Iron-accelerated cumene hydroperoxide decomposition in hexadecane and trilaurin emulsions

Free radicals arising from lipid peroxides accelerate the oxidative deterioration of foods. To elucidate how lipid peroxides impact oxidative reactions in food emulsions, the stability of cumene hydroperoxide was studied in hexadecane or trilaurin emulsions stabilized by anionic (sodium dodecyl sulfate; SDS), nonionic (Tween 20), and cationic (dodecyltrimethylammonium bromide; DTAB) surfactants. Fe(2+) rapidly (within 10 min) decomposed between 10 and 31% of the cumene hydroperoxide in Tween 20- and DTAB-stabilized emulsions at pH 3.0 and 7.0 and in the SDS-stabilized emulsion at pH 7.0 with no further decomposition of peroxides occurring for up to 3 h. In SDS-stabilized emulsions at pH 3.0, Fe(2+) decreased peroxides by 90% after 3 h. Decomposition of peroxides in the absence of added iron and by Fe(3+) was observed only in SDS-stabilized emulsions at pH 3.0. These results suggest that peroxide decomposition by iron redox cycling occurs when iron emulsion droplet interactions are high.     

Impact of tween 20 hydroperoxides and iron on the oxidation of methyl linoleate and salmon oil dispersions

To determine the role of surfactant hydroperoxides on the oxidative stability of fatty acids, the oxidation of methyl linoleate micelles and salmon oil-in-water emulsions was measured as a function of varying Tween 20 hydroperoxide concentrations. Increasing Tween 20 hydroperoxide concentrations from 3.5 to 14.7 micromol hydroperoxide/g Tween 20 decreased the lag phase of headspace hexanal formation but did not increase the total amount of hexanal formed in methyl linoleate/Tween 20 micelles. In the micelle system, Fe(2+) decreased the lag phase of hexanal formation but increased total hexanal concentrations only in micelles with the highest Tween 20 hydroperoxide concentrations (14.7 micromol hydroperoxide/g surfactant). Increasing Tween 20 surfactant hydroperoxide concentrations also increased the oxidation of salmon oil-in-water emulsions as determined by lipid hydroperoxides and headspace propanal. In both the micelle and emulsion systems, the prooxidant effect of Fe(2+) decreased with increasing Tween 20 hydroperoxide concentrations. These data show that surfactant hydroperoxides such as those in Tween 20 could decrease the oxidative stability of lipids in food emulsions.     

An investigation of the versatile antioxidant mechanisms of action of rosmarinate alkyl esters in oil-in-water emulsions

The antioxidant polar paradox postulates that nonpolar antioxidants are more effective in oil-in-water emulsions than polar antioxidants. However, this trend is often not observed with antioxidants esterified with acyl chains to vary their polarity. In this study, the nonpolar eicosyl rosmarinate (20 carbons, R20) was less effective at inhibiting lipid oxidation in oil-in-water emulsions than esters with shorter fatty acyl chains such as butyl (R4), octyl (R8), and dodecyl (R12) esters. Interestingly, in the presence of surfactant micelles, the antioxidant activity of R20 was significantly increased while the antioxidant activity of R4 and R12 was slightly decreased. The presence of surfactant micelles increased the concentration of R20 at the interface of the surfactant micelles and/or emulsion droplets as determined by partitioning studies, front-face fluorescence properties, and the ability of R20 to interact with the interfacial probe, 4-hexadecylbenzenediazonium. A possible explanation for why the antioxidant activity of R20 was so dramatically increased by surfactant micelles is that a portion of the nonpolar R20 localizes in the emulsion droplet core and the surfactant micelles are able to increase the interfacial concentrations of R20 and thus its ability to scavenge free radicals produced from the decomposition of interfacial lipid hydroperoxides.     

Formation and stabilization of antimicrobial delivery systems based on electrostatic complexes of cationic-non-ionic mixed micelles and anionic polysaccharides

