Vernonia galamensis: A rich source of epoxy acid

A percolation extraction ofVernonia galamensis seed, affording 38.6% of crude vernonia oil is described. The dark colored crude oil was degummed with water, treated with activated charcoal and bleached with a neutral agent, to give a light colored oil (Lovibond: 0.9 red, 3.5 yellow). Gas chromatographic/mass spectrometric analysis of the refined oil indicates a relative fatty acid composition of 79–81% vernolic (cis-12,13-epoxy-cis-9-octadecenoic) acid, 11–12% linoleic acid, 4–6% oleic acid, 2–3% stearic acid, 2–4% palmitic acid, and a trace amount of arachidic acid.     

Synthesis and Biological Characterization of (Z)-9-Heptadecenoic and (Z)-6-Methyl-9-Heptadecenoic Acids: Fatty Acids with Antibiotic Activity Produced by Pseudozyma flocculosa

Difficulties in isolating and purifying antibiotic fatty acids from culture filtrates of Pseudozyma flocculosa, a biocontrol agent against powdery mildew, have been limiting factors in studying the properties and understanding the mode of action of the biocontrol agent. We report a new protocol for synthesizing (Z)-9-heptadecenoic and for the first time synthesis of (Z)-6-methyl-9-heptadecenoic acids, two antibiotic fatty acids produced by P. flocculosa. This allowed reproducible and quantifiable means of assaying biological activity of the molecules. In these bioassays, both molecules exhibited antifungal activity corresponding to their expected potency. These new developments should facilitate further studies aimed at deciphering the ecological properties of P. flocculosa.     

Reduced Maternal Erythrocyte Long Chain Polyunsaturated Fatty Acids Exist in Early Pregnancy in Preeclampsia

The present prospective study examines proportions of maternal erythrocyte fatty acids across gestation and their association with cord erythrocyte fatty acids in normotensive control (NC) and preeclamptic pregnancies. We hypothesize that maternal fatty acid status in early pregnancy influences fetal fatty acid stores in preeclampsia. 137 NC women and 58 women with preeclampsia were included in this study. Maternal blood was collected at 3 time points during pregnancy (16–20th weeks, 26–30th weeks and at delivery). Cord blood was collected at delivery. Fatty acids were analyzed using gas chromatography. The proportions of maternal erythrocyte α‐linolenic acid, docosahexaenoic acid, nervonic acid, and monounsaturated fatty acids (MUFA) (p < 0.05 for all) were lower while total n‐6 fatty acids were higher (p < 0.05) at 16–20th weeks of gestation in preeclampsia as compared with NC. Cord 18:3n‐3, 22:6n‐3, 24:1n‐9, MUFA, and total n‐3 fatty acids (p < 0.05 for all) were also lower in preeclampsia as compared with NC. A positive association was observed between maternal erythrocyte 22:6n‐3 and 24:1n‐9 at 16–20th weeks with the same fatty acids in cord erythrocytes (p < 0.05 for both) in preeclampsia. Our study for the first time indicates alteration in maternal erythrocyte fatty acids at 16th weeks of gestation which is further reflected in cord erythrocytes at delivery in preeclampsia.     

Fatty Acid Profiles of Commercially Available Finfish Fillets in the United States

Fillets of 76 finfish species (293 composites of three fish) were obtained from commercial seafood vendors in six regions of the United States (i.e., Great Lakes, Mid-Atlantic, New England, Northwest, Southeast, and Southwest). Full fatty acid profiles were determined for each species and are presented here. Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) have been associated with many health benefits. Thus, fillets of each species were compared for total EPA plus DHA content, which ranged from 17 mg/100 g (pangasius/swai) to 2430 mg/100 g (Chilean sea bass). Of the top ten most popularly consumed seafoods in the US, finfish, including salmon species (717–1533 mg/100 g), Alaskan pollock (236 mg/100 g), tilapia (76 mg/100 g), channel catfish (44 mg/100 g), Atlantic cod (253 mg/100 g), and pangasius/swai (17 mg/100 g), exhibited a wide concentration range of EPA plus DHA. Large variances were found within many of the farmed species analyzed, which likely stems from dietary differences in the farm-fed diet. The results of this study provide current information on a broad range of species and will help nutritionists and the public make informed decisions regarding seafood consumption.     

