Occurrence of Conjugated Cyclopropanoid Acid in Purified Fish Oil

The presence of conjugated trienoic acids were found in the purified fish oil from the Japanese sardine by an analysis of high performance liquid chromatography equipped with a photodiode-array detector. Gas chromatography–mass spectrometry indicated that main conjugated trienoic acids were those of 16:3, 20:5, and 22:6. Conjugated trienoic acid of 16:3 was identified as a cyclopropanoid acid with conjugated triene by NMR analysis. All conjugated trienoic acids were formed by heat treatment during the deodorization of fish oil, but not found after de-gumming, alkaline refining, and bleaching. Conjugated trienoic acids of 16:3, 20:5, and 22:6 originated from 16:4n-1, 20:5n-3 (EPA), and 22:6n-3 (DHA) in the fish oil during the heat treatment for deodorization.     

Sources and Bioactive Properties of Conjugated Dietary Fatty Acids

The group of conjugated fatty acids known as conjugated linoleic acid (CLA) isomers have been extensively studied with regard to their bioactive potential in treating some of the most prominent human health malignancies. However, CLA isomers are not the only group of potentially bioactive conjugated fatty acids currently undergoing study. In this regard, isomers of conjugated α‐linolenic acid, conjugated nonadecadienoic acid and conjugated eicosapentaenoic acid, to name but a few, have undergone experimental assessment. These studies have indicated many of these conjugated fatty acid isomers commonly possess anti‐carcinogenic, anti‐adipogenic, anti‐inflammatory and immune modulating properties, a number of which will be discussed in this review. The mechanisms through which these bioactivities are mediated have not yet been fully elucidated. However, existing evidence indicates that these fatty acids may play a role in modulating the expression of several oncogenes, cell cycle regulators, and genes associated with energy metabolism. Despite such bioactive potential, interest in these conjugated fatty acids has remained low relative to the CLA isomers. This may be partly attributed to the relatively recent emergence of these fatty acids as bioactives, but also due to a lack of awareness regarding sources from which they can be produced. In this review, we will also highlight the common sources of these conjugated fatty acids, including plants, algae, microbes and chemosynthesis.     

Mid-Oleic/Ultra Low Linolenic Acid Soybean Oil: A Healthful New Alternative to Hydrogenated Oil for Frying

To determine the frying stability of mid-oleic/ultra low linolenic acid soybean oil (MO/ULLSBO) and the storage stability of food fried in it, tortilla chips were fried in MO/ULLSBO, soybean oil (SBO), hydrogenated SBO (HSBO) and ultra low linolenic SBO (ULLSBO). Intermittent batch frying tests were conducted up to 55 h of frying, and then tortilla chips were aged up to 4 months at 25 °C. Frying oils were analyzed for total polar compounds to determine the frying stability of the oil. Tortilla chips were analyzed for hexanal as an indicator of oxidative deterioration and by sensory analysis using a trained, experienced analytical panel. Results showed no significant differences between the total polar compound levels for MO/ULLSBO and HSBO after 55 h of frying, indicating a similar fry life. However, total polar compound levels for ULLSBO and SBO were significantly higher than for either MO/ULLSBO or HSBO, indicating a lower oil fry life. Hexanal levels in aged tortilla chips fried in SBO were significantly higher than in chips fried in any of the other oils. Tortilla chips fried in MO/ULLSBO and HSBO had significantly lower hexanal levels than in chips fried in ULLSBO. A sensory analysis of rancid flavor intensity showed similar trends to those for hexanal formation. The chips fried in SBO had the highest rancid flavor intensity, with significantly lower hexanal levels in chips fried in HSBO and MO/ULLSBO. Based on these results, MO/ULLSBO not only had a good fry life but also produced oxidatively stable fried food, and therefore would be a healthful alternative to HSBO. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Differences in Oxidation Kinetics Between Conjugated and Non-Conjugated Methyl Linoleate

