid oxidation in model liquid milk‐based infant and follow‐on formulas

The objective of this study was to evaluate the effect of classic sterilization on lipid oxidation of liquid infant and follow‐on formulas by analyzing formation of oxidized and dimeric TAGs. Model systems containing similar components and proportions to those normally found in manufactured samples and a mixture of high‐oleic sunflower oil, rapeseed oil, and fish oil were used to obtain a fatty acid composition profile in accordance with the EU regulations. For comparative purposes, some samples were prepared with high‐oleic sunflower or fish oil and others without the protein components and added Tween‐20. Quantification of total oxidized TAGs provided complete information of the oxidation state and showed clear advantages versus the other methods used, i.e., loss of PUFA and peroxide value. The results showed that the heat treatment used for sterilization did not lead to significant lipid oxidation, but the tocopherol concentration decreased significantly. The marked tocoherol losses found in protein‐free formulas together with the significantly lower tocopherol concentrations in infant formulas (80% whey in protein fraction) compared to follow‐on formulas (80% caseinate in protein ratio) showed the protective effect of the protein fraction, specially sodium caseinate. Practical applications: This study provides useful information on the utility of different methods used to evaluate oxidation in infant and follow‐on formulas. Quantification of total oxidized TAGs standed out because it is a direct and sensitive method and provides complete information at any stage of the oxidative process. Also, this study shows that important decreases of tocopherols may occur during formula processing and special cautions should therefore be taken during storage and commercialization to avoid additional antioxidant losses.     

Effect of droplet size on lipid oxidation rates of oil-in-water emulsions stabilized by protein

In emulsions lipid oxidation is mainly influenced by the properties of the interface. The aim of this work was to investigate the effects of droplet size and interfacial area on lipid oxidation in protein-stabilized emulsions. Emulsions, made of stripped sunflower oil (30% vol/vol) and stabilized by BSA were characterized by surface area values equal to 0.7, 5.1, and 16.3 m²·cm⁻³ oil. The kinetics of O₂ consumption and conjugated diene (CD) formation, performed on emulsions and nonemulsified controls, showed that emulsification prompted oxidation at an early stage. On condition that oxygen concentration was not limiting, the rates of O₂ consumption and CD formation were higher when the interfacial area was larger. Protein adsorbed at the interface probably restrained this pro-oxidant effect. Once most of the O₂ in the system was consumed (6–8 h), CD remained steady at a level depending directly on the ratio between oxidizable substrate and total amount of oxygen. At this stage of aging, the amounts of primary oxidation products were similar whatever the droplet size of the emulsion. Hexanal and pentane could be detected in the headspace of emulsions only at this stage. They were subsequently produced at rates not depending on oil droplet size and interfacial area.     

Antioxidant Effects of Berry Phenolics Incorporated in Oil-in-Water Emulsions with Continuous Phase β-Lactoglobulin

The purpose of this study was to evaluate the effects of berry phenolics, in this case, black currant (Ribes nigrum) anthocyanins and raspberry (Rubus idaeus) ellagitannins, in the presence of continuous phase β-lactoglobulin (β-Lg), on the oxidative stability of Brij 35-stabilized corn oil-in-water emulsions. The extent of lipid oxidation in emulsions was measured by determining the formation of lipid hydroperoxides and hexanal, and extent of protein oxidation by monitoring the loss of tryptophan and cysteine residues in the continuous phase β-Lg. Berry phenolics at concentration levels of 20 and 50 μM were able to prevent lipid oxidation with and without β-Lg in the aqueous phase. The results show that a combination of β-Lg and berry phenolics was more efficient in inhibiting hexanal formation than either component alone. Synergistic effects on antioxidant activity toward hexanal were observed only at the 20 μM levels of berry phenolics in combination with continuous phase β-Lg. The berry phenolics were also able to inhibit the oxidation of tryptophan and cysteine residues of β-Lg. The results show that the amino acid residues were oxidized prior to the propagation of lipid oxidation. This suggests that these amino acids were able to inhibit fatty acid scission. The information gained from this study would be useful in protecting emulsion-based food products from oxidative deterioration.     

Effect of surfactants on phenol removal by the method of polymerization and precipitation catalysed by Coprinus cinereus peroxidase

The removal of phenol by peroxidase‐catalysed polymerization was examined using Coprinus cinereus peroxidase in the presence of surfactants. The non‐ionic surfactants with poly(oxyethene) residues, Triton X‐100, Triton X‐405 and Tween 20, enhanced the phenol removal efficiency at a level similar to high relative molecular mass poly(ethylene glycol) (relative molecular mass 3000). Although the improvement in the removal efficiency was less than that of Triton X‐100, Span 20, sodium lauryl sulfate (SDS) and lauryl trimethylammonium bromide (DTAB) also enhanced the removal efficiency. The requirement of the enzyme for almost 100% removal of 100 mg dm^?3 phenol decreased to one‐fourth by the addition of 30 mg dm^?3 Triton X‐100. Triton X‐100, Triton X‐405, Tween 20 and DTAB could reactivate the enzyme precipitated with the phenol polymer, leading to the restarting of the phenol removal reaction. Copyright © 2003 Society of Chemical Industry     

Effect of lipid type on water‐in‐oil‐emulsions stabilized by phosphatidylcholine‐depleted lecithin and polyglycerol polyricinoleate

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 (r_s = 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 (r_s = 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.     

