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1.
Ether lipid content and fatty acid distribution in rabbit polymorphonuclear neutrophil phospholipids
This study was undertaken to determine if rabbit neutrophils contain sufficient ether-linked precursor for the synthesis of
1-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine (platelet activatin factor) by a deacylation-reacylation pathway. The phospholipids from rabbit
peritoneal polymorphonuclear neutrophils were purified and quantitated, and the choline-containing and ethanolamine-containing
phosphoglycerides were analyzed for ether lipid content. Choline-containing phosphoglycerides (37%), ethanolamine-containing
phosphoglycerides (30%), and sphingomyelin (28%) were the predominant phospholipid classes, with smaller amounts of phosphatidylserine
(5%) and phosphatidylinositol (<1%). The choline-linked fraction contained high amounts of 1-O-alkyl-2-acyl-(46%) and 1,2-diacyl-sn-glycero-3-phosphocholine (54%), with a trace of the 1-O-alk-1′-enyl-2-acyl species. The ethanolamine-linked fraction contained high amounts of 1-O-alk-1′-enyl-2-acyl-(63%) and 1,2-diacyl-sn-glycero-3-phosphoethanolamine (34%), and a low quantity of the 1-O-alkyl-2-acyl species (3%). The predominant 1-O-alkyl ether chains found in thesn-1 position of the choline-linked fraction were 16∶0 (35%), 18∶0 (14%), 18∶1 (26%), 20∶0 (16%), and 22∶0 (9%). The major 1-O-alk-1′-enyl ether chains found in thesn-1 position of the ethanolamine-linked fraction were 14∶0 (13%), 16∶0 (44%), 18∶0 (27%), 18∶1 (12%) and 18∶2 (3%). The major
acyl groups in thesn-1 position of 1,2-diacyl-sn-glycero-3-phosphocholine and 1,2-diacyl-sn-glycero-3-phosphoethanolamine were 16∶0, 18∶0 and 18∶1. The most abundant acyl group in thesn-2 position of all classes of choline- and ethanolamine-linked phosphoglycerides was 18⩺2. Although this work does not define
the biosynthetic pathway for platelet activating factor, it does show that there is ample precursor present to support its
synthesis by a deacylation-reacylation pathway. 相似文献
2.
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. 相似文献
3.
The fatty chain compositions of 1-O-alk-1′-enyl-2-acyl, 1-0-alkyl-2-acyl, and 1,2-diacyl glycerophospholipids of the Japanese oysterCrassostrea gigas (Thunberg) were investigated. Major fatty chains in thesn-1 position of 1-alk-1′-enyl-2-acyl ethanolamine phospholipids (EPL) were 18∶0 (64.7%) and 20∶1 (11.1%). Majorsn-1 chains of alkenylacyl choline phospholipids (CPL) were 18∶0 (63.3%) and 16∶0 (22.2%). In the case of 1-alkyl-2-acyl EPL,
the predominant fatty chains in thesn-1 position were 18∶0 (51.5%), 16∶0 (16.0%) and 20∶1 (12.5%); in the case of 1-alkyl-2-acyl CPL, the majorsn-1 chains were 16∶0 (44.0%) and 14∶0 (23.4%). Saturated fatty chains were predominant in both EPL and CPL. Prominent fatty
acids in thesn-2 position of the alkenylacyl EPL were 22∶6n−3 (29.0%), 20∶5n−3 (19.0%) and 22∶2 NMID (non-methylene interrupted dienes,
16.6%) contributing to about 65% of the total fatty acids, while alkenylacyl CPL was rich in the saturated acids 16∶0 (32.0%)
and 18∶0 (9.2%). In the alkylacyl EPL, 16∶0, 18∶1n−9, 18∶0 and 16∶1n−7 were prominentsn-2 fatty acids and accounted for 30.6%, 10.0%, 9.8%, and 8.3%, respectively. Polyunsaturated fatty acids were detected, but
were present at extremely low percentages. Majorsn-2 fatty acids in alkylacyl CPL were 16∶0 (25.4%), 22∶6n−3 (16.0%) and 20∶5n−3 (8.4%). The major fatty acids of diacyl EPL
were 20∶5n−3 (22.3%), 16∶0 (17.9%), and 18∶0 (16.1%), and those of diacyl CPL were 16∶0 (30.4%), 20∶5n−3 (17.6%) and 18∶1n−7
(7.4%). 相似文献
4.
