The metabolism of structured triacylglycerols

The triacylglycerol (TAG) structure in addition to the overall fatty acid profile is of importance when considering the nutritional effect of a dietary fat. This review aims at summarizing our current knowledge of the digestion, absorption, uptake, and transport of structured TAGs, with particular emphasis on the following aspects: gastric emptying, specificity of pancreatic lipase, lymphatic transport and clearance of chylomicrons, effects of lipid structure on tissue lipid compositions and the fecal loss of fats. So an overview will be provided for how the structure and fatty acid composition of TAGs affect their absorption and the distribution of the fatty acids in the body following digestion and absorption.     

The digestion of dietary triacylglycerols

Dietary triacylglycerols (TAGs) are the major lipid components in the human diet and they are carriers of energy as well as important fatty acids. Many factors affect the digestion and absorption of TAGs. Evidence is accumulating that, in addition to the overall fatty acid profile, the TAG structure and the species composition are of importance when considering the nutritional effects of a dietary fat. There is good evidence that in addition to its short-term effects in the intestine on absorption of fatty acids the TAG structure also has long-term effects resulting from differences in the profile of absorbed fatty acids. Observations on the different atherogenic potential of dietary fats have given us a clear indication of the importance of the TAG structure for absorption of saturated fatty acids. In this context, one may focus on the effects of the structure of dietary fats as such, or one may speculate additionally on the possibilities of modifying the structure of fats to affect their absorption and the distribution of the fatty acids in the body after digestion and uptake. In this review we will summarize diverse aspects of TAG digestion and absorption, as well as the influences of the fatty acid composition and the intramolecular structure of dietary TAGs on their digestion and absorption.     

Structured triacylglycerol containing medium-chain fatty acids in sn-1(3) facilitates the absorption of dietary long-chain fatty acids in rats

A study was carried out to examine if the positional distribution of medium chain fatty acids (MCF) in triacylglycerol influences dietary fat absorption in rats. Two types of structure-specific fats, one predominantly composed of MCF in sn-1(3) and iinoleic acid in sn-2 [sn1(3)MCF-structured] and the others of MCF in sn-2 and linoleic acid in sn-1(3) [sn-2MCF-structured], were initially prepared, and the two structure-specific fats were interesterified and designated as sn-1(3)MCF-interesterified and sn-2MCF-interesterified. Synthetic fat was mixed with an equal amount of cocoa butter (103 g/kg of diet) and was supplemented to the AIN93G-based diet. Rats were fed on the diets for 4 wk. Long-chain saturated fatty acids were the predominant fatty acids excreted into the feces, and the positional distribution of MCF resulted in an altered fat absorption rate (%) of 81.8, 82.5, 84.2 and 86.3 for the rats fed on the diets containing sn-2MCF-structured, sn-1(3)MCF-interesterified, sn-2MCF-interesterified and sn-1(3)MCF-structured fats, respectively. The proportion of MCF in the serum, liver and adipose tissue triacylglycerols was not affected by the MCF distribution of the dietary fats. These results indicate that the distribution of MCF in dietary triacylglycerol is a determinant of intestinal fat absorption.     

Apparent convergence (at 2-monoacylglycerol level) of phosphatidic acid and 2-monoacylglycerol pathways of synthesis of chylomicron triacylglycerols

