Occurrence of wax esters and 1-O-alkyl-2,3-diacylglycerols in goat epididymal sperm plasma membrane

Two unusual lipid classes were detected by thin-layer chromatography in the neutral lipids derived from goat cauda-epididymal sperm plasma membrane. The lipids were identified as wax esters and 1-O-alkyl-2,3-diacylglycerols based on chromatographic properties, identity of their hydrolysis products, and infrared/¹H nuclear magnetic resonance spectral evidence. The membrane containedca. 3 and 5 μg/mg protein of wax esters and alkyldiacylglycerols, respectively. The relative proportions of wax esters and alkyldiacylglycerols in the total neutral lipids were 1.5% and 2.4%, respectively. The lipids contained fatty acids with chain lengths of C₁₄ to C₂₂. The major fatty acids of the wax esters were 14∶0, 16∶0, 16∶1ω7, 18∶0 and 18∶1ω9. The fatty acids in alkyldiacylglycerol were 16∶0, 18∶0, 22∶5ω3 and 22∶6ω3. Alkyldiacylglycerol was particularly rich in docosahexaenoic acid 22∶6ω3) representing 30% of the total fatty acids. The alcohols of wax ester were all saturated with C₂₀–C₂₉ carbon chains. The deacylated products derived from alkyldiacylglycerols were identified as hexadecyl, octadecyl and octadec-9′-enyl glycerol ethers.     

Mass spectrometric analysis of the fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts

The fatty acids and nonsaponifiable lipids ofEimeria tenella oocysts were analyzed by gas liquid chromatography and combined gas liquid chromatographymass spectrometry. The fatty acids detected were identified as C_14∶0, C_16∶0, C_16∶1, C_18∶0, C_18∶1, and C_18∶2. Though the wt of the fatty acid fraction decreased during sporulation from 91 μg per 10⁶ oocysts to 47 μg per 10⁶ oocysts, the relative amounts of these fatty acids did not change appreciably. The nonsaponifiable lipids ofE. tenella consisted of cholesterol and unbranched primary alcohols of 22, 24, 26, 28, 30, and 32 carbons. Mass fragmentography demonstrated that each species of alcohol consisted of saturated and monounsaturated derivatives. Trimethylsilyl ethers of fatty alcohols were found to offer several important advantages over free alcohols for mass spectrometric characterization. Before sporulation, most fatty alcohols were in the oocyst wall. During sporulation, the wt of the nonsaponifiable lipids increased from 16 μg per 10⁶ oocysts of 44 μg per 10⁶ oocysts due largely to synthesis of C₂₄ and C₂₆ alcohols. The newly synthesized fatty alcohols were not deposited in the oocyst wall.     

Formation of a thiamine disulfide complex with fatty acid: Mechanism of formation of the complex

The formation of complexes between thiamine disulfide (TDS) orO-acetyl thiamine disulfide (O-acetyl TDS) and fatty acid or fatty acid methyl ester in methanol has been studied by fluorescence quenching and¹³C NMR relaxation (T₁) measurements. The association constants (K-values) of TDS andO-acetyl TDS with fatty acids (from 11∶0 to 18∶0, and 18∶1, 18∶2, 18∶3 and 20∶4) and fatty acid methyl esters have been determined. These values do not depend on either the number of carbon atoms or the degree of unsaturation of the fatty acid. The K-values of TDS andO-acetyl TDS with fatty acid were 7.8 M⁻¹ and 5.1 M⁻¹, respectively. The K-values of TDS andO-acetyl TDS with fatty acid methyl ester were very small. These results show that the-OH moiety in TDS and the-COOH moiety in the fatty acid are necessary for formation of the complex     

Linear, steroidal, and triterpene esters, and steryl glycosides from Festuca argentina

