Isolation of tocopherol and sterol concentrate from sunflower oil deodorizer distillate

The isolation of tocopherols and sterols together as a concentrate from sunflower oil deodorizer distillate was investigated. The sunflower oil deodorizer distillate was composed of 24.9% unsaponifiable matter with 4.8% tocopherols and 9.7% sterols, 28.8% free fatty acid (FFA) and 46.3% neutral glycerides. The isolation technology included process steps such as biohydrolysis, bioesterification and fractional distillation. The neutral glycerides of the deodorizer distillates were hydrolyzed byCandida cylindracea lipase. The total fatty acids (initial FFA plus FFA from neutral glycerides) were converted into butyl esters withMucor miehei lipase. The esterified product was then fractionally distilled in a Claisen-vigreux flask. The first fraction, which was collected at 180–230°C at 1.00 mm of Hg for 45 min, contained mainly butyl esters, hydrocarbons, oxidized products and some amount of free fatty acids. The fraction collected at 230–260°C at 1.00 mm Hg for 15 min was rich in tocopherols (about 30%) and sterols (about 36%). The overall recovery of tocopherols and sterols after hydrolysis, esterification and distillation were around 70% and 42%, respectively, of the original content in sunflower oil deodorizer distillate.     

Antioxidant Activity of Phytochemicals from Distillers Dried Grain Oil

A distillate was obtained by molecular distillation of oil extracted from distillers dried grains (DDG). The distillers dried grain oil distillate (DDGD) contained phytosterols, steryl ferulates, tocopherols, tocotrienols, and carotenoids. DDGD was tested for its impact on the oxidative stability index (OSI) at 110 °C of soybean, sunflower, and high-oleic sunflower oils, as well as the same oils that were stripped of their natural tocopherols and phytosterols. In addition, the impact of added DDGD on the stability of stripped sunflower oil during an accelerated storage study conducted at 60 °C was also determined. DDGD (0.5–1% w/w) had little impact on the OSI of soybean, sunflower, and high-oleic sunflower oil, but at levels of 0.1–1% it significantly increased the OSI for stripped soybean, sunflower, and high-oleic sunflower oil in a dose-dependent manner. DDGD also delayed peroxide value, conjugated diene, and hexanal formation during accelerated storage of stripped sunflower oil. The antioxidant activity is probably due to the combination of tocopherols, tocotrienols, and steryl ferulates.     

Fatty Acid Composition,Oxidative Stability,and Radical Scavenging Activity of Vegetable Oil Blends with Coconut Oil

Coconut (Cocos nucifera) contains 55–65% oil, having C12:0 as the major fatty acid. Coconut oil has >90% saturates and is deficient in monounsaturates (6%), polyunsaturates (1%), and total tocopherols (29 mg/kg). However, coconut oil contains medium chain fatty acids (58%), which are easily absorbed into the body. Therefore, blends of coconut oil (20–80% incorporation of coconut oil) with other vegetable oils (i.e. palm, rice bran, sesame, mustard, sunflower, groundnut, safflower, and soybean) were prepared. Consequently, seven blends prepared for coconut oil consumers contained improved amounts of monounsaturates (8–36%, p < 0.03), polyunsaturates (4–35%, p < 0.03), total tocopherols (111–582 mg/kg, p < 0.02), and 5–33% (p < 0.02) of DPPH (2,2-diphenyl-1-picrylhydrazyl free radicals) scavenging activity. In addition, seven blends prepared for non-coconut oil consumers contained 11–13% of medium chain fatty acids. Coconut oil + sunflower oil and coconut oil + rice bran oil blends also exhibited 36.7–89.7% (p < 0.0005) and 66.4–80.5% (p < 0.0313) reductions in peroxide formation in comparison to the individual sunflower oil and rice bran oil, respectively. It was concluded that blending coconut oil with other vegetable oils provides medium chain fatty acids and oxidative stability to the blends, while coconut oil will be enriched with polyunsaturates, monounsaturates, natural antioxidants, and a greater radical scavenging activity.     

