Ferric Ions Reduce the Antioxidant Activity of the Phenolic Fraction of Virgin Olive Oil

ABSTRACT: The antioxidant activity of relatively polar extracts from virgin olive oil was investigated in sunflower oil stripped of tocopherols and in tocopherol-stripped sunflower oil-in-water emulsions. The extracts were found to be effective as antioxidants in both media in the absence of added metal ions. However, the antioxidant activity was markedly reduced by the presence of added ferric chloride. In sunflower oil-in-water emulsions (pH 5.4) containing ferric chloride, all concentrations of olive oil polyphenols exhibited pro-oxidant effects. It appears that the reducing action of olive oil polyphenols accelerates oxidation of oil and especially of emulsions containing Fe (III) by reducing ferric ions to ferrous ions, which are effective pro-oxidants during storage.     

Comparative Effect of Bunium persicum and Rosmarinus officinalis Essential Oils and Their Synergy with Citric Acid on the Oxidation of Virgin Olive Oil

The objective of this study was to evaluate the effect of Bunium persicum and Rosmarinus officinalis essential oils on the oxidation of virgin olive oil during accelerated storage. The synergistic effect between citric acid and antioxidants of natural and synthetic types was investigated. The B. persicum and R. officinalis essential oils significantly retarded the oxidation of virgin olive oil. Their antioxidant capacity was comparable to butylatedhydroxytoluene and better than β-carotene. Here we show that when natural and synthetic antioxidants are combined with citric acid, they produce an extra antioxidant effect, hence the manifestation of synergy. Generally, the essential oils of B. persicum and R. officinalis can be applied to increase the oxidative stability of virgin olive oil.     

Role of emulsifier layer,antioxidants and radical initiators in the oxidation of olive oil-in-water emulsions

Lipid oxidation in oil-in-water (O/W) emulsions is largely affected by the properties of the interfacial layer surrounding the oil droplets. In this work, the effect of the emulsifier layer structure, presence of both hydrophilic and lipophilic antioxidants and radical initiators on the development of lipid oxidation in olive oil-in-water emulsions was investigated. The olive oil-in-water emulsion is a suitable model of low fat food emulsions. The rationale of the work was to study the role of the interfacial layer when both the antioxidants and the radical initiators came from the two different emulsion compartments. Emulsions were prepared by using food grade emulsifiers of the Tween series (polyoxyethylene sorbitan esters) in the water phase and Span 80 (sorbitan monoleate) in the oil phase. The properties of the interfacial layer were changed by using Tween 20, Tween 60, Tween 80, which have different hydrophobic tails. These systems were oxidized by means of both hydrophilic (AAPH (2,2′-azobis,2-methyl-propanimidamide dihydrochloride), AIPH (2,2′-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride) and lipophilic (AMVN (2,2′-azobis(2,4-dimethylvaleronitrile)) radical initiators at 40 °C. A continuous fluorescent method based on the front face technique allowed us to follow directly the development of oxidation in the whole emulsion. The combination Tween 80/Span 80 produced an interfacial layer more resistant to radical attack. Moreover, a polar paradox was verified also for radical initiators, while the results suggest that the best way to protect emulsions is to use a combination of antioxidants in both phases, to promote a synergy and the regeneration of antioxidants mediated by the interfacial layer.     

Radical scavenging-linked antioxidant activity of ethanolic extracts of diverse types of extra virgin olive oils

