Ultra‐Performance Liquid Chromatography‐Mass Spectrometry Analysis of Free and Esterified Oxygenated Derivatives from Docosahexaenoic Acid in Rat Brain

Docosahexaenoic acid (DHA), a prominent long‐chain fatty acid of the omega‐3 family, is present at high amount in brain tissues, especially in membrane phospholipids. This polyunsaturated fatty acid is the precursor of various oxygenated lipid mediators involved in diverse physiological and pathophysiological processes. Characterization of DHA‐oxygenated metabolites is therefore crucial for better understanding the biological roles of DHA. In this study, we identified and measured, by ultrahigh‐performance liquid chromatography coupled with tandem mass spectrometry, a number of oxygenated products derived from DHA in exsanguinated and nonexsanguinated brains. These metabolites were found both in free form and esterified in phospholipids. Interestingly, both (R)‐ and (S)‐monohydroxylated fatty acid stereoisomers were observed free and esterified in phospholipids. Monohydroxylated metabolites were the main derivatives; however, measurable amounts of dihydroxylated products such as protectin DX were detected. Moreover, exsanguination allowed discriminating brain oxygenated metabolites from those generated in blood. These results obtained in healthy rats allowed an overview on the brain oxygenated metabolism of DHA, which deserves further research in pathophysiological conditions, especially in neurodegenerative diseases.     

Docosahexaenoic Acid and Eicosapentaenoic Acid Did not Alter <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 Conjugated Linoleic Acid Incorporation into Mice Brain and Eye Lipids

trans 10,cis 12‐CLA has been reported to alter fatty acid composition in several non‐neurological tissues, but its effects are less known in neurological tissues. Therefore, the purpose of this study was to determine if CLA supplementation would alter brain and eye fatty acid composition and if those changes could be prevented by concomitant supplementation with docosahexaenoic acid (DHA; 22:6n3) or eicosapentaenoic acid (EPA; 20:5n3). Eight‐week‐old, pathogen‐free C57BL/6N female mice (n = 6/group) were fed either the control diet or diets containing 0.5% (w/w) t10,c12‐CLA in the presence or absence of either 1.5% DHA or 1.5% EPA for 8 weeks. CLA concentration was significantly (P < 0.05) greater in the eye but not in the brain lipids of the CLA group when compared with the control group. The sums of saturated, monounsaturated, polyunsaturated fatty acids, and n3:n6 ratio did not differ between these two groups for both tissues. The n3:n6 ratio and concentrations of 20:5n3 and 22:5n3 were significantly greater, and those of 20:4n6, 22:4n6, and 22:5n6 were lesser in the CLA + DHA and CLA + EPA groups than in the control and CLA groups for either tissue. DHA concentration was higher in the CLA + DHA group only but not in the CLA + EPA group when compared with the CLA group for both tissues. The dietary fatty acids generally induced similar changes in brain and eye fatty acid concentration and at the concentrations used both DHA and EPA fed individually with CLA were more potent than CLA alone in altering the tissue fatty acid concentration.     

Non‐esterified fatty acids in blood cell membranes from patients with multiple sclerosis

The literature on non‐esterified fatty acid (NEFA) concentrations in blood cell membranes from patients with multiple sclerosis (MS) is scarce and reports on concentrations in brain tissue from these patients are inconsistent. NEFAs are needed for several biological functions, for example, as precursors for inflammatory eicosanoid synthesis. The objective of this study was therefore to compare NEFA concentrations in blood cell membranes from patients with that of healthy control subjects, and to correlate possible changes with disease outcome. NEFA C18:2n‐6 (9,12‐octadecadienoic acid) was decreased in peripheral blood mononuclear cell membranes from patients, median (quartile range): patients: 0.05 (0.02) and controls: 0.07 (0.14) µg/mg protein, p = 0.007. C18:2n‐6 also showed a weaker relationship with other fatty acids: with C16:0: patients: R = 0.40, p = 0.04; controls: R = 0.82, p = 0.000001. Saturated and MUFA showed positive correlations with the Bowel and bladder Functional System Scores (FSS). In contrast, in red blood cell membranes C18:2n‐6 and C22:0 (docosanoic acid) showed inverse correlations with the Sensory and Brainstem FSS. The decrease in NEFA C18:2n‐6 resulted in metabolic abnormalities between itself and saturated and monounsaturated NEFAs. Altered fatty acid composition in immune cell membranes would influence immune cell functions, and could possibly have contributed to the positive correlations between these fatty acids and disease outcome. Practical applications: Multiple sclerosis (MS) is a disease which presents with inflammation of the central nervous system. The cause of the disease is unknown and treatments such as anti‐inflammatory, immunosuppressive medications, and fatty acids supplements are for the alleviation of symptoms only. The results from this study however, showed an altered relationship between polyunsaturated and saturated as well as monounsaturated non‐esterified fatty acids in immune cells, which could have contributed to the inflammatory/infectious condition in these patients. The results from this study and further studies could possibly result in formulation of fatty acid supplements at correct doses or ratios for MS patients.     

