Antioxidant protection of bulk fish oils by dispersed sugars and polyhydric alcohols

Selected sugars (fructose, sucrose, or raffinose) and polyhydric alcohols (sorbitol or mannitol) were equilibrated directly with bulk fish oil (10% by weight, excess) and exposed to fluorescent lighting (2550 Lx) for 24 h at 5 degrees C. Data for room temperature-equilibrated samples revealed that polyols functioned as antioxidants in fish oil. Increased times and temperatures of equilibration (to 90-110 degrees C, 1-2 mmHg, to 2 h) greatly enhanced the antioxidant activity of polyols in fish oil exposed to light. Under accelerated oxidation conditions (60 degrees C) in the dark, dispersed sorbitol in bulk fish oil greatly suppressed the peroxide value, primarily by chelating transition metals, while fructose showed a limited antioxidant activity. Sugars with a lower molecular weight and smaller numbers of equatorial OH groups exhibited a higher rate of permeation of sugars into fish oil triacylglycerols and hence rendered greater antioxidant activities. The treatment of bulk fish oils with polyols and then using the oils in the preparation of emulsions greatly reduced their antioxidant activities as compared to those observed for treated bulk oils. The introduction of polyols dissolved in propylene glycol into bulk fish oils at 90 degrees C (0.025% polyol, 0.25 h of equilibration) provided a similar antioxidant activity to that imparted by the introduction of polyols into the oil by equilibrating excess polyols (10% by weight) with them at 90-110 degrees C for 2 h. However, regardless of the method of the introduction of polyols to bulk fish oil, an elevated temperature (90 degrees C) exposure during fish oil treatment was required to induce a notable antioxidant activity.     

Factors influencing the antioxidant and pro-oxidant activity of polyphenols in oil-in-water emulsions

The nonenzymatic oxidation of polyphenols bearing di- and trihydroxyphenol groups results in the generation of hydrogen peroxide (H?O?), a reactive oxygen species that can potentially compromise the oxidative stability of foods and beverages. An investigation of the factors that promote the oxidation of a model polyphenol, (-)-epigallocatechin-3-gallate (EGCG), was undertaken in a model lipid-based food system. Factors affecting oxidative stability, such as exogenous iron chelators (ethylenediaminetetraacetic acid; EDTA and 2,2-bipyridine; BPY) and pH (3 and 7) were evaluated in hexadecane and flaxseed oil-in-water (o/w) emulsions. At neutral pH, H?O? levels were observed to rise rapidly in hexadecane emulsions except for EDTA-containing treatments. However, EDTA-containing samples showed the highest rate of EGCG oxidation, suggesting that H?O? was rapidly reduced to hydroxyl radicals (HO?). Conversely, at pH 3, H?O? concentrations were lower across all treatments. EDTA conferred the highest degree of EGCG stability, with no loss of the catechin over the course of the study. In order to assess whether or not the H?O? production seen in oxidatively stable hexadecane emulsions translated to pro-oxidant activity in an oxidatively labile food lipid system, the effect of EGCG on the stability of flaxseed o/w emulsions was studied. EGCG displayed antioxidant activity at pH 7 throughout the study; however at pH 3, pro-oxidant activity was seen in EGCG-containing emulsions, with and without BPY. This study attempts to provide a mechanistic understanding of the conditions wherein polyphenols simultaneously exert pro-oxidant and antioxidant behavior in lipid dispersions.     

Bovine serum albumin produces a synergistic increase in the antioxidant activity of virgin olive oil phenolic compounds in oil-in-water emulsions

Virgin olive oil is valued for its flavor, but unacceptable off-flavors may develop on storage in food products containing this oil due to oxidation. The oxidative stability of oil-in-water emulsions containing bovine serum albumin (BSA) and virgin olive oil phenolic compounds was studied. Four oil-in-water emulsions with and without BSA and phenols isolated from virgin olive oil were prepared. These model systems were stored at 60 degrees C to speed up lipid oxidation. Primary and secondary oxidation products were monitored every three days. Peroxide values and conjugated diene contents were determined as measures of the primary oxidation products. p-Anisidine values and volatile compounds were determined as measures of the secondary oxidation products. This latter determination was carried out by headspace solid-phase microextraction coupled with gas chromatography. Although olive oil phenolic compounds and BSA contributed some antioxidant activity when present as individual additives, the combination of BSA with phenols in an emulsion showed 58-127% synergy, depending on which analytical method was used in the calculation. The emulsion containing phenolic compounds and BSA showed a low level of deterioration after 45 days of storage at 60 degrees C.     