Analyzing seed weight,fatty acid composition,oil, and protein contents in <Emphasis Type="Italic">Vernonia galamensis</Emphasis> germplasm by near-infrared reflectance spectroscopy

Vernonia galamensis is a potential new industrial oilseed crop from the Asteraceae family. The interest in this species is due to the presence of a high vernolic acid content of its seed oil, which is useful in the oleochemical industry for paints and coatings. The development of a rapid, precise, robust, nondestructive, and economical method to evaluate quality components is of major interest to growers, processors, and breeders. NIR reflectance spectroscopy (NIRS) is routinely used for the prediction of quality traits in many crops. This study was conducted to establish a rapid analytical method for determining the quality of intact seeds of V. galamensis. A total of 114 Vernonia accessions were scanned to determine seed weight, FA composition, oil, and protein contents using NIRS. Conventional chemical analysis for FA composition, total oil, and protein contents were performed by GC, Soxhlet extraction, and the Dumas combustion method, respectively. Calibration equations were developed and tested through cross-validation. The coefficient of determination in cross-validation for FA ranged from 0.47 (linoleic acid) to 0.55 (vernolic acid), and for oil, protein, and seed weight from 0.71 (oil) to 0.86 (seed protein). It was concluded that NIRS calibration equations developed for seed weight and seed quality traits can be satisfactorily used as early screening methods in V. galamensis breeding programs.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of Vernonia galamensis oil

Matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) has been used to identify eight triacylglycerols (TAG) in Vernonia galamensis oil (VO). The TAG include trivernolin, divernoloylstearoylglycerol, divernoloyloleoylglycerol, vernoloyllinoleoylstearoylglycerol, vernoloyllinoleoyloleoylglycerol, and vernoloyldilinoleoylglycerol. Samples for the MALDI/TOF/MS analysis were prepared with alpha-cyano-4-hydroxycinnamic acid (matrix) in an acetonitrile/tetrahydrofuran solvent system. A mol ratio of matrix/VO (44:1) gave reproducible composite spectra, resulting in resolutions greater than 8,000 and signal-to-noise ratios of above 1000 for the most abundant molecular species. 1,3-Dioleoyl-2-stearoylglycerol and 1,2-dioleoyl-3-palmitoylglycerol were used as calibration standards.     

Determination of Oil Content and Fatty Acid Composition of Sesame Mutants Suited for Intensive Management Conditions

Sesame mutants with closed capsules, determinate growth habit and wilt resistance, have been proposed to be suitable for intensive management conditions facilitating mechanized harvesting. The objective of our experiment was to determine the oil content and fatty acid composition of these mutants before they are placed on the market. Oil content and fatty acids were studied in 19 mutants, 6 breeding lines and 4 control source genotypes. The oil contents of the seeds ranged from 46.4 to 62.7%. The mutants had generally a lower oil content than the control genotypes except the wilting tolerant group. For unsaturated fatty acids, oleic acid was higher in the mutants and breeding lines while linoleic acid was lower in the seed oil. However, no mutants or breeding lines were found with radically different composition or with any undesirable lipid component. The closed capsule and determinate growth habit mutants need to be improved for oil content while their fatty acid composition is fine.     