Dietary fats are converted into chylomicron triacylglycerols via the 2-monoacylglycerol and phosphatidic acid pathways of acylglycerol formation. In view of the known positional and fatty acid specificity of the acyltransferases, the triacylglycerol structures resulting from the two pathways would be expected to differ, but this has not been demonstrated. We have performed stereospecific analyses on the chylomicron triacylglycerols from rats fed menhaden oil and the corresponding fatty acid alkyl esters, which would be expected to be assimilated via the monoacylglycerol and the phosphatidic acid pathways, respectively. The results show a remarkable similarity between the two triacylglycerol types in the fatty acid composition of the sn-1 and sn-3 positions, along with marked differences in the composition of the sn-2 positions. The triacylglycerols from rats fed oil retained about 85% of the original fatty acids in the sn-2 position, including a high proportion of the long chain polyunsaturates (e.g., 5-7% 20:5 and 4-5% 22:6). The triacylglycerols from rats fed the alkyl ester contained large amounts of endogenous fatty acids in the sn-2 position (e.g., 18% 16:1, 14% 18:1, 14% 18:2, and 2.5% 20:4), which approximated the composition of the sn-2 position of the presumed phosphatidic acid intermediates. The sn-1 position contained a much higher proportion of polyunsatured fatty acids (e.g., 12-13% 20:5, 5-6% 22:6) than the sn-2 position (e.g. 2-3% 20:5, 0-0.6% 22:6) of triacylglycerols from rats fed the ester. We conclude that the chylomicron triacylglycerols arising via the 2-monoacylglycerol and the phosphatidic acid pathways differ mainly in the composition of the fatty acids in the sn-2 position. The similarity in the acids of the sn-1 and sn-3 positions of the chylomicron triacylglycerols from rats fed oil or ester is consistent with a hydrolysis of the acylglycerol products of the phosphatidic acid pathway to 2-monoacylglycerols prior to reconversion to triacylglycerols via the monoacylglycerol pathway and secretion as chylomicrons.     

Selective partitioning of dietary fatty acids into the VLDL TG pool in the early postprandial period

Circulating triacylglycerol (TG) arises mainly from dietary fat. However, little is known about the entry of dietary fat into the major TG pool, very low-density lipoprotein (VLDL) TG. We used a novel method to study the specific incorporation of dietary fatty acids into postprandial VLDL TG in humans. Eight healthy volunteers (age 25.4 +/- 2.2 years, body mass index 22.1 +/- 2.3 kg/m2) were fed a mixed meal containing 30 g fish oil and 600 mg [1-13C]palmitic acid. Chylomicrons and VLDL were separated using immunoaffinity against apolipoprotein B-100. The fatty acid composition of lipoproteins was analyzed by gas chromatography/mass spectrometry. [1-13C]palmitic acid started to appear in VLDL TG 3 h after meal intake, and a similar delay was observed for eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Approximately 20% of dietary fatty acids entered the VLDL TG pool 6 h after meal intake. DHA was clearly overincorporated into this pool compared with [1-13C]palmitic acid and EPA. This seemed to depend on a marked elevation of this fatty acid in the nonesterified fatty acid pool. In summary, the contribution of dietary fatty acids to early postprandial VLDL TG is substantial. The role of DHA in VLDL TG production will require further investigation.     

The determination of the asymmetrical stereochemical distribution of fatty acids in triacylglycerols

The fatty acid distribution in triacylglycerols (TAGs) is a factor that contributes to the intrinsic properties of oils from different species variants. Many hypotheses have been proposed to explain the specific distribution of fatty acids in the different naturally occurring oils. Currently, the 1,3-random-2-random theory is more or less accepted, but it has been widely shown that most vegetable oils do not behave randomly in the sn-1 and sn-3 stereochemical positions. For this reason, complex methodologies have been developed to analyze the fatty acid composition of the three stereochemical positions in TAGs. In this article, we propose that by calculating the asymmetric alpha coefficient, the stereochemical asymmetry of fatty acids in TAG molecular species can be defined. This coefficient reflects the relative content of fatty acids at the sn-1 and sn-3 positions and may overcome the problems found mainly with complex sn-1, sn-2, and sn-3 stereochemical analysis of fatty acids in TAG. The alpha coefficient is calculated from the fatty acid, sn-2 fatty acid, and TAG composition of the oil. Indeed, through this coefficient, it has been possible to show that, despite having the same overall content, the stearic acid distribution in the sn-1 and sn-3 positions is not random in some oils.     

