Antioxidant Capacity of Rapeseed Extracts Obtained by Conventional and Ultrasound‐Assisted Extraction

Ultrasound‐assisted extraction (UAE) and conventional solid–liquid extraction were applied to extract total antioxidants from two rapeseed varieties. The antioxidant capacities (AC) of winter and spring rapeseed cultivars were determined by four different analytical methods: ferric reducing antioxidant power (FRAP), cupric reducing antioxidant capacity (CUPRAC), 2,2′‐diphenyl‐1‐picrylhydrazyl (DPPH), 2,2′‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS). The average AC of the studied rapeseed cultivars ranged between 4.21–10.03 mmol Trolox (TE)/100 g, 7.82–10.61 mmol TE/100 g, 8.11–51.59 mmol TE/100 g, 22.48–43.13 mmol TE/100 g for FRAP, CUPRAC, DPPH and ABTS methods, respectively. There are positive correlations between total phenolics (TPC = 804–1625 mg sinapic acid (SA)/100 g) and AC of the studied rapeseed extracts (r = 0.2650–0.9931). Results of the principal component analysis (PCA) indicate that there are differences between the total amounts of antioxidants in rapeseed samples extracted by different extraction techniques. Rapeseed extracts obtained after 18 min of ultrasonication revealed the highest content of total antioxidants. The UAE is a very useful, efficient and rapid technique of oilseed samples preparation for determination of AC by different analytical methods.     

Effect of Hydrothermal Treatment of Rapeseed on Antioxidant Capacity of the Pressed Rapeseed Oil

Response surface methodology (RSM) was used to evaluate the quantitative effects of two independent variables, rapeseed moisture content and conditioning temperature, on the antioxidant capacity (AC) and total phenolic (TPC), tocopherol (TTC), and phosphorus contents (PC) in the pressed rapeseed oils. The mean AC results for the crude rapeseed oils ranged from 199.8 to 947.2 μmolTE/100 g. TPC and PC in the crude rapeseed oils correlated significantly (P < 0.01) and positively with AC of oils (R ² = 0.9498 and 0.4396, respectively). The experimental results of AC, TPC, and PC were close to the predicted values calculated from the polynomial response surface model equations (R ² = 0.9801, 0.9747 and 0.9165, respectively). The effect of oil processing temperature on AC and TPC was about 1.5 times greater than the effect of moisture level in rapeseed.     

Comparison of Two Analytical Methods for Assessing Antioxidant Capacity of Rapeseed and Olive Oils

The oxygen radical absorbance capacity (ORAC) and the ferric reducing antioxidant power (FRAP) methods were used for the determination of antioxidant capacities (AC) of rapeseed oils at different steps of technological process and olive oils. The mean ORAC and FRAP results obtained for rapeseed oils (1,106–160 and 552–95.6 μmol TE/100 g) were higher than for olive oils (949–123 and 167–32.1 μmol TE/100 g). Although, FRAP values were lower than ORAC values for all studied oils, there is a linear and significant correlation between these two analytical methods (r = 0.9665 and 0.9298, P < 0.0005) for rapeseed and olive oils, respectively). Also, total phenolic compounds in rapeseed oils and olives correlated with antioxidant capacities (correlation coefficient ranged between 0.9470 and 0.8049). The refining process of rapeseed oils decreased the total phenolics content and antioxidant capacities by about 80%.     