Distribution of hydroxytyrosol and hydroxytyrosol acetate in olive oil emulsions and their antioxidant efficiency

We employed a kinetic method to determine the distributions of the antioxidants hydroxytyrosol (HT) and hydroxytyrosol acetate (HTA) between the oil, aqueous, and interfacial regions of a model food emulsion composed of stripped olive oil, acidic water, and a blend of Tween 80 and Span 80 [hydrophilic–lipophilic balance (HLB) = 8.05] as an emulsifier. HT is oil-insoluble, but HTA is both oil- and water-soluble (partition constant P(O)(W) = 0.61). Results indicate that, at a given emulsifier volume fraction Φ(I), the fraction of HTA in the interfacial region is higher than that of HT. The percentage of both antioxidants increases with an increasing Φ(I), so that % HT > 40% at Φ(I) = 0.005 and % HT > 80% at Φ(I) = 0.04. HTA appears to be a better antioxidant than HT, as shown by an accelerated oxidative test (Schaal oven method). A correlation between their distribution in the emulsion and their efficiency was established.     

Antioxidant activity of oregano, parsley, and olive mill wastewaters in bulk oils and oil-in-water emulsions enriched in fish oil

The antioxidant activity of oregano, parsley, olive mill wastewaters (OMWW), Trolox, and ethylenediaminetetraacetic acid (EDTA) was evaluated in bulk oils and oil-in-water (o/w) emulsions enriched with 5% tuna oil by monitoring the formation of hydroperoxides, hexanal, and t-t-2,4-heptadienal in samples stored at 37 degrees C for 14 days. In bulk oil, the order of antioxidant activity was, in decreasing order (p < 0.05), OMWW > oregano > parsley > EDTA > Trolox. The antioxidant activity in o/w emulsion followed the same order except that EDTA was as efficient an antioxidant as OMWW. In addition, the total phenolic content, the radical scavenging properties, the reducing capacity, and the iron chelating activity of OMWW, parsley, and oregano extracts were determined by the Folin-Ciocalteau, oxygen radical absorbance capacity, ferric reducing antioxidant power, and iron(II) chelating activity assays, respectively. The antioxidant activity of OMWW, parsley, and oregano in food systems was related to their total phenolic content and radical scavenging capacity but not to their ability to chelate iron in vitro. OMWW was identified as a promising source of antioxidants to retard lipid oxidation in fish oil-enriched food products.     

Antioxidant activity of selected Spanish wines in corn oil emulsions

Wines contain phenolic compounds that may be useful for preventing lipid oxidation as dietary antioxidants. This study was aimed at evaluating the antioxidant activity in corn oil emulsions of seventeen selected Spanish wines and two California wines. The inhibition of hydroperoxide formation at 10 microM gallic acid equivalents (GAE) varied from 8.4% to 40.2% with the red wines, from 20.9% to 45.8% with the rosé wines, and from 6.5% to 47.0% with the white wines. The inhibition of hydroperoxide formation at 20 microM GAE varied from 11.9% to 34.1% with the red wines, from 0.1% to 34. 5% with the rosé wines, and from 3.3% to 37.2% with the white wines. The inhibition of hexanal formation at 10 microM GAE varied from 23. 6% to 64.4% with the red wines, from 42.7% to 68.5% with the rosé wines, and from 28.4% to 68.8% with the white wines. The inhibition of hexanal formation at 20 microM GAE varied from 33.0% to 46.3% with the red wines, from 11.3% to 66.5% with the rosé wines, and from -16.7% to +21.0% with the white wines. The antioxidant effect decreased with increasing concentration. This antioxidant activity was related to the five main groups of phenolic compounds identified in wines by HPLC. The relative antioxidant activity correlated positively with the total phenol content of wines (by the Folin-Ciocalteu method and by HPLC), benzoic acids, anthocyanins, flavan-3-ols, and flavonols, for the inhibition of hydroperoxides and hexanal at 10 and 20 microM GAE.     

Chemical and antioxidant properties of casein peptide and its glucose Maillard reaction products in fish oil-in-water emulsions

Maillard reaction products (MRPs) were prepared by reacting casein peptides with different concentrations of glucose at 80 °C for up to 12 h. The chemical properties of MRPs and their effects on lipid oxidation in fish oil-in-water emulsions were investigated. Increasing browning development and absorbance in 294 nm in the MRPs caused an increase in DPPH radical scavenging, but a decrease in iron chelation, which could be related to the loss of free amino groups in the peptides. The MRPs produced with longer reaction time or higher glucose concentrations were less effective in inhibiting lipid oxidation in emulsions at pH 7.0 compared to casein peptides alone. However, the antioxidant activity of MRPs in emulsions at pH 3.0 was not decreased by prolonged heating. The bitterness of MRPs was less than that of the original casein peptides, and bitterness decreased with increasing heating time and glucose concentrations. Therefore, the Maillard reaction was a potential method to reduce the bitterness of casein peptides while not strongly decreasing their antioxidant activity.     

