Impact of Free Fatty Acids and Phospholipids on Reverse Micelles Formation and Lipid Oxidation in Bulk Oil

Association colloids such as phospholipid reverse micelles could increase the rate of lipid oxidation in bulk oils. In addition to phospholipids, other surface active minor components in commercial oils such as free fatty acids may impact lipid oxidation rates and the physical properties of reverse micelles. In this study, the effects of free fatty acids on changes in the critical micelle concentration (CMC) of 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) in stripped corn oil (SCO) were determined by using the 7,7,8,8-tetracyanoquinodimethane solubilization technique. Different free fatty acids including myristoleic, oleic, elaidic, linoleic and eicosenoic were added at 0.5 % by wt along with the DOPC into the bulk oils. There was no significant effect of free fatty acids with different chain length, configuration and number of double bonds on the CMC value for DOPC in bulk oil. However, increasing concentrations of oleic acid (0.5 to 5 % by wt) caused the CMC value for DOPC in bulk oils to increase from 400 to 1,000 μmol/kg oil. Physical properties of DOPC reverse micelles in the presence of free fatty acids in bulk oils were also investigated by the small angle X-ray scattering technique. Results showed that free fatty acids could impact on the reverse micelle structure of DOPC in bulk oils. Moreover, free fatty acid decreased pH inside reverse micelle as confirmed by the NMR studies. The oxidation studies done by monitoring the lipid hydroperoxide and hexanal formation revealed that free fatty acids exhibited pro-oxidative activity in the presence and absence of DOPC. Different types of free fatty acids had similar pro-oxidative activity in bulk oil.     

Inhibited Oxidation of Lipids II: Comparison of the Antioxidative Properties of Some Hydroxy Derivatives of Benzoic and Cinnamic Acids

The antioxidative properties of p-hydroxy-benzoic acid, vanillic acid, syringic acid, 3,4-dihydroxy-benzoic acid, p-coumaric acid, ferulic acid, sinapic acid and caffeic acid in lard autoxidation at 100°C are compared. The effect of phenolic acids is investigated within the concentration range 0.02 – 0.20 wt %. It is proved that the derivatives of the benzoic acid have weaker inhibiting properties than is the case of the corresponding analogues of the cinnamic acid due to the more active participation of the inhibitor in the elementary reactions of propagation and initiation of the radical chain process. The activity (a complex parameter demonstrating the efficiency and strength of the antioxidant) of the phenolic acids investigated decreases in the sequence: caffeic acid >3,4-dihydroxy-benzoic acid > sinapic acid > syringic acid>ferulic acid>p-coumaric acid>vanillic acid. The increase in concentration of the acids investigated is most advisable in the case of sinapic, syringic and ferulic acids which are not consumed in side reactions.     

Primary Metabolites and Polyphenols in Rapeseed (Brassica napus L.) Cultivars in China

Defatted meals of 10 rapeseed (Brassica napus L.) varieties were investigated for their total phenolic, phenolic acid (free, esterified, and insoluble-bound forms), and tannin contents. The antioxidant capacities (AC) of methanol extracts from samples were assessed using the 2,2′-diphenyl-1-picrylhydrazyl radical (DPPH•), Folin–Ciocalteu method and ferric reducing antioxidant power (FRAP), and β-carotene–linoleic acid tests. In the fraction of free phenolic acids, sinapic, caffeic, ferulic, syringic, gallic, and p-coumaric acids were identified. In the fraction of esterified phenolic acids, sinapine, sinapoyl glucoside, and disinapoyl gentiobiose were identified. After basic hydrolysis, sinapic, ferulic, cinnamic, and 4-hydroxybenzoic acids were identified, and sinapic acid (SA) constituted 98.3% to 99.6% of the total esterified phenolic acids. Eleven components (sinapic, protocatechuic, p-coumaric, syringic, vanillic, gallic, caffeic, ferulic, salicylic, cinnamic, and 4-hydroxybenzoic acids) in the fraction of insoluble-bound phenolic acids were identified. The AC of the samples correlated with the total phenolic content. Overall, the total phenolics showed a better correlation with AC than the individual phenolic compounds. Moreover, SA, sinapoyl glucoside, and disinapoyl gentiobiose showed a highly significant and strong positive correlation with the AC of rapeseed meals, and the derivatives of cinnamic acid showed a higher correlation with AC than the derivatives of benzoic acid. The change in the canolol content in rapeseeds under microwave irradiation is discussed. The correlation of the canolol formed with SA and its derivatives is discussed.     