Physical Properties and Fatty Acid Profiles of Oils from Black,Kidney, Great Northern,and Pinto Beans

Four common beans (black, kidney, great northern, and pinto) were extracted with hexane and found to contain about 2% triacylglycerols. The fatty acids in these bean oils were mainly linolenic (41.7–46 wt%), linoleic (24.1–33.4 wt%), palmitic (10.7–12.7 wt%) and oleic (5.2–9.5 wt%). Because of the high levels of polyunsaturated fatty acids, the bean oils had iodine values between 174 and 177 g/100 g (compared to 130 g/100 g for soybean oil). Yet, the bean oils exhibited high oxidative stability due to the presence of high amounts of tocopherols (2,670–2,970 ppm). The bean oils had lower pour points (−18 to −11 °C) compared to −9 °C for soybean oil. Among the four bean oils, kidney bean oil had the highest acid value (15.4 mg KOH/g) and kinematic viscosities over a wide range of temperatures.     

Evening primrose (Oenothera spp.) oil and seed

Evening primrose (Oenothera spp.) seed contains ca. 15% protein, 24% oil, and 43% cellulose plus lignin. The protein is unusually rich in sulphur-containing amino acids and in tryptophan. The component fatty acids of the oil are 65–80% linoleic and 7–14% ofγ-linolenic, but noα-linolenic acid. The 1.5–2% unsaponifiable matter has a composition very similar to that of cottonseed oil. The sterol fraction contains 90%β-sitosterol and the 4-methyl sterol fraction contains 48% citrostadienol;γ-tocopherol dominates its class, with someα- but no other tocopherols.     

Characterization of Oil Extracted from Buriti Fruit (Mauritia flexuosa) Grown in the Brazilian Amazon Region

Five samples of buriti oil from industrial and artisanal suppliers were characterized in terms of nutritional quality parameters (nutraceutical levels) and acidity. As a first screening, each sample was analyzed by titration, spectrophotometry and an HPLC method, and the results were compared. As expected, artisanal samples showed lower acidity and higher levels of carotenes and tocols (tocopherols and tocotrienols). A blend of industrial and artisanal samples in suitable proportions was completely characterized in terms of analytical and physico-chemical properties, i.e., fatty acid composition, iodine value, partial and total acylglycerol contents, refractive index (40 °C), saponification value, unsaponifiable matter, acidity (expressed as % of oleic acid), peroxide value, phosphorus content, oil stability index, tocol and carotene concentrations. The results of the present study showed that buriti oil is a valuable source of monounsaturated fatty acids, and vitamins A and E. No previous work in the literature has analyzed buriti oil to this extent. The chromatographic method using HPLC was effective in qualifying and quantifying tocopherols, tocotrienols and carotenes.     

Semimicro determination of total fatty acids and unsaponifiable matter

A semimicro method for determining both total fatty acids and unsaponifiable matter in fats, fatty acids, and soap is presented. The procedure involves saponification and recovery of the total fatty acids (which includes the unsaponifiables), removal of the fatty acids with anion exchange resins, and determination of the unsaponifiable matter by weight. The total fatty acid method was evaluated on seven samples and showed a standard deviation from the mean of 0.21%. The unsaponifiable matter determination gives good reproducibility with a standard deviation from the mean of 0.06%. Since this ion exchange is a direct determination of the nonionic components, the results obtained from it should be more accurate and more nearly the true values than the macro extraction method which is empirical. Presented at the annual spring meeting, American Oil Chemists’ Society, Dallas, Tex., April 4–6, 1960.     

Effect of extraction solvents on oxidative stability of crude soybean oil

Oxidative stabilities of crude soybean oils obtained by different extraction solvents such as hexane, water and Folch's solvent (mixture of two volumes of chloroform and one volume of methanol) were determined by gas chromatographic analyses of headspace and peroxide value of oil samples. For the determination of oxidative stability of oil samples, total volatile compounds formation, molecular oxygen disappearance in the headspace and peroxide value of oil samples were measured. Iodine value (133–136), saponification value (195–198), unsaponifiable matters (0.3–0.4%), iron (0.6 ppm), sterols content (2,400–2,590 ppm), tocopherols content (1,250–1,520 ppm) and fatty acid composition of crude oils obtained by different solvent extraction were not significantly different. Acid value of Folch-extracted oil was the highest as 1.3, whereas those of hexane-and aqueous-extracted oils were 0.5 and 0.4, respectively. Crude soybean oil extracted by Folch's method was found to contain the most phosphorus, while hexane- and aqueous-extracted oils contained similar amounts of phosphorous. Crude soybean oil obtained by Folch extraction was most stable in oil oxidation, and oxidative stabilities of oils obtained by hexane and aqueous extraction, which were significantly much less stable than Folch-extracted oil, were not significantly different during ten weeks storage.     