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. 相似文献
5.
In mammalian systems, platelet-activating factor, 1-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine, (PAF) is rapidly inactivated by a deacetylation/reacylation system that produces 1-O-alkyl-2-acyl-sn-glycero-3-phosphocholine which is highly enriched in arachidonic acid. There is some evidence that n−3 fatty acids may have
an impact on this system in humans but the nature of this impact is unclear. In rainbow trout, n−3 fatty acids are known to
be essential dietary components which are derived through the food chain. Substantial quantities of n−3 fatty acids are found
in trout membrane phospholipids. We show here that in sharp contrast to mammalian cells, trout cells acylate lyso platelet-activating
factor, alkyl-GPC, 1-O-alkyl-2-lyso-sn-glycero-3-phosphocholine, (lyso-PAF) with a high degree of specificity for n−3 fatty acids. When [3H]lysoPAF was incubated with these cells, only three molecular species of alkylacylglycerophosphocholine were produced, and
92% contained n−3 fatty acids. Since isolated membranes yielded similar results, it appears that the acylation proceedsvia a coenzyme A-independent transacylase as found in mammalian systems. 相似文献
6.
Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl-, and 1,2-diacyl-sn-glycero-3-phosphoethanolamine (EPL) andsn-glycero-3-phosphocholine (CPL) of Japanese oysterCrassostrea gigas were analyzed by selectedion monitoring gas chromatography/mass spectrometry using electron impact ionization. The characteristic
fragment ions, [RCH=CH+56]+ due to the alkenyl residue in thesn-1 position and [RCO+74]+ due to the acyl residue in thesn-2 position of alkenylacylglycerols, [R+130]+ due to the alkyl residue in thesn-1 position and [RCO+74]+ due to the acyl residue in thesn-2 position of alkylacylglycerols, [RCO+74]+ due to the acyl residues in thesn-1 and/orsn-2 positions of diacylglycerols, and [M−57]+ being indicative of the corresponding molecular weight, were used for structural assignments.
For alkenylacyl EPL and CPL, 19 and 16 molecular species were determined, respectively. Two molecular species, 18∶0alkenyl-22∶6n−3
and 18∶0-alkenyl-22∶2-non-methylene interrupted diene (NMID), amounted to 53.2% and 47.9%, respectively. The alkylacyl EPL
and CPL consisted of 16 and 20 molecular species, respectively, and the prominent components were 18∶0alkyl-22∶2NMID, 20∶1alkyl-20∶1n−11
(27.4%) and 20∶1alkyl-20∶2NMID (16.3%) in the former, and 16∶0alkyl-20∶5n−3 (23.0%) and 16∶0alkyl-22∶6n−3 (21.6%) in the latter.
For the diacyl EPL and CPL, 14 and 51 molecular species were determined, respectively. The major molecular species were 18∶0–20∶5n−3
(37.4%), 16∶0–20∶5n−3 (14.2%) and 18∶1n−7–22∶2NMID (13.2%) in the former, and 16∶0–20∶5n−3 (33.4%) and 16∶0–22∶6n−3 (22.3%)
in the latter. It was found that there were significant differences in the molecular species between the alkylacyl and diacyl
EPL and the alkylacyl and diacyl CPL; the number of molecular species was larger in CPL than in EPL, while the number of total
carbons and double bonds of the major molecular species were larger in the EPL than in the CPL. Alkenylacyl EPL were similar
to alkenylacyl CPL in molecular species composition. 相似文献
7.
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. 相似文献
8.