Oxidative stability of polyunsaturated fatty acids and soybean oil in an aqueous solution with emulsifiers

The oxidative stability of polyunsaturated fatty acids (PUFA) and soybean oil homogenized with emulsifiers was investigated. Model emulsions were prepared from PUFA, including linoleic acid (LA), arachidonic acid (AA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA), and from soybean oil emulsified with different emulsifiers: three Tween emulsifiers (Tween 20, Tween 60, Tween 80) and two sucrose esters (S-1170 and S-1570) were used. The results showed that the emulsions prepared from LA and the various emulsifiers, oxidized at 40°C, were unstable. However, the corresponding AA, EPA, and DHA emulsions were stable, indicating that PUFA with a higher degree of unsaturation were more stable with emulsifiers than without the emulsifiers. In the soybean oil-in-water model system, the oxidation of soybean oil with various emulsifiers was less than without the emulsifiers.     

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.     

Epoxidation of methyl oleate with molecular oxygen in the presence of aldehydes

The epoxidation of methyl oleate with molecular oxygen in the presence of aldehydes was investigated and optimized. Epoxide yields up to 99% were observed in organic solvents. The preponderant radical reaction was started by a single organic radical chain initiator, without using a metal catalyst. The radical character of the reaction was revealed by the concurrent occurrence of trans and cis epoxides and by the prevention of epoxide formation through a radical scavenger. Both branched aldehydes and the linear aldehyde n‐hexanal were well suited in organic solvents. The linear n‐hexanal enabled also a superior epoxide yield of 78% in the green solvent water. The oxidation of high‐oleic sunflower oil under the same conditions with n‐hexanal yielded 39% epoxide groups.     

Role of Water and Selected Minor Components on Association Colloid Formation and Lipid Oxidation in Bulk Oil

This study investigated the influence of water content in combination with selected minor components including oleic acid, stigmasterol, α‐tocopherol, and Trolox on their association colloid formation as well as their impact on lipid oxidation in bulk corn oil. First, surface activity of each minor component was evaluated by determining the ability of these components to lower the interfacial tension between bulk oil and water. All components but α‐tocopherol were able to decrease interfacial tension of stripped oil. Second, the critical micelle concentration (CMC) of each minor component was determined in bulk oil with no water added and in the presence of 1000 ppm of water. In the bulk oil without extraneous water, we could not determine the CMC of minor components in the range of concentrations studied. However, in the presence of 1000 ppm of water, only stigmasterol could form association colloids at the CMC of 20 mmol/kg oil. Last, the effect of water content (400 and 1000 ppm) and minor components on lipid oxidation in bulk oil was studied by following the lipid hydroperoxides and hexanal formation during storage at 55 °C. Different water content did not significantly impact the lag time of lipid oxidation compared with the control. Interestingly, water caused prooxidant by decreasing the lag time of lipid hydroperoxides and hexanal formation in bulk oil containing oleic acid, stigmasterol, and Trolox compared with the control of each system. On the other hand, there was not significant impact of water on the antioxidant activity of α‐tocopherol, a lipid soluble antioxidant in bulk oil. This study highlights the impact of water content on the surface activity of minor components as well as on the oxidative stability in bulk oil.     

Lipid oxidation inhibiting capacities of blackseed essential oil and rosemary extract

Lipid oxidation is the main deterioration process that occurs in vegetable oils containing lipid molecules with polyunsaturation. The aim of the present study was to investigate the possible effects of blackseed (Nigella sativa L.) essential oil (BEO) and rosemary (Rosmarinus officinalis L.) extract (RE) on stabilization of sunflower oil under accelerated storage conditions. RE was obtained by soxhlet extraction using methanol, whereas BEO was hydrodistilled from the blackseed extract obtained by extraction using petroleum ether (b.p. 40–60°C). The results indicate that both extracts stabilize sunflower oil to a certain extent, the extent being greater with RE than with BEO based on measurements of peroxide value, p‐anisidine value, amount of nonoxidized linoleic acid in saponified oil samples by HPLC‐DAD, concentration of conjugated diene hydroperoxide, and UV light absorption. The oil stabilizing effect of BEO against lipid oxidation, especially at concentrations of 0.06 and 0.1 g/100 g oil was found to increase as the temperature increased, according to principal component analysis results. Based on its strong lipid oxidation inhibiting capacity, RE can be used as a potential natural extract for stabilizing sunflower oil against oxidation. BEO, at carefully selected concentrations, can be suggested as an alternative supplement of plant origin for improving oil stabilization. Practical applications: Sunflower oil is a widely used vegetable oil for cooking and frying, and has a high linoleic acid content of about 40–70%. Here we show that sunflower oil can be stabilized by adding rosemary and blackseed extracts. The treatment can be useful especially in applications which require heating the oil to high temperatures.