Physicochemical,Antioxidative, and Sensory Properties of Refined Rapeseed Oils

Physicochemical characteristics, antioxidant capacity (AC), and sensory quality of rapeseed oils available on the Polish market were analyzed and compared. The fatty acid composition (saturated fatty acids = 6.91–7.58%, monounsaturated fatty acids = 64.14–66.14%, and polyunsaturated fatty acids = 27.22–30.17%), color (T420 = 54.5–83.8%), amounts of free fatty acids (0.02–0.07%), primary (PV = 0.04–2.04 meq O₂ kg⁻¹) and secondary (AV = 1.02–3.21) oxidation products, phosphorus (0.38–1.62 mg kg⁻¹), chlorophyll (0.002–0.068 mg kg⁻¹), and polycyclic aromatic hydrocarbons (Σ4PAH = 0.00–2.50 μg kg⁻¹) in the commercial rapeseed oils meet the requirements of the European Food Regulation and Codex Alimentarius standards. Moreover, total phenolic content (TPC = 40.3–467.9 mg SA kg⁻¹) in the studied oils significantly differs from each other. However, the AC of rapeseed oils was analyzed using the novel iron oxide nanoparticle-based (IONP = 5552.1 − 18,510.2 μmol TE/100 g) method and the modified ferric reducing antioxidant power (FRAP = 55.7–280.3 μmol TE/100 g), cupric reducing AC (CUPRAC = 79.6–784.0 μmol TE/100 g), 2,2-diphenyl-1-picrylhydrazyl (DPPH = 185.7–516.7 μmol TE/100 g), and 2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS = 465.6–2142.6 μmol TE/100 g) assays. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied for discrimination of the refined rapeseed oils based on fatty acid composition, physicochemical parameters, AC, and sensory properties.     

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.     

Effect of evening primrose extracts on oxidative stability of sunflower and rapeseed oils

Antioxidative activities of evening primrose seed meal extracts in sunflower and rapeseed oils were compared with that of commercially used antioxidants, namely butylated hydroxytoluene (BHT), ascorbylpalmitate as well as Grindox‐118. The study was carried out under Schaal oven conditions at 60 °C and the weight gain was followed up by p‐anisidine value measurement following the oxidation. An Oxidograph apparatus monitored the oxidation of oils at 110 °C. Among the examined extracts, the ethyl acetate extract (0.2%), containing only 87 mg/g of total phenolics, exhibited a stronger antioxidant activity than BHT (0.01%) and effectively stabilised both oils. A strong antioxidative effect was also noted for the ethanol‐ethyl acetate extract (168 mg/g of total phenolics). The study showed that addition of ethyl acetate and ethanol‐ethyl acetate extracts could extend the sunflower and rapeseed oils shelf‐life by protecting oils from further decomposition that naturally occurs during thermal treatments.     

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.     

Effect of Microwave Treatment on Sinapic Acid Derivatives in Rapeseed and Rapeseed Meal

Microwave treatment is a new method for rapeseed processing. To better understand the benefits of microwave pretreatment on rapeseed processing, qualitative and quantitative analysis of sinapic acid derivatives is needed. In this study, the effect of microwave treatment on the content of sinapic acid derivatives in rapeseed and the effect of cold-press and solvent extraction on the content of sinapic acid derivatives in rapeseed meal were evaluated using ultrahigh pressure liquid chromatography. It was found that during the microwave treatment, the content of sinapine and sinapic acid in the rapeseed increased slightly at the outset of treatment and significantly decreased thereafter. Following 7 min of microwave treatment, the content of sinapine in rapeseed exhibited its largest decrease of 16.7 %. By contrast, microwave heating of the rapeseed increased the canolol content significantly. We employed two sample paired t tests as a means to analyze the difference between meal and defatted cold-pressed cake. The results indicated that the content of sinapine and sinapic acid in defatted cake was significantly higher than that in meal, while the different extraction methods (solvent extraction and cold-press) did not appear to have a significant influence on the content of canolol in meal (p ≤ 0.05).     

Effect of Specific Oil Surface Area on the Thermal Stressing of Rapeseed Oil During Heating in an Electric Frying Pan

The effect of specific oil surface (SOS) during pan frying of rapeseed oil on its thermal stability and antioxidant capacity (AC) was evaluated. Rapeseed oils with different oil layer heights (OLH = 0.5, 1.0, 1.5, 2.0, and 2.5 cm) were heated on an electric frying pan coated with Teflon at 180 ± 10 °C until a selected end point of 25 % total polar compounds (TPC) was reached. The changes of chemical parameters of oil samples such as peroxide value, p‐anisidine value, Totox value, free fatty acids, TPC and AC using the 2,2‐diphenyl‐1‐picrylhydrazyl assay were determined. Irrespective of the applied methods, the highest changes in oil with OLH = 0.5 cm were observed. Heating in low OLH also led to the fastest time of TPC formation in rapeseed oil; the 0.5‐cm layer reached 25 % TPC in a relatively short time (71.5 min) compared to the highest OLH = 2.5 cm (t = 315.1 min). The SOS and the rate of change in the heated oils decreased with increasing OLH. Crucial effects of SOS on physicochemical oil changes were observed. The present study demonstrated the protective effect of increasing the OLH on the quality of the heated rapeseed oils.     