Effects of natural phenolic compounds on the antioxidant activity of lactoferrin in liposomes and oil-in-water emulsions

The effect of natural phenolic compounds on the antioxidant and prooxidant activity of lactoferrin was studied in liposomes and oil-in-water emulsions containing iron. The antioxidants tested with lactoferrin were alpha-tocopherol, ferulic acid, coumaric acid, tyrosol, and natural phenolic extracts obtained from three different extra-virgin olive oils and olive mill wastewater. The natural extracts of olive oils and mill wastewaters were composed mainly of polyphenols and simple phenolics, respectively. Lipid oxidation at 30 degrees C was determined by the formation of hydroperoxides and fluorescent compounds resulting from oxidized lipid interactions. All phenolic compounds showed synergistic properties in reinforcing the antioxidant activity of lactoferrin in lipid systems containing iron. The highest synergistic effects were observed for the phenolic extracts rich in polyphenols of extra-virgin olive oils and lactoferrin. This synergistic effect was higher in liposomes than in emulsions.     

Addition of sugars influences color of oil-in-water emulsions

The influence of glucose, fructose, lactose, and glycerol on the color and appearance of surfactant-stabilized oil-in-water emulsions containing a red dye was investigated. A stabilized (Tween-20) oil-in-water emulsion was diluted into sugar solutions to give a range of oil droplet and sugar concentrations. Tristimulus coordinates (L, a, b) and reflectance spectra were measured using a spectrophotometer. With increasing sugar concentration, reflectance spectra shifted to lower reflectance values. Tristimulus coordinates were reduced by approximately 50% for emulsions containing high concentrations of sugar. Adding fructose to emulsions reduced L, a, b values more significantly than adding glucose, lactose, or glycerol. Tristimulus coordinates remained constant when the temperature was raised from 20 to 80 degrees C. The experimental results were explained in terms of the change of relative refractive index at the water-oil interface. The results have important implications for the food industry as they offer a new means to control and optimize the color of food emulsions.     

Homogenization conditions affect the oxidative stability of fish oil enriched milk emulsions: lipid oxidation

In this study fish oil was incorporated into commercial homogenized milk using different homogenization temperatures and pressures. The main aim was to understand the significance of homogenization temperature and pressure on the oxidative stability of the resulting milks. Increasing homogenization temperature from 50 to 72 degrees C decreased droplet size only slightly, whereas a pressure increase from 5 to 22.5 MPa decreased droplet size significantly. Surprisingly, emulsions having small droplets, and therefore large interfacial area, were less oxidized than emulsions having bigger droplets. Emulsions with similar droplet size distributions, but resulting from different homogenization conditions, had significantly different oxidative stabilities, indicating that properties of significance to oxidation other than droplet size itself were affected by the different treatments. In general, homogenization at 72 degrees C appeared to induce protective effects against oxidation as compared to homogenization at 50 degrees C. The results thus indicated that the actual composition of the oil-water interface is more important than total surface area itself.     

Antioxidant activity of 3-dehydroshikimic acid in liposomes,emulsions, and bulk oil

The antioxidant activity of 3-dehydroshikimic acid (DHS), an intermediate in the biosynthesis of aromatic amino acids, was evaluated in three assay systems: bulk oil (lard), liposomes, and a 10% corn oil-in-water emulsion. Upon initiation of peroxidation in the liposome or emulsion systems, DHS exhibited weak antioxidant activity. In contrast, DHS displayed strong antioxidant activity in lard, suppressing peroxidation with activity comparable to that of tert-butylhydroquinone, propyl gallate, and gallic acid and superior to that of alpha-tocopherol. Two major DHS oxidation products, gallic acid and protocatechuic acid, were identified by gas chromatography/mass spectral analysis of lard extracts; both compounds are effective antioxidants in the bulk oil system. In the liposome system, DHS remained intact throughout the assay period. A small amount of gallic acid was observed in extracts of the emulsion; however, protocatechuic acid was not detected. A mechanism to explain the different activities of DHS in the three lipid systems is proposed.     