Lauric arginate (LAE) is a cationic surfactant that is of great interest to the food industry because of its strong antimicrobial activity. However, its application within foods and beverages is currently restricted because of its limited solubility in aqueous solutions and its bitter taste, which have been associated with its cationic nature. This study examines whether electrostatic complexes between cationic LAE mixed micelles and anionic polysaccharides could be used to improve LAE functionality. Two types of pectin (high and low methoxyl) were titrated into buffer solutions containing either LAE micelles or LAE/Tween 20 mixed micelles (pH 3.5, 50 mM citrate buffer). The electrical characteristics of the micelles or micelle/pectin complexes were assessed by microelectrophoresis measurements, while their stability to aggregation was evaluated by light scattering measurements. LAE micelle/pectin complexes formed large aggregates that rapidly sedimented. On the other hand, mixed micelle/pectin complexes (1:1 LAE/Tween 20, w/w) were stable to aggregation and formed clear solutions. The electrical charge of mixed micelles changed from +8 to -15 mV when the pectin concentration was increased (0.00-0.05 wt %), indicating an electrostatic interaction between anionic pectin molecules and cationic micelles. Lower concentrations of low methoxyl pectin were required (0.01 wt %) to change the net charge of mixed micelles from positive to negative than high methoxyl pectin (0.025 wt %). Our results suggest that the addition of pectin to mixed LAE/Tween 20 micelles leads to the formation of electrostatic complexes that may be useful as functional ingredients in food and other products.     

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   

Ability of surfactant headgroup size to alter lipid and antioxidant oxidation in oil-in-water emulsions

Oxidation of oil-in-water emulsion droplets is influenced by the properties of the interfacial membrane surrounding the lipid core. To evaluate how surfactant headgroup size influences lipid oxidation rates, emulsions were prepared with polyoxyethylene 10 stearyl ether (Brij 76) or polyoxyethylene 100 stearyl ether (Brij 700), which are structurally identical except for their hydrophilic headgroups, with Brij 700 containing 10 times more polyoxyethylene groups than Brij 76. Fe(2+)-promoted decomposition of cumene hydroperoxide was lower in Brij 700-stabilized than in Brij 76-stabilized hexadecane emulsions. Fe(2+)-promoted alpha-tocopherol oxidation rates were similar in hexadecane emulsion regardless of surfactant type. Brij 700 decreased production of hexanal from methyl linoleate and the formation of lipid peroxides and propanal from salmon oil compared to emulsions stabilized by Brij 76. These results indicate that emulsion droplet interfacial thickness could be an important determinant in the oxidative stability of food emulsions.     

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.     

Mechanisms of the antioxidant activity of a high molecular weight fraction of whey

The antioxidant mechanisms of whey proteins in a Tween 20-stabilized salmon oil-in-water emulsion were investigated. The antioxidant activity of the high molecular weight (HMW) fraction of whey from pasteurized milk was found to increase with concentration, as determined by its ability to inhibit TBARS and lipid peroxide formation. The ability of sulfhydryl-blocked whey to inhibit TBARS formation was reduced 60% compared to the HMW fraction alone at 7 days of storage. HMW fraction was able to scavenge peroxyl radicals, with scavenging decreasing approximately 20% when sulfhydryls were blocked. HMW fraction was able to chelate iron away from the surface of negatively charged BSA-stabilized emulsion droplets, indicating that the whey proteins were able to chelate iron. A better understanding of the mechanisms by which whey proteins inhibit lipid oxidation could increase the use of whey proteins as food antioxidants.     

New insights into the role of iron in the promotion of lipid oxidation in bulk oils containing reverse micelles

Formation of physical structures, known as association colloids, in bulk oils can promote lipid oxidation. However, the cause of this accelerated lipid oxidation is unknown. Therefore, the aim of this study was to investigate whether transition metals were important prooxidants in bulk oils containing reverse micelles produced from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and water. The Fe(III) chelator deferoxamine (DFO) increased the oxidative stability of stripped soybean oil (SSO) containing reverse micelles from 2 to 7 days. Because phosphatidylcholine (1,2-dibutyl-sn-glycero-3-phosphocholine) that does not form reverse micelles is not prooxidative, these results suggest that the prooxidant activity of DOPC reverse micelles could be due to their ability to concentrate both endogenous iron and lipid hydroperoxides at the water-lipid interface, thereby increasing the ability of iron to decompose lipid hydroperoxides. DFO was also able to improve the activity of α-tocopherol and Trolox in SSO containing DOPC reverse micelles increasing the lag phase from 2 to 11 and 13 days, respectively. DOPC reverse micelles decreased iron-promoted α-tocopherol and Trolox decomposition and decreased the ability of α-tocopherol and Trolox to decrease Fe(III) concentrations. Overall, these results suggest that iron is an important prooxidant in bulk oils containing reverse micelles; therefore, finding ways to control iron reactivity in association colloids could provide new technologies to increase the oxidative stability of oils.     