Complete stereospecific determination of conjugated linoleic acids in triacylglycerol of milk-fat

We analyzed two kinds of dairy fat differing in their contents of cis9, trans11-conjugated linoleic acid (cis9,trans 11-CLA or rumenic acid), and determined the positional distribution of this CLA-isomer within the three sn- positions of the triacylglycerol. In the high rumenic acid fat (HR), the CLA-isomers amounted to 2.1% of total fatty acids, and 0.8% in the low rumenic acid fat (LR). Over 90% of the total CLA-isomers were in the form of rumenic acid, with an identical isomeric CLA distribution in both fats. The two fats differed mainly with regards to their contents in palmitic acid, alpha-linolenic acid, and isomers of trans-C 18:1. Conversely, our stereospecific determination indicates that the positional distribution of rumenic acid is preserved among both types of fat, and is more specific for the sn-3 position of the triacylglycerol (54 to 64% of the total rumenic acid). Such a positional distribution is believed to be nutritionally relevant.     

Increased dietary triacylglycerol markedly enhances the ability of isolated rabbit enterocytes to secrete chylomicrons: an effect related to dietary fatty acid composition.

Dietary fats are efficiently absorbed in the small intestine and transported into the blood via the lymph as chylomicrons, despite enormous variations in the amount and composition of the dietary lipid. The aim of the present study was to investigate how enterocytes respond to increased dietary fats of different composition. Rabbits were fed a low fat chow diet, and chow supplemented with sunflower oil (high n-6 polyunsaturated fatty acids), fish oil (high n-3 polyunsaturated fatty acids), or an oil mixture of a composition similar to that of the typical western diet. Feeding fat for 2 weeks markedly stimulated the ability of the isolated enterocytes to synthesize and secrete apolipoprotein B48, triacylglycerol, and cholesteryl ester (up to 18-, 50-, and 80-fold, respectively) in particles of chylomicron density. The magnitude of stimulation was sunflower oil > western diet lipid > fish oil. Single doses of lipid given 18 h prior to isolation of enterocytes stimulated chylomicron secretion by only 10% of that observed after 2 weeks of dietary supplementation. Enterocytes are replaced rapidly (half-life 1-2 days) by cells which move from the crypts to the tips of the villi, where absorption of nutrients takes place.Our observations suggest that dietary lipids modulate the function of enterocytes as they move from the crypts, so that the cells are 'turned-on' to lipid absorption. The results also show that diets of different fatty acid composition vary in their effects.     

Metabolism of chylomicrons by the isolated rat liver

Isolated livers perfused with washed corn oil chylomicrons labeled in vivo with palmitic acid-1-(14)C removed a large proportion of the chylomicrons. Slices from these livers oxidized chylomicron fatty acid esters to both carbon dioxide and acetoacetate. The liver slices also generated free fatty acids from chylomicron lipids and converted chylomicron triglycerides to phospholipids. Similar activities were observed in rat liver slices prepared shortly after the intravenous administration of chylomicrons to intact rats. The observed chylomicron uptake and lipid conversions were similar in livers from both fed and fasted rats. Fasting increased the oxidation of chylomicron fatty acid esters by livers labeled in vivo and by perfusion. In livers removed from intact rats given labeled chylomicrons, the triglyceride-(14)C to phospholipid-(14)C ratio was high, a finding unexpected if the liver had acquired this (14)C by removal of circulating fatty acids formed by extrahepatic lipolysis. These results demonstrate the ability of the liver to remove and utilize chylomicrons directly and suggest that direct removal accounts for a significant portion of the chylomicron fatty acids utilized by the liver of intact rats.     

Chemical synthesis and NMR characterization of structured polyunsaturated triacylglycerols

The chemical synthesis of pure triacylglycerol (TAG) regioisomers, that contain long chain polyunsaturated fatty acids, such as arachidonic acid (AA) or docosahexaenoic acid (DHA), and saturated fatty acids, such as lauric acid (La) or palmitic acid (P), at defined positions, is described. A single step methodology using (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate (PyBOP), an activator of carboxyl group commonly used in peptide synthesis and occasionally used in carboxylic acid esterification, has been developed for structured TAG synthesis. Identification of the fatty acyl chains for each TAG species was confirmed by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) and fatty acid positional distribution was determined by (1)H and (13)C NMR spectra. The generic described procedures can be applied to a large variety of substrates and was used for the production of specific triacylglycerols of defined molecular structures, with high regioisomeric purity. Combination of MS and NMR was shown to be an efficient tool for structural analysis of TAG. In particular, some NMR signals were demonstrated to be regioisomer specific, allowing rapid positional analysis of LC-PUFA containing TAG.     

