Incorporation of the toxic aldehyde 4-hydroxy-2-<Emphasis Type="Italic">trans</Emphasis>-nonenal into food fried in thermally oxidized soybean oil

The toxic aldehyde 4-hydroxy-2-trans-nonenal (HNE) is an oxidation product of linoleic acid and is formed during the thermal oxidation of soybean oil at frying temperature. This investigation was conducted to determine whether HNE would be incorporated into food fried in thermally oxidized soybean oil. Commercially available liquid soybean oil was heated at 185°C for 5 h prior to frying uniform pieces of potato (1×0.5×7 cm). The oil was sampled prior to and after frying and was analyzed for the presence of HNE and other polar lipophilic aldehydes and related carbonyl compounds by HPLC. The oil was also extracted from the fried potato pieces and was analyzed identically to the frying oil. HNE was found to be a major polar lipophilic compound in the thermally oxidized frying oil, as previously published by this laboratory, and in the oil extracted from the fried potato. Similar concentrations of HNE were found in the oil prior to and after frying and in the oil extracted from the fried potato (57.53±16.31, 52.40±6.10, and 59.64±11.91 mg HNE per 100 g oil, respectively). These results indicate that toxic HNE was readily incorporated into food fried in thermally oxidized oil; extensive consumption of such fried foods could be a health concern.     

The effect of intermittent and continuous heating of soybean oil at frying temperature on the formation of 4-hydroxy-2-trans-nonenal and other α-, β-unsaturated hydroxyaldehydes

4-Hydroxy-2-trans-nonenal (HNE) is a cytotoxic secondary lipid peroxidation product of linoleic acid. Previous investigations in this laboratory showed that HNE is formed in thermally oxidized soybean oil, which is high in linoleic acid. Continuous exposure of the oil to frying temperature (185°C) for up to 6 h graduallyincreased the formation of HNE and other polar lipophilic aldehydes. Additional investigations in this laboratory showed that HNE is absorbed into food fried in thermally oxidized oil in the same concentration as was found in the oil. In the present experiment, the effect of intermittent heating on the formation of HNE in soybean oil was compared with continuous heating. Soybean oil samples were heated either for 1 h each day for five sequential days or for 5 h continuously at 185±5°C. The thermally oxidized soybean oil samples were analyzed by HPLC for the presence of HNE and three other polar lipophilic α-,β-unsaturated hydroxyaldehydes: 4-hydroxy-2-trans-hexanal, 4-hydroxy-2-trans-octenal, and 4-hydroxy-2-trans-decenal. Under intermittent and continuous heating over a total of 5 h, the concentration of these compounds increased similarly. These results indicate that the formation of HNE and other hydroxyaldehydes at frying temperature is a cumulative result of oxidation of PUFA over time.     

Simultaneous determination of lipophilic aldehydes by high-performance liquid chromatography in vegetable oil

A very sensitive high-performance liquid chromatography (HPLC) method was developed for the simultaneous separation and measurement of nonpolar and polar lipophilic secondary lipid peroxidation products in vegetable oil. Seventeen nonpolar and 13 polar lipophilic aldehydes and related carbonyl compounds, derived from thermally oxidized soybean oil as 2,4-dinitrophenyl hydrazones, were separated simultaneously by reversed-phase HPLC. Detection limit for the individual compounds is 1 ng. Thirteen of the nonpolar carbonyl compounds were identified as: butanal, 2-butanone, pentanal, 2-pentanone, hexenal, hexanal, 2,4-heptadienal, 2-heptenal, octanal, 2-nonenal, 2,4-decadienal, decanal, and undecanal. Three of the polar carbonyl compounds were identified as: 4-hydroxy-2-hexenal, 4-hydroxy-2-octenal, and 4-hydroxy-2-nonenal. The detection of the toxic 4-hydroxy-2-nonenal, a major compound, and 4-hydroxy-2-hexenal, a minor compound, in heated soybean oil is of particular importance because these toxic compounds have been shown to be absorbed from the diet.     