Ester waxes and steryl glycosides of the grass Festuca argentina were studied. Saponification of the waxes from the petroleum ether extract led to n-hexacosanol as the major single linear alcohol, along with pentacyclic triterpenols, such as β-amyrin, germanicol, isobaurenol, lupeol, hopenol-a and hopeol, and low amounts of sterols, such as cholesterol, campesterol, stigmasterol, sitosterol and dihydrositosterol, identified by gas chromatography/mass spectrometry (GC/MS). Fatty acids were identified as methyl esters as C_12∶0, C_14∶0, C_16∶0, C_18∶0, C_18∶2, and C_20∶0. The occurrence of a wide chainlength range of fatty acids and a single linear alcohol closely matched for other reports on the tribe Festuceae. On the contrary, pentacyclic triterpenols with a variety of skeletons, especially isobauerenol, are not usual as esters of fatty acids in the Gramineae. Low amounts of steryl glycosides were also obtained from the methylene chloride percolate of the methanol extract. Upon acetylation followed by hydrolysis, aglycones were identified by capillary gas-liquid chromatography (GLC) and GC/MS. As Δ⁷-cholesterol, campesterol, stigmasterol, sitosterol, dihydrositosterol, and the sugars as glucose, xylose, and arabinose by GLC of the respective alditol acetates. This is the first report on the linear, steryl, and triterpenyl esters of F. argentina. It is noteworthy that Δ⁷-steryl glycosides are rare, and steryl monoarabinosides have not been proviously reported on the family Gramineae.     

Fatty acids in the lipids ofDrosophila heads: Effects of visual mutants,carotenoid deprivation and dietary fatty acids

Lipids ofDrosophila heads were extracted and separated by high-performance thin-layer chromatography. Fatty acid compositions of major phospholipids as well as of triglycerides were analyzed by gas-liquid chromatography. Proportions of the major fatty acids (14∶0, 16∶0, 16∶1, 18∶0, 18∶1, 18∶2, 18∶3) varied depending on the lipid analyzed. Docosahexaenoic acid (22∶6), common in vertebrate photoreceptors and brain, and arachidonic acid (20∶4), a precursor of eicosanoids, were lacking. A comparison of the fatty acid composition of the dietvs. the head suggested thatDrosophila can desaturete but may not be able to elongate fatty acid carbon chains. Fatty acid analyses were carried out after the following visual system alterations: i) the transduction mutant whereno receptorpotential results from a deficit in phospholipase C; ii) an allele ofeyes absent; iii) the mutantouterrhabdomeresabsent which lacks visual pigment and rhabdomeres in the predominant type of compound eye receptor, rhabdomeres 1 through 6; and iv) carotenoid deprivation which reduces opsin and rhabdomere size. We also evaluated aging by comparing newly-emergedvs. aged wild-type flies. Alterations in fatty acid composition based on some of these manipulations were found. Based on comparisons between flies reared on media differing in C₁₆ and C₁₈, there is an indication that diet readily affects tissue fatty acid composition.     

Unsaturated fatty acids of mycobacteria

The double bond locations have been determined for the mono-unsaturated fatty acids, C₁₄ to C₂₆ ofM. smegmatis andM. bovis BCG. The 14∶1 and 16∶1 fatty acids fromM. smegmatis are principally Δ¹⁰, while the 17∶1, 18∶1 and 19∶1 fatty acids from both organisms are Δ⁹. In the case ofM. smegmatis, the 20∶1, 22∶1 and 24∶1 fatty acids are principally Δ¹¹, Δ¹³ and Δ¹⁵, respectively, while the 22∶1, 24∶1 and 26∶1 fatty acids of BCG are principally Δ¹³, Δ¹⁵ and Δ¹⁷, respectively.     