The oxidation kinetics of conjugated methyl linoleate was compared with that of non-conjugated methyl linoleate under mild oxidation conditions (30 °C in the dark). Samples of methyl 9-cis,11-trans-linoleate, methyl 10-trans,12-cis linoleate and methyl 9-cis,12-cis linoleate were assayed separately and in mixtures. For comparative purposes, methyl α-linolenate and methyl oleate were also used. Two complementary analytical approaches were selected to monitor the progress of oxidation, (1) the traditional follow-up of residual substrate by gas liquid chromatography, and (2) an analytical procedure by high-performance size-exclusion chromatography (HPSEC) for direct measurement of the oxidation compounds formed. The HPSEC method enabled us to quantitate oxidized monomers, dimers and polymers concomitantly in a rapid and direct analysis. Results showed that conjugated methyl linoleate samples oxidized later than their non-conjugated counterparts, and showed a very different oxidation pattern. Thus, formation of oxidized monomers was negligible and the first and major compounds formed were polymerization products. Also, under the conditions used, non-conjugated and conjugated methyl linoleate samples in 1:1 mixtures led to decreased oxidation rate of non-conjugated methyl linoleate and increased oxidation rate of conjugated methyl linoleate. This study supports the view that oxidation kinetics of conjugated dienes differ substantially from that of methylene-interrupted dienes.     

红花油制取共轭亚油酸的研究

以新疆克拉玛依厂的红花油为原料,以丙三醇为溶剂,在KOH的碱性催化作用下,将红花油先转化成亚油酸钾;再利用异构化反应制得浅黄色的共轭亚油酸产品。对产品进行了薄层层析法和紫外分光光度法定性分析,并定量分析了红花油异构化反应的程度。本研究对红花油的深加工将起到很好的推动作用。     

Insight into the Enzymatic Degumming Process of Soybean Oil

An enzymatic degumming trial of soybean oil was carried out at a capacity of 400 tons/day by applying microbial phospholipase A₁ from Thermomyces lanuginosus/Fusarium oxysporum. When the pH was kept in the range of 4.8–5.1, less than 10 mg/kg of phosphorous content of The oil was obtained. The gum and oil were easily separated after centrifugation and the oil loss was minimal under the process conditions. Through analysis of phospholipids compounds in the gum by Electrospray Ionization-Mass Spectrometer and phosphorous content, it could be seen that both glycerophospholipids and lysophospholipids existed with contents of 45.7 and 54.3%, respectively. The performance of enzymatic degumming was found to be related to the production of glycerophospholipids.     

松香改性豆油酸醇酸树脂的合成研究

以大豆油脚为原料提取豆油脂肪酸,并依此研究了松香改性豆油酸醇酸树脂的合成.获得的树脂和漆产品性能良好,降低了污染和能源消耗,较天然桐油和亚麻油等原料有明显优势,经济效益高.     

Adsorption Isotherms for Bleaching Soybean Oil with Activated Attapulgite

Activated attapulgite was characterized and used as bleaching clay (adsorbent) for soybean oil. Adsorption isotherms for bleaching soybean oil were determined to investigate the applicability of the Langmuir and Freundlich equations and to elucidate the adsorption characteristics of oil on activated attapulgite. The Freundlich model was found to provide a better fit with the experimental data than the Langmuir model. The larger Freundlich constant, K _F at higher temperature indicated more effective adsorption. The heat evolved for oil bleaching increased as the levels of activated attapulgite increased from 0.5 to 3%, due to the increase in adsorptive sites with increasing attapulgite levels as well as multilayer adsorption driven by van der Waals’ forces at smaller amounts of adsorbents. There are enough adsorptive sites with 3% attapulgite to adsorb the pigments associated with soybean oil bleaching. The amount of attapulgite has no effect on ΔH _a when it is >3%, and ΔH _a is about 32 kJ/mol.     