The contents and compositions of the 1-O-alk-1′-enyl-2-acyl, 1-O-alkyl-2-acyl, and 1,2-diacyl glycerophospholipids in the muscle and viscera of the ascidianHalocynthia roretzi, and of the gonad of the sea urchinStrongylocentrotus intermedius, which are eaten to some extent in Alaska and in Asia, were analyzed by gas-liquid chromatography. 1-O-Alk-1′-enyl-2-acyl glycerophospholipids were found in all of the samples, accounting for 64.4–69.0% of the ethanolamine glycerophospholipid
(EPL). By contrast, the levels of the 1-O-Alk-1′-enyl-2-acyl choline glycerophospholipids (CPL) were low (3.1–5.7%). CPL was rich in the 1-O-alkyl-2-acyl subclass amounting to 12.5–23.9% in the ascidian sample. The level of CPL in the sea urchin gonad was extremely
high, amounting to 46.1%. The most prominent alkyl chains in thesn-1 position of CPL from the ascidian muscle were 16∶0 (44.6%), 18∶1 (26.5%), and 18∶0 (10.7%), and of CPL from the sea urchin
gonad were 18∶0 (36.2%), 16∶0 (33.0%), and 18∶1 (17.8%). Unusually high levels of odd-numbered alkyl chains, e.g., 19∶0 andanteiso 17∶0, were detected in the CPL of all samples. The prominent alkenyl chains of EPL were 18∶0 (69.4%), 16∶0 (10.0%), and 18∶1
(8.54%) (not counting the vinyl double bond) for the sea urchin gonad. Relatively high levels of 20∶1 alkenyl chains were
also present. The glycerolsn-2 positions contained high proportions of polyunsaturated fatty acids. Thus, 20∶5n-3 (43.6%) and 22∶6n-3 (20.1%) were most
abundant in the alkylacyl CPL from the ascidian muscle and 20∶5n-3 (54.9%) and 20∶4n-6 (30.1%) in alkylacyl CPL from the sea
urchin gonad. Despite a possible interconversion of the alkyl and alkenyl chains of each class of the ether phospholipids,
they showed few features in common. 相似文献
9.
We studied changes in lipid composition of human promyelocytic leukemia cells (HL-60) on differentiation to the macrophage/monocytic
lineage by treatment with the phorbol ester, 12-O-tetradecanoyl-phorbol-13-acetate. Differentiation was accompanied by: (i)
a decrease in the level of phospholipids; (ii) a greater amount of triacylglycerols; (iii) an increase in 1-alk-1′-enyl-2-acyl-
and 1-alkyl-2-acyl-sn-glycero-3-phosphoethanolamine and a decrease in 1-alkyl-2-acyl-sn-glycero-3-phosphocholine; and (iv) an increase in the level of arachidonic acid in ethanolamine phospholipids. The increased
levels of ether-linked lipids and of arachidonic acid in ethanolamine phospholipids are consistent with an enhanced biosynthesis
of platelet-activating factor and eicosanoids, which are particularly important in the macrophage function. 相似文献
10.
This study examined the effects of n−3 and n−6 polyunsaturated fatty acid alimentation on murine peritoneal macrophage phospholipids.
Mice were fed complete diets supplemented with either corn oil predominantly containing 18∶2n−6, borage oil containing 18∶2n−6
and 18∶3n−6, fish/corn oil mixture containing 18∶2n−6, 20∶5n−3 and 22∶6n−3, or fish/borage oil mixture containing 18∶2n−6,
18∶3n−6, 20∶5n−3 and 22∶6n−3. After two weeks, the fatty acid levels of glycerophosphoserines (GPS), glycerophosphoinositols
(GPI), sphingomyelin (SPH), and of the glycerophosphocholine (GPC) and glycerophosphoethanolamine (GPE) phospholipid subclasses
were determined. We found that mouse peritoneal macrophage GPC contain primarily 1-0-alkyl-2-acyl (range for the dietary groups, 24.6–30.5 mol %) and 1,2-diacyl (63.2–67.2 mol %), and that GPE contains 1-O-alk-1-enyl-2-acyl (40.9–47.4 mol. %) and 1,2-diacyl (44.2–51.2 mol %) subclasses. In general, fish oil feeding increased
macrophage 20∶5n−3, 22∶5n−3 and 22∶6n−3 levels while simultaneously reducing 20∶4n−6 in GPS, GPI, GPE and GPC subclasses except
for 1-O-alk-1′-enyl-2-acyl GPC. Administration of 18∶3n−6 rich diets (borage and fish/borage mixture) resulted in the accumulation
of 20∶3n−6 (2-carbon elongation product of 18∶3n−6) in most phospholipids. In general, the novel combination of dietary 18∶3n−6
and n−3 PUFA produced the highest 20∶3n−6/20∶4n−6 phospholipid fatty acid ratios. This study demonstrates that marked differences
in the responses of macrophage phospholipid classes and subclasses exist following dietary manipulation. The reduction of
20∶4n−6, while simultaneously increasing 30∶3n−6 and n−3 PUFA levels, may be important in relation to the putative beneficial
effects of 20∶3n−6 and fish oil on macrophage eicosanoid and platelet activating factor (PAF) biosynthesis. 相似文献
11.