Fatty acid metabolism in marine fish: Low activity of fatty acyl Δ5 desaturation in gilthead sea bream (Sparus aurata) cells

Marine fish have an absolute dietary requirement for C₂₀ and C₂₂ highly unsaturated fatty acids. Previous studies using cultured cell lines indicated that underlying this requirement in marine fish was either a deficiency in fatty acyl Δ5 desaturase or C_18–20 elongase activity. Recent research in turbot cells found low C_18–20 elongase but high Δ5 desaturase activity. In the present study, the fatty acid desaturase/elongase pathway was investigated in a cell line (SAF-1) from another carnivorous marine fish, sea bream. The metabolic conversions of a range of radiolabeled polyunsaturated fatty acids that comprised the direct substrates for Δ6 desaturase ([1-¹⁴C]18∶2n−6 and [1-¹⁴C]18∶3n−3), C_18–20 elongase ([U-¹⁴C]18∶4n−3), Δ5 desaturase ([1-¹⁴C]20∶3n−6 and [1-¹⁴C]20∶5n−3), and C_20–22 elongase ([1-¹⁴C]20∶4n−6 and [1-¹⁴C]20∶5n−3) were utilized. The results showed that fatty acyl Δ6 desaturase in SAF-1 cells was highly active and that C_18–20 elongase and C_20–22 elongase activities were substantial. A deficiency in the desaturation/elongation pathway was clearly identified at the level of the fatty acyl Δ5 desaturase, which was very low, particularly with 20∶4n−3 as substrate. In comparison, the apparent activities of Δ6 desaturase, C_18–20 elongase, and C_20–22 elongase were approximately 94-, 27-, and 16-fold greater than that for Δ5 desaturase toward their respective n−3 polyunsaturated fatty acid substrates. The evidence obtained in the SAF-1 cell line is consistent with the dietary requirement for C₂₀ and C₂₂ highly unsaturated fatty acids in the marine fish the sea bream, being primarily due to a deficiency in fatty acid Δ5 desaturase activity.     

Cuticular lipids of insects: V. Cuticular wax esters of secondary alcohols from the grasshoppersMelanoplus packardii andMelanoplus sanguinipes

Wax esters of secondary alcohols constitute 18–20% of the cuticular lipid extract ofMelanoplus packardii and 26–31% of the cuticular lipids ofMelanoplus sanguinipes. The total number of carbons in the wax esters range from 37–54 with 41 predominating in both species. The fatty acids ofM. packardii wax esters are 16∶0, 18∶0, 14∶0, 20∶0 and 12∶0 in decreasing quantity. The fatty acids ofM. sanguinipes wax esters are 18∶0, 20∶0, 16∶0 22∶0, 14∶0, 19∶0 and 17∶0 in decreasing quantity. The secondary alcohols from the wax esters ofM. packardii are C₂₅, C₂₃ and C₂₇ in decreasing quantity, and the secondary alcohols of theM. sanguinipes are C₂₃, C₂₅, C₂₁, C₂₇, C₂₄, C₂₂ and C₂₆ in decreasing quantity. Each secondary alcohol consists of two to four isomers with the hydroxyl group located near the center of the chain. Montana Agriculture Experiment Station, Journal Series No. 332.     

Sterols,aliphatic hydrocarbons,and fatty acids of a nonphotosynthetic diatom,Nitzschia alba

The unsaponifiable lipids and total fatty acids of a nonphotosynthetic diatom,Nitzschia alba, have been examined. The major fatty acids were found to be 14∶0, 16∶0, 18∶1, and 20∶5; small amounts of 15∶0, 16∶1, 18∶0, 18∶2, 18∶3, and 20∶4 acids also were present. The unsaponifiable lipids consisted mostly of sterols, with only traces (<0.1%) of hydrocarbons (chiefly C₁₆, C₁₈, and C₂₈ normal olefins). The sterols contained brassicasterol (major) and clionasterol (minor), as well as traces of an unidentified sterol; clionasterol was present only in glycosidically bound form.     

Polyunsaturated fatty glyceride syntheses by microbial lipases

The degree of glyceride syntheses by lipase TOYO (Chromobacterium viscosum) and lipase OF (Candida cylindracea) using individual free fatty acids C_18∶1, C_18∶2, C_18∶3, C_18∶4, C_20∶4, C_20∶5 and C_22∶6 were compared. Lipase TOYO incorporated each of the fatty acids into glycerol at levels of greater than 89%. Lipase OF incorporated most of the fatty acids at levels above 70% (docosahexaenoic acid incorporation was 63%). It was concluded that these two lipases are feasible for producing glycerides from unsaturated fatty acids.     