Acute Hypercapnia/Ischemia Alters the Esterification of Arachidonic Acid and Docosahexaenoic Acid Epoxide Metabolites in Rat Brain Neutral Lipids

In the brain, approximately 90% of oxylipins are esterified to lipids. However, the significance of this esterification process is not known. In the present study, we (1) validated an aminopropyl solid phase extraction (SPE) method for separating esterified lipids using 100 and 500 mg columns and (2) applied the method to quantify the distribution of esterified oxylipins within phospholipids (PL) and neutral lipids (NL) (i.e. triacylglycerol and cholesteryl ester) in rats subjected to head-focused microwave fixation (controls) or CO₂-induced hypercapnia/ischemia. We hypothesized that oxylipin esterification into these lipid pools will be altered following CO₂-induced hypercapnia/ischemia. Lipids were extracted from control (n = 8) and CO₂-asphyxiated (n = 8) rat brains and separated on aminopropyl cartridges to yield PL and NL. The separated lipid fractions were hydrolyzed, purified with hydrophobic–lipophilic–balanced SPE columns, and analyzed with ultra-high-pressure liquid chromatography coupled to tandem mass spectrometry. Method validation showed that the 500 mg (vs 100 mg) aminopropyl columns yielded acceptable separation and recovery of esterified fatty acid epoxides but not other oxylipins. Two epoxides of arachidonic acid (ARA) were significantly increased, and three epoxides of docosahexaenoic acid (DHA) were significantly decreased in brain NL of CO₂-asphyxiated rats compared to controls subjected to head-focused microwave fixation. PL-bound fatty acid epoxides were highly variable and did not differ significantly between the groups. This study demonstrates that hypercapnia/ischemia alters the concentration of ARA and DHA epoxides within NL, reflecting an active turnover process regulating brain fatty acid epoxide concentrations.     

Effect of vacuum‐packaging on the changes of Russian sturgeon muscle lipids during frozen storage

The changes in fatty acid composition, non‐polar (triglycerols) and polar lipids (phospholipids), total free fatty acids and total cholesterol of Russian sturgeon (Acipenser gueldenstaedtii) were studied during 360 days of storage at ?18°C. It was established that total neutral lipids and phospholipids content decreased and total free fatty acids concentration increased significantly during the frozen storage. Lower non‐polar and polar lipids content and higher free fatty acids concentration of vacuum‐packaged samples in comparison with air‐packaged samples were found. The changes in total cholesterol concentration and phospholipid classes of frozen stored sturgeon were not influenced by the frozen storage period and the type of packaging. It was established that the sturgeon polar lipids consisted mainly of phosphatidylcholine – 54.98 ± 0.85%, phosphatidylethanolamine – 28.42 ± 0.61%, and phosphatidylserine – 8.64 ± 0.45%. The increase of the total free fatty acids concentration was associated with the free n ? 3 PUFA accumulation as a result of hydrolysis of non‐polar and polar lipids. During the frozen storage DHA percentage of non‐polar lipids and phospholipids decreased approximately 3 and 1.75%, respectively. After 360 days of storage at ?18°C the n ? 3/n ? 6 PUFA ratio of total lipids decreased 4.9%.     