Optimal tocopherol concentrations to inhibit soybean oil oxidation

The optimal concentration for tocopherols to inhibit soybean oil oxidation was determined for individual tocopherols (α-, γ-, and δ-tocopherol) and for the natural soybean oil tocopherol mixture (tocopherol ratio of 1∶13∶5 for α-, γ-, and δ-tocopherol, respectively). The concentration of the individual tocopherols influenced oil oxidation rates, and the optimal concentrations were unique for each tocopherol. For example, the optimal concentrations for α-tocopherol and γ-tocopherol were ∼100 and ∼300 ppm, respectively, whereas δ-tocopherol did not exhibit a distinct concentration optimum at the levels studied (P<0.05). The optimal concentration for the natural tocopherol mixture ranged between 340 and 660 ppm tocopherols (P<0.05). The antioxidant activity of the tocopherols diminished when the tocopherol levels exceeded their optimal concentrations. Above their optimal concentrations, the individual tocopherols and the tocopherol mixture exhibited prooxidation behavior that was more pronounced with increasing temperature from 40 to 60°C (P<0.05). A comparison of the antioxidant activity of the individual tocopherols at their optimal concentrations revealed that α-tocopherol (∼100 ppm) was 3–5 times more potent than γ-tocopherol (∼300 ppm) and 16–32 times more potent than δ-tocopherol (∼1900 ppm).     

Stability of furanoid fatty acids in soybean oil

Analysis of the positional distribution of the furanoid fatty acids, 10,13-epoxy-11,12-dimethyloctadeca-10, 12-dienoic acid (F20) and 12,15-epoxy-13,14-dimethyleicosa-12,14-dienoic acid (F22), in soybean oil (SBO) indicated that they were preferentially esterified with the primary-OH groups of glycerol molecules. Hydrogenation of SBO reduced the concentrations of F20 and F22 somewhat. During exposure of SBO to daylight, F20 and F22 were completely degraded within two days, whereas linoleic acid and linolenic acid were not affected. β-Carotene inhibited both the degradation of the furanoid fatty acids and their oxidation to the odorant 3-methyl-nonane-2,4-dione (MND), which contributes strongly to the light-induced off-flavor of SBO. A model experiment indicated that two days of light exposure of SBO, followed by filtration through silica gel and further refining, prevented the formation of MND during subsequent storage of the oil. Presented at the 86th Annual Meeting of the American Oil Chemists’ Society, San Antonio, Texas, May 7–11, 1995.     

Factors affecting the electrical resistivity of soybean oil methyl ester

Factors affecting the electrical resistivity of soybean oil methyl ester (which is important in some industrial applications) were investigated by the addition of polar constituents [free fatty acids (FFA), water, phospholipids, monoglyceride, sterol, tocopherol, peroxides, and β-carotene] to aluminapurified soybean oil methyl ester (APSBOMe). Investigation of measuring conditions showed that reproducible results were obtained when the potential was greater than 25 V, and the charging time was greater than 10 s. The resistivity of APSBOMe increased logarithmically as temperature decreased linearly. FFA had little effect on resistivity. Saturation with water lowered the resistivity of APSBOMe much more than that of alumina-purified soybean oil (APSBO). Phospholipids reduced the resistivity significantly when added to dry ester, but the addition of water affected the resistivity of the samples containing phospholipids only slightly. Monoglyceride, sterol, tocopherol, and hydroperoxide affected the resistivity of dry methyl ester similarly, but only monoglyceride showed a significant synergistic effect with water. Diacylperoxide and β-carotene had little effect on the resistivity of the ester.     

Transesterification of phytosterol and edible oil by lipase powder at high temperature

Phytosterol, which is hardly soluble in edible oil, was solubilized at a high concentration by converting it to FA esters by lipase-catalyzed transesterification at temperatures higher than 100°C using powdered Lipase QLM (Meito Sangyo Co., Ltd., Nagoya, Japan). Transesterification was conducted, in sunflower oil containing 10% phytosterol, without adding water or solvent, at 100°C. The conversion rate was 97.1% after 7 h of reaction. The effect of temperature on the conversion rate was also examined. Maximum enzyme activity occurred in the 100–120°C range, and 20% of the maximum activity was retained even at 130°C. When the lipase was recovered by filtration and recycled for repeated reactions at 90°C, the half-life of lipase activity was 260 h. Thus, edible oils with nutritional value could be produced by blending the phytosterol-containing sunflower oil into other edible oils.     

Factors affecting the electrical resistivity of soybean oil

The electrical resistivity of soybean oil that had been purified to remove polar constituents was determined, and the effect of measuring conditions and the addition of polar constituents (free fatty acids, phospholipids, monoglyceride, α-to-copherol, β-sitosterol, β-carotene, peroxides, and water) on resistivity was investigated. For reproducible resistivity measurements, voltages in excess of 50 volts and charging times greater than 120 s were necessary. As temperature was increased linearly, the resistivity of the oil decreased logarithmically. For making comparisons, a temperature of 24°C, a potential of 50 volts, and 120 s charging times were chosen. All polar constituents decreased the resistivity of the purified soybean oil, but water, phospholipids, and monoglycerides had the greatest effects. Water increased the resistivity-lowering effects of all other constituents except for free fatty acids, which were affected by water only slightly. The synergistic effect of water was much greater for phospholipids and monoglyceride than for other constituents.     