The present study evaluated the radical scavenging-linked antioxidant activity of hexane/80% ethanol extracts from several types of extra virgin olive oils (EVOOs) derived from varieties arbequina, hojiblanca, picual, their blends, and pure olive oil (POO). The antioxidant potential of the olive oil extracts was assessed by radical scavenging assays using DPPH (2, 2-diphenyl-1-picrylhydrazyl), ABTS (2, 2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid), and hydroxyl radical, as well as hydrogen peroxide and superoxide anion inhibitory activities. Electron donating ability (EDA) using DPPH assay of 80% ethanol extracts from EVOOs, except arbequina oil, was significantly higher than POO. EDA was markedly higher in blended and picual EVOOs than the extracts from arbequina and hojiblanca EVOOs (P < 0.05). Similarly, ABTS radical scavenging activity of the extracts from the EVOOs was in order of picual EVOO > blended EVOO > hojiblanca EVOO >or= POO >or= arbequina EVOO. Further, the superoxide anion scavenging activity of blended, picual, and arbequina EVOOs was significantly higher than that of hojiblanca EVOO and POO, which were barely detectable. Hydroxyl radical scavenging activity of arbequina and hojiblanca was higher than that of blended, picual EVOOs, and POO. In addition, hydrogen peroxide scavenging activity of the extracts from blended, arbequina, hojiblanca, picual EVOOs, and POO was 63.1 +/- 3.1%, 44.4 +/- 10.2%, 52.0 +/- 2.7%, 71.8 +/- 2.5%, and 35.7 +/- 10.0%, respectively. Our results indicate that ethanol extracts of several EVOOs contained higher radical scavenging and antioxidant activity than the POO. This antioxidant potential is partly due to the phenolic compounds present in different olive oil grade and is influenced by cultivar type.     

The antioxidant activity and stability of the phenolic fraction of green olives and extra virgin olive oil

The antioxidant activity of phenolic extracts from olives and olive oil has been assessed by scavenging of 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radicals and by studying the effects on the stability of stripped olive oil in the absence and presence of ferric chloride. The olive extracts contained a much higher concentration (1940–5800 mg kg^?1) of phenolic components than the olive oil extract (180 mg kg^?1). Some olive extracts were more effective than the olive oil extract in scavenging DPPH radicals, but the three varieties of olives examined showed relatively large differences in both polyphenol concentration and antioxidant activity of extracts. α‐Tocopherol and extracts from both olives and olive oil were effective antioxidants in stripped olive oil at 60 °C. Ferric chloride reduced the stability of stripped olive oil, but the olive extract studied was significantly more effective as an antioxidant in the presence of the metal salt than the olive oil extract or α‐tocopherol. Ferric ions catalysed the oxidation of caffeic acid, oleuropein and phenolic components of the olive and olive oil extracts in aqueous solution (pH 5.4). The olive extract oxidised more rapidly than the olive oil extract in aqueous solution. © 2001 Society of Chemical Industry     

Lipid oxidation in base algae oil and water-in-algae oil emulsion: Impact of natural antioxidants and emulsifiers

The impact of natural hydrophilic antioxidants, metal chelators, and hydrophilic antioxidant/metal chelator mixture on the oxidative stability of base algae oil and water-in-algae oil emulsion was investigated. The results showed that green tea extract and ascorbic acid had greatest protective effect against algae oil oxidation and generated four day lag phase, whereas rosmarinic acid, grape seed extract, grape seed extract polymer, deferoxamine (DFO), and ethylenediaminetetraacetic acid (EDTA) had no significant protective effect. Besides, there was no synergistic effect observed between natural antioxidants and ascorbic acid. The emulsifiers are critical to the physicochemical stability of water-in-algae oil emulsions. Polyglycerol polyricinoleate (PGPR) promoted the oxidation of emulsion. Conversely, the protective effect on algae oil oxidation was appreciated when defatted soybean lecithin (PC 75) or defatted lyso-lecithin (Lyso-PC) was added. The role of hydrophilic antioxidants in emulsion was similar to that in algae oil except EDTA which demonstrated strong antioxidative effect in emulsion. The results could provide information to build up stable food products containing polyunsaturated fatty acids (PUFA).     