Antioxidant Activity of Sesamol in Soybean Oil Under Frying Conditions

Antioxidant activity of sesamol was investigated in soybean oil using a miniaturized frying experiment with potato cubes fried at 180 °C. Oxidation of soybean oil was determined by gel permeation chromatography for polymerized triacylglycerols and by ¹H-NMR spectroscopy for reactions at reactive sites of soybean oil molecules including olefinic, bisallylic and allylic protons during frying. Sesamol showed lower antioxidant activity than 0.02 % (w/w) tert-butylhydroquinone (TBHQ) at the same molar concentration. Higher concentrations of sesamol provided better antioxidant effects indicating that no prooxidant activity occurred. Sesamol in this frying test showed better results than 0.02 % TBHQ when the concentration was as high as 0.66 % by weight. An HPLC experiment showed that the concentration of sesamol decreased sharply during frying. Thermogravimetric analysis indicated that sesamol is highly volatile and easily oxidizes when exposed to air. To overcome this problem, two multiple addition methods were evaluated in which sesamol was added portion by portion every hour. The multiple additions of divided portions of 0.66 % (w/w) sesamol maintained the concentration of sesamol at the minimum of 0.04–0.06 % throughout the frying process and showed improved antioxidant activity compared to one single addition of 0.66 % sesamol at the beginning of frying. One of the multiple addition methods showed 28, 18, 59, and 27 % less polymerized triacylglycerols and losses of olefinic, bisallylic and allylic protons, respectively, than 0.02 % TBHQ after 8-h frying. This study shows that sesamol can be used as an alternative for synthetic antioxidants for frying oil.     

环氧大豆油新工艺的研究

研究了采用无溶剂合成环氧大豆油的新工艺。以大豆油、冰醋酸与双氧水为原料经催化、碱洗、水洗、减压蒸馏后制得环氧值≥6.0%的高质量产品,同时通过L9(3^4)正交试验对反应的工艺条件,原料配比与影响产品质量的各种因素进行了研究,确定最佳工艺条件是大豆油：双氧水：冰醋：浓硫酸之比是1：0.33：0.23：0.02。     

Effect of Ru Nanoparticle Size on Hydrogenation of Soybean Oil

Four Ru nanoparticles of different mean sizes from 1.13 to 17.22 nm were prepared and used as catalysts for the selective hydrogenation of polyunsaturated soybean oil at 353 K and initial pressure of 1.5 MPa. The catalyst with the smallest mean size (1.13 nm) had the lowest activity, the activity increased as the mean size increased to 3.10 nm, then decreased with further increase in the mean particle size. The cis–trans isomerization rate decreased with the increase in particle size.     

Antioxidant Activity of Sesamin in Canola Oil

The present study presents the antioxidant activity of sesamin in canola oil compared with that of butylated hydroxytoluene (BHT) by monitoring the oxygen consumption and the decrease in linoleic acid and α-linolenic acid. The oxidation of canola oil was conducted at 35, 60, 90, 120 and 180 °C with addition of 50–400 ppm sesamin. Results from the oxygen consumption test showed that sesamin dose-dependently inhibited the oxidation of canola oil at concentrations of 50–200 ppm at temperatures of 60–180 °C, however, sesamin lost its antioxidant activity at a low temperature of 35 °C. The fatty acid analysis also demonstrated that sesamin at 50, 100 and 200 ppm dose-dependently prevented the oxidation of linoleic acid and α-linolenic acid in canola oil. Both the oxygen consumption and the fatty acid analysis demonstrated sesamin was less effective than BHT as an antioxidant at temperatures of 60–180 °C. It was therefore concluded that sesamin could prevent the lipid oxidation of frying fats and oil, however, its antioxidant activity was not as potent as that of BHT.     

Physicochemical Properties of Conjugated Linoleic Acid-Rich Soy Oil

CLA-rich soy oil (CLARSO) has been produced by linoleic acid isomerization in soy oil TAG. The objective was to determine the physicochemical properties of the novel CLARSO relative to conventional refined bleached deodorized soy oil (RBDSO). Iodine value decreased in CLARSO samples despite unsaturation being unchanged, probably because conjugated double bonds in triacylglycerol (TAG) of CLARSO impede the complete addition of iodine. Thermal analysis by differential scanning calorimetry showed the melting point temperature increased with the increase in the CLARSO CLA concentration, and melting point broadening occurred in CLA contained samples. Dynamic viscosity of CLARSO conducted from 4 to 44 °C increased with the increase in CLA concentration, relative to RBDSO. Greatest viscosity differences occurred at the lower temperatures. Refractive indices and density were not greatly affected. The change in physical properties was attributed to the increased intermolecular hydrophobic interaction force due to conjugated double bonds and trans,trans isomers, relative to RBDSO. This may provide hard fat characteristics that may be useful for use in producing margarine or shortenings. Furthermore, the higher viscosity at refrigerator temperatures may be useful in salad oil and refrigerated sauces to enable suspension of particles and maintain a rich, thicker texture.     