Role of minor constituents in the photooxidation of virgin olive oil

Virgin olive oil was photooxidized at 2 and 40°C and at fluorescent light intensities of 0, 620, 2710, and 5340 lux. As expected, higher fluorescent light intensities induced higher peroxide formation in the oil. The thiobarbituric acid reactive substances (TBARS) were found to be good indicators of photooxidation during the early stage of the reaction. Pheophytin A and β-carotene were light- and temperature-sensitive, whereas α-tocopherol and total polyphenols were mostly affected by light. Pheophytin A functioned as a photosensitizer, resulting in rapid oxidation of the oil. β-Carotene was a strong natural inhibitor of photooxidation for all light intensities at 2°C, suggesting quenching properties for singlet oxygen. However, β-carotene antioxidant activity was reduced at 40°C because of its rapid destruction.     

Optimizing headspace sampling temperature and time for analysis of volatile oxidation products in fish oil

Headspace-gas chromatography (HS-GC), based on adsorption to Tenax GR®, thermal desorption and GC, has been used for analysis of volatiles in fish oil. To optimize sampling conditions, the effect of heating the fish oil at various temperatures and times was evaluated from anisidine values (AV) and HS-GC. AV indicated sample degradations at 90°C but only small alterations between 60 and 75°C. HS-GC showed increasing response with temperature and time. Purging at 75°C for 45 min was selected as the preferred sampling condition for oxidized fish oil.     

Activity of antioxidants in solution and in irradiated heterogeneous system

The efficiency of some common antioxidants, α-tocopherol, butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), was studied relative to β-carotene in a homogeneous solution and in a model system of an irradiated solid food. Relative reactivities in homogeneous solution covered a range of three orders of magnitude, α-tocopherol being the best and BHT the poorest antioxidant of the three. In irradiated systems consisting of oleic acid coated on a solid support (egg white), the range of reactivities was much narrower within one order of magnitude. In solution, there was a parallelism of the relative reactivities with oxidizing alkoxyl radicals derived from oleic acid hydroperoxides andtert-butyl hydroperoxide. On the solid support the relative reactivities of α-tocopherol and BHA with oleic acid radiation-induced oxidizing radicals were reversed, BHA appearing the best. Efficient antioxidants do not retain their great antioxidant activity in comparison with the moderate ones on transition from a homogeneous solution to a heterogeneous system. Relative efficiencies of antioxidants do not critically depend on the nature of oxidizing radicals in heterogeneous media.     

Oxidation kinetics of β-carotene in oleic acid solvent with addition of an antioxidant, α-tocopherol

Oxidation experiments with β-carotene were performed in oleic acid solvent with addition of an antioxidant, α-tocopherol. A kinetic model was proposed based on a reaction mechanism consisting of the oxidation of β-carotene, oleic acid, and α-tocopherol; the antioxidation reactions of β-carotene and oleic acid by α-tocopherol; the cross-reaction of β-carotene and oleic acid; and the radical-exchange reaction of β-carotene and α-tocopherol. The model quantitatively described the oxidation behavior of β-carotene over a wide range of temperatures, oxygen compositions, and initial antioxidant concentrations. The model simulated well the time over which β-carotene was almost totally consumed under practical storage conditions at room temperature in air.     

Comparison of four analytical methods for the determination of peroxide value in oxidized soybean oils

Previous work in our laboratory demonstrated that soybean oil oxidation, expressed as PV, can be determined using NIR transmission spectroscopy as an alternative to the official AOCS iodometric titration method. In the present study, a comparison of four peroxide analytical methods was conducted using oxidized soybean oil. The methods included the official AOCS iodometric titration, the newly developed NIR method, the PeroxySafe^™ kit, and a ferrous xylenol orange (FOX) method, the latter two being colorimetric methods based on oxidation of iron. Five different commercially available soybean oils were exposed to fluorescent light to obtain PV levels of 0–20 meq/kg; periodic sampling was done to ensure having representative samples throughout the designated range. A total of 46 oil samples were analyzed. Statistical analysis of the data showed that the correlation coefficient (r) and standard deviation of differences (SDD) between the standard titration and NIR methods were r=0.991, SDD=0.72 meq/kg; between titration and the PeroxySafe^™ kit were r=0.993, SDD=0.56 meq/kg; and between the standard titration and FOX method were r=0.975, SDD=2.3 meq/kg. The high correlations between the titration, NIR, and PeroxySafe^™ kit data indicated that these methods were equivalent.     