Lipid oxidation-related characteristics of gim bugak (Korean fried cuisine with <Emphasis Type="Italic">Porphyra</Emphasis>) affected by frying oil

The effect of frying oil on the lipid oxidation, antioxidants, and in vitro antioxidant activity of gim bugak was studied. Bugak was prepared by pan-frying at 180 °C in unroasted sesame, soybean, extra virgin olive, or palm oil. The degree of lipid oxidation based on conjugated dienoic acid and p-anisidine values was higher in the bugak fried in soybean or sesame oil with high contents of polyunsaturated fatty acids and tocopherols. However, the oil oxidation was lower in olive and palm oils, which showed higher degradation of tocopherols and polyphenols than in sesame or soybean oil during frying. Although the bugak fried in palm oil contained less antioxidants than that fried in soybean or sesame oil, the in vitro antioxidant activity was not different (p > 0.05). Results suggest that palm oil can replace unroasted sesame oil for the preparation of gim bugak with improved lipid oxidative stability and health functionality.     

秦岭山脉野生蒲公英提取物的抗氧化活性及其对胡麻油氧化稳定性的影响

以秦岭山脉野生蒲公英全草为原料,采用超声波纤维素酶同步法提取总活性成分。对蒲公英提取物的DPPH自由基清除能力、超氧阴离子自由基清除能力、羟自由基清除能力和总还原能力进行了测定,并与人工合成VC进行了比较,同时采用加速氧化的方法评价蒲公英提取物对胡麻油氧化稳定性的影响,并与BHT、迷迭香提取物进行比较。结果表明:蒲公英提取物比人工合成VC有更高的抗氧化活性; 3种抗氧化剂抗氧化能力大小为迷迭香提取物(700 mg/kg)蒲公英提取物(700 mg/kg) BHT(200 mg/kg),并且蒲公英提取物添加量与胡麻油的氧化稳定性呈正相关。因此,秦岭山脉野生蒲公英全草总活性成分提取物可作为天然抗氧化剂用于延缓食用油氧化。     

二相离心加工工艺对初榨橄榄油理化指标和氧化稳定性的影响

橄榄油的品质不但与品种有关,还受加工工艺的影响。以‘豆果’‘鄂植8号’‘克罗莱卡’3个品种油橄榄果为原料,研究了二相离心加工工艺对初榨橄榄油脂肪酸组成、色度、酸值、过氧化值、紫外吸光度、微量伴随物、抗氧化能力和氧化稳定性的影响,并与三相离心加工工艺进行对比。结果表明:在融合温度30℃、融合时间45 min条件下,初榨橄榄油的品质较好;‘克罗莱卡’初榨橄榄油中多酚含量最高,氧化稳定性最好,与三相离心加工工艺相比,二相离心加工工艺生产的初榨橄榄油多酚含量显著提高。     

On the extraction and antioxidant activity of phenolic compounds from winery wastes

Winery waste (from red winemaking, variety Agiorgitiko) was extracted under various conditions using different solvents. The minimum time required for ensuring maximum extraction of phenols was 180 min at a solvent to sample ratio 9:1 v/w and at pH 1.5. The antioxidant activity of solvent extracts was investigated by DPPH radical scavenging method, by determination of peroxide value on virgin olive oil and by the Rancimat method on sunflower oil. Ethanol extract exhibited the highest antioxidant activity compared to the other solvent extracts, to synthetic food antioxidants BHT, ascorbyl palmitate and to the natural food antioxidant, vitamin E. No correlation was found between antioxidant activity and total phenol content. HPLC analysis of the extracts showed that gallic acid, catechin and epicatechin were the major phenolic compounds in winery waste. Hydroxytyrosol, tyrosol, cyanidin glycosides and various phenolic acids such as caffeic, syringic, vanillic, p-coumaric and o-coumaric acids were also identified.     

Inhibition of fish oil oxidation and the radical scavenging activity of New Zealand seaweed extracts

This study describes the potential use of New Zealand seaweed extracts as antioxidants in fish oils. The extracts from two brown seaweeds (Ecklonia radiata, Macrocystis pyrifera) and two red species (Champia sp. and Porphyra sp.), were added to hoki (Macruronus novaezelandiae) oil and assessed by production of oxidation products in an elevated temperature (60 °C) storage trial. Antioxidant assays ORAC and DPPH were conducted to elucidate the radical scavenging activity of the seaweed extracts. The results showed that all the lipid-soluble seaweed extracts had some antioxidative capacity, with brown algae generally outperforming red algae species. Extracts from E. radiata performed best with significantly lower primary, secondary and total oxidation products, and higher DPPH radical scavenging ability than the commercial antioxidant, BHT. This study demonstrated the potential of brown algae seaweed extracts, in particular E. radiata, for use as antioxidants in fish oil products.     

