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.     

Lactoferrin in infant formulas: effect on oxidation

Lactoferrin is an iron transport protein present in human milk at an average concentration of 1.4 mg/mL. Commercially modified infant formulas based on cow's milk contain much lower amounts of lactoferrin (0.1 mg/mL lactoferrin) and soy based formulas have none. In addition to its role in iron transport, lactoferrin has bacteriostatic and bactericidal activities. Infant formulas are supplemented with relatively large amounts of iron (up to 12 mg/L). The effect of various concentrations of added lactoferrin and supplemental iron on lipid oxidation was tested in two different infant formulas. The extent of oxidation in the formulas as a function of time was determined by formation of hydroperoxides, production of hexanal, and fluorescence. On the basis of all three of these determinations, lactoferrin acted as an antioxidant in the absence and presence of different concentrations of supplemented iron. Lactoferrin inhibited oxidation in a concentration-dependent manner even at concentrations beyond its capacity to bind iron at its two high affinity binding sites. Lactoferrin can be used, therefore, as a dual purpose additive in infant formulas and similar food products for its antioxidant and its antimicrobial properties.     

Lipid oxidation in emulsions as affected by charge status of antioxidants and emulsion droplets

The influence of charge status of both lipid emulsion droplets and phenolic antioxidants on lipid oxidation rates was evaluated using anionic sodium dodecyl sulfate (SDS) and nonionic polyoxyethylene 10 lauryl ether (Brij)-stabilized emulsion droplets and the structurally similar phenolic antioxidants gallamide, methyl gallate, and gallic acid. In nonionic, Brij-stabilized salmon oil emulsions at pH 7.0, gallyol derivatives (5 and 500 microM) inhibited lipid oxidation with methyl gallate > gallamide > gallic acid. In the Brij-stabilized salmon oil emulsions at pH 3.0, low concentrations of the galloyl derivatives were prooxidative or ineffective while high concentrations were antioxidative. In SDS-stabilized salmon oil emulsions, oxidation rates were faster and the galloyl derivatives were less effective compared to the Brij-stabilized emulsions. Differences in antioxidant activity were related to differences in the ability of the galloyl derivatives to partition into emulsion droplets and to increase the prooxidant activity of iron at low pH.     

Ability of surfactant micelles to alter the physical location and reactivity of iron in oil-in-water emulsion

The purpose of this research was to determine how surfactant micelles influence iron partitioning and iron-promoted lipid oxidation in oil-in-water emulsions. Lipids containing ferric ions were used to produce oil-in-water emulsions, and continuous-phase iron concentrations in emulsions were measured as a function of varying continuous-phase polyoxyethylene 10-lauryl ether (Brij) concentrations. Continuous-phase iron concentrations increased with increasing surfactant micelle concentrations (0.1-2.0%) and storage time (1-7 days). At pH 3.0, the concentration of continuous-phase iron was higher than at pH 7.0. Similar trends in iron solubilization by Brij micelles were observed when either hexadecane or corn oil was used as the lipid phase. Lipid oxidation rates, as determined by the formation of lipid hydroperoxides and headspace hexanal, in corn oil-in-water emulsions containing iron decreased with increasing surfactant concentrations (0.5-2.0%). These results indicate that surfactant micelles could alter the physical location and prooxidant activity of iron in oil-in-water emulsions.     

Effect of heating oxymyoglobin and metmyoglobin on the oxidation of muscle microsomes

Myoglobin (Mb) and its iron have been proposed to be major prooxidants in cooked meats. To understand the mechanisms and differentiate between the prooxidant and antioxidant potential of oxymyoglobin (OxyMb) and metmyoglobin (MetMb), their prooxidant activity, iron content, solubility, free radical scavenging activity, and iron binding capacity were determined as a function of thermal processing. The ability of native and heat denatured OxyMb and MetMb to promote the oxidation of muscle microsomes was different. MetMb promoted lipid oxidation in both its native and denatured states. Conversely, OxyMb became antioxidative when the protein was heated to temperatures >or=75 degrees C. The increased antioxidant activity of heat denatured OxyMb was likely due to a decrease in its prooxidative activity due to its loss of solubility. These data show that the impact on oxidative reactions of Mb is the result of the balance between its antioxidant and prooxidant activities.     