Lipid oxidation in a menhaden oil-in-water emulsion stabilized by sodium caseinate cross-linked with transglutaminase

Transglutaminase-catalyzed cross-linking of interfacial proteins in oil-in-water has been shown to influence physical stability, but little is known about how this reaction impacts lipid oxidation. Therefore, this study evaluated the influence of transglutaminase-induced interfacial protein cross-linking on the oxidative stability of casein-stabilized menhaden oil-in-water emulsions. Interfacial casein in menhaden oil-in-water emulsions cross-linked by transglutaminase (pH 7.0) produced a cohesive interfacial protein layer that could not be removed from the emulsion droplet by Tween 20. Although transglutaminase cross-linked the interfacial casein, these emulsions did not show increased oxidative stability when compared to untreated emulsions as determined by measurement of lipid hydroperoxides and thiobarbituric acid reactive substances. These results indicate that increasing the cohesiveness of proteins at the interface of oil-in-water emulsions does not inhibit lipid oxidation. This could be due to the ability of prooxidative species such as iron to diffuse through the cross-linked protein layer where it could promote the decomposition of lipid hydroperoxides into free radicals that could oxidize unsaturated fatty acids in the emulsion droplet core.     

Lipid oxidation in fish oil enriched mayonnaise: calcium disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration

The antioxidative effects of gallic acid, EDTA, and extra emulsifier Panodan DATEM TR in mayonnaise enriched with 16% fish oil were investigated. EDTA reduced the formation of free radicals, lipid hydroperoxides, volatiles, and fishy and rancid off-flavors. The antioxidative effect of EDTA was attributed to its ability to chelate free metal ions and iron from egg yolk located at the oil-water interface. Gallic acid reduced the levels of both free radicals and lipid hydroperoxides but promoted slightly the oxidative flavor deterioration in mayonnaise and influenced the profile of volatiles. Gallic acid may therefore promote the decomposition of lipid hydroperoxides to volatile oxidation products. Addition of extra emulsifier reduced the lipid hydroperoxide levels but did not influence the level of free radicals or the oxidative flavor deterioration in mayonnaisse; however, it appeared to alter the profile of volatiles. The effect of the emulsifier on the physical structure and rheological properties depended on the presence of antioxidants.     

Heme-mediated production of free radicals via preformed lipid hydroperoxide fragmentation

Electron spin resonance (ESR) spectroscopy and the spin-trapping technique were used to investigate the capacity of several hemoglobin (Hb) forms of rainbow trout (oxyHb and metHb), free hemin (oxidized form of heme group), and hemin complexed with bovine serum albumin (BSA) to promote formation of free radicals via fragmentation of preformed lipid hydroperoxides. Cumene hydroperoxide (CumOOH) was used as a model for lipid hydroperoxide, and free radicals were monitored by stabilizing with the spin traps alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) and 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Two different types of free radicals, hydroxyl and carbon-centered radicals, were identified as a result of the interaction of the heme-containing systems and CumOOH. Carbon-centered radicals were found to be mainly heme-mediated because the addition of the iron-chelating agent EDTA did not affect the formation of POBN/carbon-centered adducts. Hemin alone was the best promoter for the production of POBN/carbon-centered radicals in the presence of low hydroperoxide concentrations (below equimolar condition over heme group), whereas hemin/BSA and oxyHb were more active in generating radicals at high hydroperoxide concentrations or after successive interactions with hydroperoxides. This finding can be explained by the coexistence of two different facts: (i) the interaction between hemin and lipid hydroperoxides seems to be more efficient in the case of free hemin compared to heme-protein complexes and (ii) a faster degradation of hemin is produced without the presence of a protein fraction, globin or albumin. The comparison of oxyHb and metHb also suggested that both Hb redox states have similar capacities to generate oxidative stress via cleavage of preformed lipid hydroperoxides.     

Oxidative reactions during early stages of beer brewing studied by electron spin resonance and spin trapping