1-O-alkyl-2,3-diacylglycerols in the skin surface lipids of the hairless mouse

A neutral lipid class was isolated by thin-layer chromatography from the skin surface lipids of the hairless mouse. The fraction migrated faster than triglycerides and had a migration rate similar to that of diacyl alkanediols (diester wax). Upon deacylation, however, the long-chain diols were identified as 1-alkylglycerol ethers based on their chromatographic properties and on the mass spectra of their nicotinylidene derivatives. Thus, the skin lipid fraction was identified as 1-O-alkyl-diacylglycerol. The alkyl moieties were all saturated and even-numbered and ranged in chainlength from C₁₆ to C₂₂ with 1-O-hexadecylglycerol amounting to 34% of the total glycerol ether moieties. The fatty acids derived from this lipid fraction were mostly monoenoic with chainlengths ranging from C₁₆ to C₂₄. The major acyl component was eicosenoic acid (20∶1) representing 61% of the total fatty acids.     

Lipid composition of cultured endothelial cells in relation to their growth

Human endothelial cells in culture were examined in different growth conditions. The human endothelial cell line, EA.hy 926 cell line, was used and cells were studied either in exponential growth phase, at confluence, or growth-arrested by serum deprivation. Phospholipids were separated and analyzed by high-performance thin-layer chromatography, and their fatty acids were quantified by gas-liquid chromatography. No significant differences in the phospholipid distributions were found between exponentially growing and confluent endothelial cells in which phosphatidylcholine (PC) represented the major phospholipid. In comparison, serum-deprived cells exhibited higher proportions of sphingomyelin and lower content of PC. We also found that among the total lipids, cholesterol level for dividing endothelial cells was lower than for cells growth-arrested either by serum deprivation or by contact inhibition at confluence. The global fatty acid distribution was not affected by the growth conditions. Thus, oleate (18∶1n−9 and 18∶1n-7), palmitate (C_16∶0), and stearate (C_18∶0) were the main components of endothelial cell membranes. However, the fatty acid distributions obtained from each phospholipid species differed with the growth status. Altogether, the data indicated that subtle modulations of endothelial cell metabolism appear upon cell growth. The resulting membrane-dependent cellular functions such as cholesterol transport and receptor activities can be expected to be relevant for lipid trafficking within the vessel wall in vitro and in vivo.     

Molecular speciation of fish sperm phospholipids: Large amounts of dipolyunsaturated phosphatidylserine

The molecular species compositions of the main diacyl phosphoglyceride classes and ether-linked subclasses from sperm of three species of fish, sea bass Dicentrarchus labrax, Atlantic salmon Salmo salar and Chinook salmon Onchorhynchus tsawytscha, were determined. The phospholipids from sperm were highly unsaturated, dipolyunsaturated fatty acid (diPUFA) molecular species comprised 64.6 to 71.8% of phosphatidylserine (PS), 10.1 to 17.4% of phosphatidylethanolamine (PE), and 3.3 to 10.1% of phosphatidylcholine (PC). In sea bass sperm, di22∶6n-3 phospholipid was the predominant diPUFA molecular species, but in both salmon species 22∶5n-3/22∶6n-3 was also a major constituent of PS. Phospholipids containing 22∶6n-3 dominated in sea bass sperm with 16∶0/22∶6n-3 as a major component of PC and PE, and 18∶0/22∶6n-3 of PE and PS in addition to di22∶6n-3 in the latter two classes. In contrast, both salmon species contained much more 20∶5n-3 and less 22∶6n-3 so that saturated/20∶5n-3 and monounsaturated/20∶5n-3 molecular species were more abundant than the corresponding molecules containing 22∶6n-3. Ether-linked lipids comprised 11.3–36.3% of choline and ethanolamine phosphoglycerides in each fish species. Molecular species containing 22∶6n-3 were the major components of 1-O-alkyl-2-acyl-glycerophosphocholine, especially 16∶0a/22∶6n-3 in sea bass and 18∶1a/∶6n-3 in the two salmon species, while in 1-O-alk-1′-enyl-2-acyl-glycerophosphoethanolamine, 16∶0a/22∶6n-3 was the major component in both salmon and 18∶0a/22∶6n-3 in sea bass with 18∶1a/22∶6n-3 abundant in all three species. In Atlantic salmon 1-O-alkyl-2-acylglycerophosphoethanolamine comprised 24.6% of ethanolamine glycerophospholipids which were predominantly 16∶0a/22∶6n-3 and 18∶1a/22∶6n-3. Phosphatidylinositol from sperm was dominated by stearoyl/C₂₀ PUFA molecular species, in sea bass overwhelmingly 18∶0/20∶4n-6, while in both salmon species 18∶0/20∶4n-6 and 18∶0/20∶5n-3 were equally abundant.     