α‐Linolenic acid metabolism in adult humans: the effects of gender and age on conversion to longer‐chain polyunsaturated fatty acids

This review summarises and evaluates current knowledge of α‐linolenic acid (αLNA) metabolism in adult humans. The principal biological role of αLNA appears to be as a precursor for the synthesis of longer‐chain n‐3 polyunsaturated fatty acids (PUFA). Stable isotope tracer studies indicate that conversion of αLNA to eicosapentaenoic acid (EPA) occurs but is limited in men and that further transformation to docosahexaenoic acid (DHA) is very low. A lower proportion of αLNA is used for β‐oxidation in women compared with men, while the fractional conversion to the longer‐chain n‐3 PUFA is greater, possibly due to the regulatory effects of oestrogen. Increasing αLNA intake for a period of weeks results in an increase in the proportion of EPA in plasma lipids, circulating cells and breast milk, but there is no increase in DHA, which may even decline in some pools at high αLNA intakes. Overall, αLNA appears to be a limited source of longer‐chain n‐3 PUFA in man, and so adequate intakes of preformed long‐chain n‐3 PUFA, in particular DHA, may be important for maintaining optimal tissue function. The capacity to up‐regulate αLNA transformation in women may be important for meeting the demands of the foetus and neonate for DHA.     

Purification of docosahexaenoic acid by selective esterification of fatty acids from tuna oil with Rhizopus delemar lipase

To purify docosahexaenoic acid (DHA), we attempted the selective esterification of fatty acids originating from tuna oil with lipases. Tuna oil was hydrolyzed in NaOH-ethanol solution, and the resulting fatty acid mixture [DHA, 23.2%; named tuna-free fatty acid (FFA)] was used as a starting material. Rhizopus delemar which acted lightly on DHA, was a suitable catalyst for the selective esterification of tuna-FFA, and lauryl alcohol was the best substrate. The reaction proceeded most effectively when a mixture of 2.4 g lauryl alcohol/tuna-FFA (2:1, mol/mol), 0.6 g water, and 600 U Rhizopus lipase was incubated at 30°C for 20 h with stirring at 500 rpm. Under these conditions 72% of tuna-FFA was esterified, and 84% of DHA was recovered in the unesterified fatty acid fraction. The DHA content in the fatty acid fraction rose from 23 to 73% with this reaction. To further elevate the DHA content, the unesterified fatty acids were extracted, and then esterified again under the same conditions. By this repeated esterification, DHA was purified to 89% with a recovery of 71% of its initial content.     

The effects of season on fat and fatty acids contents of shrimp and prawn species

The effects of seasons on the lipid content and fatty acid compositions of five different shrimp and prawn species (green tiger prawn – Penaeus semisulcatus, kuruma prawn – Marsupenaeus japonicus, caramote prawn – Melicertus kerathurus, deepwater pink shrimp – Parapenaeus longirostris, speckled shrimp – Metapenaeus monoceros) were evaluated. Results showed that lipid content ranged from 0.89 to 1.55% in muscle, showing that all species were considered as lean. There were significant differences (p<0.05) in the levels of saturated fatty acids (SFA), monounsaturated fatty acids and polyunsaturated fatty acids (PUFA) in terms of season and species. They were rich in n‐3 fatty acids, especially eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). The highest proportions of EPA were obtained from kuruma prawn (180.9 mg/100 g) in spring and deepwater pink shrimp (173.2 mg/100 g) and caramote prawn (146.3 mg/100 g) in summer. Kuruma prawn had the highest DHA in spring (140.8 mg/100 g) followed by deepwater pink shrimp (132.2 mg/100 g) and caramote prawn (129.6 mg/100 g) in summer. The results also showed that the seasons affected lipid content and the fatty acid composition of shrimp and prawn species. Practical Application: The beneficial effect of seafood consumption on human health has been related to the high content of n‐3 fatty acids, especially EPA (20:5n‐3) and DHA (22:6n‐3). The ratios of n‐6/n‐3, PUFA/SFA and EPA + DHA are considered as useful criteria for comparing relative nutritional and oxidation values of marine oils. In the current study, the influence of seasonality on the lipid content and the fatty acid compositions of shrimp and prawn were investigated in order to find the best source of n‐3 fatty acids during the year.     

