Fatty Acid Composition in Ergosteryl Esters and Triglycerides from the Fungus Ganoderma lucidum

Free and esterified ergosterols are detected almost solely in fungi and are often employed as a biomarker of living fungi. In this work, the fatty acid composition and δ¹³C values of major fatty acids in triglycerides and ergosteryl esters from the fungus Ganoderma lucidum were analyzed by gas chromatography–mass spectrometer and gas chromatography–isotopic ratio mass spectrometer, respectively. The results showed that the fatty acid profiles varied in triglycerides and ergosteryl esters. The percentage of saturated fatty acids in ergosteryl esters was remarkably higher than that in triglycerides, where C_18:1^Δ9c was the predominant fatty acid and constituted 61.26 % of the total fatty acids. In contrast, C_16:0 was the predominant fatty acid and constituted 71.88 % of the total fatty acids in ergosteryl esters. The study suggests that, after fungal death, free ergosterols in the cell membrane of the dead fungus were esterified with preferentially saturated fatty acids, mainly C_16:0, from triglycerides and then stored in lipid particles for a longer period while free ergosterol markedly decreased. The δ¹³C values of C_16:0, C_18:0, C_18:1 and C_18:2 in ergosteryl esters exhibit a pronounced depletion in ¹³C compared with that in triglycerides within the range of ?1.3 to ?0.9 ‰, supporting the above inference. It is again suggested that free ergosterol in the cell membrane should be used as an indicator of living fungi, and ergosteryl esters in the lipid particles should not be included in the measurement of living fungal biomass.     

Analysis of seed oils containing cyclopentenyl fatty acids by combined chromatographic procedures

The fatty acids of seed oils of the Flacourtiaceae,Hydnocarpus anthelmintica, Caloncoba echinata andTaraktogenus kurzii, have been examined by a combination of capillary gas chromatography, silver ion high performance liquid chromatography and gas chromatography-mass spectrometry. In addition to the common range of cyclopentenyl fatty acids found in such oils, 13-cyclopent-2-enyltridec-4-enoic acid was a major component ofH. anthelmintica and was identified by mass spectrometry as its picolinyl ester and dimethyldisulphide adduct. It has not previously been found in nature. In the other seed oils, the isolated double bond in the corresponding fatty acid was in position 6, as expected. Similarly,cis-4-hexadecenoic acid and C₁₆ and C₁₈ cyclopentyl fatty acids were identified for the first time inH. anthelmintica. Iso- andanteiso-methylbranched fatty acids were present in trace amounts.     

Stable isotope characterization of olive oils: II-deuterium distribution in fatty acids studied by nuclear magnetic resonance (SNIF-NMR)

Site-specific isotope fractionation of hydrogen was investigated, at natural abundance, by deuterium nuclear magnetic resonance (SNIF-NMR) on nearly two hundred olive oil samples. Owing to the complexity of the ²H-NMR spectra of the mixtures of fatty acids obtained after hydrolysis of the oils, the different signals were gathered into six clusters. Knowing the contribution to the clusters of each of the four fatty acids considered (C_16:0, C_18:0, C_18:1, and C_18:2) and the composition of the fatty acids in the mixture, it is possible to compute the site-specific isotope ratios of the clusters from the molar fractions obtained from the ²H-NMR-spectra and from the total isotope ratio of the mixture, determined by isotope ratio mass spectrometry (IRMS). The results are discussed in terms of geographical (country, region and elevation) and temporal (year) parameters and they are tentatively explained on a climatic basis.     

Stable isotope characterization of olive oils. I—Compositional and carbon-13 profiles of fatty acids

Nearly 200 olive oils produced in the Mediterranean basin, mainly in Greece, during 4 yr from 1993 to 1996, were studied by gas chromatography (GC) and on-line GC-isotope ratio mass spectrometry (GC-C-IRMS). The composition of the oils in the more abundant fatty acids (C_16:0, C_16:1, C_18:0, C_18:1, C_18:2, and C_18:3) was obtained by GC after transesterification of the triglycerides into methyl esters. Using the hyphenated GC-C-IRMS technique, the ¹³C contents of the three most abundant acids, C_16:0, C_18:1, and C_18:2, were measured with satisfactory accuracy. The results, analyzed in terms of geographical, temporal, and botanical factors, provide new criteria for the authentication of olive oils.     

