Effects of sesamol, sesamin, and sesamolin extracted from roasted sesame oil on the thermal oxidation of methyl linoleate

This study investigated the effects of lignan compounds extracted from roasted sesame oil, which were sesamol, sesamin, and sesamolin, on oxidation of methyl linoleate (ML) during heating. These compounds were added at 500 or 1000 mg/kg to ML, and α-tocopherol was used as a reference antioxidant. The ML added with lignans or α-tocopherol was heated at 180 °C for 60 min. Thermal oxidation of ML was evaluated by conjugated dienoic acid (CDA) contents, p-anisidine value (PAV), and ML retention. Contents changes of lignan compounds or α-tocopherol in ML during heating were monitored by high-performance liquid chromatography. CDA contents and PAV of samples increased and ML decreased with heating time at 180 °C. Samples added with lignan compounds showed lower CDA contents and PAV but higher ML retention than samples without lignan compounds. The antioxidant activity of sesame oil lignan compounds in ML oxidation during heating tended to be higher than that of α-tocopherol. The contents of lignan compounds in samples decreased with heating time due to their degradation, but the degradation rates were lower than that of α-tocopherol. This study suggested that sesame oil lignan compounds be used as antioxidants in oil at high temperatures for deep-fat frying due to their higher effectiveness and stability than α-tocopherol.     

Role of sugar–amino acid interaction products (MRPs) as antioxidants in a methyl linoleate model system

Effects of early Maillard reaction products (MRPs) as antioxidants in methyl linoleate model system, during refrigerated storage at 5 °C for 6 days, have been evaluated. MRPs were prepared by reacting glucose with five different amino acids – glycine, methionine, tryptophan, aspartic acid and lysine – using two different concentrations and time intervals (30 mM/1 h, 30 mM/2 h, 60 mM/1 h and 60 mM/2 h). The preformed MRPs were incorporated, after studying pH and optical density profile, in a model system comprised of methyl linoleate and microcrystalline cellulose. Antioxidative characteristics were evaluated by estimating the thiobarbituric acid-reactive substance value (TBARS) and peroxide value (PV) and monitoring the gas chromatographic degradation pattern of methyl linoleate immediately after heating, as well as after storage at 5 °C for 2, 4 and 6 days. Analysis of variance revealed highly significant differences among TBARS, PV and the % of methyl linoleate degradation (p < 0.01) values, both initially and during storage in glucose + lysine and glucose + glycine with respect to control. Other treatments, such as glucose + methionine and glucose + tryptophan exhibited moderately significant differences (p < 0.05). But glucose + aspartic acid was not significantly different (p > 0.05) Significant differences were observed between 60 mM/2 h and 30 mM/1 h of MRPs with glucose + lysine and glucose + glycine (p < 0.01). Out of the five combinations tried, glucose + lysine and glucose + glycine exhibited good antioxidative potential at 60 mM/2 h. The % of antioxidant activity was in the order 60 mM/2 h > 60 mM/1 h > 30 mM/2 h > 30 mM/1 h for the treatments glucose + lysine > glucose + glycine > glucose + tryptophan > glucose + methionine > glucose + aspartic acid, respectively.     

Flavonoids quercetin,myricetin, kaemferol and (+)‐catechin as antioxidants in methyl linoleate

The antioxidant effect of the flavonoids quercetin, myricetin, kaemferol, (+)‐catechin and rutin on methyl linoleate oxidation was investigated. In addition, the synergistic effects of flavonoids and α‐tocopherol were studied. Oxidation was monitored by conjugated diene measurement and by determining the formation of hydroperoxide isomers by HPLC. The antioxidant activity of flavonoids in non‐polar methyl linoleate differ from that previously reported in water‐containing systems, such as LDL and liposome systems. The activity of antioxidants (10–1000 μM ) measured by hydroperoxide formation decreased in the order: myricetin>quercetin>α‐tocopherol>(+)‐catechin >kaemferol=rutin. The antioxidant activity of flavonoids increased as the number of phenolic hydroxyl groups increased. In addition to the number of hydroxyl groups, other structural features such as the 2,3 double bond in the C‐ring and a glycoside moiety in the molecule had an effect on the antioxidant activity. Myricetin and rutin, especially had a synergistic effect with α‐tocopherol. Myricetin, quercetin and rutin protected α‐tocopherol from decomposition, myricetin being the most protective. The relative hydrogen‐donating activity measured by the ratio of cis,trans‐ to trans,transhydroperoxide isomers formed during oxidation decreased in the order: α‐tocopherol >myricetin>quercetin. Hydroperoxide isomeric distribution of the samples containing kaemferol or rutin did not differ from the control. Thus, although α‐tocopherol was the most effective hydrogendonor, myricetin and quercetin were more effective antioxidants in inhibiting the hydroperoxide formation in methyl linoleate. © 1999 Society of Chemical Industry     

