Influence of Droplet Charge on the Chemical Stability of Citral in Oil-in-Water Emulsions

Abstract: The chemical stability of citral, a flavor component widely used in beverage, food, and fragrance products, in oil-in-water emulsions stabilized by surfactants with different charge characteristics was investigated. Emulsions were prepared using cationic (lauryl alginate, LAE), non-ionic (polyoxyethylene (23) lauryl ether, Brij 35), and anionic (sodium dodecyl sulfate, SDS) surfactants at pH 3.5. The citral concentration decreased over time in all the emulsions, but the rate of decrease depended on surfactant type. After 7 d storage, the citral concentrations remaining in the emulsions were around 60% for LAE- or Brij 35-stabilized emulsions and 10% for SDS-stabilized emulsions. An increase in the local proton (H⁺) concentration around negatively charged droplet surfaces may account for the more rapid citral degradation observed in SDS-stabilized emulsions. A strong metal ion chelator (EDTA), which has previously been shown to be effective at increasing the oxidative stability of labile components, had no effect on citral stability in LAE- or Brij 35-stabilized emulsions, but it slightly decreased the initial rate of citral degradation in SDS-stabilized emulsions. These results suggest the surfactant type used to prepare emulsions should be controlled to improve the chemical stability of citral in emulsion systems.     

乳化体系中花生油氧化稳定性的研究

主要探讨花生油乳化体系中乳化剂类型、用量、pH值、EDTA、温度等对花生油氧化稳定性的影响,结果显示:乳化剂种类和pH对于乳状液体系的氧化稳定性有显著影响,阴离子乳化剂SDS稳定的乳化液,pH4.0的氧化速率最快;非离子乳化剂Tween20稳定的乳化液,pH的影响不是很显著;阳离子乳化剂CTAB稳定的乳化液,随着pH的升高,氧化速率变快。乳化液体系中微量金属离子对于体系也有相当大的影响,随着金属离子螯合剂EDTA浓度的增加,其乳化体系中花生油的氧化速率显著降低。乳化剂用量也会影响体系的氧化稳定性,随着乳化剂用量的增加,乳化乳化体系中花生油的氧化稳定性降低。     

Interaction between Emulsion Droplets and Escherichia coli Cells

ABSTRACT Oil‐in‐water emulsions (20% n‐hexadecane, v/v) were stabilized by dodecyltrimethylammonium bromide (DTAB), Tween 20, or sodium dodecyl sulfate (SDS). Particle size distribution and creaming stability were measured before and after adding Escherichia coli cells to emulsions. Both E. coli strains promoted droplet flocculation, coalescence, and creaming in DTAB emulsions, although JM109 cells (surface charge = ‐35 mV) caused faster creaming than E21 cells (surface charge = ‐5 mV). Addition of bacterial cells to SDS emulsions promoted some flocculation and coalescence, but creaming stability was unaffected. Droplet aggregation and accelerated creaming were not observed in emulsions prepared with Tween 20. Surface charges of bacterial cells and emulsion droplets played a key role in emulsion stability.     

Ability of whey protein isolate and/or fish gelatin to inhibit physical separation and lipid oxidation in fish oil-in-water beverage emulsion

The effect of pH on the capability of whey protein isolate (WPI) and fish gelatin (FG), alone and in conjugation, to form and stabilize fish oil-in-water emulsions was examined. Using layer-by-layer interfacial deposition technique for WPI–FG conjugate, a total of 1% protein was used to prepare 10% fish oil emulsions. The droplets size distributions and electrical charge, surface protein concentration, flow and dynamic rheological properties and physiochemical stability of emulsions were characterize at two different pH of 3.4 and 6.8 which were selected based on the ranges of citrus and milk beverages pHs, respectively. Emulsions prepared with WPI–FG conjugate had superior physiochemical stability compare to the emulsions prepared with individual proteins. Higher rate of coalescence was associated with reduction in net charge and consequent decrease of the repulsion between coated oil droplets due to the proximity of pH to the isoelectric point of proteins. The noteworthy shear thinning viscosity, as an indication of flocculation onset, was associated with whey protein stabilized fish oil emulsion prepared at pH of 3.4 and gelatin stabilized fish oil emulsion made at pH of 6.8. At pH 3.4, it appeared that lower surface charge and higher surface area of WPI stabilized emulsions promoted lipid oxidation and production of hexanal.     