Antioxidant and antilisterial activity of olive oil,cocoa and rosemary extract polyphenols

Antibacterial and antioxidant activity of polyphenols from olive oil, cocoa, and rosemary extract was tested. Antimicrobial activity against Listeria strains was assessed using broth dilution and time-kill curve methods. The 2,2-diphenyl-2-picrylhydracyl hydrate (DPPH) radical scavenging method, Folin–Ciocalteu method, and high performance liquid chromatography (HPLC) were used for phenolics identification and determination of antioxidants level. Antibacterial and antioxidant activity of main pure phenolic compounds, such as hydroxytyrosol in olive oil, epicatechin in cocoa and carnosic acid in rosemary was each compared with their extracts.     

Phenolic profile and antioxidant activities of olive mill wastewater

Olive trees play an important role in the Moroccan agro-economy, providing both employment and export revenue. However, the olive oil industry generates large amounts of wastes and wastewaters. The disposal of these polluting by-products is a significant environmental problem that needs an adequate solution. On one hand, the phytotoxic and antimicrobial effects of olive mill wastewaters are mainly due to their phenolic content. The hydrophilic character of the polyphenols results in the major proportion of natural phenols being separated into the water phase during the olive processing. On other hand, the health benefits arising from a diet containing olive oil have been attributed to its richness in phenolic compounds that act as natural antioxidants and are thought to contribute to the prevention of heart diseases and cancers. Olive mill wastewater (OMW) samples have been analysed in terms of their phenolic constituents and antioxidant activities. The total phenolic content, flavonoids, flavanols, and proanthocyanidins were determined. The antioxidant and radical scavenging activity of phenolic extracts and microfiltred samples was evaluated using different tests (iron(II) chelating activity, total antioxidant capacity, DPPH assays and lipid peroxidation test). The obtained results reveal the considerable antioxidant capacity of the OMW, that can be considered as an inexpensive potential source of high added value powerful natural antioxidants comparable to some synthetic antioxidants commonly used in the food industry.     

Changes in antioxidant concentration of virgin olive oil during thermal oxidation

The concentration of α-tocopherol, hydroxytyrosol derivatives and tyrosol derivatives was measured in samples of virgin olive oil during thermal oxidation at 60 and 100 °C. Hydroxytyrosol derivatives are the first antioxidants that are lost during thermal oxidation (until a peroxide value of 20–30 meq/kg). Tyrosol derivatives seem to be the most stable compounds, while α-tocopherol has an intermediate rate of loss at low peroxide values and is destroyed at peroxide values from 20 to 50 meq/kg. This means that hydroxytyrosol derivatives are the first compounds to be oxidized, providing therefore oxidative stability to the oil. α-Tocopherol seems to be oxidized after a significant decrease on hydroxytyrosol derivatives content. Tyrosol derivatives are the antioxidants that decrease with the lowest rate, providing the oil with the less antioxidant activity.     