Characterization of Fenugreek (<Emphasis Type="Italic">Trigonella foenum-graecum</Emphasis>) Seed Lipids

The composition and content of lipids, fatty acids, triacylglycerols, tocopherols and sterols in nine fenugreek genotypes were analyzed. Lipid content in fenugreek seeds ranged from 5.8 to 15.2%. Major fatty acids were: linoleic acid (45.1–47.5%), α-linolenic (18.3–22.8%), oleic (12.4–17.0%), palmitic (9.8–11.2%) and stearic (3.8–4.2%) acids. The ratios of n-6 to n-3 fatty acids were between 2.1 and 2.7. Similar fatty acid distribution was observed in all analyzed samples with some deviations. α-Tocopherol was the predominant component found in the fenugreek lipid antioxidants, and it constituted over 84% of the total amounts of tocopherols. It amounts ranged from 620 to 910 mg/kg lipids. β-Sitosterol was the major sterol in all samples, varying from 14,203 to 18,833 mg/kg of lipids. Campesterol and cycloartenol were other major sterols, and these compounds including β-sitosterol constituted 56–72% of all sterols. Fenugreek seed lipids consisted predominantly triunsaturated (56.9–66.5%) and diunsaturated (32.2–41.6%) triacylglycerides. Among these components trilinolein (LLL; 12.9–20.5%) dominated followed by PLL (14.0–20.4%), LnLnO (7.8–17.7%), PLO (5.7–11.6%), OLL (6.9–10.6%), LLLn (3.2–9.6%), and LnLnL (3.5–7.6%). Results of the study show that fenugreek seed lipids may be a source of a nutraceutical ingredient for food applications.     

Characteristics of Oil from Hulless Barley (<Emphasis Type="Italic">Hordeum vulgare</Emphasis> L.) Bran from Tibet

The bran of hulless barley (Hordeum vulgare L.) from Tibet was investigated. This paper reports on the physicochemical characteristics, lipid classes and fatty acids of the oil from the bran. The petroleum (60–90 °C) extract of hulless barley bran was found to be 8.1%. The investigated physiochemical parameters included density at 40 °C (0.96 g/cm³), refractive index at 40 °C (1.41), melting point (30.12 °C), acid value (11.6 mg KOH/g), peroxide value (19.41 μg/g), saponification value (337.62 mg KOH/g), iodine value (113.51 mg iodine/g) and unsaponifiable matter (4.5% of total lipids).The amount of neutral lipids in the crude oil was the highest (94.55% of total lipids), followed by glycolipids (4.20% of the total lipid) and phospholipids (1.25% of the total lipid). Linoleic acid (75.08% of total fatty acids) followed by palmitic acid (20.58% of total fatty acids), were the two major fatty acids in the oil. The results show that the oil from the hulless barley bran could be a good source of valuable essential fatty acids.     

