Polyhydroxy fatty acids and their derivatives from plant oils

A novel process for the industrial production of hydroxylated fatty acids involves epoxidation of plant oils and their derivatives, followed by catalytic epoxy ring opening in the presence of water or other hydrogen donors, such as alcohols, diols, and amines. Depending on the starting material, epoxidation followed by opening of the oxirane ring leads to fatty acids that contain vicinal diol groups or to other substituted hydroxylated fatty acid derivatives. As an example for the preparation of a substituted hydroxylated fatty acid derivative, the reaction of epoxidized rapeseed oil with monobutylamine as hydrogen donor is described. Apart from the intended formation of hydroxyl groups with vicinal aminoalkyl groups, partial aminolysis of the ester compound was also observed. Another example describes the reaction of epoxidized rapeseed oil with different molar proportions of 1,4-butanediol as hydrogen donor. Depending on the molar proportion of the hydrogen donor, interesterification, or intermolecular ether formation were observed as side reactions. The properties of various technical hydroxylated fatty acids and their derivatives, prepared according to this novel process, are given, and potential applications of these products are suggested.     

Analysis of estolides in technical hydroxylated fatty acids from plant oils

Gel permeation chromatography of hydroxylated fatty acids (HOFA), prepared from various plant oils by a novel technical process, showed the presence of considerable amounts of estolides formed by intermolecular esterification of the HOFA. Thin-layer chromatographic fractionation followed by gas chromatography of the fractions revealed that the nonpolar estolides contain predominantly saturated fatty acids esterified tothero-9, 10-dihydroxy octadecanoic acid or dihydroxy tetrahydrofuran octadecanoic acids, e.g., 9,12-dihydroxy-10, 13-epoxy octadecanoic acid and 10,13-dihydroxy-9, 12-epoxy octadecanoic acid. The fractions of polar estolides consist mainly of intermolecular esters of the above dihydroxy fatty acids.     

Effect of fatty acids and tocopherols on the oxidative stability of vegetable oils

The oxidative stability of vegetable oils is determined by their fatty acid composition and antioxidants, mainly tocopherols but also other non‐saponifiable constituents. The effect of fatty acids on stability depends mainly on their degree of unsaturation and, to a lesser degree, on the position of the unsaturated functions within the triacylglycerol molecule. Vegetable oils contain tocopherols and tocotrienols, especially α‐ and γ‐tocopherols, as their main antioxidants. The antioxidant behavior of tocopherols represents a complex phenomenon as they are efficient antioxidants at low concentrations but they gradually lose efficacy as their concentrations in the vegetable oils increase. The “loss of efficacy” of tocopherols, sometimes referred to as a “pro‐oxidant effect”, is witnessed by an increase in the rate of oxidation during the induction period, despite elongation of this phase. The phenomenon is much obvious for α‐tocopherol, but is also evident for other tocopherols. In agreement with nature's wisdom, the tocopherol levels in vegetable oils seem to be close to the optimal levels needed for the stabilization of these oils. The presence of other antioxidants in the oils, e.g. carotenoids, phenolic compounds, and Maillard reaction products, may synergize with tocopherols and minimize this loss of efficacy.     

Densities of vegetable oils and fatty acids

Complete data for density as a function of temperature have been measured for a number of vegetable oils (crambe, rapeseed, corn, soybean, milkweed, coconut, lesquerella), as well as eight fatty acids in the range C₉ to C₂₂ at temperatures from above their melting points to 110°C (230°F). The specific gravity and density measurements were performed according to American Society for Testing and Materials (ASTM) standard test methods D 368, D 891 and D 1298 for hydrometers and a modified ASTM D 369 and D 891 for pycnometers. Correlation constants, based on the experimental data, are presented for calculating the density of fatty acids and vegetable oils in the range of temperature from 24°C (75°F) or the melting point of the substance, to 110°C (230°F). The constants are valuable for designing or evaluating such chemical process equipment as heat exchangers, reactors, process piping and storage tanks. Estimated density of fatty acids by a modified Rackett equation is also presented.     