The lipids of the oriental hornet,Vespa orientalis F.

Analysis of the hornet’s hemolymph revealed the presence of C₁₆ and C₁₈ fatty acids (70%), which were accompanied by minor quantities (ranging from 0.1% to 0.6%) of the following acids: C_10∶0, C_11∶0, C_12∶0, C_13∶0, C_14∶0, C_15∶0, C_16∶0, and C_17∶0. The hemolymph of the queen larvae contained more C_18∶1 than the hemolymph of the worker larvae, and the percentage of C_16∶1 was higher in the fat body and the midgut than in the hemolymph. The significance of these results is discussed.     

The effect of lyophilization on the solvent extraction of lipid classes,fatty acids and sterols from the oysterCrassostrea gigas

The lipid class compositions of adult Pacific oysters [Crassostrea gigas (Thunberg)] were examined using latroscan thin-layer chromatography/flame-ionization detection (TLC/FID), and fatty acid compositions determined by capillary gas chromatography and gas chromatography/mass spectrometry (GC/MS). The fatty acid methyl esters were separated using argentation TLC and also analyzed as their 4,4-dimethyloxazoline derivatives using GC/MS. Major esterified fatty acids inC. gigas were 16∶0, 20∶5n−3, and 22∶6n−3. C₂₀ and C₂₂ nonmethylene interrupted (NMI) fatty acids comprised 4.5 to 5.9% of the total fatty acids. The NMI trienoic fatty acid 22∶3(7,13,16) was also identified. Very little difference was found in the proportions of the various lipid classes, fatty acids or sterols between samples of adult oysters of two different sizes. However, significant differences in some of the lipid components were evident according to the method of sample preparation used prior to lipid extraction with solvents. Lyophilization (freeze drying) of samples led to a significant reduction in the amounts of triacylglycerols (TG) extracted by solvents in two separate experiments (7.0 and 52.5% extracted). Extracts from lyophilized samples had less 16∶0, C₁₈ unsaturated fatty acids, and 24-ethylcholest-5-en-3β-ol, while C₂₀ and C₂₂ unsaturated fatty acids comprised a higher proportion of the total fatty acids. There was no significant change in the amounts of polar lipids, total sterols, free fatty acids or hydrocarbons observed in extracts from lyophilized samples relative to extracts from nonlyophilized samples. Addition of water to the freezedried samples prior to lipid extraction greatly improved lipid yields and resulted in most of the TG being extracted.     

1-O-alk-1′-enyl-2-acyl-glycerophosphoethanolamine content and molecular species composition in fish brain

