Microwave roasting effects on the physico-chemical composition and oxidative stability of sunflower seed oil

The purpose of the present study was to explore the influences of microwave heating on the composition of sunflower seeds and to extend our knowledge concerning the changes in oxidative stability, distribution of FA, and contents of tocopherols of sunflower seed oil. Microwaved sunflower seeds (Helianthus annuus L.) of two varieties, KL-39 and FH-330, were extracted using n-hexane. Roasting decreased the oil content of the seeds significantly (P<0.05). The oilseed residue analysis revealed no changes in the contents of fiber, ash, and protein that were attributable to the roasting. Analysis of the extracted oils demonstrated a significant increase in FFA, p-anisidine, saponification, conjugated diene, conjugated triene, density, and color values for roasting periods of 10 and 15 min. The iodine values of the oils were remarkably decreased. A significant (P<0.05) decrease in the amounts of tocopherol constituents of the microwaved sunflower oils also was found. However, after 15 min of roasting, the amount of α-tocopherol homologs was still over 76 and 81% of the original levels for the KL-39 and FH-330 varieties, respectively. In the same time period, the level of σ-tocopherol fell to zero. Regarding the FA composition of the extracted oils, microwave heating increased oleic acid 16–42% and decreased linoleic acid 17–19%, but palmitic and stearic acid contents were not affected significantly (P<0.05).     

Oxidation of sunflower oil during storage

Effects of temperature and oxygen concentration on oxidative deterioration during storage of crude sunflower oils, obtained by pressing and solvent extraction, were studied. Oxidation was monitored through several analytical and chromatographic methods that determine chemical and physical changes or analyze specific oxidation compounds at different stages of the process: peroxide value, p-anisidine value, free fatty acids, weight gain, total content and distribution of polar compounds, and composition of fatty acids. Extracted oil showed a higher oxidative stability than pressed oil. Oxidative deterioration was strongly dependent on temperature, oxygen availability, and the ratio of exposed surface to sample volume. A kinetic model of two series reactions was developed to represent oxidation rate in terms of peroxide value, the reaction rate constants and their temperature dependence being evaluated by nonlinear regression. Finally, good correlations between the percentage of polar compounds or oxidized triglyceride monomers and the peroxide value were found.     

Pan-frying stability of NuSun oil,a mid-oleic sunflower oil

Pan-frying is a popular frying method at home and in many restaurants. Pan-frying stabilities of two frying oils with similar iodine values (IV)—mid-oleic sunflower oil (NuSun oil; IV=103.9) and a commercial canola oil (IV=103.4)—were compared. Each oil sample was heated as a thin film on a Teflon-coated frying pan at ∼180°C to a target end point of ≥20% polymer. High-performance size-exclusion chromatography analysis of the mid-oleic sunflower and canola oil samples indicated that the heated samples contained 20% polymer after approximately 18 and 22 min of heating, respectively. The food oil sensor values increased from zero to 19.9 for the canola sample and from zero to 19.8 for the mid-oleic sunflower sample after 24 min of heating. The apparent first-order degradation rate for the mid-oleic sunflower sample was 0.102±0.008 min⁻¹, whereas the rate for the canola sample was 0.092±0.010 min⁻¹. The acid value increased from approximately zero prior to heating to 1.3 for the canola sample and from zero to 1.0 for the mid-oleic sunflower sample after 24 min of heating. In addition, sensory and volatile analyses of the fried hash browns obtained from both oils indicated there were no significant differences between the two fried potato samples.     