Physico-Chemical Characteristics of Citrus Seeds and Seed Oils from Pakistan

The physico-chemical characteristics of the seeds and seed oils of four citrus species, Mitha (Citrus limetta), Grapefruit (Citrus paradisi), Mussami (Citrus sinensis), and Kinnow (Citrus reticulata) were investigated. The hexane-extracted oil content of citrus seeds ranged from 27.0 to 36.5%. The protein, fiber and ash contents were found to be 3.9–9.6%, 5.0–8.5%, and 4.6–5.6%, respectively. The extracted oils exhibited an iodine value of 99.9–110.0; refractive index (40 °C), 1.4639–1.4670; density (24 °C), 0.920–0.941 mg/mL; saponification value, 180.9–198.9; unsaponifiable matter, 0.3–0.5%; acid value (mg KOH/g of oil), 0.5–2.2 and color (1-in. cell) 1.4–3.0R + 15.0–30.0Y. The oils revealed a good oxidative stability as indicated by the determinations of specific extinctions at 232 and 270 nm (2.3–4.4 and 0.6–0.9, respectively), p-anisidine value (2.2–3.2) and peroxide value (1.6–2.4 mequiv/kg of oil). The citrus seed oils mainly consisted of linoleic acid (36.1–39.8%). Other prominent fatty acids were palmitic acid (25.8–32.2%), oleic acid (21.9–24.1%), linolenic acid (3.4–4.4%), and stearic acid (2.8–4.4%). The contents of tocopherols (α, γ, and δ) in the oil were 26.4–557.8, 27.7–84.1, and 9.1–20.0 mg/kg, respectively. The results of the present study demonstrated that the seeds of citrus species investigated are a potential source of valuable oil which might be utilized for edible and other industrial applications.     

Quality Changes and Tocopherols and γ-Orizanol Concentrations in Rice Bran Oil During the Refining Process

The quality changes and the concentrations of tocopherols and γ-oryzanol, during successive steps of rice bran oil refining (RBO), were studied. For this purpose, samples of crude, degummed, neutralized, bleached, dewaxed and deodorized RBO were taken from an industrial plant and analyzed. The moisture, pH, acidity, peroxide value and unsaponifiable matter, were determined. The fatty acid composition was evaluated by GC, and the concentrations of tocopherols and γ-oryzanol were determined using HPLC with fluorescence and UV–Vis detection, respectively. To identify γ-oryzanol components, fractions of the HPLC eluant were collected and analyzed using mass spectrometry. Oil refining reduced the peroxide value and acidity to 1 and 3% of the values obtained in crude RBO, respectively. The fatty acid composition were not significantly altered during refining. The concentrations of the tocopherols in RBO followed the order α > (β + γ) > δ. The total concentration of tocopherols was 26 mg/100 g, and remained practically unaltered during refining. Up to nine components were distinguished in γ-oryzanol. After collecting the elution fractions, up to six components were identified by electrospray mass spectrometry. Refining reduced the total concentration of γ-oryzanol to 2% of its initial value.     

A Simple Two-Step Method for Simultaneous Isolation of Tocopherols and Free Phytosterols from Soybean Oil Deodorizer Distillate with High Purity and Recovery

Most of the methods reported for isolating phytosterols and tocopherols from soybean oil deodorization distillate (SODD) involved complicated steps or failed to obtain high content and recovery. In this study, we succeeded in isolating α-, δ-, γ-tocopherols, and free phytosterols (campesterol, stigmasterol, and β-sitosterol) from SODD with high content and recovery. Our protocol involved a simple two-step method. SODD was separated into non-polar and polar fraction by modified soxhlet extraction. Cold saponification was chosen instead of conventional saponification which is carried out at a temperature no lower than 60°C. This study of cold saponification was applied to the polar fraction to remove free fatty acids and acylglycerols. SODD contains 9.13 ± 0.28% tocopherols and 9.75 ± 0.12% free phytosterols, was converted to a final product which contains 38.08 ± 0.36% tocopherols and 55.51 ± 0.56% free phytosterols. The total recovery of tocopherols and free phytosterols is 94 ± 0.19%.     

Bleaching rapeseed and soybean oils with synthetic adsorbents and attapulgites

Efficiencies of synthetic adsorbents and attapulgites in bleaching alkali-refined rapeseed and soybean oils ranged from 13–53% and 93–97%, respectively. The Freundlich equation was more applicable than the Langmuir equation to the experimental adsorption isotherms of β-carotene on attapulgites. Bleaching with attapulgites reduced tocopherols by 12.5–29.5% in rapeseed oil and by 18.9–44.8% in soybean oil. Cosmetic-grade attapulgite was superior to the others in bleaching efficiency, equilibrium amount adsorbed and removal of free fatty acids.     