Chemo‐enzymatic synthesis and evaluation of novel structured phenolic lipids as potential lipophilic antioxidants

Chemo‐enzymatic synthesis of structured triacylglycerol bearing ferulic acid as a phenolic acid at sn‐1/3 position is described in the present work. Four compounds of varying chain lengths, namely 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐hexanoyloxy‐propyl ester, 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐octanoyloxy‐propyl ester, 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐dodecanoyloxy‐propyl ester, and 3‐(4‐hydroxy‐3‐methoxy‐phenyl)‐acrylic acid‐2,3‐bis‐9‐octadecenoyloxy‐propyl ester were synthesized, and their structures were confirmed by IR, NMR, and MS. Antioxidant activity of the structured phenolic lipids were evaluated using three different in vitro antioxidant assays such as 2, 2‐diphenyl‐1‐picrylhydrazyl free radical (DPPH^•) scavenging, antioxidant potency in lipid matrix using rancimat, and by the rate of inhibition of autoxidation of linoleic acid in micelles. Ferulic acid and dodecylgallate were used as reference antioxidant compounds. DPPH^• assay did not show any improvement in the antioxidant activity of ferulic acid with lipophilic modification. However, the antioxidant potency of the structured phenolic lipids measured by rancimat method as well as by the rate of inhibition of autoxidation of linoleic acid in micelle showed improvement in antioxidant activity compared to ferulic acid. This is probably due to better solubility of the synthesized phenolic lipids in a hydrophobic medium and appropriate anchorage in Tween 20 micelle. The observed activities of the structured phenolic lipids are comparable to dodecyl gallate in rancimat assay, but superior to dodecyl gallate in Tween 20 micellar system.     

Kinetics of lipid oxidation in the presence of cinnamic acid derivatives

The effects of seven (prenyl‐ and methoxy‐) derivatives of cinnamic acid (0.1 mM) on the kinetics of lipid (sunflower oil triacylglycerols, TGSO) bulk phase oxidation at 80 °C have been compared. Synthesis of prenyl cinnamic acid derivatives: 3‐prenyl‐4‐hydroxy‐cinnamic acid (PHC), 3,5‐diprenyl‐4‐hydroxy‐cinnamic acid (DPHC), 2,2‐di‐methyl‐6‐carboxy‐ethenyl‐2H‐benzopyran (DMCB), 2,2‐dimethyl‐6‐carboxy‐ethenyl‐8‐prenyl‐2H‐benzopyran (DCEPB) present in Brazilian propolis has been performed. The monoprenyl derivative (PHC) has been found to exert a higher antioxidant activity as compared to the diprenyl derivative (DPHC). However, cinnamic acid derivatives DMCB and DCEPB have caused no change in the kinetics of TGSO oxidation. The results obtained have been compared with those on related compounds containing a cinnamic acid moiety as a structural feature, such as 4‐hydroxy‐cinnamic (p‐coumaric), 3‐methoxy‐4‐hydroxy‐cinnamic (ferulic) and 3,5‐dimethoxy‐4‐hydroxy‐cinnamic (sinapic) acids, as well as with data on butylated hydroxytoluene (BHT) and α‐tocopherol (αToc). PHC has shown a stronger antioxidant efficiency than BHT, p‐coumaric and ferulic acid, but a weaker antioxidant efficiency than α‐Toc and sinapic acid. The observed antioxidant effect of DPHC was stronger than that of p‐coumaric and ferulic acids and weaker than that of α‐Toc, BHT and sinapic acid.     