Previous studies in our laboratory have shown that marine oils, with high levels of eicosapentaenoic (EPA, 20∶5n−3) and docosahexaenoic
acids (DHA, 22∶6n−3), inhibit the growth of CT-26, a murine colon carcinoma cell line, when implanted into the colons of male
BALB/c mice. Anin vitro model was developed to study the incorporation of polyunsaturated fatty acids (PUFA) into CT-26 cells in culture. PUFA-induced
changes in the phospholipid fatty acid composition and the affinity with which different fatty acids enter the various phospholipid
species and subspecies were examined. We found that supplementation of cultured CT-26 cells with either 50 μM linoleic acid
(LIN, 18∶2n−6), arachidonic acid (AA, 20∶4n−6), EPA, or DHA significantly alters the fatty acid composition of CT-26 cells.
Incorporation of these fatty acids resulted in decreased levels of monounsaturated fatty acids, while EPA and DHA also resulted
in lower levels of AA. While significant elongation of both AA and EPA occurred, LIN remained relatively unmodified. Incorporation
of radiolabeled fatty acids into different phospholipid species varied significantly. LIN was incorporated predominantly into
phosphatidylcholine and had a much lower affinity for the ethanolamine phospholipids. DHA had a higher affinity for plasmenylethanolamine
(1-O-alk-1′-enyl-2-acyl-sn-glycero-3-phosphoethanolamine) than the other fatty acids, while EPA had the highest affinity for phosphatidylethanol-amine
(1,2-diacyl-sn-glycero-3-phosphoethanolamine). These results demonstrate that,in vitro, significant differences are seen between the various PUFA in CT-26 cells with respect to metabolism and distribution, and
these may help to explain differences observed with respect to their effects on tumor growth and metastasis in the transplantable
model. 相似文献
12.
M. P. Murari R. Murari S. Parthasarathy C. A. Guy V. V. Kumar B. Malewicz Wolfgang J. Baumann 《Lipids》1990,25(10):606-612
Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain
length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in
the long aliphatic chain. First,rac-1(3)-O-alkylglycerol is prepared by alkylation ofrac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy
group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl
group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation
of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic
displacement of the bromine with trimethylamine givesrac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated
with snake venom phospholipase A2 (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The “unnatural” 3-O-alkyl-2-O-acyl-sn-glycerol-1-phosphocholine enantiomer, which is not susceptible to phospholipase A2 cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates
and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions. 相似文献
13.
Racemic heavy isotope analogs of 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) and 1-O-alkyl-2-O-acetyl-sn-glycero-3-phosphocholine (PAF) were prepared for use as internal standards to facilitate quantitative studies based on mass
spectrometry. Starting from pentadencane-1,15-diol andrac-glycerol-1,2-acetonide, a convergent synthesis of 1-O-[16′-2H3]hexadecyl and 1-O-[18′-2H3]octadecylrac-glycero-3-phosphocholine and their acetyl derivatives is described. Three deuterium atoms were introduced at the terminal
position of the 1-O-alkyl group by displacement of thep-toluensulfonyl group from 1-O-alkyl-15′-p-toluensulfonate and 1-O-alkyl-17′-p-toluensulfonate with [2H3]-methylmagnesium iodide. The 1-O-alkyl-17′-p-toluensulfonate was obtained by reaction of the 1-O-alkyl-15′-p-toluensulfonate with allylmagnesium bromide, followed by reductive ozonolysis and treatment withp-toluenesulfonyl chloride. The hydroxyl group at C-2 was protected by a benzyl group and removed at a late stage in the synthesis.
This provided the corresponding lysoderivatives or allowed preparation of racemic PAF by subsequent acetylation of the free
hydroxy group. The phosphocholine moiety was introduced at glycerol C-3 by reaction with bromoethyldichlorophosphate and trimethylamine.
