Comparing Antioxidant Effectiveness of Natural and Synthetic Free Radical Scavengers in Thermally-Oxidized Lard using DPPH Method

ABSTRACT: Antioxidant effectiveness of free radical scavengers (FRSs) of α-tocopherol, sesamol, butylated hydroxytoluene (BHT), and tert-butylhydroquinone (TBHQ) were evaluated in thermally-oxidized lard using methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH), conjugated dienoic acid (CDA), and p-anisidine value (p-AV). Absorbance of DPPH with lard containing 2.5 μmol/g FRSs were low before oxidation while those with control lard was high due to the hydrogen atom donating ability of FRSs. During oxidation, DPPH absorbance with lard containing FRSs increased differently up to the certain point depending on the types of FRSs. DPPH absorbance of lard without FRSs started to decrease upon oxidation, which indicates that free radical scavenging compounds were generated from oxidized lipids. Results of CDA and p-AV showed that the highest antioxidant capacity was in the order of TBHQ = sesamol, BHT, and α-tocopherol. Antioxidant effectiveness of FRS should consider the hydrogen atom donating rates of FRS, the reactivity and stability of FRS at treatment temperature, and characteristics of radicals from FRSs, which may be predicted by the results of DPPH method.     

Correlation of antioxidant content and absorbance changes of DPPH during lipid oxidation

Absorbance of DPPH in isooctane has been developed to determine the degree of lipid oxidation and antioxidant capacities in lipid systems. Lard with or without addition of sesamol, a free radical scavenger, was thermally oxidized and absorbance of DPPH in isooctane, conjugated dienoic acid (CDA) values, p-anisidine value (p-AV), and sesamol content were analyzed. Changes of DPPH absorbance in early stages of oxidation were highly correlated to the decrease of sesamol content. In later stages of lipid oxidation, formation of radical scavenging compounds from oxidized lipids (RSOLs) played major roles in the decrease of DPPH absorbance. CDA and p-AV did not have good correlations with DPPH absorbance in lard systems. This study clearly shows that the content of free radical scavengers and/or RSOLs influenced the changes of DPPH absorbance, which cannot be determined by conventionally methods like CDA and p-AV methods.     

Application of DPPH absorbance method to monitor the degree of oxidation in thermally-oxidized oil model system with antioxidants

Changes of 2,2-diphenyl-1-picrylhydrazyl (DPPH) absorbance were monitored in thermally-oxidized lard containing free radical scavengers (FRSs). Hydrogen donating abilities of α-tocopherol to DPPH were higher than those of sesamol and butylated hydroxyanisole (BHA), indicating reactivity of DPPH and FRSs in lard depends on the types of FRSs. For the first 20 min oxidation, DPPH absorbance from lard with 3.38 μmol/g α-tocopherol, sesamol, and BHA increased by 0.324, 0.240, and 0.313, respectively while those from lard without FRS decreased by 0.350. Results of conjugated dienoic acid (CDA), and p-anisidine value (p-AV) showed that antioxidative activity were high in the order of sesamol, BHA, and α-tocopherol, which implies that hydrogen donating abilites of FRSs may not be the most critical factor to determine antioxidant effectiveness. Monitoring DPPH absorbance in oxidized lard with FRS could be useful indicators for comparing antioxidative ability of FRSs.     

Development of a method predicting the oxidative stability of edible oils using 2,2-diphenyl-1-picrylhydrazyl (DPPH)

The 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay was used to predict the oxidative stability of edible oils. The principle of DPPH method is to measure the free radicals generated from oxidized oils directly. The absorbance of DPPH from oils before thermal oxidation decreased proportionally to the concentration of free radical scavenging compounds such as butylated hydroxytoluene (BHT). Oxidized oils with high polyunsaturated fatty acid (PUFA) contents showed high changes in DPPH absorbance or free radical formation rates than those with low PUFA. Oxidized oils with high BHT content were more stable and showed slower pattern change of DPPH absorbance from positive to negative slopes than those with low BHT content. Oxidative stability of oils could be predicted considering the initial values of DPPH absorbance, the free radical formation rates, and the oxidation period for pattern changes. The results from DPPH method on the oxidative stability of vegetable oils agreed with conventional methods such as p-anisidine value (p-AV), conjugated dienoic acids (CDA), or total polar matter (TPM).     