Ethanolamine glycerophospholipids from the brains of both trout and cod comprised 36–38% of 1-O-alk-1′-enyl-2-acyl-glycerophosphoethanolamine (GPE) determined using two methods. In 1-O-alk-1′-enyl-2-acyl-GPE from trout brain, the main molecular species were 18∶1a/18∶1, 18∶0a/18∶1 and 16∶0a/18∶1, which totalled 63.3%, while polyunsaturated fatty acid (PUFA) containing species totalled only 18.2%. 1-O-Alk-1′-enyl-2-acyl-GPE from cod brain was much more unsaturated with PUFA containing species totalling 52.6%, of which 18∶0a/20∶5n−3, 18∶1a/20∶5n−3 and 18∶1a/22∶6n−3 were predominant. In cod 18∶1a/18∶1, 18∶0a/18∶1 and 16∶0a/18∶1 were the only other species present at over 5% each, totalling 31.8%. In both cod and trout, small amounts of species containing 22∶4n−6 were found. The results of this and earlier studies indicate that there is considerable specificity of composition at the level of molecular species between different lipid classes and subclasses. Molecular species of 1-O-alk-1′-enyl-2-acyl-GPE are abbreviated as follows:e.g., 16∶0a/18∶1 GPE is 1-O-hexadec-1′-enyl-2-oleoyl-sn-glycero-3-phosphoethanolamine. The corresponding diacyl species, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine, is abbreviated as 16∶0/18∶1.     

Molecular species composition of glycerophospholipids from white matter of human brain

The molecular species composition of the major glycerophospholipids from white matter of human brain were determined by high-performance liquid chromatography of the 3,5-dinitrobenzoyl derivatives of the corresponding diradylglycerols. In phosphatidylcholine (PC) and phosphatidylserine (PS), molecular species containing only saturated fatty acids (SFA) and monounsaturated fatty acids (MUFA) comprised 85.7 and 82.4% of the respective totals, with 18∶0/18∶1 predominant in PS and 16∶0/18∶1 in PC. These molecular species were also abundant in phosphatidylethanolamine (PE), but in this phospholipid species containing polyunsaturated fatty acids (PUFA), largely 18∶0/22∶6n−3 and 18∶0/20∶4n−6, accounted for over half the total; 18∶1/18∶1 was also abundant in PE. In contrast, 1-O-alk-1′-enyl-2-acylsn-glycero-3-phosphoethanolamine (GPE) had much more SFA- and MUFA-containing species, predominantly 16∶0a/18∶1, 18∶0a/18∶1 and 18∶1a/18∶1, with low amounts of species containing 20∶4n−6 and 22∶6n−3. In alkenylacyl GPE, 22∶4n−6 was the major PUFA and 16∶0a/22∶4n−6 and 18∶1a/22∶4n−6 the main PUFA-containing species. There was six times more 22∶6n−3, twice as much 20∶4n−6 and half the amount of 22∶4n−6 in PE as compared to alkenylacyl GPE. Molecular species are abbreviated as follows:e.g., 16∶0/18∶1 PE is 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine; the corresponding alkenylacyl species, 1-O-hexadec-1′-enyl-2-oleoyl-sn-glycero-3-phosphoethanolamine is 16∶0a/18∶1.     

Phospholipid composition of the granular amebocyte from the horseshoe crab, Limulus polyphemus

The phospholipid composition was determined for the amebocyte of the primitive arthropod Limulus polyphemus. The total fatty acid composition of the cells' lipids was analyzed by gas chromatography/mass spectrometry (GC/MS) of fatty acid methyl esters (FAME). The FAME analysis revealed high levels of 20-carbon polyunsaturated fatty acids (PUFA), especially arachidonic (20∶4n-6) and eicosapentaenoic (20∶5n-3) acids. Almost 20% of the total lipid profile was comprised of dimethyl acetals of 16- to 20-carbon chain lengths, indicative of plasmalogens in the phospholipid pool. Phospholipids, analyzed by high-pressure liquid chromatography, included phosphatidylethanolamine (PE), phosphatidylcholine (PC), phosphatidylserine (PS), phosphatidylinositol (PI), sphingomyelin (SPH), and cardiolipin (CL). PE and PC levels predominated at 42.2 and 36.3%, respectively. Smaller amounts of PS (9.0%) and PI (6.2%) were present, as well as low levels of SPH (4.6%), CL (1.6%), and trace amounts of lysophosphatidylcholine. The major phospholipid species, PE, PC, PS and PI, were collected and their molecular species were examined by electrospray-ionization mass spectrometry. The molecular species within the phospholipid classes reflected the high levels of PUFA seen in the total lipid profile. PI was mainly composed of 18∶0a/20∶4. Over half of the PS consisted of 18∶0a/18∶1 and 18∶0a/20∶4. The major PE species were 20∶1p/20∶5, 20∶1p/20∶4, 18∶0p/20∶5, and 18∶0p/20∶4. PC had the largest distribution of molecular species, and its most abundant species were 16∶0e/20∶5, 16∶0e/20∶4, and 16∶0p/20∶4. The presence of 16∶0e/20∶4 is the first documentation of a specific precursor to platelet-activating factor in an invertebrate hemocyte. Note: at the sn-1 position: [a=1=O-acyl, e=1-O-alkylether, and p=1-O-alk-1′-enyl (plasmalogen)].     