New insights into the antioxidant activity of Trolox in o/w emulsions

The antioxidant activity of Trolox was investigated in emulsions containing different emulsifiers, and decreased in the order Brij 58 > CTAB > SDS. Two degradation products were isolated and identified as Trolox quinone and a keto-derivative. In addition to the stability of Trolox, the effects of the degradation products on lipid oxidation were investigated. In emulsions with SDS, the quinone and the keto-derivative contributed to the overall pro-oxidant effect of Trolox, whereas they had no effect in emulsions containing CTAB or Brij 58. It was concluded that the microenvironment at the o/w interface has a marked influence on the antioxidant and pro-oxidant effects of Trolox and its degradation products via molecular interactions and by affecting its molecular mobility.     

Effects of protein concentration and oil-phase volume fraction on the stability and rheology of menhaden oil-in-water emulsions stabilized by whey protein isolate with xanthan gum

The influences of protein concentration (0.2, 1, 2 wt%) and oil-phase volume fraction (5%, 20%, 40% v/v) on emulsion stability and rheological properties were investigated in whey protein isolate (WPI)-stabilized oil-in-water emulsions containing 0.2 wt% xanthan gum (XG). The data of droplet size, surface charge, creaming index, oxidative stability, and emulsion rheology were obtained. The results showed that increasing WPI concentration significantly affected droplet size, surface charge, and oxidative stability, but had little effect on creaming stability and emulsion rheology. At 0.2 wt% WPI, increasing oil-phase volume fraction greatly increased droplet size but no significant effect on surface charge. At 1 or 2 wt% WPI, increasing oil-phase volume fraction had less influence on droplet size but led to surface charge more negative. Increasing oil-phase volume fraction facilitated the inhibition of lipid oxidation. Meanwhile, oil-phase volume fraction played a dominant role in creaming stability and emulsion viscosity. The rheological data indicated the emulsions may undergo a behavior transition from an entropic polymer gel to an enthalpic particle gel when oil-phase volume fraction increased from 20% to 40% v/v.     

Effect of the pH on the lipid oxidation and polyphenols of soybean oil-in-water emulsion with added peppermint (<Emphasis Type="Italic">Mentha piperita</Emphasis>) extract in the presence and absence of iron

This study evaluated the pH effect on the lipid oxidation and polyphenols of the emulsions consisting of soybean oil, citric acid buffer (pH 2.6, 4.0, or 6.0), and peppermint (Mentha piperita) extract (400 mg/kg), with/without FeSO₄. The emulsions in tightly-sealed bottles were placed at 25 °C in the dark, and lipid oxidation and polyphenol contents and composition were determined. The lipid oxidation was high in the emulsions at pH 4.0 in the absence of iron, however, iron addition made them more stable than the emulsions at pH 2.6 or 6.0. Total polyphenols were remained at the lowest content during oxidation in the emulsions at pH 4.0, and iron reduced and decelerated polyphenol degradation. The results strongly suggest that polyphenols contributed to decreased lipid oxidation of the emulsion via radical scavenging and iron-chelation, and rosmarinic acid along with catechin, caffeic acid, and luteolin were key polyphenols as radical scavengers in the extract.     

Effect of α-lactalbumin and β-lactoglobulin on the oxidative stability of 10% fish oil-in-water emulsions depends on pH

The objective of this study was to investigate the influence of pH on lipid oxidation and protein partitioning in 10% fish oil-in-water emulsions prepared with different whey protein isolates with varying ratios of α-lactalbumin and β-lactoglobulin. Results showed that an increase in pH increased lipid oxidation irrespective of the emulsifier used. At pH 4, lipid oxidation was not affected by the type of whey protein emulsifier used or the partitioning of proteins between the interface and the water phase. However, at pH 7 the emulsifier with the highest concentration of β-lactoglobulin protected more effectively against oxidation during emulsion production, whereas the emulsions with the highest concentration of α-lactalbumin were most stable to oxidation during storage. These differences were explained by differences in the pressure and adsorption induced unfolding of the individual protein components.     

Influence of heat processing and calcium ions on the ability of EDTA to inhibit lipid oxidation in oil-in-water emulsions containing omega-3 fatty acids

The nutritional benefits of ω-3 fatty acids make them excellent candidates as functional food ingredients if problems with oxidative rancidity can be overcome. Oil-in-water emulsions were prepared with 2% salmon oil, stabilized by 0.2% Brij 35 at pH 7. To determine the effects of heating (50–90 °C), ethylenediaminetetraacetic acid (EDTA), and calcium on the oxidative and physical stability of salmon oil-in-water emulsions, particle size, thiobarbituric acid reactive substances (TBARS), and lipid hydroperoxides were measured. The heat-processed emulsions showed no significant difference, in particle size, TBARS or hydroperoxides during storage, from unheated emulsions. Above 2.5 μM, EDTA dramatically decreased lipid oxidation in all samples. Addition of calcium to emulsions containing 7.5 μM EDTA significantly increased both TBARS and hydroperoxide formation when calcium concentrations were 2-fold greater than EDTA concentrations. These results indicate that heat-processed salmon oil-in-water emulsions with high physical and oxidative stability could be produced in the presence of EDTA.     