Antioxidant Activities and Phenolic Compositions of Wheat Germ as Affected by the Roasting Process

Wheat germ is a good source for wheat germ oil, and it is a by‐product with highly concentrated nutrients from the wheat flour‐milling industries. In the present study, raw wheat germ was firstly heat‐treated at 180 °C for 20 min in a fluidized bed dryer, and further roasted at 180 °C for different periods of time. Roasting influence on total phenolic content (TPC), antioxidant activities, and phenolic compositions of wheat germ were evaluated. The roasting process significantly increased the TPC and antioxidant activities including free radical scavenging against DPPH and ABTS radicals, FRAP, and ORAC. In particular, the wheat germ roasted at 180 °C for 20 min showed higher antioxidant activity than those roasted at 180 °C for 5 and 10 min. Three major phenolic acids, namely, ferulic, chlorogenic, and caffeic acid, and four main flavonoids, namely, schaftoside and its isomers or adduct of sinapic acid were identified by HPLC. In general, the content of individual phenolic compounds decreased with prolongation of the roasting time except for ferulic acid. The results suggest that the antioxidant activities of wheat germ can be enhanced by roasting, and the enhancement effect might be partially attributed to the formation of Maillard reaction products (MRP).     

Recovery of Oil,Erucic Acid,and Phenolic Compounds from Rapeseed and Rocket Seeds

Erucic acid‐enriched oil, sought for industrial purposes, from rapeseed (agronomic plant) and rocket seeds (non‐agronomic plant) was extracted by three different processes: supercritical CO₂, mechanical expression, and hexane extraction. Oil extraction yields were determined and the extracted oils were characterized for their fatty acid and phenolic compound compositions. Higher oil yields were achieved using hexane compared to mechanical expression and supercritical CO₂ extractions. Fatty acid analysis indicated a higher content of erucic acid in rapeseed oil than in rocket oil. In addition, supercritical CO₂ extraction allowed better recovery of phenolic compounds with high antioxidant activities. The most prominent identified polyphenols were vanillin, sinapic acid, syringic acid, and apigenin.     

Effect of lipid unsaturation on the antioxidative activity of some phenolic acids

Antioxidative properties ofp-hydroxybenzoic, vanillic, syringic, 3,4-dihydroxybenzoic,p-coumaric, ferulic, sinapic and caffeic acids were studied in the concentration range 0.02–0.20 wt% during autoxidation at 100°C of lard and sunflower oil methyl esters (MEL and MESO, respectively). In both lipid systems, the derivatives of benzoic acid had weaker inhibiting properties than did the corresponding analogues of cinnamic acid. The effectiveness and strength of the antioxidative action were considerably lower in the lipid system MESO, which was rich in linoleic acid and was more easily oxidized. Thep-hydroxybenzoic, vanillic, syringic andp-coumaric acids in this system exercised no inhibiting effect. We established that the molecules of the investigated phenolic acids initiated the chain radical process of autoxidation, and the formed antioxidant radicals propagated the chains as a result of the reaction with the lipid substrate. These reactions proceeded at a higher rate in MESO than in MEL.     

Antioxidative effect of the main sinapic acid derivatives from rapeseed and mustard oil by‐products

Amongst oilseeds, rapeseed and mustard are rich sources of phenolic compounds, which also prominent in the by‐products of their respective oil processing or in commercial rapeseed and mustard press cakes. These cakes are rich sources of sinapic acid derivatives, which could be extracted as free sinapic acid or sinapine, the choline ester of sinapic acid. Sinapic acid is a widely investigated antioxidative compound. However, the main compound in the press cakes is present as sinapine. Investigations on the free‐radical‐scavenging activity of sinapic acid and sinapine indicate that sinapine had a significant but lower activity as compared to sinapic acid. Apart from this, sinapic acid, sinapine and different tocopherols were compared as antioxidants for inhibition of the formation of lipid oxidation products in purified rapeseed oils. The oxidation at 40 °C was monitored by the formation of hydroperoxides and propanal. The experiments indicate that in contrast to tocopherol mixtures addition of sinapic acid causes increasing inhibition of hydroperoxide formation when enhancing the concentration from 50 to 500 μmol/kg oil. Sinapine was not able to inhibit the formation of hydroperoxides, compared to sinapic acid. This indicates that sinapic acid‐rich extracts, as compared to sinapine‐rich fractions, could better inhibit the lipid oxidation in bulk lipid systems.     