Evaluation of solvent effects on the DPPH reactivity for determining the antioxidant activity in oil matrix

Reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical in methanol, ethanol, isopropanol, isooctane, and ethyl acetate, was evaluated to assess the antioxidant capabilities in medium chain triacylglycerol. DPPH loss values were obtained over 30 min, with sampling every 5 min. Even the same concentration of antioxidants showed different DPPH reactivity depending on solvent. In methanol, 5 min was enough for α-tocopherol to react with DPPH, whereas BHT did not react with DPPH even after 30 min. Gallate series showed higher DPPH reactivity than TBHQ, sesamol, or BHA in methanol, while lower reactivity in isooctane. Antioxidants in ethanol and isopropanol reacted with DPPH less efficiently compared to those in methanol, the exception being sesamol. DPPH reactivity of gallate series in isooctane was lower than that of sesamol, TBHQ, and α-tocopherol. Combinatorial usage of methanol and isooctane for DPPH reactivity could provide reliable information on the antioxidant capacities of chemicals in edible oils.Supplementary InformationThe online version contains supplementary material available at 10.1007/s10068-020-00874-9.     

Comparison of microwave irradiation and conventional thermal heating on volatile profiles and degree of oxidation in corn oil

Volatile profiles and degree of oxidation in corn oils after microwave treatment for 50 min were compared to oils with conventional heating at 180°C for 4 h. Oil microwaved for 10 and 50 min showed a similar degree of oxidation compared to the oil heated at 180°C for 1 and 3 h, respectively, based on the primary and secondary oxidation products. However, the total volatile contents of 50 min-microwaved oil were significantly lower than that of corn oil heated for 1 h at 180°C (P < 0.05). Microwave treatment accelerated the rates of lipid oxidation by 4.6 times compared to 180°C thermal oxidation. Relatively short treatment with microwave irradiation may not provide sufficient time to generate volatiles from oil. Microwaved corn oil for 50 min had higher contents of hexanal and t-2-heptenal and lower contents of 2,4-decadienal and nonanal than the oils heated at 180°C for 3 h. Reactive oxygen species may be involved in volatile formation in microwave-irradiated oils.     

Dietary oxidised lipids,health consequences and novel food technologies that thwart food lipid oxidation: an update

Processed foods are popular and their consumption is expected to grow globally. Food processing and manufacturing promote lipid oxidation in foods rich in polyunsaturated fatty acids and cholesterol. This review focuses on how various food manufacturing/processing techniques promote lipid oxidation in grains, meats and meat products, dairy and fats/oils. This review also considers emerging evidence from animal and human studies that suggest a link between dietary oxidised lipid consumption and chronic disease risk. An update on novel food technologies that limit food lipid oxidation is discussed so as to inform both food scientists and dietitians/nutritionists to direct future efforts in not only continuing to bring these novel technologies to the market place but also conduct clinical trials to establish their role in human health.     

Potential use of extra virgin olive oil in bakery products rich in fats: a comparative study with refined oils

The lipid fraction of bakery products undergoes a significant degradation during baking, with an increase in undesirable oxidised substances, that can act as catalysts for further oxidative reactions during storage reducing the product shelf life. The use of extra virgin olive oil in bakery products rich in fat in place of refined oils was studied, assessing the evolution of the oxidative and hydrolytic degradation during storage. Two‐way analysis of variance, followed by Tukey's HSD test for multiple comparisons, covariance and principal component analyses were carried out to compare the effect of the type of oils. The data obtained showed that the evolution of the oxidation levels in the analysed samples during storage was related to the type of oil used in the production process. Particularly, the use of extra virgin olive oil led to significantly lower values of hydroperoxides, ultraviolet absorption constants, triacylglycerol oligopolymers and oxidised triacylglycerols.     

Enzymatic Determination of Cholesterol Oxides

For measurement of the concentration of oxidised cholesterols in foodstuffs, a method was developed by adapting the well-known enzymatic determination of cholesterol. A linear correlation was found between the absorbance measured after enzymatic reaction and the concentrations of 7α-hydroxycholesterol, 7β-hydroxycholesterol, 7-ketocholesterol, cholesterol-5α, 6α-epoxide in the range 1–12 μg. The usefulness of this method was demonstrated by determination of the four cholesterol oxidation products separated by TLC from the non-saponifiable lipid fraction of 5-month-old whole-egg powder (stored under different conditions) and of biscuit enriched with egg powder. The main advantages of the combination of TLC and the enzymatic method, beyond its rapidity and sensitivity, are that the determination of cholesterol oxidation products can be carried out in parallel with many samples containing small amounts of oxidised cholesterols even in the presence of a large quantity of cholesterol.     

Three extraction methods for determination of lipids in fish meal: Evaluation of a hexane/isopropanol method as an alternative to chloroform-based methods

Three different extraction methods were compared for the determination of lipids in both oxidised and antioxidant-stabilised brown fish meal. The three methods under investigation were those of Smith-Ambrose-Knobl using chloroform/methanol/water, Bligh and Dyer also using chloroform/methanol/water but monophasic, and Hara and Radin using hexane/isopropanol. The fat content, determined gravimetrically, was significantly lower (P < 0.05) when hexane/isopropanol was used for lipid extraction from both oxidised and antioxidant-stabilised fish meal, than when either of the chloroform systems was used. Determination of lipid classes in the lipid extracts using silica gel thin-layer chromatography on Chromarods-SIII, with flame ionisation detection by latroscan, suggested that the lower lipid recovery by the hexane/isopropanol method may be due to a less effective extraction of the more polar lipid classes. including oxidation products, present in brown fish meal.     