基于气相色谱法的油酸甲酯和亚油酸甲酯热氧化降解特性研究

利用气相色谱法分别测定油酸甲酯和亚油酸甲酯在不同温度下的氧化曲线,同时采用微分法和积分法对热氧化降解反应方程的参数进行了计算,进而确定了反映油酸甲酯和亚油酸甲酯热氧化降解历程的宏观反应动力学方程。微分法动力学分析结果表明:油酸甲酯热氧化降解反应的平均反应级数为1.37,活化能为5.48 k J/mol,反应动力学模型为rA=-dcA/dt=7.06exp(-5.48/RT)c1.37A;亚油酸甲酯热氧化降解反应的平均反应级数为2.49,活化能为392.73 k J/mol,反应动力学模型为rA=-dcA/dt=1.13×1047exp(-392.73/RT)c2.49A。积分法动力学分析结果表明:当反应级数n=1时,油酸甲酯热氧化降解反应的活化能为27.68 k J/mol,反应动力学模型为rA=-dcA/dt=1 690.55exp(-27.68/RT)cA,亚油酸甲酯热氧化降解反应的活化能为107.04 k J/mol,反应动力学模型为rA=-dcA/dt=2.20×1013exp(-107.04/RT)cA;当反应级数n≠1时,油酸甲酯热氧化降解反应的平均反应级数为1.45,活化能为31.29 k J/mol,反应动力学模型为rA=-dcA/dt=369.19exp(-31.29/RT)c1.45A,亚油酸甲酯热氧化降解反应的平均反应级数为1.60,活化能为108.90 k J/mol,反应动力学模型为rA=-dcA/dt=9.27×1013exp(-108.90/RT)c1.60A。积分法得到的活化能数值更为接近,因此更适合研究油酸甲酯和亚油酸甲酯的热氧化降解反应动力学。     

The effects of exogenous ethylene and methyl jasmonate on the accumulation of phenolic antioxidants in selected whole and wounded fresh produce

Selected fruits and vegetables were exposed to wounding, methyl jasmonate (MJ) or ethylene (ET) stress and effects on the phenylpropanoid metabolism were determined. Lettuce, cilantro, cabbage, green beans, apples, plums, peaches, table grapes, strawberries, bell peppers, asparagus, celery, carrots, radishes, potatoes, and jicama were evaluated for phenolic content and antioxidant capacity (AOX). The phenolic synthesis response to the stresses was tissue-dependent, including decreases, increases or no effects. The use of phytohormones enhanced the wound response on some crops, confirmed by an increase in phenylalanine ammonia lyase (PAL) activity and HPLC phenolic profiles. Several reasons could explain the phenolic accumulation, including the plant genetic machinery, the presence of a common signalling response and differences in phenolic synthesis and degradation kinetics. The synthesized phenolics increased the overall AOX (μg trolox/g FW) of the tissue. Furthermore, the specific AOX (μg trolox/mg phenolics) of the synthesized phenolic compounds was influenced by type of tissue and phytohormone used.     

Inhibition of methyl linoleate autoxidation by phenolics and other related compounds under mild oxidative conditions