Antioxidant activity of crude tannins of canola and rapeseed hulls

The antioxidant activity of crude tannins of canola and rapeseed hulls was evaluated by β-carotene-linoleate, α,α-diphenyl-β-picrylhydrazyl (DPPH) radical, and reducing power assays. Crude tannins were extracted from three samples of Cyclone canola (high-tannin) hulls and Kolner, Ligaret, and Leo Polish rapeseed (low-tannin) hulls with 70% (vol/vol) acetone. The total phenolic content in crude tannin extracts ranged between 128 and 296 mg of sinapic acid equivalents per 1 g of extract. The ultraviolet spectra of methanolic solution of canola extracts showed two absorption maxima (282 and 309 nm), whereas those of rapeseed extracts exhibited a single maximum (326 nm). Crude tannins isolated from canola hulls exerted significantly (P<0.025) greater antioxidant activity than those from rapeseed in all three assays. The scavenging effect of all crude tannins, at a dose of 1 mg, on the DPPH radical ranged from 35.2 to 50.5%. The reducing power of Cyclone canola hull extracts on potassium ferricyanide was significantly (P≤0.0025) greater than that of rapeseed hull extracts, and the observed data correlated well (r=0.966; P=0.002) with the total content of phenolics present.     

A rapid high-performance liquid chromatographic method for the determination of sinapine and sinapic acid in canola seed and meal

A high-performance liquid chromatographic (HPLC) method has been developed to separate sinapine and sinapic acid from other phenolics in canola seed and meal in a single run. The separation was achieved with a reverse-phase C18 column. Owing to the higher recovery of phenolics and ease of use, refluxing with 100% methanol for 20 min was selected as the extraction method for HPLC analysis and determination of total phenolics using Folin-Ciocalteu reagent. A 10-min isocratic/linear/concave gradient and a 15-min isocratic/linear gradient were selected as the best gradients for the separation of these phenolic compounds. Peak identities for sinapine and sinapic acid were verified with ion exchange separation followed by HPLC analysis. The method was calibrated using sinapine bisulfate and sinapic acid standards; correlation coefficients (R ²) for the calibration curves were 0.997 and 0.999 for sinapine bisulfate and sinapic acid, respectively. The extinction coefficient of sinapine was determined to be 1.16 times that of sinapic acid at the detector wavelength (330 nm). Applying this method to routine canola phenolic analyses can greatly reduce the cost by simplifying the procedures and reducing the time required for each determination.     

Breeding rapeseed for oil and meal quality

Significant variation in fatty acid composition occurs within the seed oils of theBrassica genus, which includes the mustards and rapeseed. Research into the inheritance and biosynthesis of fatty acids has shown that at least two biosynthetic pathways exist in the developing rapeseed and some of the steps are under direct genetic control. The plant breeder has the basic knowledge in this oilseed crop to produce seed oils with defined fatty acid composition, and a practical example is the commercial development of Canbra oil, the rapeseed oil from which erucic acid has been eliminated.Brassica seed meals contain thioglucosides which may cause metabolic disturbances when fed to certain classes of livestock. The major thioglucosides in rapeseed meal are those giving rise to 3-butenyl and 4-pentenyl isothiocyanate and 5-vinyl-2-oxazolidinethione. Partial success in eliminating these compounds has been achieved by breeding strains of turnip rape (B. campestris) which do not contain the glucosides of 4-pentenyl isothiocyanate and oxazolidinethione, and the identification of aB. napus variety with very low levels of all three glucosides. These findings suggest that complete removal of these sulfur compounds may be possible through plant breeding. Contribution No. 309, Research Station, Canada Department of Agriculture, Saskatoon, Saskatchewan, Canada. Presented at the AOCS Meeting, Chicago, October 1967.     