Analysis of hydroxylated fatty acids from plant oils

A novel process has been described recently for the preparation of hydroxylated fatty acids (HOFA) and HOFA methyl esters from plant oils. HOFA methyl esters prepared from conventional and alternative plant oils were characterized by various chromatographic methods (thin-layer chromatography, high-performance liquid chromatography, and gas chromatography) and gas chromatography-mass spectrometry as well as¹H and¹³C nuclear magnetic resonance spectroscopy. HOFA methyl esters obtained fromEuphorbia lathyris seed oil, low-erucic acid rapeseed oil, and sunflower oil contain as major constituents methylthreo-9,10-dihydroxy octadecanoate (derived from oleic acid) and methyl dihydroxy tetrahydrofuran octadecanoates, e.g., methyl 9,12-dihydroxy-10,13-epoxy octadecanoates and methyl 10,13-dihydroxy-9,12-epoxy octadecanoates (derived from linoleic acid). Other constituents detected in the products include methyl esters of saturated fatty acids (not epoxidized/derivatized) and traces of methyl esters of epoxy fatty acids (not hydrolyzed). The products that contain high levels of monomeric HOFA may find wide application in a variety of technical products.     

Cyclopropenoid fatty acids of six seed oils from malvaceae

The seeds ofAlyogine hakeifolia, Alyogine huegelii,Gossypium australe, Hibiscus coatesii, Lawrencia viridigrisea andRadyera farragei (Malvaceae) contained 13.5-18.6% oil. Linoleic acid predominated (60.0-68.2%) in the component fatty acids of all the oils, followed by palmitic (9.9-18.1%) and oleic acids (7.8-15.8%). Cyclopropene fatty acids, malvalic and sterculic, were present in small concentrations (1.0-4.4%, 0.1-1.5% respectively). Dihydrosterculic acid was present in small quantities (trace-2.1%). *To whom correspondence should be addressed at Department of Chemistry, P.O. Box 320, University of Papua New Guinea, Papua, New Guinea.     

Organogelation of plant oils and hydrocarbons by long-chain saturated FA,fatty alcohols,wax esters,and dicarboxylic acids

Conversion of oils into gels generally involves altering the chemical characteristics of the liquid. We describe here the gelling of vegetable oils, essential oils, and hydrocarbons at ambient temperature, without changing the chemical characteristics of the liquids, using saturated FA having carbon chain lengths of 10 to 31. The gelling ability of the added FA increased linearly with their chain lengths. Structure-function studies demonstrated that the carboxyl group, position of an additional hydroxyl group, and acyl chain length played an important role in gelation. Long-chain saturated fatty alcohols, wax esters, and dicarboxylic acids also had the ability to gel plant oils and hydrocarbons.     

Viscosities of vegetable oils and fatty acids

Data for viscosity as a function of temperature from 24 to 110°C (75 to 230°F) have been measured for a number of vegetable oils (crambe, rapeseed, corn, soybean, milk-weed, coconut, lesquerella) and eight fatty acids in the range from C₉ to C₂₂. The viscosity measurements were performed according to ASTM test methods D 445 and D 446. Several correlations were fitted to the experimental data. Correlation constants for the best fit are presented. The range of temperature in which the correlations are valid is from 24°C (75°F), or the melting point of the substance, to 110°C (230°F). The correlation constants are valuable for designing or evaluating such chemical process equipment as heat exchangers, reactors, distillation columns, mixing vessels and process piping.     

N‐3 fatty acids and conjugated linoleic acids of longissimus muscle in beef cattle