Evaluation of antioxidant and prooxidant activities of bamboo Phyllostachys nigra var. Henonis leaf extract in vitro

Solvent-extracted bamboo leaf extract (BLE) containing chlorogenic acid, caffeic acid, and luteolin 7-glucoside was evaluated in vitro for free radical scavenging and antioxidant activities using a battery of test methods. BLE exhibited a concentration-dependent scavenging activity of DPPH radical. BLE prolonged the lag phase and suppressed the rate of propagation of liposome peroxidation initiated by peroxyl radical induced by 2,2'-azobis(2-amidinopropane dihydrochloride (AAPH) at 37 degrees C. BLE also prevented human low-density lipoprotein oxidation, mediated by Cu(2+), which was monitored by the lower formation of conjugated diene and fluorescence and a reduced negative charge of apo-B protein. Finally, BLE protected supercoiled DNA strand against scission induced by AAPH-mediated peroxyl radical. Prooxidant activity of BLE was seen in a Cu(2+)-induced peroxidation of structured phosphatidylcholine liposome, indicating catalytic peroxidation due to a relatively high reducing power of BLE. It was concluded that the BLE has both antioxidant activity and prooxidant activity; the antioxidant activity was attributed to free radical scavenging activity, and the prooxidant activity, albeit minor, resulted from the reducing power of plant phenolics in the presence of transitional metal ions.     

Antioxidant,prooxidant, and cytotoxic activities of solvent-fractionated dandelion (Taraxacum officinale) flower extracts in vitro

This study was conducted to investigate the chemical antioxidant and bioactive properties of the water (WF) and ethyl acetate fractions (EAF) derived from dandelion (Taraxacum officinale) flower extract (DFE). HPLC analysis showed the presence of both luteolin and luteolin 7-glucoside in the DFE, which contributed to noted in vitro antioxidant and Caco-2 cell cytotoxic activities. Both WF and EAF of DFE exhibited free radical scavenging activities in a stable 2,2-diphenyl-1-picrylhydrazyl radical model and reduced the breakage of supercoiled DNA strand induced by both non-site-specific and site-specific hydroxyl radical. Oxidation of structured phosphatidylcholine liposome induced by peroxyl radical was reduced in the presence of both EAF and WF. EAF had greater (p < 0.05) affinity to scavenge peroxyl radical than WF, as measured by the formation of conjugated diene. At low concentration, prooxidant activity of both fractions was observed in Cu(2+)-induced structured liposome and hLDL oxidation models, thus indicating that the reducing power of the DFE had resulted in generation of reactive cuprous ion. However, at high concentrations the EAF did not promote oxidation in the presence of Cu(2+), suggesting that the free radical scavenging activity of this fraction was sufficient to minimize the potential oxidative mechanism attributed to the metal ion reducing activity associated with prooxidant activity.     

Lipid peroxidation by "free" iron ions and myoglobin as affected by dietary antioxidants in simulated gastric fluids

Grilled red turkey muscle (Doner Kabab) is a real "fast food" containing approximately 200 microM hydroperoxides, homogenized in simulated gastric fluid and oxidized more rapidly at pH 3.0 than at pH 5.0, after 180 min, producing 1200 and 600 microM hydroperoxides, respectively. The effects of "free" iron ions and metmyoglobin, two potential catalyzers of lipid peroxidation in muscle foods, were evaluated for linoleic acid peroxidation at pH 3.0 of simulated gastric fluid. The prooxidant effects of free iron ions on linoleic acid peroxidation in simulated gastric fluid was evaluated in the presence of ascorbic acid. At low concentrations of ascorbic acid, the effects were prooxidative, which was reversed at high concentrations. In the presence of metmyoglobin, ascorbic acid with or without free iron enhanced the antioxidative effect. Lipid peroxidation by an iron-ascorbic acid system was inhibited totally by 250-500 microM catechin at pH 3.0. The catechin antioxidant effect was determined also in the iron-ascorbic acid system containing metmyoglobin. In this system, catechin totally inhibited lipid peroxidation at a concentration 20-fold lower than without metmyoglobin. The ability of catechin to inhibit lipid peroxidation was also determined at a low pH with beta-carotene as a sensitive target molecule for oxidation. The results show that a significant protection was achieved only with almost 100-fold higher antioxidant concentration. Polyphenols from different groups were determined for the antioxidant activity at pH 3.0. The results show a high antioxidant activity of polyphenols with orthodihydroxylated groups at the B ring, unsaturation, and the presence of a 4-oxo group in the heterocyclic ring, as demonstrated by quercetin.     