The synthetic compounds were analyzed by FAB/MS and GC/NICIMS. They were shown to contain less than 0.6% protium impurity. 相似文献
14.
The differences in distribution of geometric isomers of unsaturated PC hydroperoxides generated by free radical oxidation
were compared, as corresponding hydroxy analogs, in heterogeneous liposomes and in a homogeneous methanol solution by using
HPLC with UV detection due to the presence of conjugated dienes. Identification of fractionated peak components was carried
out by GC-MS. When the oxidation of 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine, PC(16∶0/18∶2), was initiated in liposomes by a hydrophilic azo radical initiator, and in a methanol
solution by a hydrophobic azo radical initiator, there was no significant difference in the relative percentages of 1-palmitoyl-2-(9-hydroxy-trans-10,trans-12-octadecadienoyl)-sn-glycero-3-phosphocholine (9-t,t-OH PC) and 1-palmitoyl-2-(13-hydroxy-trans-9,trans-11-octadecadienoyl)-sn-glycero-3-phosphocholine (13-t,t-OH PC) between the PC oxidized in liposomes and in the methanol solution. For the oxidation of 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine, PC(16∶0/20∶4), the relative percentage of 1-palmitoyl-2-(5-hydroxy-trans-6,cis-8,11,14-eicosatetraenoyl)-sn-glycero-3-phosphocholine (5-OH PC) was significantly higher (P<0.01) than that of 1-palmitoyl-2-(15-hydroxy-cis-5,8,11,trans-13-eicosatetraenoyl)-sn-glycero-3-phosphocholine (15-OH PC) in liposomes. For the homogeneous methanol solution of PC(16∶0/20∶4), the relative percentage
of 5-OH PC was close to that of 15-OH PC. For the PC(16∶0/20∶4) oxidized in bulk with added pentamethylchromanol, the individual
amount of 15-OH PC, 1-palmitoyl-2-(11-hydroxy-cis-5,8trans-12,cis-14-eicosatetraenoyl)-sn-glycero-3-phosphocholine (11-OH PC), 1-palmitoyl-2-(12-hydroxy-cis-5,8,trans-10,cis-14-eicosatetraenoyl)-sn-glycero-3-phosphocholine (12-OH PC), 1-palmitoyl-2-(8-hydroxy-cis-5,trans-9,cis-11,14-eicosatetraenoyl)-sn-glycero-3-phosphocholine (8-OH PC), 1-palmitoyl-2-(9-hydroxy-cis-5,trans-7,cis-11,14-eicosatetraenoyl)-sn-glycero-3-phosphocholine (9-OH PC), and 5-OH PC were close to each other compared to the corresponding values in liposomes
and in methanol solution. The results obtained by gel permeation chromatography of the PC liposomes containing hydrophilic
2,2′-azobis-2-amidinopropane) dihydrochloride (AAPH) suggest that the AAPH added to the liposomes of PC(16∶0/20∶4) was partitioned
into the water phase and out of the hydrophobic region of the fatty acyl moieties of the PC. These results confirm that the
distance that exists in the bis-allylic carbons of the unsaturated fatty acyl moieties of PC from the interface between the
hydrophilic region of PC and the water phases played an important role in influencing hydrogen abstraction to form a symmetrical
distribution of hydroperoxide isomers in both the heterogeneous liposomes and the homogeneous methanol solution. 相似文献
15.
Plasmalogens (1-O-alk-1′-enyl-2-acyl-sn-glycero-3-phosphocholines and -phosphoethanolamines) are important constituents of spermatozoa membranes and possess significant
antioxidative properties. This particularly holds as plasmalogens from spermatozoa also possess a very high content of highly
unsaturated fatty acyl residues (especially 22:6). The organic spermatozoa extracts of two different ruminants (cattle and
roe deer) were analyzed for their contents of characteristic choline plasmalogen oxidation products by matrix-assisted laser
desorption and ionization time-of-flight (MALDI-TOF) mass spectrometry. It will be shown that 1-hydroxy-2-docosahexaenoyl-sn-glycero-3-phosphocholine (LPC 22:6) and formyl-LPC 22:6 are reliable measures of lipid oxidation of spermatozoa and allow,
accordingly, conclusions about the storage conditions. All data on spermatozoa were also confirmed by the investigation of
the oxidation behavior of selected reference compounds. It will be shown that, equally if plasmalogens or diacyl PC species
are used, oxidation takes place primarily at the double bond next to the glycerol backbone. These data were additionally confirmed
by recording the corresponding post source decay (PSD) fragment ion spectra. 相似文献
16.