Determination of oxidative stability of lipids in solid samples

A gas-phase flow injection analysis (FIA) method for the direct determination of the oxidative stability of solid fat/oil samples is described. Samples are confined with a low level of oxygen in a reactor of adjustable temperature. The oxygen consumption by the sample is automatically monitored after a preset period. The temperature-dependent data exhibit Arrhenius behavior. Normally, it is difficult to directly determine the stability at ambient temperatures because of inordinately long time requirements. The close correspondence to Arrhenius behavior makes it possible to use the results obtained at higher temperature to calculate the stability of samples at lower temperature conditions, such as at ambient storage temperature. The effects of sample size, sample particle size, sample fat content and the reproducibility of the method over time were studied using synthetic and bone meal samples. The oxygen consumption was found to be linearly dependent on the amount of sample taken, inversely dependent on the particle diameter, and independent of the exact lipid content, given some minimum lipid content. The results exhibited high day-to-day reproducibility. The gasphase FIA system developed in this work is easy to operate. Compared with the currently used method, the sample throughput rate is much faster (2–3h for complete multitemperature characterization of a sample) and the sample requirement is much lower (∼1 g). Furthermore, it eliminates the need to extract and recover the fat from the sample for further processing as is required by the other methods commonly used to measure oxidative stability.     

Improving the oxidative stability of polyunsaturated vegetable oils by blending with high-oleic sunflower oil

Mixing different proportions of high-oleic sunflower oil (HOSO) with polyunsaturated vegetable oils provides a simple method to prepare more stable edible oils with a wide range of desired fatty acid composition. Oxidative stability of soybean, canola and corn oils, blended with different proportions of HOSO to lower the respective levels of linolenate and linoleate, was evaluated at 60°C. Oxidation was determined by two methods: peroxide value and volatiles (hexanal and propanal) by static headspace capillary gas chromatography. Determination of hexanal and propanal in mixtures of vegetable oils provided a sensitive index of linoleate and linolenate oxidation, respectively. Our evaluations demonstrated that all-cis oil compositions of improved oxidative stability can be formulated by blening soybean, canola and corn oils with different proportions of HOSO. On the basis of peroxide values, a partially hydrogenated soybean oil containing 4.5% linolenate was more stable than the mixture of soybean oil and HOSO containing 4.5% linolenate. However, on the basis of volatile analysis, mixtures of soybean and HOSO containing 2.0 and 4.5% linolenate were equivalent or better in oxidative stability than the hydrogenated soybean oil. Mixtures of canola oil and HOSO containing 1 and 2% linolenate had the same or better oxidative stability than did the hydrogenated canola oil containing 1% linolenate. These studies suggest that we can obviate catalytic hydrogenation of linolenate-containing vegetable oils by blending with HOSO. Presented at the AOCS/JOCS joint meeting, Anaheim, CA, April 25–29, 1993.     

Thermoxidative stability of triacylglycerols from mutant sunflower seeds

Thermoxidative stability was evaluated in triaclyglycerols (TAG) from the oils of the mutant sunflower lines CAS-3, CAS-4, and CAS-8 (with a high percentage of stearic acid), CAS-5 (with a high percentage of palmitic acid), all from standard highlinoleic genetic backgrounds, and the mutant sunflower line CAS-12 (with a high percentage of palmitic acid), from a high-oleic genetic background. These oils contained unusually high contents of TAG molecular species with one or two saturated fatty acids at the sn-1,3 positions. Purified total TAG devoid of tocopherols were subjected to controlled thermoxidative treatment at 180°C. Polymerized TAG were determined at 2-h intervals for 10 h. After this time, total polar compounds, oxidized TAG monomers, TAG dimers, and TAG oligomers were determined. TAG from highly saturated sunflower oils with levels of linoleic acid similar to those found in conventional sunflower oils (40–50%) showed enhanced thermal stability. In these TAG, the amount of polar compounds formed during the thermoxidative treatment was similar to that formed in the high oleic acid line. Excellent results were obtained for the TAG of the CAS-12 oil, which had the highest thermal stability, producing half the amount of polar compounds as the conventional line and less than two-thirds that of the high-oleic line.     