Natural abundance stable carbon isotope evidence for the routing and <Emphasis Type="Italic">de novo</Emphasis> synthesis of bone FA and cholesterol

This research reported in this paper investigated the relationship between diet and bone FA and cholesterol in rats raised on a variety of isotopically controlled diets comprising 20% C₃ or C₄ protein (casein) and C₃ and/or C₄ nonprotein or energy (sucrose, starch, and oil) macronutrients. Compoundspecific stable carbon isotope analysis (δ¹³C) was performed on the FA (16∶0, 18∶0, 18∶1, and 18∶2) and cholesterol isolated from the diet (n=4) and bone (n=8) of these animals. The dietary signals reflected by the bone lipids were investigated using linear regression analysis. δ¹³C values of bone cholesterol and stearic (18∶0) acid were shown to reflect whole-diet δ¹³C values. whereas the δ¹³C values of bone palmitic (16∶0), oleic (18∶1), and linoleic (18∶2) acids reflected dietary FA δ¹³C values. Dietary signal differences are a result of the balance between direct incorporation (or routing) and de novo synthesis of each of these bone lipids. Estimates of the degree of routing of these bone lipids gleaned from correlations between Δ¹³C _dlipid-wdiet (δ¹³C_{diet lipid}-δ¹³C_{whole diet}) spacings and Δ¹³C _blipid-wdiet (δ¹³C_{bone lipid}-δ¹³C_{whole diet} fractionations demonstrated that the extent of routing, where 18∶2>16∶0>18∶1>18∶0>cholesterol, reflected the relative abundances of these lipids in the diet. These findings provide the basis for more accurate insights into diet when the δ¹³C analysis of bone fatty FA or cholesterol is employed.     

1-O-alk-1′-enyl-2-acyl and 1-O-alkyl-2-acyl glycerophospholipids in white muscle of bonitoEuthynnus pelamis (Linnaeus)

The existence of ether-linked phospholipids, including 1-O-alk-1′-enyl-2-acyl and 1-O-alkyl-2-acyl-sn-glycero-3-phosphocholines and ethanolamines in bonitoEuthynnus pelamis (Linnaeus) white muscle, was investigated by gas chromatography and gas chromatography-mass spectrometry. Chemical ionization (iso-butane) mass spectrometry of trimethylsilyl ethers derived from the corresponding ether-linked glycerophospholipids proved effective not only for determining molecular weights but also for structural identification based on the ions [M−R]⁺, [M−RO]⁺ and [M+1]⁺. 1-O-Alk-1′-enyl-2-acyl-sn-glycero-3-phosphocholine and ethanolamine accounted for 3.0–6.0% and 3.6–7.6% of the total glycerophospholipids, respectively. 1-O-Alkyl-2-acyl-sn-glycero-3-phosphocholine and ethanolamine were also determined for one fish and accounted for 1.4% and 0.6% of the total glycerophospholipids, respectively. The predominant long chains in thesn-1 position of the glycerol moieties were 16∶0, 18∶0 and 18∶1 in the case of the alkenylacyl and alkylacyl components. Fatty acid distribution of individual glycerophospholipids was also determined.