The objective of the experiment with cattle was to produce high quality beef under different feeding conditions and to increase the concentration of essential fatty acids in muscle. In total 10 German Simmental (GS) bulls and 9 German Holstein (GH) steers were kept either on pasture (grass feeding) or in stable (concentrate feeding). Despite biohydrogenation in the rumen, linolenic acid (C18:3n‐3) contained in grass was absorbed and deposited into the lipids of muscle. This led to a significantly (p ≤ 0.05) higher content of n‐3 fatty acids in the muscle lipids of grazing cattle. The relative amount of total n‐3 fatty acids increased from 1.4 g/100 g fatty acid methyl ester (%FAME) in the intensively fed Simmental bulls to 5.5 %FAME in grass fed cattle. The n‐6/n‐3 ratio of pasture grazing GS bulls was 1.3 in contrast to 13.7 of the animals kept in the byre. The total n‐3 fatty acid concentration in beef muscle increased from 24.6 mg (concentrate) to 108.6 mg/100 g wet weight (grazing). In GH steers the total n‐3 fatty acid concentration was significantly (p ≤ 0.05) increased up to 86.3 mg/100 g wet weight in pasture grazing steers compared to 28.8 mg/100 g wet weight in animals fed the concentrate. The relative content (%FAME) of CLAcis‐9, trans‐11 (0.6 vs 0.56 %FAME in GS; 0.55 vs 0.52 %FAME in GH) in muscle was not significantly increased by grazing on pasture in comparison to concentrate feeding neither in GS bulls nor in GH steers, respectively.     

Furanoid fatty acids in oils from soybeans lacking lipoxygenase isoenzymes

The concentrations of 10, 13-epoxy-11, 12-dimethyloctadeca-10, 12-dienoic acid (F20) and 12,15-epoxy-13, 14-dimethyleicosa-12, 14-dienoic acid (F22) were determined by a stable isotope dilution assay in oils extracted from the soybean cultivar Century and from five soybean genotypes that lacked one or two of the three lipoxygenase isoenzymes. The concentrations of F20 and F22 ranged between 190–225 mg/kg oil and 91–132 mg/kg oil, respectively. The concentration differences were not correlated to the differences in lipoxygenase activities of the soybeans.     

Evaluation of the role of saturated fatty acids in sedimenting canola oils

Canola oil is generally a clear oil which does not require winterization. However, sediment formation has become an increasing problem in Australian canola oil. Canola oil stored at temperatures between −5 and 21°C formed sediment more rapidly at lower temperatures. The sediment and clear fractions of a group of sedimenting canola oils were analyzed and compared. Both fractions contained wax esters of carbon number C42–C52, the sediment fractions containing between 0.37 and 3.09 mg g⁻¹ and clear fractions containing between 0.12 and 0.85 mg g⁻¹. The triacylglycerol profiles of sediment fractions contained four compounds, PPO, PPP, PSO and PPS (where P is palmitoyl, O is oleoyl, and S stearoyl), that were not detected in clear fractions. The contents of palmitic acid and total saturated fatty acids were higher in the sediment fraction than the clear fraction. Added PPP clouded a clear oil as effectively as stearyl behanate and more than OOO or lauryl arachidate. Sedimentation may be linked to environmental conditions, as seed grown in 1997, a dry year, produced more problem oils than seed grown in previous years that had more nearly average rainfall.     

The fatty acid composition of lipids from muscle and adipose tissues of pigs fed various oil mixtures differing in their ratio between oleic acid and linoleic acid

High concentrations of polyunsaturated fatty acids (PUFA) in meat have detrimental effects on its technical properties. The present study was carried out to investigate whether PUFA levels in pork can be reduced by increasing the concentrations of oleic acid in pig diets. To this end a bifactorial experiment was carried out with 48 female growing finishing pigs. Six different diets were used with two different concentrations of linoleic acid (12 vs. 24 g/kg) and three different concentrations of oleic acid (12 vs. 18 vs. 24 g/kg). The experiment started at a body weight (BW) of 58 kg and continued until 115 kg BW. The fatty acid composition of total lipids of backfat, perirenal fat and musculus (m.) longissimus dorsi was analysed. Concentrations of linoleic acid and total PUFA in backfat and perirenal fat were affected only by the dietary linoleic acid content but not at all by the dietary oleic acid content. Increasing the dietary concentration of oleic acid raised the level of oleic acid in those tissues at the expense of saturated fatty acids, suggesting competition between monounsaturated fatty acids and saturated fatty acids for incorporation into triglycerides. At the low dietary linoleic acid concentration, the percentages of linoleic acid and total PUFA in total lipids of m. longissimus dorsi were also unaffected by the dietary oleic acid content. In contrast, at the high dietary linoleic acid concentration, percentages of linoleic acid and total PUFA of the m. longissimus dorsi were reduced by increasing the dietary concentration of oleic acid, suggesting that oleic acid and linoleic acid compete for incorporation into muscle lipids. Thus, at high dietary linoleic acid levels the fatty acid composition of the m. longissimus dorsi was favourably affected by high dietary oleic acid concentrations; in backfat and perirenal fat, however, no beneficial effect of high dietary oleic acid levels was seen.     