Oxidation Processes in Sicilian Olive Oils Investigated by a Combination of Optical and EPR Spectroscopy

Abstract: Extra virgin olive oil (EVOO) is recognized as one of the healthiest foods for its high content of antioxidants, which forestall and slow down radical formation. Free radical‐initiated oxidation is considered one of the main causes of rancidity in fats and oils. As a consequence, reliable protocols for the investigation of oil oxidation based on selective, noninvasive, and fast methods are highly desirable. Here we report an experimental approach based on UV‐Vis absorbance, steady‐state fluorescence, and electron paramagnetic resonance (EPR) spectroscopy for studying oxidation processes induced by temperature for a period up to 35 d on Sicilian EVOO samples. We followed the decrease in β‐carotene content during incubation time and observed changes in polyphenols and tocopherols during the oxidation processes, focusing on the time scale of those changes. Using EPR spectroscopy, the free radical formation in different oil samples is reported, providing a fingerprint for both the antioxidant content and temporal features of the oxidation process at its early stage. Practical Application: We monitor β‐carotene and chlorophyll in an auto‐oxidation process. A protocol based on spectroscopic measurements is presented and can be used for the quality control process of commercial olive oil.     

Radical Scavenging,Total Antioxidant Capacity,and Antiproliferative Activity of Phenolic Extracts from Extra Virgin Olive Oil by Cultivar ‘Frantoio’

The beneficial health effects of extra virgin olive oil are due to both its high content of monounsaturated fatty acids and its high content of phenolic compounds, which have recently attracted research interest. In this context, the aim of this work was to examine the in vitro antioxidant and antiproliferative activities of the phenolic extract obtained from extra virgin olive oil from O. europea cultivar ‘Frantoio’ (samples 1–4), one of the main varieties cultivated in Italy. The total phenolic content was determined by Folin–Ciocalteu method and instead the phenolic profile was obtained by HPLC coupled to a diode array detector and mass spectrometry. Extra virgin olive oil extracts exhibited high antioxidant activity through different mechanisms of action and these activities are related to the phenolic content. Sample 3 demonstrated the strongest free radical scavenging activity with IC₅₀ value of 56.5 μg/mL. The reducing ability measured with FRAP assay revealed that samples ranged from 91.3 to 156 μM Fe(II)/g. The same interesting trend was observed with Trolox equivalent antioxidant capacity value. Moreover, the virgin olive oils showed a good oxidative stability ranging between 19 to 32 h. Antiproliferative activity evaluated by SRB assay revealed that phenolic extracts from the cultivar ‘Frantoio’ showed a strong antiproliferative activity against CORL-23 cell line with an IC₅₀ value of 14.5 and 55.9 μg/mL for samples 3 and 1, respectively, and these results are comparable to the positive control vinblastine. Overall, these results showed that extra virgin olive oils from the cultivar ‘Frantoio’, may represent an interesting source of phenolic compounds as functional components that could be consumed in diets and/or used for the elaboration of functional food and pharmaceutical industries.     

Processing and storage effects on the oxidative stability of hemp (Cannabis sativa L.) oil‐in‐water emulsions

Hempseed oil was used to form oil‐in‐water emulsions, and the effect of heating, storage and light on the oxidative stability of the dispersed phase was investigated. Lipid oxidation rate increased following thermal processing and light exposure, whereas oxidation markers remained relatively unaffected during emulsions storage at 4 °C for 10 days. Induction times of the emulsions were reduced up to 26% and the concentration of thiobarbituric acid reactive substances increased up to 4.5‐fold, depending on the processing conditions. Selected berries as potential sources of natural antioxidants were screened for polyphenol and anthocyanin content in order to investigate their ability to retard lipid oxidation in comparison with a commercially available synthetic counterpart. Raspberry powder extract significantly improved the oxidative stability of hemp‐based emulsion compared with the control and was even more effective compared to a synthetic antioxidant when samples were subjected to heat treatment.     

Effect of storage on refined and husk olive oils composition: Stabilization by addition of natural antioxidants from Chemlali olive leaves