Characterization of chilean hazelnut (Gevuina avellana mol) seed oil

The fatty acid composition, tocopherol and tocotrienol content, and oxidative stability of petroleum benzene-extracted Gevuina avellana Mol (Proteaceae) seed oil were determined. Positional isomers of monounsaturated fatty acids were elucidated by gas chromatography-electron impact mass spectrometry after 2-alkenyl-4,4-dimethyloxazoline derivatization. This stable oil (Rancimat induction period at 110°C: 20 h) is composed of more than 85% monounsaturated fatty acids and about equal amounts (6%) of saturated and polyunsaturated (principally linoleic) fatty acids. Unusual positional isomers of monounsaturated fatty acids, i.e., C_16:1 Δ¹¹, C_18:1 Δ¹², C_20:1 Δ¹¹, C_20:1 Δ¹⁵, C_22:1 Δ¹⁷, and presumably C_22:1 Δ¹⁹ were identified. The C_18:1 Δ¹² and C_22:1 Δ¹⁹ fatty acids are described for the first time in G. avellana seed oil. While only minute quantities of α-, γ-tocopherols and β-, γ- and δ-tocotrienols were found, the oil contained a substantial amount of α-tocotrienol (130 mg/kg). The potential nutritional value of G. avellana seed oil is discussed on the basis of its composition.     

Tomato Seed Oil I Fatty Acid Composition,Stability and Hydrogenation of the Oil

Tomato seed oil was investigated to study their components of fatty acids, stability and hydrogenation conditions. The estimation of the fatty acids of tomato seed oil from Ace variety and tomato seed oil extracted from local waste in comparison with cotton seed oil (the most familiar edible oil in Egypt) - Giza 69 variety - extracted by n-hexane and oil obtained by pressing shows that more than 50% of the total fatty acids are linoleic. Palmitic acid was found in a range between 20% to 29% and oleic acid was in a range between 13% to 18%. Other fatty acids like stearic, arachidic, and linolenic acid were less than 3%. The induction periods (at 100°C) for oils of fresh, roasted and stored tomato seeds were found to be 7, 10, and 5 hours respectively. The hydrogenation conditions of crude tomato seed oil were 180°C, 3 kg/cm² and 0.2% nickel catalyst for three hours of hydrogenation to reach a melting point of 50.7°C and an iodine value of 42.     

Natural Abundance Carbon Isotopic Analysis Indicates the Equal Contribution of Local Synthesis and Plasma Uptake to Palmitate Levels in the Mouse Brain

Saturated fatty acids are the most abundant fatty acids in the brain, however, there has been some debate regarding the ability of intact dietary saturated fatty acids to be incorporated into the brain. In the present study, we use compound specific isotope analysis to measure the natural abundance carbon isotopic signature of brain, liver, and blood palmitic acid (PAM) and compare it to the dietary PAM and sugar isotopic signatures to calculate the relative contribution of both the incorporation of intact and endogenously synthesized PAM to these pools. Mice were equilibrated to the study diet, and extracted fatty acids were analyzed with gas chromatography isotope ratio mass spectrometry to determine the carbon isotopic signature of PAM (δ¹³C_PAM). Liver, serum total, and serum unesterified fatty acid δ¹³C_PAM ranged between ?20.6 and ?21.1 mUr and were approximately 8.5 mUr more enriched in ¹³C when compared to the dietary PAM signature. Brain δ¹³C_PAM was found to be more enriched than liver or blood pools (?16.7 ± 0.2 mUr, mean ± SD). Two end‐member‐mixed modeling using the carbon isotopic signature of dietary PAM and dietary sugars determined the contribution of synthesis to the total tissue PAM pool to range between 44% and 48%. This suggests that endogenous synthesis and dietary PAM are near equal contributors to brain, liver, and blood PAM pools. In conclusion, our data provide evidence that brain PAM levels are maintained by both local endogenous synthesis and through the uptake of intact PAM from the blood.     