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

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

Destabilization of the Emulsion Formed during Aqueous Extraction of Soybean Oil

Characterization and destabilization of the emulsion formed during aqueous extraction of oil from soybean flour were investigated. This emulsion was collected as a cream layer and was subjected to various single and combined treatments, including thermal treatments and enzymatic treatments, aimed at recovery of free oil. The soybean oil emulsion formed during the aqueous extraction processing of full fat flour contains high molecular weight glycinin and β-conglycinin proteins and smaller oleosin proteins, which form a multilayer interface. Heat treatment alone did not modify the free oil recovery but freeze–thaw treatment increased the oil yield from 3 to 22%. After enzymatic treatment of the emulsion, its mean droplet size changed from 5 to 14 μm and the oil recovery increased to 23%. This increase could be attributed to the removal (due to enzymatic hydrolysis) of large molecular weight polypeptides from the emulsion interface, resulting in partial emulsion destabilization. When enzymatic treatment was followed by a freeze–thaw step, the oil recovery increased to 46%. This result can be attributed to the thinner interfacial membrane after enzymatic hydrolysis, partial coalescence during freeze–thaw, and coalescence during centrifugation. Despite the reduction in emulsion stability achieved, additional demulsification approaches need to be pursued to obtain an acceptably high conversion to free oil.     

Kinetic Parameters of a Homogeneous Transmethylation of Soybean Oil

The kinetic parameters of a truly homogeneous base-catalyzed transmethylation of soybean oil at four temperatures from 23 to 50 °C have been determined for the first time. The addition of oxolane, as well as a high methanol/oil molar ratio (27:1), was used to achieve and maintain a monophasic system throughout the reactions. Second order rate constants were determined in terms of the concentrations of the mechanistic reactants, which were the glycerides and methoxide ions (and not methanol). Doubling the methoxide concentration increased the reaction rate twofold. At 23 °C the rate constants for the conversion of triglycerides to diglycerides, diglycerides to monoglycerides, and monoglycerides to glycerol were 6.3, 15.3 and 13.0 L mol⁻¹ min⁻¹, respectively. These increased to 54.2, 136 and 139 L mol⁻¹ min⁻¹ at 50°C. These latter values (adjusted to 60 °C) were 65, 770 and 190 times larger, respectively, than values cited previously (and adjusted to the methoxide basis) for a transmethylation of Pongamia oil, which was also claimed to be homogeneous. Activation energies for all three steps were the same (63 kJ mol⁻¹). Pre-exponential factors showed that in diglycerides and triglycerides the second and third ester chains sterically hindered the attack of methoxide ions on the ester carbonyl groups.     

Viscoelastic Properties of a Biological Hydrogel Produced from Soybean Oil

Hydrogels formed from biopolymers or natural sources have special advantages because they may have biodegradable and biocompatible properties. The viscoelastic properties of a newly developed biological hydrogel made from epoxidized soybean oil (ESO) were investigated. The material called HPESO is a hydrolytic product of polymerized ESO (PESO). HPESO exhibited viscoelastic solid or gel behavior above 2% (wt. %) concentration at room temperature and viscous liquid behavior at 55 °C. The thermal assembly disassembly reassembly function of the HPESO hydrogel was completely reversible. The viscoelastic properties of HPESO were dependent on concentration. Analysis of modulus and concentration dependence and stress relaxation measurement indicated that HPESO was a physical gel where the cross-linkers between the molecules were physical junctions. HPESO hydrogel also exhibited fast initial recovery of its viscoelastic properties after being subjected to mechanical shear disruption. The function and behavior of the HPESO hydrogel suggest that this biomaterial may be suitable for applications in drug delivery and scaffolds of bioengineering and tissue engineering. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Antioxidant Activity of Added Phenolic Compounds in Freeze-Dried Microencapsulated Sunflower Oil