Characterization of the volatile constituents in the essential oil of Pistacia lentiscus L. from different origins and its antifungal and antioxidant activity

Essential oil (EO) from aerial parts (leaves, juvenile branches, and flowers when present) of Pistacia lentiscus L. growing wild in five localities of Sardinia (Italy) was extracted by steam-distillation (SD) and analyzed by gas chromatography (GC), FID, and GC-ion trap mass spectrometry (ITMS). Samples of P. lentiscus L. were harvested between April and October to study the seasonal chemical variability of the EO. A total of 45 compounds accounting for 97.5-98.4% of the total EO were identified, and the major compounds were alpha-pinene (14.8-22.6%), beta-myrcene (1-19.4%), p-cymene (1.6-16.2%), and terpinen-4-ol (14.2-28.3%). The yields of EO (v/dry w) ranged between 0.09 and 0.32%. Similar content of the major compounds was found in samples from different origins and seasonal variability was also observed. The EOs were tested for their antifungal activity against Aspergillus flavus, Rhizoctonia solani, Penicillium commune, Fusarium oxysporum. Two samples were weakly effective against Aspergillus flavus. Furthermore, terpinenol and alpha-terpineol, two of the major components of EO of Pistacia lentiscus L., totally inhibited the mycelian growth of A. flavus. Quite good antioxidant activity of the EO was also found.     

Changes in phenolic composition and antioxidant activity of virgin olive oil during frying

The concentration of hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA) in virgin olive oil decreased rapidly when the oil was repeatedly used for preparing french fries in deep-fat frying operations. At the end of the first frying process (10 min at 180 degrees C), the concentration of the dihydroxyphenol components was reduced to 50-60% of the original value, and after six frying operations only about 10% of the initial components remained. However, tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA) in the oil were much more stable during 12 frying operations. The reduction in their original concentration was much smaller than that for hydroxytyrosol and its derivatives and showed a roughly linear relationship with the number of frying operations. The antioxidant activity of the phenolic extract measured using the DPPH test rapidly diminished during the first six frying processes, from a total antioxidant activity higher than 740 micromol of Trolox/kg down to less than 250 micromol/kg. On the other hand, the concentration of polar compounds, oxidized triacylglycerol monomers (oxTGs), dimeric TGs, and polymerized TGs rapidly increased from the sixth frying operation onward, when the antioxidant activity of the phenolic extract was very low, and as a consequence the oil was much more susceptible to oxidation. The loss of antioxidant activity in the phenolic fraction due to deep-fat frying was confirmed by the storage oil and oil-in-water emulsions containing added extracts from olive oil used for 12 frying operations.     

Contribution of the phenolic fraction to the antioxidant activity and oxidative stability of olive oil

Antioxidant activity of the phenolic fraction of extra virgin olive oil (EVOO) was measured by means of a chemical and an electrochemical method. Both methods were tested in predicting the oxidative spoilage and stability to oxidation of 22 EVOO samples and resulted correlated with peroxide values and oxidative stability measured by Rancimat. The main phenolic compounds of EVOOs were detected by HRGC. To study the contribution of single polyphenols (PPs) to antioxidant activity of phenolic fraction and oxidative stability of EVOOs, multivariate statistical analyses were applied on HRGC data. An isomer of oleuropein aglycon was shown to affect significantly antioxidant activity of phenolic fraction but not oil stability to oxidation. No individual compounds was identified as the main cause of the overall antioxidant activity, and the total polyphenol determination by the Folin reagent was better correlated to antioxidant activity and oxidative stability than each tested PP or PPs groups such as o-diphenols.     

Role of hydrocolloids in the creaming of oil in water emulsions

The influence of guar gum and xanthan gum on the creaming of 10% oil in water emulsions has been investigated. The presence of very low concentrations of the polysaccharides (typically < approximately 0.075%) was found to induce depletion flocculation of the emulsion droplets and increased the rate of creaming. However, at higher polysaccharide concentrations (typically > approximately 0.1%) the creaming rate was reduced due to the increased viscosity of the aqueous phase. For most systems a delay period was noted before creaming started, which was found to be dependent on the zero shear viscosity of the continuous phase and independent of polysaccharide type. The delay period increased significantly at zero shear viscosities approaching 1 Pa s. A mathematical model has been used to fit the creaming rate profiles and a simple exponential relationship obtained between delay time and polysaccharide concentration.     