Microstructural design to reduce lipid oxidation in oil-inwater emulsions

The influence of emulsifier type (Tween 20 and sodium caseinate (CAS)) and oil phase volume fraction (5% and 30%) on emulsion oxidative stability was investigated. The primary and secondary lipid oxidation products of emulsions stored at 40 °C were measured over 7 days. The results indicated that the oxidative stability of samples stabilised with CAS was significantly higher compared with emulsions stabilised with Tween 20. We propose that this is due to iron binding ability of CAS. Moreover, the impacts of Pickering emulsions (Silica particles) on lipid oxidation were studied and compared with Tween 20 stabilised emulsions. The results showed that silica particles could increase the oxidative stability of 20% sunflower oil-in-water emulsions by acting as a physical barrier between pro-oxidants located in continuous phase and hydroperxide at droplet interface.     

Influence of interfacial composition on oxidative stability of oil-in-water emulsions stabilized by biopolymer emulsifiers

The objective of this research was to evaluate the influence of storage pH (3 and 7) and biopolymer emulsifier type (Whey protein isolate (WPI), Modified starch (MS) and Gum arabic (GA)) on the physical and oxidative stability of rice bran oil-in-water emulsions. All three emulsifiers formed small emulsion droplets (d₃₂ < 0.5 μm) when used at sufficiently high levels: 0.45%, 1% and 10% for WPI, MS and GA, respectively. The droplets were relatively stable to droplet growth throughout storage (d₃₂ < 0.6 μm after 20 days), although there was some evidence of droplet aggregation particularly in the MS-stabilized emulsions. The electrical charge on the biopolymer-coated lipid droplets depended on pH and biopolymer type: −13 and −27 mV at pH 3 and 7 for GA; −2 and −3 mV at pH 3 and 7 for MS; +37 and −38 mV at pH 3 and 7 for WPI. The oxidative stability of the emulsions was monitored by measuring peroxide (primary products) and hexanal (secondary products) formation during storage at 37 °C, for up to 20 days, in the presence of a pro-oxidant (iron/EDTA). Rice bran oil emulsions containing MS- and WPI-coated lipid droplets were relatively stable to lipid oxidation, but those containing GA-coated droplets were highly unstable to oxidation at both pH 3 and 7. The results are interpreted in terms of the impact of the electrical characteristics of the biopolymers on the ability of cationic iron ions to interact with emulsified lipids. These results have important implications for utilizing rice bran oil, and other oxidatively unstable oils, in commercial food and beverage products.     

Impact of iron encapsulation within the interior aqueous phase of water-in-oil-in-water emulsions on lipid oxidation

Iron (Fe³⁺) was encapsulated within the internal aqueous phase of water-in-oil-in-water (W/O/W) emulsions, and then the impact of this iron on the oxidative stability of fish oil droplets was examined. There was no significant change in lipid droplet diameter in the W/O/W emulsions during 7 days storage, suggesting that the emulsions were stable to lipid droplet flocculation and coalescence, and internal water diffusion/expulsion. The initial iron encapsulation (4 mg/100 g emulsion) within the internal aqueous phase of the water-in-oil (W/O) emulsions was high (>99.75%), although, a small amount leaked out over 7 days storage (≈10 μg/100 g emulsion). When W/O/W emulsions were mixed with fish oil droplets the thiobarbituric acid-reactive substances (TBARS) formed decreased (compared to fish oil droplets alone) by an amount that depended on iron concentration and location, i.e., no added iron < iron in external aqueous phase < iron in internal aqueous phase. These differences were attributed to the impact of W/O droplets on the concentration and location of iron and lipid oxidation reaction products within the system.     

Effects of solubility characteristics of sensitiser and pH on the photooxidation of oil in tuna oil-added acidic O/W emulsions

The effects of sensitisers and pH on the oil oxidation of acidic O/W emulsions were studied under light by measuring hydroperoxide content and headspace oxygen consumption in the emulsions. The emulsions consisted of canola and tuna oil (2:1 w/w, 32%), diluted acetic acid (64%), egg yolk powder (4%), chlorophyll b or erythrosine (5 μM), and/or diazabicyclooctane (DABCO) or sodium azide (0.5 M). The emulsion pH values were 2.67, 3.68, and 6.27. Chlorophyll increased oil oxidation in the emulsion under light via singlet oxygen production while erythrosine did not. DABCO significantly decreased photooxidation of the oil containing chlorophyll, suggesting singlet oxygen involvement. However, sodium azide increased photooxidation of the oil containing chlorophyll possibly via azide radical production under acidic conditions. The oil photooxidation was higher in the emulsion containing chlorophyll at pH 6.27 than at pH 2.67 or 3.68, primarily by singlet oxygen and secondarily by free radicals produced from hydroperoxide decomposition.     