迷迭香提取物对水酶法提取的植物油抗氧化性的影响

研究两种不同溶剂（甲醇和乙醇）提取的迷迭香提取物,对五种水酶法制得植物油抗氧化性的影响。通过脂肪酸组成、氧化诱导时间、DPPH自由基清除能力、ABTS+自由基清除能力等指标,对油样抗氧化性进行评价。结果表明,两种溶剂提取的迷迭香提取物均可以有效提高水酶法制得植物油的抗氧化能力,其中甲醇作为溶剂的迷迭香提取物抗氧化能力较强。      

Dissimilarity of the oxidations of rapeseed and butter oil triacylglycerols and their mixtures in the absence of tocopherols

Although fatty acid composition is the most important attribute used to control oxidation stability, all edible oils are affected by lipid oxidation irrespective of whether they are highly unsaturated or not. The aim of the study was to compare the oxidation of rapeseed oil (RO) and butter oil (BO) triacylglycerols (TAGs) and their mixtures containing 10% or 20% of the other. Oxidation of the TAGs at 40°C was followed by formation of primary and secondary products. Statistical methods were used to interpret the data. The RO and BO TAGs and their mixtures began to oxidise without any induction periods. In the RO TAGs more hydroperoxides and p‐anisidine reactive compounds were formed than in the BO TAGs. The BO TAGs oxidised more than would be expected by their fatty acid composition. High susceptibility of BO TAGs to oxidation was caused by the easy breakdown of their hydroperoxides. Heptadienal and heptenal were specific products of oxidised RO TAGs and heptanal and nonenal of oxidised BO TAGs. Mixtures of RO and BO TAGs behaved according to which was dominant in the mixture. However, as little as 10% of RO or BO TAG introduced its specific oxidation products to the mixture. © 1999 Society of Chemical Industry     

Fatty acid composition, antioxidants and lipid oxidation in chicken breasts from different production regimes

Chicken breast from nine products and from the following production regimes: conventional (chilled and frozen), organic and free range, were analysed for fatty acid composition of total lipids, preventative and chain breaking antioxidant contents and lipid oxidation during 5 days of sub‐ambient storage following purchase. Total lipids were extracted with an optimal amount of a cold chloroform methanol solvent. Lipid compositions varied, but there were differences between conventional and organic products in their contents of total polyunsaturated fatty acids and n‐3 and n‐6 fatty acids and n‐6:n‐3 ratio. Of the antioxidants, α‐tocopherol content was inversely correlated with lipid oxidation. The antioxidant enzyme activities of catalase, glutathione peroxidase and glutathione reductase varied between products. Modelling with partial least squares regression showed no overall relationship between total antioxidants and lipid data, but certain individual antioxidants showed a relationship with specific lipid fractions.     

Anti‐radical power gives insight into early lipid oxidation events during frying

The aim of this research was to use anti‐radical power (ARP) to study early lipid oxidation events during frying. The 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH?) test was used to determine the ARP. As oil does not dissolve completely in methanol, which is generally used for the DPPH? test, butanol was used instead. Changing the solvent did not influence the value of the ARP. The decrease of the ARP highly correlated with the increase of the peroxide value for soybean oil heated at 110 °C (R² = 0.99). Sensory analysis showed that rancidity of soybean oil and frying oil, heated at 180 °C, was perceived before the ARP decreased. Once the oil was perceived as rancid, the intensity of rancidity did not change significantly upon further heating. The ARP of soybean oil was found to decrease faster at 110 °C than at 180 °C, suggesting different mechanisms of radical formation. The total polar compounds of frying oil in which French fries were fried did not differ significantly from frying oil that was heated alone. However, frying of French fries caused more hydrolysis of the oil, while the ARP decreased faster when the oil was heated alone. Copyright © 2006 Society of Chemical Industry     

A novel approach to monitor the oxidation process of different types of heated oils by using chemometric tools

The oxidative stability of seven oils with different fatty acid profiles was assessed. Oxidation at 0, 2 and 4 h at 180 °C was monitored by measuring the absorbance of thiobarbituric acid reactive substances (TBARS) along the absorption spectrum (300–600 nm), the volatile aldehydes (HS-SPME–GC–MS) and the fatty acid profile (FID-GC).TBARS absorption spectrum behavior depended on the lipid composition of heated oils. Higher absorbance increments during heating were noticed at 390 nm compared to 532 nm (from 2 to 21 fold higher depending on the oil), pointing to its better sensitivity to detect oxidation. Furthermore, a close relationship between ABS₃₉₀, the loss of polyunsaturated fatty acids and their corresponding oxidation compounds (volatile aldehydes) was revealed by Principal Component Analysis.Multiparametric equations allowed predicting the formation of volatile aldehydes of heated oils by measuring only two parameters: TBARS₃₉₀ during their heating, and the lipid profile in unheated oils (MUFA, ω-3 and ω-6). Results pointed out the interest of choosing ABS₃₉₀ when the oxidative evolution of vegetable oils under heating is assessed by the TBARS test.     