Substitution of trans fatty acids in foods on the Danish market

Three surveys of the content of trans fatty acids (TFA) in foods on the Danish market were carried out before and after the Danish regulation was introduced in January 2004 restricting the use of industrially produced (IP)‐TFA to a maximum of 2 g per 100 g fat in any food product. For this purpose, food samples were collected in 2002–3, 2004–5, and 2006–7. Of these, 60 paired samples (defined as samples included in two of the three investigations and with higher levels of IP‐TFA in the first determination than in the second) were identified. Comparisons of the fatty acid profiles showed that, in 68% of the products (e.g. sweets, cakes and cookies as well as fast food such as pie and tortilla), IP‐TFA were mainly substituted with saturated fatty acids (SFA). In some cases, the SFA source was coconut fat, whereas in other products, palm oil was added instead of partially hydrogenated oils. However, in important cases like frying fats, healthier fat substitutes with monounsaturated fatty acids were used. The surveys showed that the IP‐TFA content has been reduced or removed from most products with originally high IP‐TFA content, like French fries, microwave oven popcorn and various bakery products, so that IP‐TFA are now insignificant for the intake of TFA in Denmark.     

Acidity of oryzanol and its contribution to free fatty acids value in vegetable oils

Model oil systems containing physically refined rice bran oil to which oryzanol was added were examined to determine the effects of oryzanol concentration on FFA values. When oryzanol was added to the model oils at a 0.5% level and FFA was determined, increases in FFA value were 0.28% as determined with phenolphthalein, 0.58% with thymolphthalein, and 0.07% with alkali blue 6B. Oils containing added oryzanol at 0.5–1.5% showed a proportionate increase in FFA values with an average increase of 0.413% per gram of oryzanol. A direct titration of purified oryzanol showed an acidity of 42.5% expressed as FFA. In spectroscopic studies, the phenolic group in the ferulic acid moiety of oryzanol was titrated by sodium hydroxide. Based on these data, indicator correction factors for oryzanol's acidity and a formula for calculating real FFA content of vegetable oils containing oryzanol were developed.     

Accumulation of cardiac fatty acids in rats fed synthesized oils containing C22 fatty acids

Synthesized oils containing a high proportion of oleic, eicosenoic or docosenoic acid were fed to weanling rats as 20% w/w of the diet. After 1 week, a high intake of eicosenoate produced cardiac fat droplets detected histologically, whereas erucate (22∶1 Δ 13) or cetoleate (22∶1 Δ 11) caused an appreciably greater accumulation of cardiac lipid characterized by the dietary fatty acids.     

Use of tetrabutylammonium tribromide for voltametric titration of unsaturation in vegetable oils and fatty acids

The use of tetrabutylammonium tribromide as reagent for bromination of carbon-carbon double bonds of fatty acids and vegetable oils, followed by a voltametric titration of tribromide and bromide ions, has been studied. This method is easy and fast, and results show good accuracy and high sensitivity.     

Remarks on official methods employing boron trifluoride in the preparation of methyl esters of the fatty acids of fish oils

Some “official methods” for preparing methyl esters of the fatty acids from oils or fats may be referred to by users as the boron trifluoride (BF₃) method and invariably have two stages. The first stage, brief treatment with alkali [commonly NaOH in methanol (MeOH), sometimes NaOCH₃] and heat has been popularly described as a saponification step for over 30 yr. In fact, the disappearance of visible fat or oil is mostly transesterification, which can be accomplished in a few minutes under mild conditions. Free fatty acids (FFA) originally present, or produced by saponification, are not converted to methyl esters at this stage. The second stage, heating in BF₃-MeOH, has in practice been as short as 2 min. It can convert all FFA to methyl esters, but this step requires at least 30 min. Examples from the recent literature illustrate the necessity of extending the time for BF₃-MeOH transesterification of lipids or oils and methylation of FFA. No alkali transesterification is needed. Presented in part at the 88th Annual Meeting of the American Oil Chemists’ Society, Seattle, WA, May 1997.     