Iron-Catalyzed Oxidation of Menhaden Oil as Affected by Emulsifiers

The ability of Tween 20 and whey protein isolate (WPI) to influence lipid oxidation was investigated by evaluating the effects of emulsifier concentration and physical location on iron-catalyzed oxidation of emulsified Menhaden oil. Addition of Tween 20 or WPI to the aqueous phase of a 0.5 wt% Tween 20 stabilized emulsion increased lipid oxidation as determined by both thiobarbituric acid reactive substances (TBARS) and lipid peroxides. Tween 20 (2.0 wt%) and WPI (0.05–1.0 wt%) combinations inhibited TBARS formation 23–60%. Oxidation of a WPI-stabilized emulsion decreased with decreasing pH (3–7) but in a Tween 20 stabilized emulsion oxidation increased with decreasing pH. The low oxidation rate for the WPI-stabilized emulsion at pH 3 was increased when Tween 20 displaced WPI from the droplet interface. Results indicate that the oxidative stability of emulsifed Menhaden oil could be increased by controlling emulsifier type, location and concentration.     

Microencapsulation properties of two different types of n-octenylsuccinate-derivatised starch

Aim of the present study was to evaluate the suitability of two different types of n-octenylsuccinate-derivatised starch, which significantly differed in viscosity, for microencapsulation of a fish oil rich in long-chain polyunsaturated fatty acids. Stable feed emulsions for microencapsulation could be prepared with both types of n--octenylsuccinate starch, however at a high oil load (50%), a low pH (pH 4.5) of the emulsion was crucial for emulsion stability. At 50% oil content, lower oil droplet size in reconstituted spray-dried emulsions and lower content of non-encapsulated oil was reached by low viscosity starch compared to medium viscosity starch. Conjugated dienes were significantly increased in samples with a high oil load and 40% starch indicating that to a certain degree lipid oxidation already occurred in these samples during the drying process. Finally, moderate spray-drying conditions must be considered as advantageous, since ballooning of the particles and lipid oxidation during spray drying were limited compared to drying at high spray-drying temperatures.     

Antioxidant and emulsifying properties of potato protein hydrolysate in soybean oil-in-water emulsions

The efficacy of a previously developed antioxidative potato protein hydrolysate (PPH) for the stabilisation of oil droplets and inhibition of lipid oxidation in soybean oil-in-water (O/W) emulsions was investigated. Emulsions (10% lipid, pH 7.0) with PPH-coated oil droplets were less stable than those produced with Tween 20 (P < 0.05). However, the presence of PPH, whether added before or after homogenisation with Tween 20, retarded emulsion oxidation, showing reduced formation of peroxides up to 53.4% and malonaldehyde-equivalent substances up to 70.8% after 7-d storage at 37 °C (P < 0.05), when compared with PPH-free emulsions. In the emulsions stabilised by PPH + Tween 20, 8–15% of PPH was distributed at the interface. Adjustment of the pH from 3 to 7 markedly increased ζ-potential of such emulsions (P < 0.05). Inhibition of lipid oxidation by PPH in soybean O/W emulsions can be attributed to both chemical and physical (shielding) actions.     

Antioxidative Activities of Ginkgo biloba Extract on Oil/Water Emulsion System Prepared from an Enzymatically Modified Lipid Containing Alpha‐Linolenic Acid

Abstract: The desired mix of alpha‐linolenic acid (ALA)‐enriched structured lipid (SL) and physically blended lipid (PB) was prepared from grape seed oil and perilla oil at a weight ratio of 3:1. The major triacylglycerol species (LnLnL) in PB was drastically increased after interesterification (SL), from 0.5% to 16.8%. After the reaction, the total unsaturated fatty acid at the sn‐2 position was decreased from 98.83% in PB to 91.36% in SL. The reduction of vitamin E compounds was also observed. Compared with a PB‐based emulsion, SL‐based emulsions showed oxidative instability, as assessed by lipid hydroperoxide (LOOH) and 2‐thiobarbituric acid‐reactive substances (TBARS) values, which was mainly due to the SL which contained less LA, ALA, and ΣUSFA at the sn‐2 position and less γ‐tocopherol than did PB. PB‐, and SL‐based emulsions with Ginkgo biloba extract (GBE) which showed significantly lower values of LOOH and TBARS compared to a blank control. GBE was effective in retarding the oxidation of the emulsion by quenching the free radicals in the water phase of the emulsion and inhibiting the formation of primary and secondary oxidation products. These results indicate that GBE could be used as an antioxidant additive for stabilizing ALA‐enriched emulsions. Practical Application: The results suggest the possibility to supplement Ginkgo biloba extract in alpha linolenic acid‐enriched structured lipid‐based emulsions which would increase the therapeutic value and enhance the antioxidant potential of the emulsions.     