Identification of Recycled Cooking Oil and Edible Oils by Iodine Determination and Carbon Isotopic Analysis

Elemental iodine determination by ICP‐MS and carbon isotope analysis by EA‐IRMS were jointly employed to identify recycled cooking oil from edible oils. Iodine in 204 oils demonstrated that recycled cooking oils can be distinguished from soybean oil, maize oil, colza oil, peanut oil, sunflower oil and olive oil with the exception of tea oil and mixed oil. These two types of oils can be definitively distinguished from recycled cooking oil in the carbon isotope ratio analysis. It was proposed to use total iodine analysis as the primary screening method and the carbon isotope ratio measurement as a secondary method for confirmation and verification. For routine screening, threshold values of Iodine determination and δ¹³C measurement were determined to be 20 ng g^?1 iodine and a range of ?27.3 to ?28.5 of δ¹³C, respectively.     

Purity assessments of major vegetable oils based on δ13C values of individual fatty acids

The fatty acid compositions and δ¹³C values of the major fatty acids of more than 150 vegetable oils were determined to provide a database of isotopic information for use in the authentication of commercial maize oil. After extraction of oils from seeds, nuts or kernels, and methylation, fatty acid compositions were determined by capillary gas chromatography. All compositions were within the ranges specified by the Codex Alimentarius. Gas chromatography combustion-isotope ratio mass spectrometry was employed to determine the δ¹³C values of the major fatty acids of the oils. A large number of pure maize oils and potential adulterant oils from various parts of the world were studied to assess the sources of variability in δ¹³C values. Such information is vital to establishing the compound specific isotope technique as a reliable means of assessing vegetable oil purity. Variability in δ¹³C values was related to the geographical origin of the oil, year of harvest, and the particular variety of oil. This suggests that the ultimate δ¹³C values of fatty acids are determined by a combination of environmental and genetic factors.     

Analysis of conjugated octadecatrienoic acids inmomordica balsamina seed oil by GLC and13C NMR Spectroscopy

Separation of conjugated octadecatrienoic acids by open tubular gas liquid chromatography (GLC) was performed using glass capillary columns coated with Carbowax 20 M and with OV-1. The equivalent chain length of geometrical isomers of the conjugated octadecatrienoic acids belonging to the two series C_18:3Δ^8.10.12 and C_18:3Δ^9.11.13 were determined. The application of these results to the study of theMomordica balsamina seed oil shows that this oil contains two conjugated octadecatrienoic fatty acids in appreciable amounts, punicic acid (50%) and α-eleostearic acid (13%). The isomerization of conjugated acids inM. balsamina seed oil was followed for one year. Quantitation of octadecatrienoic acids using GLC gave results similar to those obtained with¹³C NMR.     

Modifications of butter stearin by blending and interesterification for better utilization in edible fat products

This work primarily aims to further modify the stearin fractions, obtained from anhydrous milk fat, after fractionation by dry process and by solvent process using isopropanol, for extending their scope of utilization in edible fat products. Butter stearin fractions, on blending with liquid oils like sunflower oil and soybean oil in different proportions, offer nutritionally important fat products with enriched content of essential fatty acids like C_18∶2 and C_18∶3. The butter stearin fraction from isopropanol fractionation, when interesterified with individual liquid oils by Mucor miehei lipase as a catalyst, yields fat products having desirable properties in making melange spread fat products with reasonable content of polyunsaturated fatty acids and almost zero trans fatty acid content.     

The triglyceride composition,structure, and presence of estolides in the oils ofLesquerella and related species

Members of the genusLesquerella, native to North America, have oils containing large amounts of hydroxy fatty acids and are under investigation as potential new crops. The triglyceride structure of oils from twenty-fiveLesquerella species in the seed collection at our research center has been examined after being hydrolysis-catalyzed by reverse micellar-encapsulated lipase and alcoholysis-catalyzed by immobilized lipase. These reactions, when coupled with supercritical-fluid chromatographic analysis, provide a powerful, labor-saving method for oil triglyceride analysis. A comprehensive analysis of overall fatty acid composition of these oils has been conducted as well.Lesquerella oils (along with oils from two other Brassicaceae:Physaria floribunda andHeliophilia amplexicaulis) have been grouped into five categories: densipolic acid-rich (Class I); auricolic acid-rich (Class II); lesquerolic acid-rich (Class III); an oil containing a mixture of hydroxy acids (Class IV); and lesquerolic and erucic acid-rich (Class V). The majority of Class I and II triglycerides contain one or two monoestolides at the 1- and 3-glycerol positions and a C₁₈ polyunsaturated acyl group at the 2-position. Most Class III and IV oil triglycerides contain one or two hydroxy acids at the 1- and 3-positions and C₁₈ unsaturated acid at the 2-position. A few of the Class III oils have trace amounts of estolides. The Class V oil triglycerides are mostly pentaacyl triglycerides and contain monestolide and small amounts of diestolide. Our triglyceride structure assignments were supported by¹H nuclear magnetic resonance data and mass balances.     