Accretion of Dietary Docosahexaenoic Acid in Mouse Tissues Did Not Differ between Its Purified Phospholipid and Triacylglycerol Forms

Recent studies suggest that dietary krill oil leads to higher omega-3 polyunsaturated fatty acids (n-3 PUFA) tissue accretion compared to fish oil because the former is rich in n-3 PUFA esterified as phospholipids (PL), while n-3 PUFA in fish oil are primarily esterified as triacylglycerols (TAG). Tissue accretion of the same dietary concentrations of PL- and TAG-docosahexaenoic acid (22:6n-3) (DHA) has not been compared and was the focus of this study. Mice (n = 12/group) were fed either a control diet or one of six DHA (1%, 2%, or 4%) as PL-DHA or TAG-DHA diets for 4 weeks. Compared with the control, DHA concentration in liver, adipose tissue (AT), heart, and eye, but not brain, were significantly higher in mice consuming either PL- or TAG-DHA, but there was no difference in DHA concentration in all tissues between the PL- or TAG-DHA forms. Consumption of PL- and TAG-DHA at all concentrations significantly elevated eicosapentaenoic acid (20:5n-3) (EPA) in all tissues when compared with the control group, while docoshexapentaenoic acid (22:5n-6) (DPA) was significantly higher in all tissues except for the eye and heart. Both DHA forms lowered total omega-6 polyunsaturated fatty acids (n-6 PUFA) in all tissues and total monounsaturated fatty acids (MUFA) in the liver and AT; total saturated fatty acid (SFA) were lowered in the liver but elevated in the AT. An increase in the DHA dose, independent of DHA forms, significantly lowered n-6 PUFA and significantly elevated n-3 PUFA concentration in all tissues. Our results do not support the claim that the PL form of n-3 PUFA leads to higher n-3 PUFA tissue accretion than their TAG form.     

Fish Oil Decreases C-Reactive Protein/Albumin Ratio Improving Nutritional Prognosis and Plasma Fatty Acid Profile in Colorectal Cancer Patients

Previous studies have shown that n‐3 polyunsaturated fatty acids n‐3 (n‐3 PUFA) have several anticancer effects, especially attributed to their ability to modulate a variety of genomic and immune responses. In this context, this randomized, prospective, controlled clinical trial was conducted in order to check whether supplementation of 2 g/day of fish oil for 9 weeks alters the production of inflammatory markers, the plasma fatty acid profile and the nutritional status in patients with colorectal cancer (CRC). Eleven adults with CRC in chemotherapy were randomized into two groups: (a) supplemented (SG) daily with 2 g/day of encapsulated fish oil [providing 600 mg/day of eicosapentaenoic acid (EPA) + docosahexaenoic acid (DHA)] for 9 weeks (n = 6), and (b) control (CG) (n = 5). All outcomes were evaluated on the day before the first chemotherapy session and 9 weeks later. Plasma TNF‐α, IL‐1β, IL‐10 and IL‐17A, the pro/anti‐inflammatory balance (ratio TNF‐α/IL‐10 and IL‐1β/IL10) and serum albumin, showed no significant changes between times and study groups (p > 0.05). C‐reactive protein (CRP) and the CRP/albumin ratio showed opposite behavior in groups, significantly reducing their values in SG (p < 0.05). Plasma proportions of EPA and DHA increased 1.8 and 1.4 times, respectively, while the ARA reduced approximately 0.6 times with the supplementation (9 weeks vs baseline, p < 0.05). Patients from SG gained 1.2 kg (median) while the CG lost ?0.5 kg (median) during the 9 weeks of chemotherapy (p = 0.72). These results demonstrate that 2 g/day of fish oil for 9 weeks of chemotherapy improves CRP values, CRP/albumin status, plasma fatty acid profile and potentially prevents weight loss during treatment.     

Alpha‐Linolenic Acid,but Not Palmitic Acid,Negatively Impacts Survival,Asexual Reproductive Rate,and Clonal Offspring Size in Hydra oligactis