Association Colloids Formed by Multiple Surface Active Minor Components and Their Effect on Lipid Oxidation in Bulk Oil

Association colloids formed by surface active minor components play an important role in the oxidative stability of bulk oils. To imitate the formation of nanostructures in refined oils, multiple surface active minor components including phospholipids, free fatty acids, diacylglycerols and sterols were added to stripped corn oil. The critical micelle concentration (CMC) of the mixed components was determined. The impact of mixed minor components at below and above their CMC on oxidative stability of bulk oil and on antioxidant activity of α-tocopherol and Trolox was investigated. The CMC of the mixed surface active components in bulk oil was 20 µmol/kg oil in the presence of 383 ± 2 ppm of water. 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) played an important role on the formation of association colloids since it was the most important component in forming the association colloids as confirmed by CMC and fluorescence probe studies. The association colloids formed by the mixed components showed prooxidative activity in bulk oil as determined by monitoring the formation of lipid hydroperoxide and hexanal. The activity of α-tocopherol or Trolox was not changed by mixed components association colloids. These results suggest that association colloids both physically and chemically impacted the oxidative stability and activity of antioxidants in bulk oil.     

Antioxidant activity of almonds and their by-products in food model systems

Antioxidant activities of almond whole seed, brown skin, and green shell cover extracts, at 100 and 200 ppm quercetin equivalents, were evaluated using a cooked comminuted pork model, a β-carotene-linoleate model, and a bulk stripped corn oil system. Retention of β-carotene in a β-carotene-linoleate model system by almond whole seed, brown skin, and green shell cover extracts was 84–96, 74–83, and 71–93%, respectively. In a bulk stripped corn oil system, green shell cover extract performed better than brown skin and whole seed extracts in inhibiting the formation of both primary and secondary oxidation products. In a cooked comminuted pork model system, green shell cover and brown skin extracts inhibited the formation of TBARS, total volatiles, and hexanal more effectively than did the whole seed extract. HPLC analysis revealed the presence of caffeic, ferulic, p-coumaric, and sinapic acids as the major phenolic acids in all three almond extracts examined.     

Impact of Phosphoethanolamine Reverse Micelles on Lipid Oxidation in Bulk Oils

Phospholipids are important minor components in edible oil that play a role in lipid oxidation. Surface active phospholipids have an intermediate hydrophilic–lipophilic balance value, which allows them to form association colloids such as reverse micelles in bulk oil. These association colloids can influence lipid oxidation since they create lipid–water interfaces where prooxidants and antioxidants can interact with triacylglycerols. In this study, we examined the formation of reverse micelles in a stripped oil system by dioleoyl phosphoethanolamine (DOPE) and the effect of these physical structures on lipid oxidation kinetics. The critical micelle concentration (CMC) of DOPE was approximately 200 µmol/kg oil at 45 °C. Oxidation kinetics studies showed that DOPE was prooxidative when it was above its CMC (400 and 1,000 µM), reducing the lag phase from 14 days (control) to 8 days. The addition of combinations of DOPE and dioleoyl phosphocholine (DOPC) resulted in formation of mixed micelles with a CMC of 80 µmol/kg oil at 45 °C. These mixed micelles were also prooxidative when concentrations (100 and 500 µM) were above the CMC, decreasing the lag phase from 14 to 8 days. These findings provide a better understanding of the role of phospholipids in lipid oxidation of edible oil and could contribute to better antioxidant solutions.     