Rapid quantitative determination of free fatty acids in fats and oils by fourier transform infrared spectroscopy

Rapid direct and indirect Fourier transform infrared (FTIR) spectroscopic methods were developed for the determination of free fatty acids (FFA) in fats and oils based on both transmission and attenuated total reflectance approaches, covering an analytical range of 0.2–8% FFA. Calibration curves were prepared by adding oleic acid to the oil chosen for analysis and measuring the C=O band @ 1711 cm^–1 after ratioing the sample spectrum against that of the same oil free of fatty acids. For fats and oils that may have undergone significant thermal stress or extensive oxidation, an indirect method was developed in which 1% KOH/methanol is used to extract the FFAs and convert them to their potassium salts. The carboxylate anion absorbs @ 1570 cm^–1, well away from interfering absorptions of carbonyl-containing oxidation end products that are commonly present in oxidized oils. Both approaches gave results comparable in precision and accuracy to that of the American Oil Chemists’ Society reference titration method. Through macroprogramming, the FFA analysis procedure was completely automated, making it suitable for routine quality control applications. As such, the method requires no knowledge of FTIR spectroscopy on the part of the operator, and an analysis takes less than 2 min.     

Dietary C18:1 trans fatty acids increase conjugated linoleic acid in adipose tissue of pigs

The effect of dietary C18:1 trans fatty acids on back fat composition in pigs was investigated with special emphasis on conjugated linoleic acids (CLA). A total of 12 × 4 siblings of Large White and Swiss Landrace breed were housed in groups and fattened from 22 to 103 kg live weight. Pigs were fed a control diet (barley, wheat, soybean meal) or experimental diets which consisted of the control diet with a 5% replacement of olein or stearin fractions of pork fat, or partially hydrogenated fat. The hydrogenated fat was rich in C18:1 trans fatty acids but contained only negligible amounts of CLA. In contrast olein and stearin fractions contained far less C18:1 trans fatty acids but some CLA. In the control diet no C18:1 trans fatty acids and only traces of CLA were detected. The partially hydrogenated fat led to the highest CLA content in back fat (0.44%). Intermediate amounts of CLA were measured in pigs fed the fractionated pork fat (0.22/0.23%). In pigs fed the control diet, also small amounts of CLA were detected. The results indicate that CLA may be produced by endogenous Δ9‐desaturation out of dietary trans vaccenic acid in pigs.     

Influence of triacylglycerol characterics on the determination of free fatty acids in vegetable oils by fourier transform infrared spectroscopy

A rapid and direct Fourier transform infrared (FTIR) spectroscopic method using a 25-μm NaCl transmission cell was developed for the determination of free fatty acids (FFA) in six important vegetable oils (corn, soybean, sunflower, palm, palm kernel, and coconut oils) that differ in fatty acid profile. The calibrations were established by adding either standard FFA (oleic, lauric acids) or a representative mixture of FFA obtained after saponification of the refined oils. For all oils, up to a FFA level of 6.5% for coconut oil, the best correlation coefficient was obtained by linear regression of the free carboxyl absorption at 1711 cm⁻¹. All correlation coefficients were greater than 0.993, and no significant difference between the calibration methods could be detected. Upon validation of the calibration, no significant difference (α=0.05) between the “actual” and the “FTIR predicted” FFA values could be observed. The calibration models developed for the six oils differed significantly and indicate the need to develop a calibration that is specific for each oil. In terms of repeatability and accuracy, the FTIR method developed was excellent. Because of its simplicity, quick analysis time of less than 2 min, and minimal use of solvents and labor, the introduction of FTIR spectroscopy into laboratory routine for FFA determination should be considered.