The influence of carotenoids and tocopherols on the stability of safflower seed oil during heat-catalyzed oxidation

The stability and antioxidant effects of carotenoids and tocopherols in safflower seed oil were evaluated under thermal (75°C) and oxidative conditions and the oxidative stability index (OSI) determined. The antioxidant capability of butylated hydroxytoluene (BHT) was also compared with that of β-carotene in a model system. Lycopene and β-carotene (1 to 2000 ppm) were heated (75°C) and exposed to air (2.5 psi) in an oxidative stability instrument. β-Carotene had no antioxidant effect at concentrations below 500 ppm, because it did not alter the induction time. Lycopene increased the induction time only slightly at low concentrations. However, at concentrations greater than 500 ppm, both β-carotene and lycopene acted as prooxidants, significantly decreasing the induction period. At the highest concentration, 2000 ppm, lycopene was more prooxidative than β-carotene. α- and γ-Tocopherol (concentration, 1000 ppm) delayed the induction time by 16 and 26 h, respectively. There was no cooperative interaction between α-tocopherol and β-carotene in delaying the onset of oxidation. Furthermore, BHT was significantly more antioxidative than β-carotene. Thus, under thermal and oxidative conditions, β-carotene could not delay the onset of oxidation. The tocopherols and BHT were effective in suppressing the onset of oxidation, as determined by the oxidative stability measurement.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

Cis-trans isomerization of octadecatrienoic acids during heating. Study of pinolenic (cis-5,cis-9,cis-12 18∶3) acid geometrical isomers in heated pine seed oil

To understand the heat-inducedcis-trans isomerization of ethylenic bonds in octadecatrienoic acids, pine seed oil, which contains the unusual nonmethylene-interrupted pinolenic (cis-5,cis-9,cis-12 18∶3) acid as a major component, was heated under vacuum at 240°C for 6 h together with linseed and borage oils. As a results, a small percentage of pinolenic acid undergoescis-trans isomerization. The main isomer that accumulates is thetrans-5,cis-9,trans-12 18∶3 acid. Minor amounts of the three mono-trans isomers are also present. Identification of isomers was realized by combining gas-liquid chromatography on a CP Sil 88 capillary column, argentation thin-layer chromatography and comparing the equivalent chainlengths of artifacts to those of isomers present in NO₂-isomerized pine seed oil. Hydrazine reduction was used to demonstrate that there was no positional shift of double bonds. Heat-induced geometrical isomerization of pinolenic acid differs from that of α- and γ-linolenic acids in at least two aspects. The reaction rate is slower (about one-fourth), and mono-trans isomers are formed in low amounts.     

Continuous transesterification of biodiesel in a helicoidal reactor using recycled oil

The main problem with biodiesel is the high cost of oils made from oleaginous crops. For this reason, various raw materials have been analysed with a view to reducing production costs and obtaining a product that can compete with the price of petrodiesel. Recycled oil is one of the most promising alternatives in the production of biodiesel because not only is the cheapest raw material but it also avoids the expense of treating the oil as a residue.Another way to reduce costs is to make the process more economical. Conventional technology uses sodium hydroxide as the basic catalyst and large-scale batch reactors, whose mechanical agitation requires high energy consumption due to residence times of at least 60 min and temperatures of 60 °C.In this paper we use a recycled pretreated oil to compare conventional transesterification with continuous transesterification in a tubular reactor. In this reactor the reactants (oil, methanol and sodium hydroxide) flow through a helicoidal tube submerged in a heating bath at 60 °C. The reactor has five outlets distributed non-uniformly to enable samples to be taken at different reaction times. This is to reduce the reaction time and avoid the need for mechanical agitation. With the aim of improving the quality of the biodiesel obtained, we varied the helicoidal system by incorporating a static micromixer and supplying energy in the form of ultrasound from the heating bath. This reactor produced biodiesel and glycerine at compositions roughly equal to those obtained in the batch process (89% FAME content at 75 min) but did so continuously (2.5 mL/min) and just 13 min after the reactants were integrated in a single line using a T device. Both the oil and the biodiesel were characterized and analysed in accordance with European standard UNE EN14214 for biodiesel.