A comparative study on the susceptibilities of soybean,sunflower and peanut oils to singlet molecular oxygen photooxidation

The susceptibilities of crude soybean, sunflower and peanut oils to singlet oxygen photooxidation were determined in a kinetic study. The accumulation of photosensitized hydroperoxides, determined spectroscopically, and the quenching of singlet molecular oxygen phosphorescence by the crude oils and their fatty acid methyl esters were compared. The relative tendency to photooxidation for the oils and the methyl esters was soybean ≫ sunflower > peanut. This trend was independent of the method employed in the determination of initial photodamaging. Soybean oil was demonstrated to be the most unstable product, not only due to the presence of highly unsaturated fatty acids, but also due to the absence of natural constituents, capable of providing a protective antioxidant effect. This protection was more effective in sunflower and peanut oils.     

Crystallization of sunflower oil waxes

Activation free energies of nucleation (ΔG _c ) were calculated using induction times of crystallization measurements. Results showed that ΔG _c decreased exponentially as wax concentration increased at a constant crystallization temperature (T _c ). In contrast, for a constant supersaturation, ΔG _c increased from 12 to 22°C but decreased between 22 and 35°C. Melting behavior of purified waxes and solutions of purified waxes in sunflower oil were studied by DSC after crystallization at fast and slow cooling rates (20 and 1°C/min, respectively). Low supercooling temperatures (T _c >65°C) showed an increase in the onset temperature (T ₀ ) as T _c increased for both fast and slow cooling rates. Broader peaks were obtained for samples crystallized at a slow cooling rate at the same T _c . Regarding the solutions of waxes in sunflower oil, the wax concentration (supersaturation of the system) controlled crystallization as well as T _c . As T _c increased, the enthalpy (ΔH) decreased at a constant wax concentration. When wax concentration decreased, ΔH decreased at a constant T _c . For a low driving force, a small shoulder was obtained in the DSC diagrams owing to some type of fractionation. These results showed that wax crystallization is affected by different experimental parameters, such as T _c and cooling rate, depending on the wax concentration of the sample.     

Effect of oil replenishment during deep-fat frying of frozen foods in sunflower oil and high-oleic acid sunflower oil

Frying stability of sunflower oil (SO) with 23% oleic acid and 61% linoleic acid, and of high-oleic acid sunflower oil (HOSO) with 74% oleic acid and 13% linoleic acid was studied during 20 discontinuous deep-fat fryings of various frozen foods, with or without frequent replenishment of the used oil with fresh oil. Alterations of both oils were measured by column, gas-liquid and high-performance size-exclusion chromatography. Total polar content and compounds, related to thermoxidative changes, and diacylglycerides, related to hydrolytic changes, increased in all oils during frying but reached higher levels in SO than in HOSO. Nevertheless, the increased levels of diacylglycerides observed may result from the frozen potatoes prefried in palm oil. Oleic acid in HOSO and linoleic acid in SO significantly decreased, but the fatty acid modifications that occurred during the repeated fryings were not only related to thermoxidative alteration but also to interactions between the bath oil and the fat in the fried products. Data from this study also indicated that HOSO performed more satisfactorily than SO in repeated fryings of frozen foods. Moreover, frequent addition of fresh oil throughout the deep-frying process minimized thermoxidative and hydrolytic changes in the frying oils and extended the frying life of the oils.     

Enzymatic transesterification of sunflower oil in an aqueous-oil biphasic system

A biphasic oil-aqueous system for FAME production by enzymatic catalysis was studied. The transesterification of sunflower oil with methanol was catalyzed by free or immobilized lipases from Rhizomucor miehei (Palatase 20 000 L) and Humicola insolens (Lipozyme TL 100 L). The effects of protein amount, temperature, pH, and molar ratio of methanol to sunflower oil on the enzymatic reaction using free lipase were evaluated; the best results were obtained with H. insolens, at pH 5, 40°C, and 36.8 mg of protein. By using this lipase immobilized in Hypol^® 2002 (64. 8 mg of protein) at a 6∶1 methanol/oil molar ratio and a 2∶1 volumetric oil/water phase ratio, an ester content of 96.1% and a conversion of 91.2% were achieved. The immobilized lipase could be reused, although a 30% reduction in conversion efficiency was observed after four uses.     