Unsaturated C18 α-hydroxy acids inSalvia nilotica

The oil ofSalvia nilotica Jacq. (Labiatae) seed contains 0.6% α-hydroxyoleic, 4.2% α-hydroxylinoleic, and 5.4% α-hydroxylinolenic acids. The first two have not been found previously in seed oils. In addition to the common fatty acids, also identified were small amounts of three unsaturated C₁₇ acids and one branched chain C₁₇ acid. Methyl esters of the component fatty acids were fractionated by both column and thin-layer chromatography. These esters were identified by combination of gas chromatography, GC-mass spectrometry, ozonolysis-GC, infrared, and nuclear magnetic resonance.     

Characterization of triglycerides isolated from jojoba oil

Triglyceride compounds isolated from jojoba seed oil by column chromatography were composed predominantly of C_18′ C_20′ C_22′ and C₂₄ n−9 fatty acids with minor amounts of saturated C₁₆. Chain length and double-bond positions were determined by gas-liquid chromatography and gas-liquid chromatography-mass spectrometry of the corresponding methyl ester and picolinyl ester derivatives. Triglyceride structures were analyzed directly by ion trap mass spectrometry. The analysis of minor compounds, can provide highly specific information about the identity of an oil.     

Vegetable oil raw materials

Vegetable oils that are important to the chemical industry include both edible and industrial oils, which contribute 24% and 13.5%, respectively, compared to 55% for tallow, to the preparation of surfactants, coatings, plasticizers, and other products based on fats and oils. Not only the oils themselves but also the fatty acids recovered from soapstock represent a several billion pound resource. Coconut oil is imported to the extent of 700-1,000 million pounds per year. Its uses are divided about equally between edible and industrial applications. Safflower oil has a relatively small production, but 15–25% of the oil goes into industrial products. Soybean oil, the major edible oil of the world, is produced in the United States at the rate of 11,000 million pounds per year with more than 500 million pounds going into industrial uses, representing 5% of the total production. Castor oil is imported to the extent of about 100 million pounds per year. Linseed oil production has declined drastically over the last 25 years but still amounts to about 100 million pounds per year. Oiticica and tung oils are imported in lesser amounts than castor and linseed oils. New crops that have industrial potential, as well as the traditional vegetable oil crops, include seed oils from crambe,Limnanthes, Lesquerella, Dimorphotheca, Vernonia, andCuphea plants. Crambe oil contains up to 65% erucic acid. Oil fromLimnanthes contains more than 95% of fatty acids above C₁₈.Lesquerella oil contains hydroxy unsaturated acids resembling ricinoleic acid from castor oil.Dimorphotheca oil contains a conjugated dienol system.Vernonia oils contain as much as 80% epoxy acids. TheCuphea oils contain a number of short chain fatty acids. Of these, crambe,Limnanthes, andVernonia are probably the most developed agronomically. Competition between vegetable oils and petrochemicals for the traditional fats and oil markets has been marked over the past 25 years, but prices for petrochemicals have accelerated at a greater rate than those for vegetable oils; and, it is now appropriate to reexamine the old as well as the new markets for fatty acids.     

Trigonella foenum-graecum L. Seed Oil Obtained by Supercritical CO2 Extraction

Supercritical CO₂ extraction (SC-CO₂) of fenugreek (Trigonella foenum-graecum L.) seed oil and its chemical composition and antioxidant activity were investigated. A central composite design combined with response surface methodology was used to study extraction conditions including pressure, temperature, and time. The optimum extraction conditions were 28.5?MPa extraction pressure, 41?°C extraction temperature, and 118?min extraction time, where 3.78?% yield was predicted. Fenugreek seed oil extracted under optimum conditions by SC-CO₂ was mainly composed of 28.3?% C18:3, 33.45?% C18:2, 9.89?% C16, 8.1?% C18:1, 3.7?% C18, 0.71?% C20, and 0.61?% C22. The fenugreek oil was rich in unsaturated fatty acids (nearly 70?% of the total fatty acids), and polyunsaturated fatty acids accounted for 61.42?% (mass percentage) of the total amount. The 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity increased from 12.5 to 88.4?% when the concentration was increased from 1 to 12?mg/ml. The reducing power of the seed oil was concentration-dependent. The antioxidant activity of the supercritical fluid extraction extract was superior to those obtained by Soxhlet extraction.     