Hydra, as sit‐and‐wait predators with limited food selectivity, could serve as model organisms for the analysis of the effect of a particular dietary component on growth and reproduction. We investigated the effect of food quality and of diets enriched with palmitic (PAM) or α‐linolenic acid (ALA) on the life history traits of two hydra species: Hydra oligactis and Hydra vulgaris. We tested the hypothesis that a diet enriched with polyunsaturated fatty acids (PUFA) can stimulate growth and reproduction in simple metazoans with a sit‐and‐wait type of predatory strategy. Our results revealed that a diet based on Artemia nauplii, which are not a natural food for freshwater hydra, stimulated growth, asexual reproduction, and survival in hydra. Artemia nauplii were characterized by the highest lipid content of all used food sources. The analysis of the fatty acid content of hydra indicated the domination the n‐6 fatty acids over n‐3 (eicosapentaenoic acid [EPA], docosahexaenoic acid [DHA], and ALA). Arachidonic acid appeared to be the dominant PUFA in Hydra, irrespective of diet supplementation with palmitic acid or ALA. The dietary supplementation of ALA negatively affected the survival, asexual reproductive rate, and size of clonal offspring of H. oligactis and had no effect on the life history traits of H. vulgaris. Our results also suggest that the hydras are not able to efficiently convert ALA into other essential fatty acids, such as EPA and DHA. To our knowledge, this is the first report about the adverse effects of n‐3 fatty acid supplementation in primitive metazoans such as hydra.     

Daily Enteral DHA Supplementation Alleviates Deficiency in Premature Infants

Docosahexaenoic acid (DHA) is an essential fatty acid (FA) important for health and neurodevelopment. Premature infants are at risk of DHA deficiency and circulating levels directly correlate with health outcomes. Most supplementation strategies have focused on increasing DHA content in mother's milk or infant formula. However, extremely premature infants may not reach full feedings for weeks and commercially available parenteral lipid emulsions do not contain preformed DHA, so blood levels decline rapidly after birth. Our objective was to develop a DHA supplementation strategy to overcome these barriers. This double‐blind, randomized, controlled trial determined feasibility, tolerability and efficacy of daily enteral DHA supplementation (50 mg/day) in addition to standard nutrition for preterm infants (24–34 weeks gestational age) beginning in the first week of life. Blood FA levels were analyzed at baseline, full feedings and near discharge in DHA (n = 31) or placebo supplemented (n = 29) preterm infants. Term peers (n = 30) were analyzed for comparison. Preterm infants had lower baseline DHA levels (p < 0.0001). Those receiving DHA had a progressive increase in circulating DHA over time (from 3.33 to 4.09 wt% or 2.88 to 3.55 mol%, p < 0.0001) while placebo‐supplemented infants (receiving standard neonatal nutrition) had no increase over time (from 3.35 to 3.32 wt% or 2.91 to 2.87 mol%). Although levels increased with additional DHA supplementation, preterm infants still had lower blood DHA levels than term peers (4.97 wt% or 4.31 mol%) at discharge (p = 0.0002). No differences in adverse events were observed between the groups. Overall, daily enteral DHA supplementation is feasible and alleviates deficiency in premature infants.     

Purification of docosahexaenoic acid from tuna oil by a two-step enzymatic method: Hydrolysis and selective esterification

Purification of docosahexaenoic acid (DHA) was attempted by a two-step enzymatic method that consisted of hydrolysis of tuna oil and selective esterification of the resulting free fatty acids (FFA). When more than 60% of tuna oil was hydrolyzed with Pseudomonas sp. lipase (Lipase-AK), the DHA content in the FFA fraction coincided with its content in the original tuna oil. This lipase showed stronger activity on the DHA ester than on the eicosapentaenoic acid ester and was suitable for preparation of FFA rich in DHA. When a mixture of 2.5 g tuna oil, 2.5 g water, and 500 units (U) of Lipase-AK per 1 g of the reaction mixture was stirred at 40°C for 48 h, 83% of DHA in tuna oil was recovered in the FFA fraction at 79% hydrolysis. These fatty acids were named tuna-FFA-Ps. Selective esterification was then conducted at 30°C for 20 h by stirring a mixture of 4.0 g of tuna-FFA-Ps/lauryl alcohol (1:2, mol/mol), 1.0 g water, and 1,000 U of Rhizopus delemar lipase. As a result, the DHA content in the unesterified FFA fraction could be raised from 24 to 72 wt% in an 83% yield. To elevate the DHA content further, the FFA were extracted from the reaction mixture with n-hexane and esterified again under the same conditions. The DHA content was raised to 91 wt% in 88% yield by the repeated esterification. Because selective esterification of fatty acids with lauryl alcohol proceeded most efficiently in a mixture that contained 20% water, simultaneous reactions during the esterification were analyzed qualitatively. The fatty acid lauryl esters (L-FA) generated by the esterification were not hydrolyzed. In addition, L-FA were acidolyzed with linoleic acid, but not with DHA. These results suggest that lauryl DHA was generated only by esterification.     