Fractionation of rapeseed meal into hour and hull components

Fine-ground rapeseed meal can be fractionated by liquid cyclone processes into flour and hull fractions. The process can be applied to expeller meal or to the marc after solvent extraction. A nonpolar solvent such as hexane is particularly effective because residual oil in the products is also substantially reduced. The flour, obtained in yield of about66% of the meal, contained over 45% protein and 5-8% of crude fiber. Rapeseed meal is relatively low in digestible energy and the flour fraction would have greater application as a protein supplement in pig and poultry feeds.     

Allelochemicals produced during glucosinolate degradation in soil

A variety of plant pests are suppressed by the incorporation of cruciferous plant material into soil. Although this effect is attributed to decomposition of glucosinolates into toxic products, little is known concerning glucosinolate degradation in the soil environment. Arenas (30 × 18 × 8 cm) that contained soil amended with 30 g defatted winter rapeseed meal (Brassica napus L.)/kg soil on one half and unamended soil on the other were constructed. Isothiocyanate concentrations in the soil were measured using infrared analysis of CC1₄ extracts, and ionic thiocyanate (SCN^–) using ion chromatography on aqueous extracts. Quantities were monitored during a 100-hr time period in conjunction with a wireworm bioassay. Isothiocyanate production reached a maximum of 301 nmol/g soil at 2 hr, but decreased by 90% within 24 hr. Production of SCN^– reached a maximum of 180 nmol/g soil at 8 hr but persisted longer than isothiocyanate. Separate late instar wire-worms (Limonius infuscatus Mots.) were repelled by the presence of rapeseed meal in less than 24 hr even though the meal was shown in separate experiments not to be toxic. We propose that rapidly produced isothiocyanates are responsible for this repellency, but other products such as SCN^– may play a role.     

Comparative Study of Fatty Acid Composition,Total Phenolics,and Antioxidant Capacity in Rapeseed Mutant Lines

There is limited variability within rapeseed germplasm in Morocco. Induced mutation was recently used to generate novel genetic variability and develop mutant lines combining desirable traits. In this context, nine promising advanced rapeseed M₂ mutant lines and the wild-type variety “INRA-CZH2” were evaluated for their seed oil content, fatty acid composition, total phenolic content (TPC), and free-radical scavenging activity (FRSA) by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 3-ethylbenzothiazoline-6-sulfonic acid (ABTS) methods. The results showed significant variability among all mutants in seed oil content (38.14–42.04%) and fatty acids (SAFA = 5.49–10.99%, MUFA = 50.33–71.62%, PUFA = 22.89–8.68%). The mutant H2M-5 exhibited the highest fraction of MUFA and the lowest proportion of SAFA and PUFA, while the mutant H2M-4 showed the highest SAFA and PUFA amounts and the lowest MUFA level. TPC varied from 2.16 to 4.35 mg GAE/100 g. The highest amount was found in the mutant H2M-1, which is about twice that of other mutants and the wild-type variety. FRSA differed significantly among the samples, and the variations observed for DPPH and ABTS methods were 40.5–59.28% and 40.31–59.86%, respectively. FRSA was positively correlated to TPC in the sampled oils (r = 0.801 and 0.802, P < 0.01). This is the first report emphasizing the biochemical potential of rapeseed varieties and novel mutants in Morocco. H2M-1, H2M-4, and H2M-5 were proposed for the Rapeseed National Breeding Program, as they showed higher levels in some biochemical traits of interest.     

Distribution and Antioxidant Activities of Free,Conjugated, and Insoluble-Bound Phenolics from Seven Species of the Genus Camellia

Free phenolic (FP), conjugated phenolic (CP), and insoluble-bound phenolic (IBP) acids were extracted from the seeds of seven species of oil-tea camellia and their antioxidant activities were evaluated. The results indicated that Camellia vietnamensis has the highest total phenolic content (TPC) (31.84 ± 0.11 g of gallic acid equivalent [GAE] kg⁻¹) and that Camellia polyodontia has the lowest TPC (12.34 ± 0.22 g GAE kg⁻¹) in the kernel. The average TPC among the species is similar in both the kernels and in the shells, and the content order of the three forms of phenolic compounds is FP > IBP > CP. HPLC-MS analysis showed the presence of 9–11 phenolic compounds in the FP, CP, or IBP extracts of the seven species of oil-tea camellia seed. Among the phenolics identified, ferulic acid, catechin, and epicatechin were the major contributors of antioxidant activity. Hierarchical cluster analysis conducted based on the phenolic properties showed that C. vietnamensis and Camellia semiserrata belong to the group characterized by high antioxidant capacities (FRAP, ferric-ion-reducing antioxidant power; ABTS assay), and Camellia chekiangoleosa and Camellia oleifera are arranged in a group with moderate phenolic properties. The other species constitute the third cluster with low phenolic content and antioxidant activity. The study demonstrated that oil-tea camellia seed contains significant amounts of phenolic acids. In addition, extracts from various parts of the seed could be interesting novel sources of natural antioxidants.     