Methyl linoleate (MeLo) is a commercially available substrate widely used for studying the inhibitory properties of pure compounds and plant extracts against lipid oxidation. In this paper, 13 phenolic (benzoic and cinnamic acids, aldehydes and derivatives, and flavonoids) and other related compounds (butylated hydroxyanisole, butylated hydroxytoluene and tocopherols) as well as nine complex mixtures rich in phenolics (wines) or tocopherols (soybean oil extracts) were assayed for their inhibitory activity against MeLo autoxidation under mild conditions (40 °C, darkness and atmospheric pressure). Samples were also assayed for their free radical‐scavenging capacity against 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH^?). Protocatechuic aldehyde, a compound that has not been previously evaluated by either of the two methods, showed the highest antioxidant activity. Some variations in the antioxidant ranking for some compounds were found between our results and those obtained by other authors using accelerated conditions for MeLo oxidation. Antioxidant activity of wines and soybean oil extracts was related to their richness in phenolics and tocopherols respectively. Correlation between antioxidant capacity measured by the MeLo and DPPH^? methods was found for wines but not for the other samples studied. Therefore the measure of the free radical‐scavenging capacity of a compound is not always a reliable indicator of its lipid oxidation inhibitory ability. Copyright © 2004 Society of Chemical Industry     

尿素包合法从葡萄籽油中富集高纯度亚油酸甲酯及包合物表征分析

为提升葡萄籽的使用价值,以葡萄籽油为原料,采用尿素包合法富集高纯度亚油酸甲酯。研究了脂肪酸甲酯与尿素质量比、尿素与95%乙醇质量比、包合时间和包合温度对包合效果的影响,并采用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和扫描电子显微镜(SEM)对空白尿素结晶物和包合固形物进行表征。结果表明:制备高纯度亚油酸甲酯的最佳工艺条件为脂肪酸甲酯与尿素质量比1∶2、尿素与95%乙醇质量比1∶4、包合温度5℃、包合时间10 h,在此条件下得到的亚油酸甲酯含量为94.83%,收率为40.41%;FTIR和XRD分析表明,尿素包合反应没有新的官能团生成,且脂肪酸甲酯的包合降低了尿素的结晶度;SEM图像显示,尿素与脂肪酸甲酯形成了六棱体包合物。综上,尿素包合法为富集葡萄籽油中的高纯度亚油酸甲酯的有效方法。     

Suppression of the oxidation of methyl linoleate encapsulated with the extract from defatted rice bran by a compressed hot water treatment

Bran extracts prepared by a compressed hot water treatment at 120, 150, and 180 °C for 7.5 min were used in association with maltodextrin for encapsulation of methyl linoleate. Mixtures of the bran extracts at 120 and 150 °C showed a higher emulsion-stabilizing ability than that at 180 °C. The bran extracts prepared at the higher temperature provided a higher oxidative stability as shown by the longer induction period for the oxidation of the encapsulated methyl linoleate. The induction periods of the encapsulated methyl linoleate using the bran extract prepared at 250 °C for 5 min as the aqueous phase were 3–6 times longer than those of the encapsulated methyl linoleate using water.     

Suppressive effect of defatted rice bran on the oxidation of methyl linoleate

The bran collected at each of the five steps of milling yields (98–100%, 96–98%, 94–96%, 92–94% and 90–92%) was defatted. Defatted rice bran (DRB) was added to methyl linoleate (ML) under various conditions, and its suppressive effect on lipid oxidation was kinetically evaluated to investigate the effective use of surplus rice bran. The rate constant, k, empirically evaluated by the Weibull equation for the oxidation of ML with DRB, was lower than that without DRB and decreased with increasing the maximum milling yield of added DRB. The oxidation of ML strongly depended on the added amount of DRB, but the k value was almost constant for a specific amount of DBR added to ML. The dependency of the k value on relative humidity was weak, regardless of the addition of DRB. The difference between the k values for oxidation processes of ML, with and without DRB, increased with increasing temperature.     

A chemiluminescence study of the oxidation of vegetable oils and model compounds and the effects of antioxidants

Chemiluminescence was used to study the course of oxidation of sunflower oil samples at a number of temperatures between 70 and 121°C. The induction time was determined for each sample and used to estimate the shelf life of the oils at 25°C. In addition, Chemiluminescence during oxidation in air on alumina at 80°C was used to study both sunflower oil and, as a model compound, methyl linoleate with and without added artificial antioxidants. By using the method of inhibitors, the reaction rate and level of hydroperoxide were determined. It was also possible to determine the level of naturally occurring antioxidant in the vegetable oil.     