Two samples of refined olive and husk oils have been analysed in order to evaluate the influence of storage time on their quality. The following parameters were determined: peroxide values, absorption coefficients K270 and K232, Rancimat induction time, sterols and fatty acid contents. Six months storage at 50 °C in the dark revealed a loss in oil stability. This finding was reflected by the greater increase in peroxide value and a decrease of Rancimat induction time and sterol content. The enrichment of refined olive and husk oils with olive leaves and its hydrolysate extract resulted in an appreciable resistance to oxidative deterioration due to its phenolic antioxidants content. Oleuropein and hydroxytyrosol were the major compounds in Chemlali olive leaves extract and hydrolysate solution, respectively. The antiradical activity of leaves extract as well as its hydrolysate solution was evaluated and compared to that of the BHT. The antioxidant activity of the enriched refined olive and husk oils with leaves and hydrolysate extracts at 400 ppm showed that the latter had the highest protective effect against oil oxidation. Oils with added hydrolysate extract had the lower peroxide value and the higher stability measured with a Rancimat method. After six months of storage the induction time increased from 23.3 to 83.5 h for refined olive oil and from 16.6 to 49 h for husk oil. Furthermore, during oil storage, there was no significant variation in fatty acid composition. However, the total sterol concentration of the oils treated with hydrolysate extract increased. The results suggested that hydrolysate and leaves extracts are excellent antioxidants and can serve as substitutes for synthetic antioxidants.     

Chemical stability of extra-virgin olive oil added with oregano essential oil

Extra virgin olive oil is highly consumed and well known for its nutritional and health benefits. However, it is fatty food highly susceptible to lipid oxidation. The objective of this study was to evaluate the preserving effect of oregano (Origanum vulgare L. spp vulgare called "oregano compacto") essential oil on physical and chemical properties in extra virgin olive oil during storage. Oregano essential oil composition was analyzed by GC-MS. This essential oil was added into extra virgin olive oil at 0.05%. The samples were stored in 3 different conditions: darkness, light exposure, and temperature (60 °C). Chemical indicators of lipid oxidation (peroxide value, p-anisidine value, conjugated dienes, free fatty acidity, and carotenoid and chlorophyll contents) were measured. High content in carvomenthol (22.52%), terpinolene (19.77%), thymol (13.51%), and γ-terpinene (10.30%) were detected in oregano essential oil. Olive oil samples without oregano essential oil stored at 60 °C and exposure at artificial light had the highest peroxide values during storage. Higher p-anisidine and K232 values after day 7 of storage were detected in temperature, darkness, and light exposure treatments. Light treatment was the main factor that degraded chlorophyll causing loss of color. The highest chlorophyll content (3.87 mg/kg) was observed in olive oil with essential oil at the end of storage. In general, olive oil samples added with oregano essential oil had lower peroxide, conjugated dienes, and p-anisidine values and higher chlorophyll and carotenoid contents during storage. Oregano essential oil retards lipid oxidation process in olive oil prolonging its shelf life. PRACTICAL APPLICATION: Oregano essential oil was and is used with the purpose of flavoring and aromatizing food. This essential oil due to its composition has shown antioxidant activity. Synthetic antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) are thought to be promoters of carcinogenesis. Extra virgin olive oil is widely consumed because of its nutritional benefits and sensory properties which are very important to be preserved in the product. In this study, the oregano essential oil showed remarkable antioxidant activity in olive oil. Therefore, this essential oil could be considered for the industry as natural antioxidant not only to be used in olive oil but also in other fatty food products to substitute synthetic ones.     

A comparison between olive oil and extra-virgin olive oil used as covering liquids in canned dried tomatoes: hydrolytic and oxidative degradation during storage

The hydrolytic and oxidative degradation of olive oil and extra‐virgin olive oil, used as covering liquids in canned dried tomatoes, was studied during storage by means of conventional (acidity, peroxide value, p‐anisidine value) and non conventional (polar compounds) analyses. The effects of the addition of spices were also considered. The hydrolysis and oxidation of olive oil increased faster and was higher than that of extra‐virgin olive oil in terms of absolute values but some other indices, such as percentage of oligopolymers and percentage of oxidized triglycerides, increased faster in extra‐virgin olive oil than in olive oil. The antioxidant effect given by a higher concentration of polyphenols in the extra‐virgin olive oil was shown by a reduced amount of secondary oxidation. However, olive oil and extra‐virgin olive oils showed similar behaviour in terms of peroxide formation.