Effect of natural antioxidants in virgin olive oil on oxidative stability of refined,bleached, and deodorized olive oil

The factors influencing the oxidative stability of different commercial olive oils were evaluated. Comparisons were made of (i) the oxidative stability of commercial olive oils with that of a refined, bleached, and deodorized (RBD) olive oil, and (ii) the antioxidant activity of a mixture of phenolic compounds extracted from virgin olive oil with that of pure compounds andα-tocopherol added to RBD olive oil. The progress of oxidation at 60°C was followed by measuring both the formation (peroxide value, PV) and the decomposition (hexanal and volatiles) of hydroperoxides. The trends in antioxidant activity were different according to whether PV or hexanal were measured. Although the virgin olive oils contained higher levels of phenolic compounds than did the refined and RBD oils, their oxidative stability was significantly decreased by their high initial PV. Phenolic compounds extracted from virgin olive oils increased the oxidative stability of RBD olive oil. On the basis of PV, the phenol extract had the best antioxidant activity at 50 ppm, as gallic acid equivalents, but on the basis of hexanal formation, better antioxidant activity was observed at 100 and 200 ppm.α-Tocopherol behaved as a prooxidant at high concentrations (>250 ppm) on the basis of PV, but was more effective than the other antioxidants in inhibiting hexanal formation in RBD olive oil.o-Diphenols (caffeic acid) and, to a lesser extent, substitutedo-diphenols (ferulic and vanillic acids), showed better antioxidant activity than monophenols (p- ando-coumaric), based on both PV and hexanal formation. This study emphasizes the need to measure at least two oxidation parameters to better evaluate antioxidants and the oxidative stability of olive oils. The antioxidant effectiveness of phenolic compounds in virgin olive oils can be significantly diminished in oils if their initial PV are too high.     

Antioxidant activity of rapeseed phenolics and their interactions with tocopherols during lipid oxidation

Commercial rapeseed press cakes are rich sources of phenolic compounds, namely, sinapic acid derivatives, which can be extracted as free sinapic acid and its bound forms (such as sinapine, the choline ester of sinapic acid). Fractionated rapeseed extracts rich in sinapic acid and sinapine were compared for their capacity to inhibit the formation of lipid oxidation products. Oxidation at 40°C was monitored by the formation of hydroperoxides (indicating primary oxidation products) and propanal (secondary oxidation products). The 70% methanolic extract of rapeseed meal, added as an equivalent of 500 μmol/kg oil (based on sinapic acid equivalent for sinapic acid-rich extracts or sinapine equivalent for sinapinerich extracts) showed good antioxidative activity compared with the addition of 500 μmol/kg oil sinapic acid. Apart from this, the interaction between a mixture of α-/γ-tocopherol and sinapic acid was investigated using response surface methodology for the experimental design. The experiments indicated that the addition of sinapic acid (concentration dependent) caused inhibition of peroxide formation, complementing further lower endogenous tocopherol concentration in oils. This paper was initially presented at the 95th AOCS Annual Meeting and Expo in Cincinnati, Ohio, May 1–4, 2004.     

Phenolic Acids and Antioxidant Capacity of Distillers Dried Grains with Solubles (DDGS) as Compared with Corn

Three sets of ground corn and the corresponding distillers dried grains with solubles (DDGS) were collected from three commercial plants and analyzed for individual phenolic acids and antioxidant capacity. This study was undertaken to investigate the influence of processing on phenolic acids content and antioxidant capacity of corn and the corresponding processed DDGS samples. The five phenolic acids identified in corn and DDGS were vanillic, caffeic, p-coumaric, ferulic, and sinapic acids. Ferulic and p-coumaric acids accounted for about 80% of the total identified and quantified phenolic acids. The phenolic acids profile of DDGS was comparable to that of corn. The content of total phenolic acids per gram basis, in DDGS was 3.40 fold higher and antioxidant capacity was 2.58 fold more than that of corn. These observations suggest that there was little degradation in individual phenolic acids content during dry grind processing. Furthermore, significant variation in measured individual and total phenolic acids, and antioxidant capacity among processing plants existed for both corn and DDGS. Results from this study will be valuable to bioethanol manufacturers and the feed industry.     