Fatty Acids in Liver,Muscle and Gonad of three Tropical Rays including Non-Methylene-Interrupted Dienoic Fatty Acids

Scientific investigation of lipids in Elasmobranchs has been conducted mainly on shark species. Because rays seem to be neglected, this study was performed to examine the complete fatty acid (FA) composition with a particular interest for long-chain polyunsaturated FA (PUFA) content in different tissues of three ray species including parts usually discarded. The total FA and PUFA profiles of total lipids were determined in muscle, liver, and gonad of Rhinobatos cemiculus, Rhinoptera marginata, and Dasyatis marmorata, the most often caught ray species from the East Tropical Atlantic Ocean. Fifty FA were characterized as methyl esters and N-acyl pyrrolidides by gas chromatography/mass spectrometry, showing significant levels of 20:5n-3 (EPA) (up to 5.3%) and 22:5n-3 (DPA) (up to 7.3%), high levels of 20:4n-6 arachidonic (ARA) (4.8–8.6% of total FA) and 22:6n-3 (DHA) (up to 20.0%). The results show that muscle, liver and gonad of rays can provide high amounts of essential PUFA, specially DHA, for direct human nutrition or the food processing industry. High proportions of DHA were particularly found in all samples of R. cemiculus (11.6–20.0%), and in muscle and liver of D. marmorata (11.1–16.1%). Regarding the high amounts of (n-3) PUFA, this study shows that these rays deserve a better up-grading, including the normally discarded parts, and describes the occurrence of unusual NMID FA in all tissues studied. Five non-methylene-interrupted dienoic fatty acids (NMID FA) (0–3.4%) were reported, including previously known isomers, namely 20:2 Δ7,13, 20:2 Δ7,15, 22:2 Δ7,13, 22:2 Δ7,15, and new 22:2 Δ6,14. These acids are quite unusual in fish and unprecedented in rays. The 22:2 Δ6,14 acid occurred in gonads of male specimens of R. cemiculus at 2.9%.     

Mass spectrometric characterization ofVernonia galamensis oil

Vernonia galamensis seed oil is a natural source of epoxidized triacylglycerols, which consist of 52% trivernolin and a mixture of other triacylglycerols. Epoxidized oils are used for industrial applications, such as coatings and plastic formulations. To determine the major molecular species present in Vernonia oil, desorption chemical ionization/mass spectrometry and mass spectrometry/mass spectrometry were used to determine its glyceride composition. Seven triacylglycerols predominated: divernoloylarachidonate, trivernolin, divernoloylstearate, divernoloyloleate, divernoloyllinoleate, dilinolenoyl vernolate and divernoloylpalmitate.     

Determination of the Fatty Acid Composition of Acorn (Quercus), Pistacia lentiscus Seeds Growing in Algeria

The fruits of two plants from Algeria (Quercus and Pistacia lentiscus) were investigated. The paper reports the chemical characteristics and the fatty acid composition of the oil extracts from the fruits. The black fruits of P. lentiscus has the highest crude fat of 32.8%, followed by the red fruits with 11.7%, and the lowest value of 9% in Quercus (acorn). The acid value was highest in red fruits of P. lentiscus oil (24.0 mg KOH/g), followed by the black fruits oil and lowest in acorn oil. The relatively high iodine value in the oils indicates the presence of many unsaturated bonds. Saponification value was highest in the Quercus ilex oil (166.7 mg KOH/g), while the lowest value was in the black fruits of P. lentiscus oil. Gas-liquid chromatography revealed that the three dominant fatty acids found are: palmitic C16:0 (16.3–19.5%), oleic C18:1 (55.3–64.9%), linoleic C18:2 (17.6–28.4%). The oils contain an appreciable amount of unsaturated fatty acids (78.8–83.5%).     

Variation in Fatty Acid Compositions, Oil Content and Oil Yield in a Germplasm Collection of Sesame (Sesamum indicum L.)