Distribution of unusual fatty acids in the triacylglycerols of sea buckthorn mesocarp oil

The structure of unusual fatty acid (FA) components of triacylglycerols (TAGs) of mature sea buckthorn (Hippophae rhamnoides L.) mesocarp oil was determined by GLC and MS, and the positional-species composition (PSC) of these TAGs was estimated using the methods of TAG chemical deacylation, TLC, GLC, and computer calculation. It was shown that the unusual FAs comprised n-cis-Δ9-hexadecenoic, n-cis-Δ9,12-hexadecadienoic (palmitolinoleic), and n-cis-Δ11-octadecenoic (cis-vaccenic) acids. The hexadecenoic acid predominated in the oil, and in its distribution in TAGs, it was similar to the total FAs differing from them only in some prevalence in the triunsaturated TAGs and in the TAGs with a shorter acyl chain, as well as in the sn-2 position of TAGs. Palmitolinoleic (16:2) acid comprised only 5% of total FAs, and it was exclusively concentrated in the sn-2 position of TAGs. As regards its distribution between various positional types and forms of TAGs, the 16:2 acid was similar to oleate and total FAs. As compared to the total TAGs, the TAGs with 16:2 acid were characterized by a lower FA chain length as well as by a highest unsaturation. The TAGs with vaccenic acid (V-TAGs) considerably exceeded O-TAGs, i.e., the TAGs containing oleic acid, another 18:1 positional isomer, both in their content in the total TAGs and in their unsaturation. In the composition of positional types and fractions of various unsaturation, O-TAGs were similar to the total TAGs, while V-TAGs were characterized by a very unusual structure, viz., a very high triunsaturated TAG level and an extremely low concentration of 1,3-disaturated-2-monounsaturated TAGs. In addition, oleic acid, like most other unsaturated FAs, was incorporated predominantly in the sn-2 position of TAGs, while vaccenic acid, being also unsaturated, was nevertheless by 90% concentrated in the sn-1,3 positions of V-TAGs. Unusual FAs were related to each other in the mechanism of their biosynthesis. In fact, hexadecenoic acid biosynthesis produced by palmitic acid desaturation, was, on the one hand, further desaturated forming palmitolinoleic acid, and, on the other hand, converted to vaccenic acid via C₂ elongation.     

Dietary mold oil rich in gamma linolenic acid increases insulin-dependent glucose utilization in isolated rat adipocytes

Effects of dietary fats differing in fatty acid composition on insulin-stimulated glucose metabolism in adipocytes isolated from rat white adipose tissue were compared. Rats were fed experimental diets containing various fats differing in fatty acid composition for 7 days. In the first experiment, rats were fed palm oil mainly consisting of palmitic (45.3%) and oleic acids (39.1%) or safflower oil rich in linoleic acid (71.6%). In the second trial, rats were fed palm oil, or a fat mixture rich in linoleic acid or mold oil rich in gamma-linolenic acid. Contents of fatty acids except for linoleic and gamma-linolenic acid were comparable between the fat mixture and mold oil. The former was devoid of gamma-linolenic acid and contained 42.0% linoleic acid, while the latter contained 25.9% gamma-linolenic and 15.7% linoleic acids. In the first experiment, the insulin-dependent increase in glucose oxidation and incorporation into lipids was higher in rats fed safflower oil compared to those fed palm oil. In the second experiment, the insulin-dependent increase in glucose oxidation and incorporation into lipids was higher in rats fed the fat mixture and mold oil than in those fed palm oil. However, the extent of the increase in these parameters was much greater in rats fed mold oil than in those fed the fat mixture. Therefore, dietary gamma-linolenic acid compared to linoleic acid increases glucose metabolism in response to insulin stimuli in isolated rat adipocytes.     