Effects of lactoferrin, phytic acid, and EDTA on oxidation in two food emulsions enriched with long-chain polyunsaturated fatty acids

The influence of the addition of metal chelators on oxidative stability was studied in a milk drink and in a mayonnaise system containing highly polyunsaturated lipids. Milk drinks containing 5% (w/w) of specific structured lipid were supplemented with lactoferrin (6-24 muM) and stored at 2 degrees C for up to 9 weeks. Mayonnaise samples with 16% fish oil and 64% rapeseed oil (w/w) were supplemented with either lactoferrin (8-32 muM), phytic acid (16-124 muM), or EDTA (16-64 muM) and were stored at 20 degrees C for up to 4 weeks. The effect of the metal chelators was evaluated by determination of peroxide values, secondary volatile oxidation products, and sensory analysis. Lactoferrin reduced the oxidation when added in concentrations of 12 muM in the milk drink and 8 muM in the mayonnaise, whereas it was a prooxidant at higher concentrations in both systems. In mayonnaise, EDTA was an effective metal chelator even at 16 muM, whereas phytic acid did not exert a distinct protective effect against oxidation. The differences in the equimolar effects of the metal chelators are proposed to be due to differences in their binding constants to iron and their different stabilities toward heat and low pH.     

Antioxidant potential of hydroxycinnamic acid glycoside esters

Hydroxycinnamic acids are natural antioxidants found in fruits, vegetables, and cereals. In this study, the antioxidant activity of various types of hydroxycinnamoyl glycoside esters that mimic the structure of polymeric carbohydrates was studied in different model systems prone to oxidation, namely, liposomes and emulsions. In addition, radical scavenging activity against the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical was tested. It was found that the esterification in the primary hydroxyl group of the glycoside resulted in the improved radical scavenging activity of both sinapoyl and feruloyl glycosides compared to conjugation to the secondary hydroxyl group. Increased activity was also observed, particularly in the case of feruloyl glucosides in inhibiting the oxidation of liposomes emulsions. The results showed that sinapic and ferulic acid glycoside esters were as effective or more efficient antioxidants than their free forms. In conclusion, the strength of their antioxidant effect depends on the nature of conjugation.     

Antioxidant mechanisms of caseinophosphopeptides and casein hydrolysates and their application in ground beef

Caseinophosphopeptides (CPP) and casein hydrolysates have been shown to bind prooxidant metals such as iron, but their effectiveness as metal chelators to inhibit lipid oxidation in foods has still not been fully investigated. Thus, the antioxidant activity of CPP and casein hydrolysates was studied in phosphatidylcholine liposome model systems. CPP (< 1.0 mg/mL) and casein hydrolysates (0.3-1.7 mg/mL) were effective inhibitors of TBARS development when oxidation was promoted by ferric/ascorbate. High amounts of CPP (> 1.0 mg/mL) were prooxidant, whereas casein hydrolysates were observed to be only antioxidative. In the presence of peroxyl radicals, casein hydrolysates were more effective scavengers than enriched CPP (3-15 mM). In cooked ground beef, TBARS formation was inhibited 75, 39, and 17% by 0.5% enriched CPP, casein hydrolysates, and low molecular weight casein hydrolysates, respectively, after 4 days of storage. The results show that CPP and casein hydrolysates are promising sources of natural antioxidants for foods.     

Activities of antioxidants are affected by colloidal properties of oil-in-water and water-in-oil emulsions and bulk oils

The activity of alpha-tocopherol, Trolox, propyl gallate, gallic acid, methyl carnosoate, and carnosic acid was studied in two oil-in-water (o/w) emulsions, in two water-in-oil (w/o) emulsions, and in bulk oil with and without added emulsifiers. All antioxidants had either moderate or higher activity in bulk oil than in the emulsions. In most emulsions, the most polar antioxidants, propyl gallate and gallic acid, exhibited either prooxidant activity or no antioxidant activity. Methyl carnosoate was the most active antioxidant in w/o emulsions but was less active than Trolox in o/w emulsions. alpha-Tocopherol was less active in bulk oil than in emulsions, but its activity in bulk oil was markedly enhanced by the addition of o/w emulsifiers. Partitioning of antioxidants, hydrogen bonding, interphase transport, surface accessibility, and interaction of emulsifier with antioxidants are considered to be important parameters that determine antioxidant activity in lipid-containing systems.     