An electron spin resonance (ESR)-based method was used for evaluating the levels of radical formation during mashing and in sweet wort. The method included the addition of 5% (v/v) ethanol together with the spin trap alpha-4-pyridyl(1-oxide)- N- tert-butylnitrone (POBN) to wort, followed by monitoring the rate of formation of POBN spin adducts during aerobic heating of the wort. The presence of ethanol makes the spin trapping method more selective and sensitive for the detection of highly reactive radicals such as hydroxyl and alkoxyl radicals. Samples of wort that were collected during the early stages of the mashing process gave higher rates of spin adduct formation than wort samples collected during the later stages. The lower oxidative stability of the early wort samples was confirmed by measuring the rate of oxygen consumption during heating of the wort. The addition of Fe(II) to the wort samples increased the rate of spin adduct formation, whereas the addition of Fe(II) during the mashing had no effect on the oxidative stability of the wort samples. Analysis of the iron content in the sweet wort samples demonstrated that iron added during the mashing had no effect on the iron level in the wort. The moderate temperatures during the early steps of mashing allow the endogenous malt enzymes to be active. The potential antioxidative effects of different redox-active enzymes during mashing were tested by measuring the rate of spin adduct formation in samples of wort. Surprisingly, a high catalase dosage caused a significant, 20% reduction of the initial rate of radical formation, whereas superoxide dismutase had no effect on the oxidation rates. This suggests that hydrogen peroxide and superoxide are not the only intermediates that play a role in the oxidative reactions occurring during aerobic oxidation of sweet wort.     

柴油机燃用水乳化柴油着火时刻的化学动力学特性

以4100QBZL-2型增压直喷柴油机为研究对象,利用美国劳伦斯利弗莫尔国家实验室(LLNL)的正庚烷第三版详细模型进行化学动力学计算,对被测发动机上燃用纯柴油,体积分数为:10%。、20%、30%的水乳化柴油时缸内的着火时刻进行模拟研究,并将化学动力学计算结果与试验结果及计算流体力学与正庚烷简化模型(CFD-SKLE)的耦合计算结果进行对比分析。研究结果表明:水乳化柴油所引起的着火时刻延迟是由于乳化燃料中的水分在缸内的物理现象所引起。从化学动力学的角度来分析,乳化燃料内的水分可以促进H、O、OH、HO2等自由基在低温反应(冷焰)阶段的大量生成,为随后的高温(热焰)反应提供了条件,最终使着火时刻提前。通过对掺水后正庚烷氧化反应的敏感性分析可知,水分会在正庚烷氧化的低温反应时期对过氧烷基的异构化过程与过氧化氢酮的分解过程产生了促进作用,从而加速正庚烷氧化的链式反应的进行。     

Effects of released iron, lipid peroxides, and ascorbate in trout hemoglobin-mediated lipid oxidation of washed cod muscle

Approximately 7% of the iron associated with hemoglobin was released from the heme protein during 2 degrees C storage in washed cod muscle. EDTA (2.2 mM) neither accelerated nor inhibited hemoglobin-mediated lipid oxidation based on the formation of lipid peroxides and TBARS. This suggested that low molecular weight iron was a minor contributor to hemoglobin-mediated lipid oxidation in washed cod muscle. Ascorbate (2.2 mM) was a modest to highly effective inhibitor of hemoglobin-mediated lipid oxidation depending on which washed cod preparation was assessed. Experimental evidence suggested that the ability of residual ascorbate to breakdown accumulating lipid hydroperoxides to reactive lipid radicals can explain the shift of ascorbate from an antioxidant to a pro-oxidant. Increasing the lipid peroxide content in washed cod muscle accelerated hemoglobin-mediated lipid oxidation and decreased the ability of ascorbate to inhibit lipid oxidation. Preformed lipid peroxide content in cod muscle was highly variable from fish to fish.     

Ability of surface-active antioxidants to inhibit lipid oxidation in oil-in-water emulsion

Lipid oxidation in dispersed lipids is prevalent at the oil-water interface where lipid hydroperoxides are decomposed into free radicals by transition metals. Free radical scavenging antioxidants are believed to be most effective in lipid dispersions when they accumulate at the oil-water interface. The surface activity of antioxidants could be increased by their conjugation to hydrocarbon chains. In this study, p-hydroxyphenylacetic acid (HPA) was conjugated with either a butyl or dodecyl group. The HPA conjugates were more effective at decreasing interfacial tension than unconjugated HPA, indicating that they were able to adsorb at lipid-water interfaces. However, free HPA was a more effective antioxidant than butyl and dodecyl conjugates in Menhaden oil-in-water emulsions as determined by both lipid hydroperoxides and thiobarbituric acid reactive substances. The increased antioxidant activity of free HPA could be due to its more effective free radical scavenging activity and its higher concentration in the lipid phase of oil-in-water emulsions in the presence of surfactant micelles where it can act as a chain-breaking antioxidant.     