Regiospecific distribution of fatty acids in triacylglycerols of Artemia franciscana nauplii enriched with fatty acid ethyl esters

This paper reports the positional distribution of fatty acids in triacylglycerols (TAG) of Artemia franciscana nauplii enriched with each of palmitic (16:0), oleic (18:1n-9), linoleic (18:2n-6), linolenic (18:3n-3), eicosapentaenoic (20:5n-3), and docosahexaenoic (22:6n-3) acid ethyl esters. TAG extracted from the enriched and unenriched nauplii were subjected to regiospecific analysis to determine the fatty acid compositions of the sn-1(3) and sn-2 positions of TAG. In the unenriched nauplii, 16:0, 18:1n-9, and 18:2n-6 were preferentially located in the sn-1(3) position followed by the sn-2 position [i.e. sn-1(3)>sn-2], whereas 18:3n-3 was concentrated in the sn-2 position [i.e. sn-2>sn-1(3)]. Contents of 20:5n-3 and 22:6n-3 were low. After the nauplii were enriched with each of the ethyl esters for 18 h, fatty acid fed to the nauplii showed higher content in the sn-1(3) position than in the sn-2 position [i.e. sn-1(3)>sn-2]. Distribution pattern of 18:3n-3 changed from sn-2>sn-1(3) to sn-1(3)>sn-2 during the enrichment with 18:3n-3 ethyl ester. Increases in all of the fatty acids in TAG were attributed to that in the sn-1(3) position much more than that in the sn-2 position. Artemia nauplii appear to be characterized by preferential incorporation of exogenous fatty acids into the sn-1(3) position of TAG, even though endogenous fatty acids are esterified in the opposite position.     

Reduction of postprandial triglyceridemia in humans by dietary n-3 fatty acids

Long chain n-3 fatty acids present in fish oils have been shown to reduce fasting plasma triglyceride and very low density lipoprotein levels in normal and hyperlipidemic human subjects. The present studies were designed to examine whether dietary n-3 fatty acids influence chylomicron formation and metabolism in healthy volunteers. In the first study seven subjects were fed either saturated fat, vegetable oil, or fish oil-based diets for 4 weeks each, and test meals containing 50 g of the background fat were administered after the second week of each diet. The postprandial rise in triglyceride levels was significantly lower following the fish oil test meal as compared to the saturated fat or vegetable oil test meals. In the second study, six subjects eating their usual home diets were given two fat tolerance tests. The first contained saturated fat and the second, given 1 week later, contained fish oil. There was no difference in the postprandial triglyceride response between the fish oil and the saturated fat meals. A third study was then conducted with eight volunteers in which saturated fat and fish oil test meals were administered during saturated fat and fish oil background diets in a crossover design. The presence of fish oil in the background diet reduced postprandial lipemia regardless of the type of fat in the test meal. Although there was no effect of the fish oil diet on the lipoprotein lipase and hepatic lipase activity of postheparin plasma measured in vitro, stimulation of in vivo lipolysis was not ruled out. Our results suggest that chronic (but not acute) intake of fish oil may inhibit the synthesis or secretion of chylomicrons from the gut. However, accelerated clearance due to decreased VLDL competition cannot be excluded.     

The effect of triacyl-sn-glycerol structure on the metabolism of chylomicrons and triacylglycerol-rich emulsions in the rat