Plant cells in culture are capable of incorporating exogenous 1-O-alkyl-sn-glycerols into various neutral and ionic ether lipids. 1-O-Alkyl-2-acyl-sn-glycerol-3-phosphocholines, the major class of compounds thus formed, are used for the preparation of platelet activating
factor (PAF) in high yields. Similarly, the prochiral 2-O-alkyl-sn-glycerols are transformed to chiral 2-O-alkyl glycerophospholipids from which compounds can be obtained that exhibit antiviral activity in plant and animal cells.
Reaction of 1-O-alkyl-2-acyl-sn-glycerol-3-phosphocholines with phospholipase D in the presence of ethanolamine leads to 1-O-alkyl-2-acyl-sn-glycerol-3-phosphoethanolamines, which serve as starting material, for the preparation of 1-O-alkyl-2-acyl-sn-glycero-3-phospho-(N-acyl)ethanolamines, compounds known to have antitumor activity.
Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl
Ether Lipids, Tokyo, Japan, May 1989.
Dedicated to Professor Morris Kates, Ottawa, on the occasion of his retirement. 相似文献
17.
Phospholipid molecular species from human placenta lipids 总被引:1,自引:0,他引:1
The phospholipid molecular species from a large-scale preparation of human placenta lipids were analyzed. The major placental
phospholipids were choline glycerophospholipids (CPL) (53.2 wt%), sphingomyelin (21.7 wt%) and ethanolamine glycerophospholipids
(EPL) (14.6 wt%). 1,2-Diacyl-glycerophosphocholine was the most abundant subclass of CPL (91.7 mol%), while EPL contained
1,2-diacyl (54.6 mol%) and 1-alk-1′-enyl-2-acyl (43.8 mol%) subclasses. The level of polyunsaturated fatty acids (PUFA) in
total phospholipids was remarkably constant (38.4–39.9 mol%) within all placental batches tested. The long-chain PUFA, mainly
20∶4n−6 and 22∶6n−3 of the n−6 and n−3 series, respectively, were found in high proportion in all phospholipid classes, especially
in EPL (46.7 mol%) and in inositol glycerophospholipids (IPL) (39.9 mol%). CPL and serine glycerophospholipids were much richer
in 18∶1n−9 and 18∶2n−6. High levels of molecular species with arachidonic acid in thesn-2 position were found particularly in 1-alk-1′-enyl-2-acyl-glycerophospho-ethanolamine (with 24.0 mol% 16∶0 and 22.0 mol%
18∶0 insn-1 position) and in 1,2-diacyl glycerophosphoinositol with 42.6 mol% 18∶0 insn-1 position. EPL subclasses were rich in 22∶6n−3, which occurs mainly as 16∶0/22∶6n−3 (11.7 mol%) in the polasmalogen form
and as 18∶0/22∶6n−3, 16∶0/22∶6n−3 and 18∶1/22∶6n−3 in the diacyl forms. Based on their availability and composition, placental
phospholipids could be of interest, for example, for supplementing artificial milk preparations with n−3 and n−6 long-chain
PUFA for newborn infants with insufficiently developed 18∶2n−6 and 18∶3n−3 desaturation/elongation. 相似文献
18.
Junko Sugatani Kazuyo Fujimura Masao Miwa Kiyoshi Satouchi Kunihiko Saito 《Lipids》1991,26(12):1347-1353
The molecular heterogeneity of 1-alkyl-2-acetyl-sn-glycero-3-phosphocholine (alkylacetyl-GPC) and 1-acyl-2-acetyl-sn-glycero-3-phosphocholine (acylacetyl-GPC) in normal rat glandular stomach was studied by gas chromatography/mass spectrometry
(GC/MS) and tandem mass spectrometry. The percentage compositions of the molecular species of 1-alkyl-2-acetyl-GPC and 1-acyl-2-acetyl-GPC
in the antrum were, respectively. 1-alkyl [16∶0 (34%) and 18∶0 (66%)]-2-acetyl-GPC and 1-acyl [16∶0 (60%), 18∶0 (14%) and
18∶1 (26%)]-2-acetyl-GPC. The alkyl chain composition of 1-alkyl-2-acyl-GPC was quite different from that of 1-alkyl-2-acyl-GPC
in both the antrum and corpus, demonstrating a high degree of selectivity of alkyl chain utilization in PAF biosynthesis.