On the composition of Iranian olive oil

Two samples of virgin olive oil and one sample of hexane-extracted husk oil coming from Iran were examined. The analyses included physical and chemical characteristics, the composition of total fatty acids and fatty acids at the glyceride 2-position by gas liquid chromatography (GLC) of methyl esters, the triglycerides composition calculation according to Vander Wal theory, the separation of the alcoholic fractions (sterols, 4-methylsterols, triterpene alcohols, triterpene dialcohols and aliphatic alcohols) of the unsaponifiable matter by thin layer chromatography (TLC), the quantitation and the composition of these fractions by GLC of TMS derivatives. The results were in line with data from literature for olive oils of different origin, with the exception of: a high content of unsaponifiable matter (1.75 and 1.95% for virgin oils, 5.33% for husk oil); a high amount of sterols for husk oil (562 mg/100 g oil); a low content of SE 30 apparent β-sitosterol for husk oil (91.1%); a low amount of triterpene dialcohols (1 mg/100 g oil) and triterpene alcohols (78 and 91 mg/100 g oil) for virgin oils; a content of cycloartenol (60.2–66.9%) higher than the 24-methylenecycloartanol one (22.8–26.6%; a content of C₂₄ linear saturated alcohol (33.9–38.0%) slightly higher than the C₂₆ alcohol one (29.3–32.8%).     

Physicochemical Properties of Garden Cress (<Emphasis Type="Italic">Lepidium sativum</Emphasis> L.) Seed Oil

Garden cress (Lepidium sativum L.) is an edible, underutilised herb, grown mainly for its seeds in India. Physicochemical properties, minor components (unsaponifiable matter, tocopherols, carotenoids), fatty acid composition and storage stability of garden cress seed oil (GCO) were studied. Cold press, solvent and supercritical CO₂ extraction methods were employed to extract the oil. The total oil content of garden cress (GC) seeds was 21.54, 18.15 and 12.60% respectively by solvent, supercritical CO₂ and cold press methods. The physical properties of GCO extracted by the above methods were similar in terms of refractive index, specific gravity and viscosity. However, cold pressed oil showed low PV and FFA compared to the oil extracted by other methods. α-Linolenic acid (34%) was the major fatty acid in GCO followed by oleic (22%), linoleic (11.8%), eicosanoic (12%), palmitic (10.1%) erucic (4.4%), arachidic (3.4%) and stearic acids (2.9%). Oleic acid (39.9%) and α-linolenic acid (42.1%) were the predominant fatty acids at the sn-2 position. The total tocopherol and carotenoid content of GCO was 327.42 and 1.0 μmol/100 g oil, respectively. The oil was stable up to 4 months at 4 °C. Tocopherol and BHT offered the least protection, while ascorbyl palmitate (200 ppm) offered the maximum protection to the oil, when subjected to the accelerated oxidative stability test. Thus GCO can be considered as a fairly stable oil with a high content of α-linolenic acid.     

Genotype and growing location effects on phytosterols in canola oil

There is little information available about phytosterols in canola (Brassica napa L.) oil and the effects of genotype and growing locations from Virginia and the mid-Atlantic region of the United States, a potential area for the establishment of domestic production to provide edible oil. Our objectives were to characterize the phytosterols, phospholipids, unsaponifiable matter, and FA in oil from Virginia-grown canola. Among 11 canola genotypes grown at two locations during 1995–1996 significant variations existed for oil content and FA profiles, but not for contents of phospholipids, unsaponifiable matter, total phytosterols, campesterol, stigmasterol, and β-sitosterol, Total phytosterol content in the oil of Virginia-grown canola varied from 0.7 to 0.9% with a mean of 0.8%. This concentration compared favorably with oil from Canadian canola, which typically contains 0.5 to 1.1% total phytosterols. The mean contents of brassicasterol, campesterol, stigmasterol, β-sitosterol, Δ⁵-avenasterol, and Δ⁷-stigmatenol as percentages of total phytosterols in Virginia-grown canola were: 9.7, 32.0, 0.6, 49.3, 4.99, and 3.5%, respectively. Growing location did not affect phytosterols in Virginia-grown canola oil but had significant effects on contents of phospholipids, and saturated (myristic, stearic, and arachidic) and unsaturated (palmitoleic, linoleic, linolenic, eicosenoic, and erucic) FA.     