Evaluation of antioxidant activity of vetiver (Vetiveria zizanioides L.) oil and identification of its antioxidant constituents

Antioxidant capacities of vetiver (Vetiveria zizanioides) oil were evaluated by two different in vitro assays: the DPPH* free radical scavenging assay and the Fe2+-metal chelating assay. Results showed that the vetiver oil (VO) possessed a strong free radical scavenging activity when compared to standard antioxidants such as butylated hydroxytoluene (BHT) and alpha-tocopherol. However, its metal chelating capacity was relatively weak. VO (10 microL/mL) dissolved in methanol exhibited approximately 93% free radical scavenging activity in the DPPH* assay and approximately 34% Fe2+ chelating activity in the metal chelating assay. By contrast, 10 mM BHT and 0.1 mM alpha-tocopherol exhibited 93 and 89% free radical scavenging activities in the DPPH* assay, respectively, and 1 mM EDTA exhibited approximately 97% activity in the metal chelating assay. Among the complex constituents in the crude VO, beta-vetivenene, beta-vetivone, and alpha-vetivone, which had shown strong antioxidant activities, were isolated and identified using various chromatographic techniques including silica gel open column chromatography, silica HPLC, and GC-MS. These results show that VO and some of its inherent components can be potential alternative natural antioxidants.     

Impact of extra virgin olive oil and ethylenediaminetetraacetic acid (EDTA) on the oxidative stability of fish oil emulsions and spray-dried microcapsules stabilized by sugar beet pectin

The influence of EDTA on lipid oxidation in sugar beet pectin-stabilized oil-in-water emulsions (pH 6, 15% oil, wet basis), prepared from fish oil (FO) and fish oil-extra virgin olive oil (FO-EVOO) (1:1 w/w), as well as the spray-dried microcapsules (50% oil, dry basis) prepared from these emulsions, was investigated. Under accelerated conditions (80 °C, 5 bar oxygen pressure) the oxidative stability was significantly (P < 0.05) higher for FO and FO-EVOO formulated with EDTA, in comparison to corresponding emulsions and spray-dried microcapsules formulated without EDTA. The EDTA effect was greater in emulsions than in spray-dried microcapsules, with the greatest protective effect obtained in FO-EVOO emulsions. EDTA enhanced the oxidative stability of the spray-dried microcapsules during ambient storage (~25 °C, a(w) = 0.5), as demonstrated by their lower concentration of headspace volatile oxidation products, propanal and hexanal. These results show that the addition of EDTA is an effective strategy to maximize the oxidative stability of both FO emulsions and spray-dried microcapsules in which sugar beet pectin is used as the encapsulant material.     

Direct analysis of total antioxidant activity of olive oil and studies on the influence of heating

Aim of this study was to evaluate the total antioxidant activity (TAA) of extra virgin olive oil (EVOO) and the effect of heating on the alpha-tocopherol content and TAA in relation to the presence of polyphenols, heating time, and temperature. Experiments included the measurement by ABTS decolorization assay of antioxidant capacity of alpha-tocopherol and 14 simple phenolic compounds present in EVOO, either dissolved in ethanol or added to refined olive oil, and the evaluation of TAA, total phenols, and alpha-tocopherol of six commercial EVOO and three olive oils. Finally, four experimental oils were prepared from refined olive oil containing a fixed amount (300 ppm) of alpha-tocopherol and increasing amounts of polyphenols (25, 125, 225, and 326 ppm) extracted from EVOO. The thermal stability of experimental oils under domestic heating conditions (heating time from 30 to 120 min, heating temperature from 160 to 190 degrees C) was studied by evaluating the loss of alpha-tocopherol and TAA according to a Latin square design. Results indicate that TAA of commercial oils is mainly due to their phenol and alpha-tocopherol content. Heating experiments suggest that polyphenols from EVOO are effective stabilizers of alpha-tocopherol during olive oil heating, thus contributing to the nutritional value of cooked foods.     

Homogenization conditions affect the oxidative stability of fish oil enriched milk emulsions: oxidation linked to changes in protein composition at the oil-water interface

Fish oil was incorporated into milk under different homogenization temperatures (50 and 72 degrees C) and pressures (5, 15, and 22.5 MPa). Subsequently, the oxidative stability of the milk and changes in the protein composition of the milk fat globule membrane (MFGM) were examined. Results showed that high pressure and high temperature (72 degrees C and 22.5 MPa) resulted in less lipid oxidation, whereas low pressure and low temperature (50 degrees C and 5 MPa) resulted in faster lipid oxidation. Analysis of protein oxidation indicated that especially casein was prone to oxidation. The level of free thiol groups was increased by high temperature (72 degrees C) and with increasing pressure. Furthermore, SDS-PAGE and confocal laser scanning microscopy (CLSM) indicated that high temperature resulted in an increase in beta-lactoglobulin adsorbed at the oil-water interface. This was even more pronounced with higher pressure. Less casein seemed to be present at the oil-water interface with increasing pressure. Overall, the results indicated that a combination of more beta-lactoglobulin and less casein at the oil-water interface gave the most stable emulsions with respect to lipid oxidation.