The amount of 1-acyl-2-acetyl-GPC was much greater than that of 1-alkyl-2-acetyl-GPC. The molecular heterogeneity of 1-alkyl-2-acetyl-GPC
and 1-acyl-2-acetyl-GPC in the corpus was similar to that in the antrum. Water-immersion stress affected not only the amount
of 1-alkyl-2-acetyl-GPC and 1-acyl-2-acetyl-GPC, but also their molecular heterogeneity in the antrum and corpus. Whereas
the amounts of 1-hexadecyl-2-acetyl-GPC and 1-acyl [16∶0, 18∶0 and 18∶1]-2-acetyl-GPC decreased markedly (to less than one-fifth)
in the antrum after such stress for 1 hr, the amount of 1-octadecyl-2-acetyl-GPC increased markedly (up to 4-fold) in the
corpus and severe lesions were observed after stress for 7 hr. The changes may be associated with the pathogenicity of gastric
ulcers.
Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl
Ether Lipids, Tokyo, Japan, May 1989. 相似文献
19.
A reverse-phase high performance liquid chromatography (HPLC) method was developed which resolved isomers of lysophosphatidylcholine
(LPC) differing in the location of the aliphatic chain (sn-1 orsn-2 position) and the position (Δ6 or Δ9) or geometric configuration (cis ortrans) of the olefin group in monounsaturated species. LPC isomers containing an acyl substituent at thesn-2 position eluted before their 1-acyl-sn-glycero-3-phosphocholine (1-acyl LPC) counterparts. The retention times of both thesn-1 andsn-2 isomers of monounsaturated species increased in the order Δ9-cis < Δ9-trans < Δ6-cis. The integrated ultraviolet absorbance (203 nm) in binary mixtures of the Δ9-cis and Δ6-cis 2-acyl lysophospholipid isomers correlated with the lipid phosphorus content of corresponding column eluates (r-0.994). Thus, the present method will facilitate synthesis of isomerically pure diradylphospholipids by providing homogeneous
lysophospholipid precursors and help simplify the quantitative analysis of unsaturated lysophospholipid species. 相似文献
20.
Edward N. Lambremont 《Lipids》1972,7(8):528-533
When14C-labeled acetate, fatty acids or fatty alcohols were injected into or fed to the tobacco budworm, acyl, alkyl and alk-1-enyl
moieties of the phospholipids incorporated radioactivity. Fatty acids were the principal precursor in acyl bond formation
and fatty alcohols in the synthesis of alkyl and alk-1-enyl glyceryl ethers. Detailed analysis of the etherlinked phosphoglycerides
revealed that most of the radioactivity was in the ethanolamine phosphoglycerides, and very little14C was found in the choline phosphoglycerides. In experiments of a short duration, the alkyl glyceryl ethers incorporated more
radioactivity than the alk-1-enyl glyceryl ethers. The reverse was found with long term experiments, when the alk-1-enyl ethers
had higher radioactivity. In addition to demonstrating the synthesis of ether-linked ethanolamine phosphoglycerides, the data
suggested that fatty alcohols and acids were interconverted by insects and that the alk-1-enyl ethers were derived from the
alkyl ethers.
Presented at the AOCS Meeting, Houston, May 1971.
The following abbreviations and terminology will be used: PE, PC, PI and PS for the generic terms ethanolamine, choline, inositol
and serine phosphoglycerides, respectfully. Alkyl glyceryl ether for 1-alkyl-2-acyl-sn-glycerol-3-phosphoryl-, and alk-1-enyl glyceryl ether for 1-alk-1′-enyl-2-acyl-sn-glycerol-3-phosphoryl-(commonly called plasmalogen). These are adapted from the tentative rules published inJ. Lipid Res. 8:522–528 (1967). 相似文献