The variation in oil content, oil yield and fatty acid compositions of 103 sesame landraces was investigated. The landraces varied widely in their oil quantity and quality. The oil content varied between 41.3 and 62.7%, the average being 53.3%. The percentage content of linoleic, oleic, palmitic and stearic acids in the seed oil ranged between 40.7–49.3, 29.3–41.4, 8.0–10.3 and 2.1–4.8%, respectively. Linolenic and arachidic acids were the minor constituents of the sesame oil. Linoleic and oleic acids were the major fatty acids of sesame with average values of 45.7 and 37.2%, respectively. The total means of oleic and linoleic acids as unsaturated fatty acids of sesame were about 83% which increases the suitability of the sesame oil for human consumption. The superiority of the collection was observed in oil content. The oil content of a few accessions was above 60%, proving claims that some varieties of sesame can reach up to 63% in oil content. The accessions with the highest oil content were relatively richer in the linoleic acid content while there were some landraces in which linoleic and oleic acid contents were in a proportion of almost 1:1. The results obtained in this study provide useful background information for developing new cultivars with a high oil content and different fatty acid compositions. Several accessions could be used as parental lines in breeding programmes aiming to increase sesame oil quantity and quality.     

Pilot plant extraction of oil fromVernonia galamensis seed

Vernonia galamensis seed containing 40–42% oil and 30–34% epoxy acid, (cis-12,13-epoxy-cis-9-octadecenoic) was processed to oil and meal. Seed conditioning, pressing and solvent extraction research were conducted in pilot facilities at the French Oil Mill Machinery Co. (Piqua, OH). The robust lipase system was successfully inactivated by treating 200 lb. batches ofV. galamensis seed in a cooker/conditioner at 195–200°F and >10% moisture. Conditioned seed was mechanically pressed and the press discharge cone setting was varied during operation from 1/32″ to 3/32″ to demonstrate the feasibility of both full pressing and prepressing. Prepressing successfully reduced oil level in the press cake to ca. 20%. Press cake was extracted with hexane in a 1.5-ft³ batch-type, four-stage percolation unit with a 6″ square extraction cross section. Solvent extraction reduced oil level in the defatted meal to 1–2%. The defatted meal was desolventized and toasted. Excessive foaming of the vernonia oil extract made complete solvent stripping in the oil stripping unit difficult.     

Validation of Two Methods for Fatty Acids Analysis in Eggs

A comparative study between two methods (lipid extraction followed by saponification and methylation, and direct methylation) to determine the fatty acids in egg yolk was evaluated. Direct methylation of the samples resulted in lower fatty acid content and greater variation in the results than the lipid extraction followed by saponification and methylation. The low repeatability observed for the direct HCl methylation method was probably due to a less efficient extraction and conversion of the fatty acids into their methyl esters as compared to the same procedure starting with the lipid extract. As the lipid extraction followed by esterification method was shown to be more precise it was validated using powdered egg certified as reference material (RM 8415, NIST) and applied to samples of egg, egg enriched with polyunsaturated omega-3 fatty acids (n-3 PUFA), and commercial spray-dried whole egg powder.     

Fatty and resin acids of spanishpinus pinaster Ait. Subspecies

The qualitative and quantitative composition of the acid fraction of wood extractives from three SpanishPinus pinaster Ait. subspecies (Atlantic, mountain Mediterranean and plain Mediterranean) were studied. Seven samples of each subspecies were prepared according to Technical Association of Pulp and Paper Standards, extracted with petroleum ether (b.p. 40–60°C) in a Soxhlet apparatus and saponified with ethanolic 0.4N potassium hydroxide. The acid fraction was methylated with diazomethane and studied by combined gas chromatography/mass spectrometry. The major constituents found were palmitic, oleic and linoleic among the fatty acids and pimaric, sandaracopimaric, levopimaric, isopimaric, abietic and dehydroabietic among the resin acids. Neoabietic and palustric acids were not found. Variations in the quantitative composition of the acid fraction enable us to distinguish the three subspecies. Main quantitative differences are found between the Atlantic subspecies and the two Mediterranean subspecies.     

Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge <Emphasis Type="Italic">Pseudospongosorites suberitoides</Emphasis>

The cyclopropane fatty acids 17-methyl-trans-4,5-methyleneoctadecanoic acid, 18-methyl-trans-4,5-methylenenonadecanoic acid, and 17-methyl-trans-4,5-methylenenonadecanoic acid were characterized for the first time in nature in the phospholipids (mainly PE, PG and PS) of the hermit-crab sponge Pseudospongosorites suberitoides. Pyrrolidine derivatization was the key in identifying the position of the cyclopropyl and methyl groups in the acyl chains and ¹H NMR was used to determine the trans stereochemistry of the cyclopropane ring. The phospholipids from the sponge also contained an interesting series of iso-anteiso Δ^5,9 fatty acids with chain-lengths between 17 and 21 carbons, with the fatty acids (5Z,9Z)-18-methyl-5,9-nonadecadienoic acid and the (5Z,9Z)-17-methyl-5,9-nonadecadienoic acid being described for the first time in sponges. The anteiso α-methoxylated fatty acid 2-methoxy-12-methyltetradecanoic acid was also identified for the first time in nature in the phospholipids of this interesting marine sponge. The novel cyclopropyl fatty acids could have originated from the phospholipids of a cyanobacterium living in symbiosis with the sponge.     

Simultaneous Determination of Free Fatty Acids and Esterified Fatty Acids in Rice Oil by Gas Chromatography

Free fatty acids (FFA) in crude rice oil were selectively and stoichiometrically derivatized to fatty acid N,N-dimethylamides (FADMA) by catalytic condensation at 45 °C, and then esterified fatty acids (eFA) were directly converted to fatty acid methyl esters (FAME) at 37 °C. The mixture of FADMA and FAME formed in a single test tube was injected into the capillary column of a gas chromatograph (GC). No mutual contamination occurred between FFA and eFA, and reliability of the method was confirmed by comparison between GC data obtained by this method and by a conventional isolation method. The advantages of the present method are that no FFA isolation procedures are required, the reactions proceed under mild temperature conditions, and FFA and eFA can be analyzed simultaneously by GC.     

One-Step Extraction and Concentration of Polyunsaturated Fatty Acids from Fish Liver

The fatty acids (FA) eicosapentaenoic acid (20:5ω-3; EPA) and docosahexaenoic acid (22:6ω-3; DHA), which have several health benefits, have been concentrated from mako shark liver (Isurus oxyrinchus). The process was carried out in one single step, in which fish liver oil was simultaneously extracted, saponified and concentrated. Additionally, the polyunsaturated fatty acids (PUFA) concentrate was winterized to crystallize the remaining saturated FA, resulting in a further increase in the concentration of DHA and EPA. Two variables, temperature and water concentration in the saponification mixture, were optimized to increase the concentration of ω-3 PUFA. Best results were obtained at 12 °C and 0% water content in the mixture, obtaining 17.8% purity and 77.6% yield of EPA; DHA purity and yield were 33.3 and 82.2%, respectively.     

Oils in the Seeds of Caneberries Produced in Korea

Seed and oil contents, and fatty acid compositions of oils of 20 caneberries grown in Korea were determined. Fatty acid compositions of the oils were analyzed using GC for the extracted and methylated oils from the berry seeds. The seeds comprised 4–10% (w/w) of the wet berries and accounted for 26–62% of the dry berries. Moisture and oil contents of the berry seeds were 8–17 and 13–28% (dry basis), respectively. More than 90% of the total fatty acids in the oils from the berry seeds were unsaturated. Linoleic and linolenic acids comprised 49–70 and 13–34%, respectively, of the oils in the berry seeds.     

Fatty acid composition and contents of trans monounsaturated fatty acids in frying fats, and in margarines and shortenings marketed in Denmark

This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C_18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C_18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C_18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C_18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C_18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.     

Fatty acid composition and contents of trans monounsaturated fatty acids in frying fats, and in margarines and shortenings marketed in Denmark

This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C_18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C_18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C_18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C_18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C_18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.