Determination of petroselinic acid inUmbelliflorae seed oils by combined GC and13C NMR spectroscopy analysis

Synthetic triolein and tripetroselinin mixtures were examined by¹³C NMR spectroscopy, showing marked chemical shift differences of the olefinic carbon atoms. Peak height ratios were compared to weight values for quantitative determination of oleic and petroselinic acids in seed oils, since these two fatty acids are quantitated together by GC analysis. Values observed for NMR peak height ratios were fairly close and agreed well with weight ratios. From overall compositions of eleic and petroselinic acids obtained by GC and relative compositions given by¹³C NMR, petroselinic acid has been determined in tenUmbelliflorae seed oils.     

General properties and the fatty acid composition of the oil from the mophane caterpillar, Imbrasia belina

A preliminary investigation of the bulk properties of the oil from the edible mophane caterpillar (phane), Imbrasia belina, showed a significant difference in the iodine values of the oils from mature and young phane. Detailed analysis of the fatty acid composition of the two oil samples was thus carried out by capillary gas chromatography (GC) and complemented with ¹H and ¹³C nuclear magnetic resonance (NMR) studies to investigate the degree of unstauration in the two oil samples. While these studies showed that the oil samples from the mature and young mophane caterpillar were much the same in fatty acid composition, the data revealed a significant divergence from a literature report on phane oil. This earlier report puts the ratio of total saturated to total unsaturated fatty acids at approximately 1:1 (48.2:48.8, in percentages) and estimates the fatty acid composition for the major fatty acids as 16:0 (31.9%), 18:0 (15.2%), 18:1 (20.4%), 18:2 (9.9%), and 18:3 (19%). The data collected from the present work, however, showed the fatty acid composition for total saturated and total unsaturated fatty acids to be 40.5 and 57.0%, respectively. This work estimated the fatty acid composition for the major fatty acids as 16:0 (27.2%), 18:0 (12.3%), 18:1 (16.1%), 18.2 (10.7%), and 18:3 (29.0%). Thus, linolenic acid was the most abundant fatty acid in the phane oil. The GC results of the present analysis were largely corroborated by studies of the composition of fatty acid classes in the phane oil estimated from integrals of ¹H and ¹³C NMR signals. Oils from other edible Lepidoptera larvae are also known to be much richer in unsaturated than saturated fatty acids.     

Full Characterisation of Crambe abyssinica Hochst. Seed Oil

This work was dedicated to reporting the full chemical and physical characterisation of Crambe abyssinica Hochst. seed oil. The oil from the seeds was extracted using n-hexane. The seeds contain about 30?% oil. Density, refractive index, colour, smoke point, viscosity, acidity, saponification value, iodine value, fatty acid methyl esters, the relative position of fatty acids in C₁ and C₃ carbon glycerol, sterols, tocopherols, peroxide value, $ \mathop E\nolimits_{{1{\text{cm}}}}^{1\,\% } $ at 232?nm, and the susceptibility to oxidation measured by the Rancimat method were determined. The oil was found to contain high levels of unsaturated fatty acids, especially C22:1 (63.77?%). The dominant saturated acid was C22:0 (2.14?%). The oil was also found to contain high levels of β-sitosterol (51.93?%), campestanol (21.98?%), and brassicasterol (12.35?%). α-, γ-, and δ-Tocopherols were detected up to levels of 7.67, 125.04, and 3.99?mg/kg, respectively. The induction period (at 110?°C and 20?l/h) of the oil was 8.83?h. The relative position of fatty acids in C₁ and C₃ position was as follows: linoleic 0.45?%, oleic 8.84?%, and erucic 90.72?%. The thermal profile of the oil presented a single peak at ?20.94?°C.