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.     

Antioxidant and prooxidant actions of prenylated and nonprenylated chalcones and flavanones in vitro

Prenylated flavonoids found in hops and beer, i.e., prenylchalcones and prenylflavanones, were examined for their ability to inhibit in vitro oxidation of human low-density lipoprotein (LDL). The oxidation of LDL was assessed by the formation of conjugated dienes and thiobarbituric acid-reactive substances (TBARS) and the loss of tryptophan fluorescence. At concentrations of 5 and 25 microM, all of the prenylchalcones tested inhibited the oxidation of LDL (50 microg protein/ml) induced by 2 microM copper sulfate. The prenylflavanones showed less antioxidant activity than the prenylchalcones, both at 5 and 25 microM. At 25 microM, the nonprenylated chalcone, chalconaringenin (CN), and the nonprenylated flavanone, naringenin (NG), exerted prooxidant effects on LDL oxidation, based on TBARS formation. Xanthohumol (XN), the major prenylchalcone in hops and beer, showed high antioxidant activity in inhibiting LDL oxidation, higher than alpha-tocopherol and the isoflavone genistein but lower than the flavonol quercetin. When combined, XN and alpha-tocopherol completely inhibited copper-mediated LDL oxidation. These findings suggest that prenylchalcones and prenylflavanones found in hops and beer protect human LDL from oxidation and that prenylation antagonizes the prooxidant effects of the chalcone, CN, and the flavanone, NG.     

Dietary iron-initiated lipid oxidation and its inhibition by polyphenols in gastric conditions

The gastric tract may be the first site where food is exposed to postprandial oxidative stress and antioxidant activity by plant micronutrients. After food intake, dietary iron, dioxygen, and emulsified lipids come into close contact and lipid oxidation may take place. This study investigated lipid oxidation and its inhibition by dietary polyphenols in gastric-like conditions. Lipid oxidation induced by heme and nonheme iron was studied in acidic sunflower oil-in-water emulsions. The emulsifier type (bovine serum albumin, phospholipids), pH, and iron form were found to be factors governing the oxidation rates. Quercetin, rutin, and chlorogenic acid highly inhibited the metmyoglobin-initiated lipid oxidation in both emulsified systems at pH 5.8. Additionally, quercetin inhibited nonheme iron-initiated processes, while it was inefficient with hematin as an initiator. The presence of human gastric juice did not influence lipid oxidation, although it diminished the antioxidant activity of phenolics. Model emulsions may thus be valuable tools to study the gastric stability of polyunsaturated lipids.     

Impact of lipid physical state on the oxidation of methyl linolenate in oil-in-water emulsions

The purpose of this research was to examine the influence of the physical state of lipids on iron-promoted oxidation of methyl linolenate in octadecane oil-in-water emulsions. Octadecane and methyl linolenate oil-in-water emulsions were prepared that contained droplets having the octadecane as either liquid or solid. The physical state of the octadecane was confirmed by a differential scanning calorimeter (DSC). The effect of the physical state of the lipid on oxidation rates was determined as a function of iron concentration (80 and 160 microM), pH (3.0 or 7.0), emulsifier type, and cooling rate. Oxidation of methyl linolenate was determined by lipid hydroperoxides and thiobarbituric acid reactive substances (TBARS). Emulsions containing solid octadecane had higher rates of lipid hydroperoxide and TBARS formation than those containing liquid octadecane. The rate at which the emulsions were cooled had no influence on oxidation rates. Oxidation rates in both emulsions increased with increasing iron concentration and decreasing pH. Oxidation rates were lowest in emulsions with cationic droplet membranes (dodecyl trimethylammonium bromide-stabilized), presumably due to the repulsion of iron from the oxidizable methyl linolenate in the emulsion droplet core. These results suggest that upon crystallization of octadecane, the liquid methyl linolenate migrated to the emulsion droplet surface, where it was more prone to oxidation because it was in closer contact with the iron ions in the aqueous phase.     