Addition of ferulic acid,ethyl ferulate,and feruloylated monoacyl- and diacylglycerols to salad oils and frying oils

To determine antioxidative effects of ferulic acid and esterified ferulic acids, these compounds were added to soybean oils (SBO), which were evaluated for oxidative stability and frying stability. Additives included feruloylated MAG and DAG (FMG/FDG), ferulic acid, ethyl ferulate, and TBHQ. After frying tests with potato chips, oils were analyzed for retention of additives and polar compounds. Chips were evaluated for hexanal and rancid odor. After 15 h frying, 71% of FMG/FDG was retained, whereas 55% of ethyl ferulate was retained. TBHQ and ferulic acid levels were 6% and <1%, respectively. Frying oils with ethyl ferulate or TBHQ produced significantly less polar compounds than SBO with no additives. Chips fried in SBO with TBHQ or ferulic acid had significantly lower amounts of hexanal and significantly less rancid odor after 8 d at 60°C than other samples. Oils were also aged at 60°C, and stability was analyzed by PV, hexanal, and rancid odor. Oils with TBHQ or FMG/FDG had significantly less peroxides and hexanal, and a lower rancid odor intensity than the control. FMG/FDG inhibited deterioration at 60°C, whereas ethyl ferulate inhibited the formation of polar compounds in frying oil. Ferulic acid acted as an antioxidant in aged fried food. TBHQ inhibited oil degradation at both temperatures. Presented at the 94th AOCS Meeting & Expo, Kansas City, MO, May 4–7, 2003.     

Antioxidant effect of mono‐ and dihydroxyphenols in sunflower oil with different levels of naturally present tocopherols

Antioxidant properties of mono‐ and dihydroxyphenolic acids and their alkyl esters were examined, with emphasis on the relationship between their molecular structure and antioxidant activity. Test media with different tocopherol level were used for determining the oxidative stability: original refined sunflower oil (total tocopherols 149.0 mg/kg), partially tocopherol‐stripped sunflower oil (total tocopherols 8.7 mg/kg) and distilled fatty acid methyl esters (FAME) as a tocopherol‐free medium. The chemical reaction of tocopherols with diazomethane tested for the purpose to eliminate their antioxidant activity failed due to the negligible degree of methylation of hydroxyl group in the tocopherol molecule. Caffeic acid and protocatechuic acid (3,4‐dihydroxyphenolic acids) and their alkyl esters were found to be more active antioxidants than monohydroxyphenolic acid (p‐hydroxybenzoic acid), 2,5‐dihydroxyphenolic acid (gentisic acid), 3‐methoxy‐4‐hydroxyphenolic acids (vanillic and ferulic acids) and their corresponding alkyl esters. Naturally present tocopherols in refined sunflower oil proved to have a synergistic effect on gentisic acid but not on its alkyl esters. In contrast, tocopherols showed an antagonistic effect on alkyl esters of caffeic acid, because their protection factors decreased with increasing level of tocopherols in the test medium. Moreover, the antioxidant activity of these alkyl esters decreased with increasing length of their alkyl chain in conformity with the polar paradox hypothesis. Practical applications: Tocopherols as naturally present antioxidants influence considerably the antioxidant activity of other antioxidants added to plant oils used as a test medium. Distilled fatty acid methyl esters prepared from refined sunflower oil may serve as an optimal tocopherol‐free test medium. Some alkyl esters of phenolic acids were evaluated to be applicable as natural more lipophilic antioxidants in comparison with phenolic acids.     

Formation and Structure of Lignin in Monocotyledons. III. Heterogeneity of Sugarcane (Saccharum officinarum L.) Lignin with Respect to the Composition of Structural Units in Different Morphological Regions

Heterogeneity of sugarcane lignin with respect to the composition of structural units in different morphological regions was studied by microautoradiography and some degradative analyses. Structure of the lignin differs among fiber, vessel and parenchyma. The lignin in the secondary wall of fiber is composed of syringyl (S)-, guaiacyl (G)- and p-hydroxyphenyl (H)-propane units with accompanying phenolic acid residues, and the proportion of these monolignols is S > G > H. The lignin in vessels of protoxylem contains more G and H units than S units, and that in vessels of metaxylem is similar to that in fibers. Phenolic acid constituent in sugarcane cell wall includes sinapic acid in addition to p-coumaric and ferulic acids. Ferulic acid deposits at the very early stage of lignification, and p-coumaric and sinapic acids increasingly deposit with the progress of lignification. Therefore, the ratio of p-coumaric acid or sinapic acid to ferulic acid increases with lignification. Parenchyma wall involves larger amount of phenolic acids than vascular bundle does. The lignin in parenchyma is difficult to isolate by Björkman procedure, because there is greater possibility to form cross-linkage among cell wall polymers through phenolic acids. The cross linkages involving phenolic acid ester also explains why the sugarcane lignin is easily degraded.     