Determination of Sinapic Acid Derivatives in Canola Extracts Using High-Performance Liquid Chromatography

A high-performance liquid chromatographic (HPLC) method with diode array detection (DAD) was used to determine the total phenolics, including sinapic acid derivatives in canola. Ten Western Canadian canola seeds, six other commodity canola seeds, their corresponding press cakes and meals were analyzed. Seeds of European 00 rapeseed and Brassica Juncea (Indian mustard) were included for comparison. Phenolic compounds were separated using a gradient elution system of water–methanol-ο-phosphoric acid solution with a flow rate of 0.8 ml/min. In addition to sinapine (SP) and sinapic acid (SA), sinapoyl glucose (SG) is reported in the methanolic extracts. The detection and quantification limits of these compounds were 0.20–0.40 and 0.50–0.80 μg/ml, respectively with recovery values over 98.0%. The content of total phenolics, SP, SA and SG in canola extracts ranged from 9.16 to 16.13, 6.39 to 12.28, 0.11 to 0.59 and 1.36 to 7.50 mg/g, respectively with significant differences among varieties.     

Microwave treatment of dehulled rapeseed to inactivate myrosinase and its effect on oil and meal quality

Rapeseed was dehulled using a Palyi pneumatic attrition system which produced 62–66% clean dehulled seed. Dehulled rapeseed was preconditioned to 7, 10 and 13% moisture levels, exposed to micro-wave irradiation for periods of up to 2.5 min and analyzed for residual thioglucoside glucohydrolase (myrosinase) activity. The 7% moisture samples heated slowly and required at least a 2.5 min treatment whereas 10 and 13% moisture samples heated more rapidly and required microwave exposures of 1.5 min or less for complete inactivation of the enzyme. The sulfur content of oils obtained from adequately microwave-treated samples (1.5 min for 10 and 13% and 2.5 min for 7% moisture samples) was equal to or lower than commercially processed crude rapeseed oils. The shorter microwave treatment of dehulled rapeseed produced considerably lighter oils and did not adversely affect the color of the meal. It also destroyed some of the rapeseed glucosinolates and improved the meal palatability. However, goitrogenic properties of microwave-treated rapeseed meal evaluated by mice feeding experiments did not appear different from untreated rapeseed meal.     

Total Phenolics of Virgin Olive Oils Highly Correlate with the Hydrogen Atom Transfer Mechanism of Antioxidant Capacity

Polar extracts of extra‐virgin olive oils (EVOO) contain a large number of phenolic compounds with antioxidant properties. The antioxidant capacity can be measured by different reaction mechanisms, as the single electron transfer (SET) or the hydrogen atom transfer (HAT). In this work, the total phenolic content (TPC) by the Folin‐Ciocalteu method and its correlation with four antioxidant capacity assays (FRAP, ABTS, DPPH^? and ORAC) were evaluated for EVOO polar extracts. It was observed that the higher the total phenolic compounds in the EVOO extracts, the higher the antioxidant capacities, regardless of the method employed. The reaction mechanism observed for TPC by Folin‐Ciocalteu method and also for FRAP, ABTS and DPPH^? antioxidant capacity assays is a single electron transfer, thus, a high correlation among their results is expected. However, the correlation between TPC and ORAC results was also high and significant, allowing to conclude that EVOO phenolic compounds are able to react by the hydrogen atom transfer mechanism, which indicates that they can act as effective radical chain‐breaking antioxidants. These results suggest that, for the EVOO polar extracts, TPC by Folin‐Ciocalteu and ORAC assays could be sufficient to evaluate their in vitro antioxidant capacity.