Impact of antioxidants dispersions on the stability and oxidation of water-in-olive-oil emulsions

Water-in-olive-oil emulsion stability was studied as a function of the composition of the water dispersed phase. In particular, different polyphenolic extracts from natural sources were dispersed in the olive oil and their impact on emulsion kinetic stability and susceptibility to oxidation was evaluated. As natural sources, extra virgin olive oil, olive mill waste and green tea leaves were chosen. To test their impact on emulsion properties, the emulsions were prepared with fixed aqueous phase content. As emulsifiers, a fixed percentage of a mixture Span 80 (sorbitan monoleate)/Tween 80 (polysorbate 80) was used. The effect of the antioxidant dispersion on emulsion oxidation was studied by triggering the oxidation reaction in the oil phase with the lipophilic radical initiator AMVN (2,2-azobis(2,4-dimethylvaleronitrile). Then, the oxidation reaction was followed by using diphenyl-1-pyrenylphosphine, which becomes fluorescent when it is oxidized by hydroperoxides. The impact of antioxidant dispersions on emulsion kinetic stability was studied by UV–Vis turbidity measurements. The oxidation results were correlated to antioxidant extracts oxygen radical adsorption capacity (ORAC) and to emulsion kinetic stability. On the whole, antioxidants dispersions delayed the oxidation reaction to different extents in dependence on their ORAC values and their components amphiphilicity. Remarkably, among the antioxidants tested, the aqueous polyphenol extract from virgin olive oil was the most effective because it protected emulsions both from oxidation and from phase separation. Additionally, from this set of experiments, the primary role of the interfacial properties of olive oil polyphenols was highlighted.     

Effect of selected ions from lyotropic series on lipid oxidation rate

Organic or inorganic salts, commonly present in foods as natural components or ingredients, can affect the hydrophobic/hydrophilic interactions among food components. In particular, modifying the physicochemical equilibrium in the media, the ionic species forming salts could affect the kinetics of chemical reactions occurring in foods. The aim of the present research was to study the influence of different ionic species from lyotropic series on the kinetics of lipid oxidation. For this purpose, salts containing antichaotropic (carbonate and acetate), neutral (Na⁺, K⁺) and chaotropic ions (Cl⁻) were added to soybean oil. Results indicate that potassium carbonate and potassium acetate present a strong antioxidant capacity, whereas no effect was detected for NaCl and KCl. The salt antioxidant activity was prevalently attributed to the antichaotropic anionic species present in the media, which could interact with hydroperoxides by virtue of their ability to form hydrogen bonds. These results appear to be of considerable interest for controlling the development of rancidity in foods.     

Iron-catalyzed lipid oxidation in emulsion as affected by surfactant,pH and NaCl

Corn oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS), Brij 35 or dodecyltrimethylammonium bromide (DTAB) were prepared to determine the influence of surface charge on iron-catalyzed lipid oxidation. Oxidation was measured using lipid peroxides, conjugated dienes, and thiobarbituric reactive substances. At pH 6.5, initial oxidation rates were in the order of SDS> Brij>DTAB. As pH was decreased from 8 to 3, oxidation of SDS-stabilized emulsions increased, while oxidation of Brij and DTAB emulsions were unaffected. NaCl (1.0%) decreased oxidation of the SDS-stabilized emulsion by 20% but had minimal influence on oxidation of Brij and DTAB emulsions. These results indicate that the surface charge of emulsion droplets plays an important role in their oxidative stability.     

Finishing steers with diets based on corn, high-tannin sorghum or a mix of both: Color and lipid oxidation in beef

We tested the hypothesis that feeding high-tannin sorghum (HTS) to steers would produce beef more resistant to oxidative deterioration. We observed lower thiobarbituric acid-reactive substances (TBARS) in Gluteus medius of steers fed HTS before it was displayed (P=0.028), which could be explained by a reduced response to stress in these animals. While steers finished with corn and corn+HTS had elevated plasma cortisol at the end of the feeding period (P=0.047 and 0.093, respectively), animals fed HTS and corn+vitamin E did not. However, feeding HTS increased the rate of discoloration and TBARS accumulation after aerobic display of Longissimus lumborum and Gluteus medius. Diet did not affect the activity of oxidation-related enzymes and fatty acid composition of muscle. The accelerated rate of lipid oxidation during display of beef could be partially explained by a numerically lower concentration of tocopherols in the tissue.     