Ability of lipid hydroperoxides to partition into surfactant micelles and alter lipid oxidation rates in emulsions

Lipid hydroperoxides are important factors in lipid oxidation due to their ability to decompose into free radicals. In oil-in-water emulsions, the physical location of lipid hydroperoxides could impact their ability to interact with prooxidants such as iron. Interfacial tension measurements show that linoleic acid, methyl linoleate, and trilinolein hydroperoxides are more surface-active than their non-peroxidized counterparts. In oil-in-water emulsion containing surfactant (Brij 76) micelles in the continuous phase, linoleic acid, methyl linoleate, and trilinolein hydroperoxides were solubilized out of the lipid droplets into the aqueous phase. Brij 76 solubilization of the different hydroperoxides was in the order of linoleic acid > trilinolein > or = methyl linoleate. Brij 76 micelles inhibited lipid oxidation of corn oil-in-water emulsions with greater inhibition of oxidation occurring in emulsions containing linoleic acid hydroperoxides. Surfactant solubilization of lipid hydroperoxides could be responsible for the ability of surfactant micelles to inhibit lipid oxidation in oil-in-water emulsions.     

Novel approach to study oxidative stability of extra virgin olive oils: importance of alpha-tocopherol concentration

The stability of extra virgin olive oils is mainly due to their relatively low fatty acids unsaturation and to the antioxidant activity of some of the unsaponifiable components. We studied the activity of alpha-tocopherol in extra virgin olive oil in its natural state, using new and simple oxidizing conditions in "thin layer" and "bulk phase". Oxidation time course was monitored at 37 degrees C or 75 degrees C. A storage test was also performed. Two parameters were evaluated: depletion of alpha-tocopherol and formation of PUFA hydroperoxides, measured as conjugated dienes (CD) and peroxide value. The value of complex polyphenols was also measured. alpha-Tocopherol concentration decreased in function of time and temperature and showed a strong inverse correlation with the increase of CD. When alpha-tocopherol reached a "threshold value" of 60-70 mg/kg, a significant increase of CD formation was observed, together with a good correlation between CD and peroxide value. The initial amount of alpha-tocopherol is one of the components that influences oil oxidative susceptibility.     

Investigating the hydrogen peroxide quenching capacity of proteins in polyphenol-rich foods

Polyphenols are widely regarded as antioxidants, due in large part to their free radical scavenging activities and their ability to disrupt radical chain propagation. However, recent studies have demonstrated that the oxidation of some polyphenolic compounds, such as the tea-derived compound (-)-epigallocatechin-3-gallate (EGCG), results in the generation of reactive oxygen species that can potentially compromise the oxidative stability of food lipids under some conditions. In this present study, the rate of hydrogen peroxide (H(2)O(2)) generation and its stability, resulting from EGCG oxidation in Tween 80- and sodium caseinate-stabilized oil-in-water (O/W) emulsions in the presence of iron (25 μM Fe(3+) from FeCl(3)), were examined. Observed H(2)O(2) levels in protein-stabilized emulsions were significantly lower across all treatments as compared to surfactant-stabilized emulsions. The lower observed H(2)O(2) concentrations seen in the protein system are likely due to the antioxidant effects of the added proteins, which either prevented the generation of or more likely scavenged the peroxide. All protein-stabilized emulsions containing EGCG showed increases in carbonyl concentrations, a marker of protein oxidation, throughout the study. The H(2)O(2) scavenging activity of aqueous phase and interfacial caseinate and whey protein isolate (WPI) was also evaluated. Both proteins showed concentration-dependent scavenging of H(2)O(2) with caseinate displaying significantly higher scavenging abilities at all concentrations. These results suggest that food proteins may play an important role in mitigating the pro-oxidant effects of polyphenols.     

硒缓解植物重金属胁迫和累积的机制

硒(Se)在提高植物抗逆性、缓解重金属胁迫以及降低植物对重金属吸收方面有着重要的作用。本文综述了Se参与缓解植物重金属胁迫和累积的机制,Se能够缓解重金属的胁迫,主要是因为在植物体内由Se转化而来的相关产物的生理生化作用产生的综合效果。Se是谷胱甘肽过氧化物酶(GSH-Px)的必需组分,GSH-Px利用谷胱甘肽(GSH)将有毒的过氧化物还原成无毒的物质,清除由重金属引起的自由基。Se可以激活植物螯合肽(PC)合成酶及增加PC合成的前体,使植物产生更多的PC,形成更多的重金属-PC配合物。Se还可以与重金属形成大分子的复合物,降低重金属的毒害。Se能够与多种重金属元素产生拮抗效应,降低植物对重金属的吸收。