Antioxidant capacity of rapeseed meal and rapeseed oils enriched with meal extract

Response surface methodology (RSM) was used to evaluate the quantitative effects of two independent variables: solvent polarity and temperature of the extraction process on the antioxidant capacity (AC) and total phenolics content (TPC) in meal rapeseed extracts. The mean AC and TPC results for meal ranged between 1181–9974 µmol TE/100 g and 73.8–814 mg sinapic acid/100 g of meal. The experimental results of AC and TPC were close to the predicted values calculated from the polynomial response surface models equations (R² = 0.9758 and 0.9603, respectively). The effect of solvent polarity on AC and TPC in the examined extracts was about 3.6 and 2.6 times greater, respectively, than the effect of processing temperature. The predicted optimum solvent polarity of ε = 78.3 and 63.8, and temperature of 89.4 and 74.2°C resulted in an AC of 10 014 µmol TE/100 g and TPC of 863 mg SAE/100 g meal, respectively. The phenolic profile of rapeseed meal was determined by an HPLC method. The main phenolics in rapeseed meal were sinapine and sinapic acid. Refined rapeseed oils were fortified with an extract – rich in polyphenols – obtained from rapeseed meal. The supplemented rapeseed oil had higher AC and TPC than the refined oil without addition of meal extracts. However, AC and TPC in the enriched oils decreased during storage. The TPC in the studied meal extracts and rapeseed oils correlated significantly (p<0.0000001) positively with their AC (R² = 0.9387). Practical applications: Many bioactive compounds extracted from rapeseed meal provide health benefits and have antioxidative properties. Therefore, it seems worth to consider the application of antioxidants extracted from the rapeseed meal for the production of rapeseed oils with potent AC. Moreover, antioxidants extracted from the rapeseed meal were added to refined rapeseed oil in order to enhance its AC. AC was then tested by FRAP assay. FRAP method is based on the reduction of the ferric tripyridyltriazine (Fe³⁺‐TPTZ) complex to the ferrous tripyridyltriazine (Fe²⁺‐TPTZ), and it is simple, fast, low cost, and robust method. FRAP method does not require specialized equipment and can be performed using automated, semi‐automatic, or manual methods. Therefore the proposed FRAP method can be employed by the fat industry laboratories to asses the AC of rapeseed oils and meal.     

Prooxidant Activity of Polar Lipid Oxidation Products in Bulk Oil and Oil-in-Water Emulsion

Lipid oxidation products can arise when oils are subjected to high temperature and exposed to oxygen. Many of these oxidation products have higher polarity than the original triacylglycerols due to the incorporation of oxygen. These polar oxidation products could have a negative impact on oxidative stability by acting as prooxidants. In this study, the influence of polar lipid oxidation products on the oxidative stability of bulk oils and oil-in-water emulsions was investigated. Polar compounds were isolated from used frying oil by silica gel column chromatography. They were added to bulk stripped corn oil (with/without reverse micelles formed by dioleoylphosphatidylcholine, DOPC) and oil-in-water (O/W) emulsion to evaluate their prooxidative activity. Polar compounds increased lipid oxidation in bulk oil with and without DOPC. The presence of DOPC reverse micelles decreased the prooxidant activity of the polar oxidation products. On the other hand, there was no significant effect of the polar compounds on oxidation of O/W emulsions. To gain a better understanding of the polar compounds responsible for the prooxidant effect, linoleic acid and linoleic hydroperoxide were added into bulk oil at the same concentration as those in the polar fraction of the frying oil. However, they did not show the same prooxidative activity compared to oil with the polar fraction.