This study was aimed at evaluating the effectiveness of phenolic antioxidants with a similar structure but having a different polarity in dried microencapsulated sunflower oil. The antioxidants tested were, on one hand, α-tocopherol and its water soluble analogue, Trolox, and on the other, gallic acid and its ester derivatives, propyl gallate and dodecyl gallate. At a moderate temperature (40 °C), the samples were oxidized under accelerated conditions by using Cu(II) as an oxidation catalyst. The progress of oxidation was followed up over time in the free and encapsulated oil fractions. The peroxide value, the total content of polymers and, when appropriate, the content of α-tocopherol were determined. Quantitative analysis of the total fraction of the non-volatile oxidation products and their distribution in oligomers, dimers and monomers was applied to samples to obtain a complete evaluation of oxidation. Finally, as a complementary measure, the antioxidants were also assessed by direct application of the Rancimat test at 100 °C on the dried microencapsulated oil samples. Results showed that the antioxidants of lower polarity in each series, i.e. tocopherol and dodecyl gallate, were to a great extent the most protective antioxidants. The results obtained by the Rancimat test were consistent with those found during oxidation at moderate temperature. Furthermore, the addition of Cu(II) reduced proportionally the oxidative stability index of the dried microencapsulated samples.     

Conjugated Linoleic Acids and CLA-Containing Phospholipids Inhibit NO Formation in Aortic Endothelial Cells

This study examined the effects of five CLA isomers and the non-conjugated LA on nitric oxide (NO) production, an important modulator of vasodilation, inflammation, and cytotoxicity. Bovine aortic endothelial cells (BAECs) were pretreated with pure CLAs (c9, c11-, c9, t11-, t9, t11-, t10, c12-, c11, c13-CLA) and the non-conjugated c9, c12-analog, then stimulated by the ionophore A23187 followed by fluorescence monitoring of NO production. CLAs (5 μM) decreased NO formation in the range of 20–40% relative to non-fatty acid-treated controls with the t9, t11- and t10, c12-CLAs being the most effective. The inhibitory effect of either of these CLAs was not time dependent over a 120 min time interval. Phosphatidylcholine (PC) and phosphatidylethanolamine (PE) play crucial roles in membrane structure and cell signaling. Since CLAs are usually esterified in these phospholipids (PLs), the effects of three CLA-containing PLs and 2-linoleoyl-PC on NO production by A23187-stimulated BAECs were also examined. c9, t11-CLA-PC and 2-linoleoyl-PC dose-dependently inhibited NO production over a 60–1,000 μM concentration range whereas c9, c11-CLA-PC and c9, t11-CLA-PE were ineffective. Both c9, t11-CLA-PC and linoleoyl-PC exhibited a time-dependent decrease in NO production from 5 to 120 min. The results of the present study suggest that the influence of several C18 polyunsaturated fatty acids incorporated into cellular phospholipids on the A23187-induced formation of NO by BAECs is strongly dependent on the positional and geometric nature of the double bonds.     

Effect of Attapulgite Pore Size Distribution on Soybean Oil Bleaching

The pore size distribution and specific surface area of the attapulgite was a crucial parameter for the uptake of pigments of oil. Bleaching of the soybean oil with three attapulgites with different pore size distribution, which were assigned a, b, and c, respectively was investigated. The specific surface area and the pore size distribution of the attapulgites were characterized. The Freundlich isotherm analysis was used to evaluate the sorption capacity of the three attapulgite. Sample b gave the highest surface area and sample c the lowest. Sample b exhibited a wider pore distribution (8–65 Å) whereas samples a and c had more micropores smaller than 15 Å. Sample a, in contrast to samples b and c, was characterized by some larger pores (100–170 Å). The sorption capacity followed the sequence: attapulgite sample c > attapulgite sample a > attapulgite sample b. The sorption capacity was decided by the pore size distribution. The more pores with a distribution range 8–32 Å (i.e., close to the diameter of the pigments), the more pigments removed. The attapulgite sample c, which had most pores (8–32 Å) was the best.