A systematic study was undertaken to observe the effects of dietary (dioleoyl) triacyl-sn-glycerol structure on chylomicron composition and metabolism. First studied was a series of 1,2-dioleoyl-3-(saturated)acyl-sn-glycerols, where the fatty acid esterified at the 3-position was varied from 14 to 24 carbons. Next a series of 1,3-dioleoyl-2-acyl glycerols was studied, with various fatty acids esterified at the glycerol 2-position. These stereospecific triacyl-sn-glycerols were fed to donor rats and lymph chylomicrons were isolated, analyzed, and reinjected into recipient rats to study their disappearance from plasma and delivery to tissues. As shown by their compositions, chylomicrons obtained after feeding triacylglycerols containing all sn-3 fatty acid of chain length greater than 20 carbons were under-represented, possibly due to poorer digestion by lipases, or poorer absorption by the intestine. The 18-carbon saturated chain fatty acid (stearic acid) was equally well represented in chylomicrons whether in the 2- or 3-position of the fed triacylglycerol. The presence of increased amounts of long-chain saturated fatty acids in donor chylomicron triacylglycerols affected the metabolism of chylomicrons injected into the bloodstream of recipient rats. In particular the rate of removal of labeled cholesteryl esters, tracing removal of the partially degraded chylomicron remnants was slowed by the saturated chains, with palmitic acid and the 20-carbon fatty acid, arachidic acid, showing the most severe effects. There were clear differences in the removal from plasma of injected lymph chylomicrons derived from fed triacylglycerols containing stearic acid in either the 2- or 3-position, with evidence for remnants from the symmetrical triacylglycerols being less rapidly removed from the circulating blood. This effect was investigated further by injected model emulsions of chylomicrons, where the 2-position was substituted with saturated or transunsaturated acyl chains. Quantitation of removal from the blood stream of these model lipoproteins confirmed that a saturated or transunsaturated long chain fatty acid at the 2-position of the emulsion triacylglycerols slowed remnant removal from the blood. In some cases, with both lymph chylomicron and with emulsions, the lipolytic step mediated by lipoprotein lipase was also slowed.     

Characterisation of castor oil by on-line and off-line non-aqueous reverse-phase high-performance liquid chromatography-mass spectrometry (APCI and UV/MALDI)

A non-aqueous reverse-phase HPLC method, based on two columns in series, has been used to separate the major triacylglycerols (TAGs) from commercial castor oil and to perform either on-line negative ion atmospheric pressure chemical ionisation (APCI), or off-line positive ion matrix-assisted laser desorption ionisation (MALDI)/MS. The resulting Mass Spectra showed chloride-attached TAG molecules [M + CI]- in the case of negative-ion APCI, and sodium-attached TAG molecules [M + Na]+ in the case of positive-ion MALDI. For MALDI time-of-flight (TOF)/MS, a liquid binary matrix system consisting of sodium ferrocyanide and glycerol was applied, resulting in excellent TAG sensitivity, which was necessary for the determination of trace amounts of TAGs in castor oil. Both techniques allowed unambiguous molecular mass determination of the intact TAG molecules with no thermal degradation. Furthermore, seamless post source decay (PSD) fragment ion analysis by means of a curved field reflector TOF mass spectrometer allowed the determination of the fatty acid composition of each individual TAG. Castor oil contained eight different TAGs which were successfully determined by both APCI and MALDI techniques. In each TAG, at least two units of 12-hydroxy-9-octadecenoic acid (ricinoleic acid) were present. The following fatty acids were determined by seamless PSD fragment ion analysis and APCI/MALDI molecular mass determination as TAG substructures: ricinoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, dihydroxy stearic acid and eicosenoic acid. Triricinolein was the dominating TAG.     

Changes in Triacylglycerol Composition in Maturing Sea Buckthorn (Hippophaë rhamnoides) Seeds

Sea buckthorn (Hippophaë rhamnoides L.) seeds on the 29th, 53rd, 80th, and 107th day after pollination were used for determining, by lipase hydrolysis, the qualitative and quantitative composition of the triacylglycerol (TAG) positional types, groups, and positional species, as well as the factor of selectivity of incorporation of unsaturated fatty acids, octadecenoic, linoleic, and linolenic, into the sn-2-position of TAGs. Until the 80th day after pollination, there was a predominant formation of triunsaturated TAGs, which included linolenic and linoleic acid residues. After the 80th day, the absolute content of these major components of total TAGs markedly decreased, and an increase in total TAG content was mainly accounted for by the rise in the level of those TAG species, which included saturated fatty acids, palmitic and stearic (monosaturated–diunsaturated and disaturated–monounsaturated), as well as in the level of sn-2-octadecenoyl species belonging to the triunsaturated and palmito–diunsaturated types of TAGs. At each maturation stage, the quantitative dynamics of separate TAG species was determined by the content of fatty acid species available for TAG formation and the factor of selectivity of these species. The decrease in the content of a certain group of triunsaturated TAGs found here seems to be caused by their metabolization during seed maturation.     