Quantitative determination of phospholipids in sunflower oil

Phospholipids from sunflower oil samples were enriched by using solid-phase extraction (SPE) cartridges and subsequently separated and analyzed by high-performance liquid chromatography (HPLC) with an ultraviolet detector. The recovery of individual phospholipids at different total concentrations in model oils and the repeatability of the method were investigated. The results demonstrated the utility of SPE-HPLC for quantitative analysis of phospholipids in sunflower oil and the effectiveness for concentrating, separating, identifying, and quantitating phospholipids in samples with phosphatide contents as low as 0.1%. Samples of sunflower oil at different stages of processing were analyzed, and phospholipid profiles in hexane-extracted oil, hot-pressed oil, and water-degummed oils were compared.     

Nitrogen bubble refining of sunflower oil in shallow pools

High-temperature steam deodorization of sunflower oil results in the formation of unwanted by-products, such as trans isomers and polymers, and partial destruction of vitamins. There is an urgent need to develop a process that replaces steam with an inert gas such as nitrogen. The use of nitrogen bubble sparging at low temperatures has recently been reported as a technique to strip volatiles from edible oils. In this study, a hypothesis was proposed that nitrogen bubbles sparged at temperatures of 25 to 150°C are able to remove odoriferous, surface-active, or volatile contaminants from shallow pools of sunflower oil. Analysis of the composition of sunflower oil that had been sparged at 3 mbar pressure showed that both the odor and peroxide content of the oil were considerably reduced to values that are commercially acceptable. Odor improvement occurred at temperatures between 100 and 150°C, while the peroxide content reduction was achieved at a temperature of 150°C. There were no significant improvements in the free fatty acid concentration or color.     

Ethanolic extraction of sunflower oil in a pulsing extractor

Oil extraction by ethanol from partially defatted prepressed sunflower seeds in pulsed and nonpulsed extractors was compared. The oil yield was increased by 8.7% after short extraction periods (up to 6.06 residence times) with a pulsing flow, which was probably due to reduction in the axial dispersion that induces a greater concentration gradient between the miscella surrounding the solid and the bulk miscella.     

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.     

Effects of quenching mechanisms of carotenoids on the photosensitized oxidation of soybean oil

The effects of 0, 1.0 × 10”⁻⁵, 2.5 × 10⁻⁵, and 5.0 × 10⁻⁵ M β-apo-8'-carotenal, β-carotene, and canthaxanthin on the photooxidation of soybean oil in methylene chloride containing 3.3 × 10⁻⁹ M chlorophyll b were studied by measuring peroxide values and conjugated diene content. β-Apo-8'-carotenal, β-carotene, and canthaxanthin contain 10,11, and 13 conjugated double bonds, respectively. The peroxide values and conjugated diene contents of oils containing the carotenoids were significantly lower (P<0.05) than those of control oil containing no carotenoid. As the number of conjugated double bonds of the carotenoids increased, the peroxide values of soybean oils decreased significantly (P<0.05). The quenching mechanisms and kinetics of the carotenoids in the photosensitized oxidation of soybean oil were studied by measuring peroxide values. The steady-state kinetics study showed that carotenoids quenched singlet oxygen to reduce chlorophyll-sensitized photooxidation of soybean oil. The singlet-oxygen quenching rate constants ofβ- apo-8'-carotenal, β-carotene, and canthaxanthin were 3.06 × 10⁹, 4.60 × 10⁹, and 1.12 × 10¹⁰ M⁻¹sec⁻¹, respectively.     