Study of the oxidative degradation of farmed salmon lipids by means of Fourier transform infrared spectroscopy. Influence of salting

Farmed salmon fillets were dry‐salted for 24 h. Both salted and unsalted samples were submitted to oxidative conditions at 50 °C in an oven with circulating air. Lipids of both samples were extracted daily from aliquots and studied by Fourier transform infrared spectroscopy. The infrared spectra of salmon lipids are similar to those of vegetable edible oils, with differences in the frequency and absorbance of some bands due to their different acyl group compositions. The infrared spectra of salted and unsalted fish lipid samples remain unchanged during a period of time, which is shorter for the salted salmon. After this period, changes in the frequency and absorbance of some bands of the spectrum are observed owing to the presence of oxidation products. Therefore the reduction in the oxidative stability of farmed salmon lipids caused by the dry‐salting process is proved and the usefulness of this technique for studying the oxidative stability of fish lipid samples as well as their oxidation degree is shown. Copyright © 2004 Society of Chemical Industry     

Effect of storage on chemical and sensory profiles of peanut pastes prepared with high‐oleic and normal peanuts

BACKGROUND: Peanut paste and peanut butter have high oil contents and are thus susceptible to developing rancidity and off‐flavours through lipid oxidation. Preservation of the chemical and sensory quality of these products is one of the main problems in the peanut industry. The purpose of this study was to compare the chemical and sensory stability of peanut paste prepared with high‐oleic peanuts (cv. Granoleico, GO‐P) with that of peanut paste prepared with normal peanuts (cv. Tegua, T‐P) from Argentina. RESULTS: Chemical (peroxide and p‐anisidine values and conjugated dienes) and sensory (roasted peanutty, oxidised and cardboard flavours) indicators of lipid oxidation were measured in peanut pastes stored at 4, 23 and 40 °C. Chemical indicator values and oxidised and cardboard flavours showed lower increments in GO‐P than in T‐P during storage. T‐P had significantly higher peroxide value than GO‐P. Roasted peanutty flavour showed a lower decrease in GO‐P. Peanut paste prepared with high‐oleic peanuts had four (at 4 °C), two (at 23 °C) and three (at 40 °C) times longer shelf‐life than peanut paste prepared with normal peanuts. CONCLUSION: These results indicate that high‐oleic Granoleico kernels provide peanut paste with higher protection against lipid oxidation. Copyright © 2010 Society of Chemical Industry     

Iron‐mediated lipid oxidation in 70% fish oil‐in‐water emulsions: effect of emulsifier type and pH

The objective of this study was to investigate the protective effect of five different emulsifiers on iron‐mediated lipid oxidation in 70% fish oil‐in‐water emulsions. The emulsifiers were either based on protein (whey protein isolate and sodium caseinate) or based on phospholipid (soy lecithin and two milk phospholipids with different phospholipid contents, MPL20 and MPL75). Lipid oxidation was studied at pH 4.5 and 7.0, and results were compared to lipid oxidation in neat fish oil. Results showed that all emulsions oxidised more than neat oil. Furthermore, emulsions prepared with proteins oxidised more at low pH than at high pH, and casein emulsions oxidised the least (Peroxide value (PV) at day 7 was 0.5–0.7 meq kg^?1). Among emulsions prepared with phospholipids, emulsions with MPL75 were the most oxidised followed by emulsions prepared with lecithin and MPL20. Thus, PV in MPL75 emulsions was 5.0–5.5 meq kg^?1 at day 7 compared with 0.9–1.9 meq kg^?1 in MPL20 emulsions.     

Tocopherol content,peroxide value and sensory attributes in roasted peanuts during storage

The objective of this study was to determine changes in tocopherol content, peroxide value (PV) and sensory attributes from roasted peanuts during storage at 40 °C. There were no differences in tocopherol contents between roasted and raw peanuts except in α‐tocopherol content that decreased after roasting. All tocopherol contents decreased during storage. On the contrary, lipid oxidation indicators such as PV and the intensity ratings of oxidised and cardboard flavour increased during storage. On the other hand, the intensity ratings of roasted peanutty flavour decreased with storage time. Good correlations were observed between tocopherol contents and PVs. Tocopherol contents could be used as indicator of oxidative state in peanut products.