Modification of seed oil content and acyl composition in the brassicaceae by expression of a yeast sn-2 acyltransferase gene.

A putative yeast sn-2 acyltransferase gene (SLC1-1), reportedly a variant acyltransferase that suppresses a genetic defect in sphingolipid long-chain base biosynthesis, has been expressed in a yeast SLC deletion strain. The SLC1-1 gene product was shown in vitro to encode an sn-2 acyltransferase capable of acylating sn-1 oleoyl-lysophosphatidic acid, using a range of acyl-CoA thioesters, including 18:1-, 22:1-, and 24:0-CoAs. The SLC1-1 gene was introduced into Arabidopsis and a high erucic acid-containing Brassica napus cv Hero under the control of a constitutive (tandem cauliflower mosaic virus 35S) promoter. The resulting transgenic plants showed substantial increases of 8 to 48% in seed oil content (expressed on the basis of seed dry weight) and increases in both overall proportions and amounts of very-long-chain fatty acids in seed triacylglycerols (TAGs). Furthermore, the proportion of very-long-chain fatty acids found at the sn-2 position of TAGs was increased, and homogenates prepared from developing seeds of transformed plants exhibited elevated lysophosphatidic acid acyltransferase (EC 2.3.1.51) activity. Thus, the yeast sn-2 acyltransferase has been shown to encode a protein that can exhibit lysophosphatidic acid acyltransferase activity and that can be used to change total fatty acid content and composition as well as to alter the stereospecific acyl distribution of fatty acids in seed TAGs.     

Stereochemical course of intestinal absorption and transport of mustard-seed oil triacylglycerols in the rat

Male rats with thoracic duct cannulae were intubated with mustard-seed oil or the corresponding fatty acid methyl esters and the lymph was collected over 0-24 h. The chylomicron and very low density lipoprotein fractions were obtained by conventional ultracentrifugation. The triacylglycerols and glycerophospholipids were isolated and the positional distribution and molecular association of fatty acids were determined by stereospecific and chromatographic methods. The oleic, linoleic, and linolenic acids were recovered in the lymph in the proportion in which they occurred in the fat fed, while eicosenoic, erucic, and lignoceric acids were rejected to about the same extent by the two pathways of intestinal triacylglycerol biosynthesis. It is shown that the lymph triacylglycerols arising via the monoacylglycerol or the phosphatidic acid pathway possess structures that are closely similar to each other and to that of the original mustard-seed oil. It is proposed that this is a result of comparable fatty acid and positional specificity of the acyltransferases associated with the acylglycerol synthesis in the animal and plant tissues and the wide range of fatty acid chain lengths in the mustard-seed oil.     

Postprandial metabolism of docosapentaenoic acid (DPA, 22:5n−3) and eicosapentaenoic acid (EPA, 20:5n−3) in humans

The study of the metabolism of docosapentaenoic acid (DPA, 22:5n?3) in humans has been limited by the unavailability of pure DPA and the fact that DPA is found in combination with eicosapentaenoic acid (EPA, 20:5n?3) and docosahexaenoic acid (DHA, 22:6n?3) in natural products. In this double blind cross over study, pure DPA and EPA were incorporated in meals served to healthy female volunteers. Mass spectrometric methods were used to study the chylomicron lipidomics. Plasma chylomicronemia was significantly reduced after the meal containing DPA compared with the meal containing EPA or olive oil only. Both EPA and DPA were incorporated into chylomicron TAGs, while there was less incorporation into chylomicron phospholipids. Lipidomic analysis of the chylomicron TAGs revealed the dynamic nature of chylomicron TAGs. The main TAG species that EPA and DPA were incorporated into were EPA/18:1/18:1, DPA/18:1/16:0 and DPA/18:1/18:1. There was very limited conversion of DPA and EPA to DHA and there were no increases in EPA levels during the 5 h postprandial period after the DPA meal. In conclusion, EPA and DPA showed different metabolic fates, and DPA hindered the digestion, ingestion or incorporation into chylomicrons of the olive oil present in the meal.