原子荧光法测定葵花油中的砷

采用氢化物发生原子荧光法测定葵花油中的砷。探讨了负高压、盐酸、硼氢化钾浓度等对测定As的影响。在选定的仪器操作条件下,As的最低检出限为0.07μg.L-1,相对标准偏差为1.5%。该法测定葵花油中的As,操作简便、快速、灵敏度高。     

Effect of randomization on the oxidative stability of corn oil

Randomized corn oil TAG oxidized much faster than natural oil, but after purification with alumina, they oxidized at the same rate. We showed that this effect could not be attributed to a difference, in total tocopherols in the randomized and natural oils. Polar material recovered from the alumina treatment was fractionated by TLC, and a pro-oxidant effect was found in the fractions containing MAG and DAG. However, MAG and DAG, although mild pro-oxidant could not account for the pro-oxidant effect generated by randomization. No other compounds could be detected in the MAG fraction by MS. The pro-oxidant effect of randomized oil disappeared when EDTA or citric acid was added in sufficient amounts. The pro-oxidant effect of randomized corn oil was increased by the incorporation of additional copper or iron at a concentration that did not catalyze oxidation of the purified oil. Treatment of corn oil with ascorbic acid, ascorbyl-6-palmitate, ethyl acetoacetate, ethyl diacetoacetate, and acetylacetone did not reproduce the effect of the unknown pro-oxidant. Although the identity of the pro-oxidant is still unknown, we have confirmed that it is produced during randomization; it does not have pro-oxidant activity alone, but it facilitates the catalytic activity of the transition metal ions.     

Cyclic FA monomers in high-oleic acid sunflower oil and extra virgin olive oil used in repeated frying of fresh potatoes

The measurement of FA profile, polar material, oligomers, oxidized triacylglycerols (OTG), total polyphenols, and cyclic FA monomers (CFAM) was used to evaluate the alteration of a high-oleic sunflower oil (HOSO) and an extra virgin olive oil (EVOO) used in 75 domestic fryings of fresh potatoes with frequent replenishment (FR) of unused oil. CFAM were absent in the unused EVOO but appeared in small amounts in the unused HOSO. Although polar material, oligomers, OTG, and CTAM contents increased and linoleic acid and polyphenols content decreased in both oils during repeated frying, the changes produced should be considered small and related to the use of very stable oils and FR. Throughout the 75 fryings, the total CFAM concentration was higher in HOSO than in EVOO. OTG increased more quickly in EVOO, whereas oligomers increased more quickly in HOSO. Polar material and oligomer content appear significantly correlated (r=0.9678 and r=0.9739, respectively; for both, P<0.001) with the CFAM content. A 25% polar material and 12% oligomer content would correspond to about 1 mg·kg⁻¹ oil of CFAM. Data suggest that both oils, particularly EVOO, perform very well in frying, with a low production of oligomers, polar materials, and CFAM.     

Effect of processing on the composition and oxidative stability of coconut oil

The effect of various processing procedures on the composition and oxidative stability of coconut oil has been studied. The crude oil is relatively stable but major reductions in oxidative stability occur during the bleaching of oil degummed with phosphoric acid; during alkali refining; during the deodorization of oil degummed with citric acid and bleached; and during the deodorization of oil processed with a combined phosphoric acid degumming and bleaching operation. The reasons for the loss of oxidative stability during processing are discussed with reference to changes in the composition of the oil. Residual traces of citric acid or phosphoric acid play an important role in stabilizing processed oils. The tocopherol content is also important, although no additional stabilization of the oil occurs on adding levels of tocopherol above those present naturally in the crude oil. A combined phosphoric acid degumming and bleaching process leads to smaller losses of tocopherols than sequential treatments.     

Parameter optimization for the enzymatic hydrolysis of sunflower oil in high-pressure reactors

This study is concerned with the hydrolysis of sunflower oil in the presence of lipase preparation Lipolase 100T (Aspergillus niger lipase). Supercritical carbon dioxide was used as a solvent for this reaction. In a high-pressure stirred tank reactor operated in a batch mode, the effects of various process parameters (temperature, pressure, enzyme/substrate ratio, pH, and oil/buffer ratio) were investigated to determine the optimal reaction rate and conversion for the hydrolysis process. The optimal concentration of lipase was 0.0714 g/mL of CO₂-free reaction mixture, and the highest conversions of oleic acid (0.193 g/g of oil phase) and linoleic acid (0.586 g/g of oil phase) were obtained at 50°C, 200 bar, pH=7, and an oil/buffer ratio of 1∶1 (w/w).