Identification of a Δ4‐desaturase from the microalga Ostreococcus lucimarinus

Very long chain PUFA (VLCPUFA) like DHA are essential and health‐beneficial components of the human diet. Due to a shortfall in VLCPUFA supply, research is ongoing to establish VLCPUFA production in heterologous systems like for example oilseed plants. For this purpose it is crucial to identify the required enzymes from primary producers of VLCPUFA. Here, we describe a cDNA from the microalga Ostreococcus lucimarinus coding for a Δ4‐fatty acid desaturase. It exhibits a cytochrome b₅ domain fused to its amino terminus and three histidine boxes that are typically found in front‐end desaturases. Heterologous expression of the partly codon‐optimized version of the cDNA in yeast revealed that the encoded protein catalyzes the desaturation of (n‐3)‐ as well as (n‐6)‐substrates with a preference for VLCPUFA. In yeast it localized at the endoplasmic reticulum (ER) membrane and analysis of the product distribution into different lipid classes suggested that the enzyme most likely acts in a lipid‐dependent manner. Practical applications : The identified Δ4‐desaturase may be useful for the production of DHA in transgenic oleaginous organisms like annual oilseed crops.     

N‐3 fatty acids for human nutrition: stability considerations

Currently there is great interest in dietary n‐3 fatty acids to promote health. The food industry aims to produce food products enriched in α‐linolenic acid (Ln), eicosapentaenoic acid (EPA) and/or docosahexaenoic acid (DHA) to reduce some of the physiological effects of linoleic acid (L), the major polyunsaturated fatty acid in our diet. However, the goal is hampered by the susceptibility of the n‐3 fatty acids to oxidation. As a result the sensory and nutritional quality of such foods deteriorates. Lipid scientists therefore have to find a way to stabilise these fatty acids. Innovative technologies to protect n‐3 polyunsaturates using antioxidants, adequate preparation, refining and packaging of the oil are needed. In this paper we review the inherent stability and the stabilisation of these nutritionally valuable polyunsaturated fatty acids.     

Synthesis of acetyl, docosahexaenoyl-glycerophosphocholine and its characterization using nuclear magnetic resonance

Docosahexaenoic acid (DHA) circulates in mammals in lipoproteins and bound to serum albumin as a nonesterified fatty acid as well as esterified in lysophosphatidylcholine (lysoPC). 1-Lyso,2-DHA-glycerophosphocholine (GPC) is an unstable isomer because of a primary alcohol at the sn-1 position. To keep DHA at the sn-2 position of lysoPC, its usual position for the corresponding lysoPC to be acylated into PC in tissues, we synthesized 1-acetyl,2-DHA-GPC and confirmed its structure by use of nuclear magnetic resonance (NMR) spectroscopy in comparison with its positional isomer, 1-DHA,2-acetyl-GPC. 1-Lyso,2-DHA-GPC was prepared from 1-stearoyl,2-DHA-GPC by enzymatic hydrolysis and purified by high-performance liquid chromatography. The isomerization of 1-lyso,2-DHA-GPC into 1-DHA,2-lyso-GPC was obtained by keeping the former overnight at room temperature under nitrogen. Both lysoPC isomers were acetylated by acetic anhydride into 1-acetyl,2-DHA-GPC and 1-DHA,2-acetyl-GPC, respectively, and the resulting phospholipids were fully characterized by NMR. In particular, the 1,2 substitution pattern of the acetyl and DHA chains could be easily detected by 2D heteronuclear multibond correlation. We conclude that 1-acetyl,2-DHA-GPC might be considered as a stable form of 1-lyso,2-DHA-GPC for its delivery to tissues, if the latter exhibits acetyl hydrolase activity.     