Impact of thermal processing on the antioxidant mechanisms of continuous phase β-lactoglobulin in oil-in-water emulsions

The influence of native and thermally (50–95 °C) denatured β-lactoglobulin (β-Lg) on the oxidative stability of surfactant-stabilized menhaden oil-in-water emulsions (pH 7.0) was evaluated. β-Lg (500 μg/g oil) heated at 95 °C for 30 min provided the best protection against lipid oxidation, inhibiting the formation of lipid hydroperoxides and thiobarbituric acid reactive substances (TBARS) by 87% and 88%, respectively, following 7 days of storage. The possible mechanisms of antioxidant activity of native and heated β-Lg were evaluated by measuring peroxyl radical scavenging and iron chelating capacities of the protein treatments, as well as reactive sulfhydryl concentrations and tryptophan fluorescence (a marker of protein conformation changes). The aforementioned in vitro assays only partially corroborated the results from the oxidizing emulsion system since β-Lg heated at 95 °C exhibited the lowest iron chelation capacity and free sulfhydryl concentration, yet displayed the highest peroxyl radical scavenging capacity and inhibition of lipid oxidation in oil-in-water emulsions of all treatments tested. The results of this study demonstrate the feasibility of proteins as a natural class of antioxidants in food emulsions, and further elucidate the possible mechanisms by which proteins inhibit lipid oxidation.     

Grape skin extracts as a sustainable source of antioxidants in an oil-in-water emulsion: an alternate natural approach to synthetic antioxidants using principal component analysis

Grape (Kyoho) skin, used to retard lipid oxidation in edible oil foods, was investigated to reduce lipid oxidation in an oil-in-water (O/W) emulsion during 20 day of storage. The antioxidant efficacy of Kyoho skin extracts in O/W emulsions was determined by the measurement of secondary oxidation products. Moreover, principal component analysis (PCA) was conducted to determine similarities between emulsions treated with or without Kyoho skin extracts and standards. The data revealed that Kyoho skin extracts exhibited >93% inhibition and reported a similar p-anisidine (4.30–20.71) and TBARS (6.08–11.15 mg MDA L⁻¹) values over the standards during 20 day of storage. PCA (PCs 1 (51.83%) and 2 (18.85%)) demonstrated a similarity in the contribution of Kyoho skin extracts over the synthetic antioxidants in O/W emulsion. Overall, these findings highlighted the possibility of using Kyoho skin extracts as natural antioxidants to decrease oxidative rancidity in foods.     

Free-radical scavenging and antioxidative activities of some polysaccharides in emulsions

The antioxidant activity in linoleate emulsion systems, radical scavenging activity and inhibition of autoxidation in sunflower oil-in-water emulsions were studied in the presence of polysaccharide produced by Rhizobium meliloti (RPS), xanthan, curdlan, and carboxymethylcellulose (CMC) and compared to tertiary butylhydroxyquinone (TBHQ). The antioxidant activity in the linoleate emulsion was improved with increasing pH from 3 to 9 and concentration of polysaccharide from 20 to 60 mg/100 g emulsion, while it decreased with increase in storage temperature between 30 and 90 °C. The antioxidant activity of xanthan, curdlan, and RPS at concentration of 40 mg/100 g emulsion was equal to that of TBHQ at 20 mg/100 g emulsion. RPS showed the highest thermal stability and the lowest linoleic oxidation values compared to TBHQ, xanthan, and curdlan at 90 °C. The antioxidant activity of xanthan, curdlan, and RPS in linoleate emulsions at pH 3 and 5 was in the first order with significant (P<0.05) values compared to emulsion, prepared using TBHQ.Curdlan and RPS were effective in radical scavenging being 60-90% at pH values ranging between 3 and 7. They showed an ability to inhibit lipid oxidation in sunflower oil emulsions during holding time for 50 h at 60 °C. In general, the polysaccharides RPS and curdlan can be used as food additives having many functions as stabilizers, radical scavengers, and antioxidants in emulsified foods such as mayonnaise, salad dressings, and cake products.