Effects of calf diet, antioxidants, packaging type and storage time on beef steak storage

The effect of basal dietary supplemented with vegetable oils plus vitamin E (sunflower, soybean, linseed and a basal diet control), type of packaging (MAP or vacuum), addition of natural antioxidant (grape seed, rosemary) and storage time (0, 7, 14 and 21 days) on lipid oxidation, color stability, vitamin E content, and total aerobic bacterial counts in steaks of Longissimus thoracis was studied. The triple interaction diet × time × packaging affected oxidative stability, redness and yellowness of the meat. TBARS values did not increase with time in vacuum-packaged samples for all dietary treatments. However, samples from MAP and control showed the highest TBARS values after 21 days of storage (0.72 mg MDA/kg of meat, P < 0.05). Both exogenous antioxidant extracts and MAP maintained low total aerobic counts in steaks until the 21st day. Calves should be fed a diet supplemented with L-VE, stored in MAP and treated with grape seed extract to extend the shelf life of their meat.     

抗氧化剂的功效及抗氧化活性的体外分析评价

讨论了抗氧化剂在食品和体内的功效：阻止或延缓食品成分的氧化;提高机体的抗氧化能力;治疗某些疾病。并简要介绍了体外分析评价抗氧化活性的方法：TRAP方法、FRAP方法和ABTs方法。     

Critical assessment of voltammetry for rapid screening of antioxidants in marine algae

Voltammetric methods of analysis represent an attractive option for rapid screening of large numbers of plant samples in the search for novel antioxidants. However, the technique has not found widespread use as compared to established methods such as the DPPH and Folin–Ciocalteu assays. In this study we provide a critical assessment of voltammetric methods compared to the DPPH and Folin–Ciocalteu assay by conducting antioxidant assays using these methods in a study of 99 crude samples of marine algae. Thirty samples showed the presence of antioxidants via the voltammetric assay compared with 20 samples for the DPPH assay and 16 via the FC assay. Through a detailed interpretation of the results the study suggests that voltammetric methods can identify potential antioxidants in crude samples with a higher degree of confidence than DPPH or the FC method alone and represents a viable screening method for marine algal samples.     

Activity and thermal stability of antioxidants by differential scanning calorimetry and electron spin resonance spectroscopy

Heat flux differential scanning calorimetry (DSC) and electron spin resonance spectroscopy (ESR) were used to assess the activity and the thermal stability of antioxidants in four vegetable oils. Sunflower oil (SO) and high oleic sunflower oil (HOSO), both rich in diunsaturated fatty acids (FA), low trans oil (LT) and partially hydrogenated palm oil (PHPO), both containing monounsaturated FA, were analyzed by isothermal heat flux DSC, with or without 300 mg/kg of antioxidant: ascorbyl palmitate (AP), α-tocopherol (αT), δ-tocopherol (δT) and propyl gallate (PG). DSC experiments showed that δT is the most effective antioxidant for SO and PG for the less unsaturated oils. SO and PHPO were also analyzed by ESR at 120 and 145 °C, respectively. ESR results confirm the strongest antioxidant activity of δT and PG for SO and PHPO, respectively. Therefore, the present study demonstrates that DSC and ESR are valuable technologies to study activity and stability of antioxidants at high temperature. Moreover, experiments performed in the presence of the spin-trap N-tert-butyl-α-phenylnitrone (PBN), suggest that δT delay lipid oxidation through a different reaction mechanism when compared to αT. A different mechanism between tocopherols isomers in delaying lipid oxidation has been hypotized.     

Antioxidant consumption and development of oxidation during ageing of buffalo meat produced in Argentina

Buffalo meat production is increasing in Argentina. Information on meat quality and nutritional value will be useful in marketing. This work describes the oxidative stability of the Longissimus dorsi (LD) in relation to consumption of antioxidant vitamins, fatty acid composition and color deterioration during ageing. Vitamins levels found in fresh beef were 4.22±0.93; 0.24±0.05 and 0.25±0.06μg/g for α- and γ-tocopherol, and β-carotene, respectively. Vitamin loss was almost 90% throughout an ageing period of 25 days at 2°C. Concomitantly, TBARS levels increased from 0.076±0.018 to 0.14 6±0.032mg MDA/kg beef. Hexanal and pentanal levels were low and no correlations with oxidation were detected (P>0.05). The predominant color changes in aged beef were reduced redness and yellowness with an increase in lightness (P<0.05). Vitamin levels and TBARS were used to develop a prediction equation for post-mortem aging.