Antioxidant activity of olive pulp and olive oil phenolic compounds of the arbequina cultivar

The aim of this study was to characterize antioxidant activities of phenolic compounds that appear in olive pulp and olive oils using both radical scavenging and antioxidant activity tests. Antiradical and antioxidant activities of olive pulp and olive oil phenolic compounds were due mainly to the presence of a 3,4-dihydroxy moiety linked to an aromatic ring, and the effect depended on the polarity of the phenolic compound. Glucosides and more complex phenolics exhibited higher antioxidant activities toward oxidation of liposomes, whereas in bulk lipids aglycons were more potent antioxidants with the exception of oleuropein. Lignans acted as antioxidants only in liposomes, which could partly be due to their chelating activity, because liposome oxidation was initiated by cupric acetate. The antioxidant activity of virgin olive oil is principally due to the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA), a secoiridoid derivative (peak RT 36, structure unidentified), and luteolin.     

Use of caseinophosphopeptides as natural antioxidants in oil-in-water emulsions

Chelators are valuable ingredients used to improve the oxidative stability of food emulsions. Caseins and casein peptides have phosphoseryl residues capable of binding transition metals. Thus, the ability of enriched caseinophosphopeptides to inhibit lipid oxidation in corn oil-in-water emulsions was investigated. Enriched caseinophosphopeptides (25 microM) inhibited the formation of lipid oxidation at both pH 3.0 and 7.0 as determined by lipid hydroperoxides and hexanal. Calcium (0-100 mM) had no influence on the antioxidant activity of the enriched caseinophosphopeptides. Casein hydrolysates were more effective inhibitors of lipid oxidation than the enriched caseinophosphopeptides at equal phosphorus content. Thus, antioxidant properties might not be uniquely attributed to chelating metals by phosphoseryl residues but also by scavenging free radicals. Overall, the observed antioxidant activity of casein hydrolysates means they could be utilized to decrease oxidative rancidity in foods.     

The effects of surfactant type, pH, and chelators on the oxidation of salmon oil-in-water emulsions.

Lipid oxidation in emulsions is influenced by the ability of transition metals to associate with emulsion droplets. The oxidative stability of 5% salmon oil-in-water emulsion was influenced by surfactant type, with oxidation rates being greatest in emulsions stabilized by anionic sodium dodecyl sulfate (SDS) followed by nonionic Tween 20 and cationic dodecyltrimethylammonium bromide (DTAB). EDTA inhibited lipid oxidation in all the emulsions, and apo-transferrin inhibited oxidation in the Tween 20-stabilized emulsions at pH 7.0, suggesting that continuous-phase iron was an active prooxidant. Iron associated with Tween-20 stabilized hexadecane emulsion droplets could be partitioned into the continuous phase by lowering the pH to 相似文献   

Oxidation of skeletal muscle myofibrillar proteins in oil-in-water emulsions: interaction with lipids and effect of selected phenolic compounds

The effect of selected phenolic compounds, namely, gallic acid, cyanidin-3-glucoside, (+)-epicatechin, chlorogenic acid, genistein and rutin (50 and 200 microM), and alpha-tocopherol (50 microM) against the oxidation of oil-in-water emulsions (37 degrees C/10 days) containing 1% myofibrillar proteins (MPs), was investigated. Emulsions containing 1% bovine serum albumin (BSA) were also prepared for comparative purposes. Protein oxidation was assessed by measuring the loss of natural tryptophan fluorescence and the protein carbonyl gain by using fluorescence spectroscopy. Lipid oxidation was concurrently analyzed by measuring the increase of conjugated dienes (CDs) and hexanal. Proteins inhibited lipid oxidation in oil-in-water emulsions, and MPs showed a more intense antioxidant activity than BSA. MPs were also more resistant to oxidative deterioration than BSA. The different antioxidant capacity of MPs and BSA and their susceptibility to suffer oxidative reactions might be derived from their different amino acid composition and three-dimensional structures. The addition of the phenolic compounds resulted in a variety of effects, including both antioxidant and pro-oxidant effects. Gallic acid, cyanidin-3-glucoside, and genistein were the most efficient inhibitors of lipid and protein oxidation. The chemical structure of the phenolic compounds as well as the nature and conformation of the proteins were greatly influential on the overall effect against oxidative reactions.