Profiling of Phytosterols, Tocopherols and Tocotrienols in Selected Seed Oils from Botswana by GC–MS and HPLC

The phytosterol, tocopherol, and tocotrienol profiles for mkukubuyo, Sterculia africana, manketti, Ricinodendron rautanenni, mokolwane, Hyphaene petersiana, morama, Tylosema esculentum, and moretologa-kgomo, Ximenia caffra, seed oils from Botswana have been determined. Normal-phase HPLC analysis of the unsaponifiable matter showed that among the selected oils, the most abundant tocopherol and tocotrienol were γ-tocopherol (2232.99 μg/g) and γ-tocotrienol (246.19 μg/g), detected in manketti and mkukubuyo, respectively. Mokolwane oil, however, contained the largest total tocotrienol (258.47 μg/g). Total tocol contents found in manketti, mokolwane, mkukubuyo, morama, and moretologa-kgomo oils were 2238.60, 262.40, 246.20, 199.10, and 128.0 μg/g, respectively. GC–MS determination of the relative percentage composition of phytosterols showed 4-desmethylsterols as the most abundant phytosterols in the oils, by occurring up to 90% in moretologa-kgomo, mkukubuyo, and manketti seed oils, with β-sitosterol being the most abundant. Mokolwane seed oil contained the largest percentage composition of 4,4-dimethylsterols (45.93%). Besides 4-desmethylsterols (75%), morama oil also contained significant amounts of 4,4-dimethylsterols and 4-monomethylsterols (15.72% total). GC–MS determination of the absolute amounts of 4-desmethylsterols, after SPE fractionation of the unsaponifiable matter, confirmed that β-sitosterol was the most abundant phytosterol in the test seed oils, with manketti seed oil being the richest source (1326.74 μg/g). The analysis showed total 4-desmethylsterols content as 1617.41, 1291.88, 861.47, 149.15, and 109.11 μg/g for manketti, mokolwane, mkukubuyo, morama, and moretologa-kgomo seed oils, respectively.     

Impacts of Refining and Antioxidants on the Physico-Chemical Characteristics and Oxidative Stability of Watermelon Seed Oil

Compositional analyses of seeds from two cultivars (Mateera and Sugar baby) was performed to evaluate their suitability as oilseeds. Watermelon seeds and kernels contained 21.9–25.5 % and 38.9–46.9 % oil of exceptionally high quality. The crude oil was expelled with a screw press and then refined to obtain a odor free and colorless oil. The moisture content, unsaponifiable matter content, refractive index, and specific gravity were within the narrow ranges. Refining influenced the color, acid value, saponification value, peroxide value, and free fatty acid contents. Linoleic acid (C18:2) was the principal fatty acid constituting 64.5–67.2 % of the total fatty acids. Oxidative stability increased with the addition of tocopherols, butylated hydroxyl anisole (BHA), and tert-butyl hydroxyl quinine (TBHQ). The high amount of polyunsaturated fatty acids (PUFA) along with physicochemical properties were similar to soybeans, sunflower and other common vegetable oils, suggesting the suitabilty of watermelon seed oil for industrial production.     

Changes in Fatty Acids,Tocochromanols, Carotenoids and Chlorophylls Content During Flaxseed Development

A comparative study was performed to determine tocopherols, tocotrienols, fatty acids, and pigments content during the development of three varieties of flaxseed (H52, O116 and P129). Seed samples were collected at regular intervals from 7 to 56 days after flowering (DAF). The highest content of chlorophyll (89.72–130.5 mg/kg oil) was detected at 7 DAF. The maximum level of carotenoids (52.10–65.55 mg/kg oil) was reached at 21 DAF. During seed development, unsaturated fatty acids are the major component, reaching 85% of the total fatty acids while saturated fatty acids content were about 15%. The maximum level of γ-tocopherol (585 mg/kg oil) was reached at 42 DAF in P129 variety. These results may be useful for evaluating the flaxseed quality and determining its optimal harvest period.