Characterization of the glycerolipid composition of a high‐palmitoleic acid sunflower mutant

The glycerolipid composition of a high‐palmitoleic acid sunflower (Helianthus annuus L.) mutant accumulating up to 20% of n‐7 fatty acids was studied. This line produces oil with a complex triacylglycerol (TAG) composition, containing species that have not been previously identified in sunflower. In this regard, palmitoleic acid was esterified in an unexpected way in the three positions of the TAG molecules. The polar glycerolipid composition of the mutant was also studied, in order to identify and quantify the changes in membrane lipids imposed by the sunflower enzymatic machinery during the accumulation of the unusual n‐7 fatty acids. The high‐palmitoleic mutant accumulated important quantities of n‐7 fatty acids in the polar lipid fraction, especially in the phosphatidylcholine lipid class. However, the total polar lipid content of these lines was not affected. On the other hand, the mutations responsible for the n‐7 lipid accumulation induced an important decrease in the oil yield of the new mutant.     

Stearidonic acid (18:4n‐3): Metabolism,nutritional importance,medical uses and natural sources

Stearidonic acid (SA, 18:4n‐3) is a polyunsaturated fatty acid (PUFA) that constitutes the first metabolite of α‐linolenic acid (ALA, 18:3n‐3) in the metabolic pathway leading to C_20–22 PUFA, such as eicosapentaenoic acid (EPA, 20:5n‐3), and docosahexaenoic acid (DHA, 22:6n‐3), which recently have received much attention because of their various physiological functions in the human body. Recently, several studies indicated that dietary SA increased EPA more efficiently than ALA. Thus, vegetable oils containing SA may become a dietary source of n‐3 fatty acids that is more effective in increasing tissue n‐3 PUFA concentrations than the current ALA‐containing vegetable oils. Nevertheless, few SA sources occur in nature, although there are still a large number of species untested to date. SA has been detected in variable amounts in several species of algae, fungi and animals tissues, but the seeds of some plant families seem to be better sources of SA, especially Echium (Boraginaceae) species. This work reviews the nutritional significance, medical uses and natural occurrence of SA.     

Fetal erythrocyte phospholipid polyunsaturated fatty acids are altered in pregnancy complicated with gestational diabetes mellitus

Insulin resistance and altered maternal metabolism in gestational diabetes mellitus (GDM) may impair fetal arachidonic acid (AA) and docosahexaenoic acid (DHA) status. The objectives were to test the hypothesis that fetal polyunsaturated fatty acids would be altered with GDM and identify factors related to fetal phospholipid (PL) AA and DHA. Maternal and cord vein erythrocyte PL fatty acids were determined in GDM (n=13) and healthy pregnant women (controls, n=12). Cord vein erythrocyte PL AA and DHA concentrations were significantly lower in GDM vs. controls. Maternal blood hemoglobin A₁C was inversely correlated to fetal erythrocyte PL DHA and AA in controls and GDM (n=25). Pregravid body mass index was negatively associated with fetal PL DHA. The data support the hypothesis that there is impairment in fetal accretion of DHA and AA in GDM.     

Preparation of Infant Formula Fat Analog Containing Capric Acid and Enriched with DHA and ARA at the sn-2 Position

An infant formula fat analog with capric acid mostly esterified at the sn‐1,3 positions, and substantial amounts of palmitic, docosahexaenoic (DHA), and arachidonic (ARA) acids at the sn‐2 position, was prepared by physically blending enzymatically synthesized structured lipids (SL) with vegetable oils. The components of the blend included high sn‐2 palmitic acid SL enriched with capric acid (SL_CA), canola oil (CAO), corn oil (CO), high sn‐2 DHA (DHAO_m), and high sn‐2 ARA (ARAO_m) enzymatically modified oils. Each component was proportionally blended to match the fatty acid profile of commercial fat blends used for infant formula. The infant formula fat analog (IFFA₁) was characterized for total and positional fatty acids (FA), triacylglycerol (TAG) molecular species, thermal behavior, and tocopherol content. IFFA₁ contained 17.37 mol% total palmitic acid of which nearly 35 % was located at the sn‐2 position. The total capric acid content was 13.93 mol%. The content of DHA and ARA were 0.49 mol% (48.18 % at sn‐2) and 0.57 mol% (35.80 % at sn‐2), respectively. The predominant TAG were OPO (24.09 %), POP (15.70 %), OOO (11.53 %), and CLC (7.79 %). The melting completion and crystallization onset temperatures were 18.65 and ?2.19 °C, respectively. The total tocopherol content was 566.45 μg/g. This product might be suitable for commercial production of infant formulas.