Average Number Of Double Bonds Research Articles

Interrelationships between low density lipoprotein receptor defect, serum fatty acid composition, and serum cholesterol concentration

It is known that, in the general human population, serum fatty acid composition is correlated with serum triacylglycerol and cholesterol concentrations. The goal of the present study was to analyze whether the same is true of individuals who have a low density lipoprotein receptor (LDL-R) defect. Concentrations of 16 different fatty acids, cholesterol, triacylglycerol, and major lipoproteins in serum were determined in eight individuals who had (FH-North Karelia), the most common LDL-R defect in Finland, which causes familial hypercholesterolemia, and in their 30 relatives belonging to a single large pedigree as controls. The average number of double bonds (i.e., degree of desaturation) in serum fatty acids correlated negatively with the concentrations of serum total cholesterol ( r = 0.27, P < 0.05) and total triacylglycerol ( r = −0.71, P < 0.001) and positively with the number of fish meals per week ( r = 0.50, P < 0.01), which was analyzed in all pedigree members jointly. These effects were similar in individuals having LDL-R defect, in which group the correlation coefficients were −0.31 ( P = NS), −0.99 ( P < 0.001), and 0.79 ( P = NS) for serum total cholesterol, triacylglycerol, and weekly fish meals, respectively. Thus, LDL-R defect does not impair the correlation between serum fatty acid composition and serum triacylglycerol concentration. This result is in agreement with dietary studies that have shown that familial hypercholesterolemia patients respond very favorably to dietary therapy.

Long-term supplementation with a high cholesterol diet decreases the release of ATP from the caudal artery in aged rats

We examined the effects of high cholesterol (HC) diet on the spontaneous and noradrenaline-induced release of ATP, ADP, AMP and adenosine from caudal arteries and on the plasma levels of these adenyl purines in aged (100-week-old) Wistar rats. Administration of this diet for 12 weeks significantly reduced spontaneous and noradrenaline (1 μmol/L)-evoked release of adenyl purines from the caudal arteries relative to rats given the control diet. The unsaturation index of fatty acids (UI), which gives the average number of double bonds, of both the plasma and the caudal artery was significantly less in the HC diet-fed rats than in those fed the control diet. The HC diet for 12 weeks produced a slight but significant increase in systolic and diastolic blood pressure with advancing age. Regression analysis revealed a significant inverse relationship between the total amount of purines released from the artery and diastolic blood pressure and also a positive relationship between the total amount of purines released and the UI of the caudal artery. These results suggest that the high cholesterol diet decreased the release of adenyl purines from the caudal arteries of aged rats, leading to an increase in blood pressure.

Seasonal changes in fatty acid composition associated with cold-hardening in third instar larvae of Eurosta solidaginis

Third-instar larvae of the goldenrod gall fly Eurosta solidaginis (Diptera: Tephritidae) survive extended periods in winter during which tissue water is frozen. Both low temperature and reduced water activity during freezing present challenges for the structural integrity of cellular lipids. Fatty acids of both phospholipids and triacylglycerols from fat body cells of E. solidaginis were analyzed throughout fall and early winter, a period that encompasses the acquisition of freeze-tolerance, to determine if adaptations to freezing include changes in fatty acid unsaturation. The five most abundant fatty acids from both fractions were (in decreasing order) oleic (40–65%), palmitoleic (18–20%), palmitic (12–17%), linoleic (5–10%), and stearic acids (4 –7%). This represents a typical complement of Dipteran fatty acids, although oleic acid levels were higher in E. solidaginis than those reported from other Dipterans (˜28%; Downer 1985). From September to November, monounsaturates increased from 59 to 70% in phospholipids at the expense of saturated fatty acids (25% –20%) suggesting activation of a Δ9-desaturase enzyme. These changes resulted in an increase in the ratio of unsaturated to saturated fatty acids (U/S) from 3.0 to 4.2, although there was no change in the average number of double bonds per fatty acid (unsaturation index, UI ≈ 1.2 in phospholipids and 0.9 in triacylglycerols throughout the season). These changes were temporally correlated to decreasing ambient temperatures and increasing larval and fat body cell freeze-tolerance.

Membrane fatty acid composition of tissues is related to body mass of mammals

Phospholipids were extracted from tissues (heart, skeletal muscle, kidney cortex, liver and brain) of mammals representing a 9,000-fold range in body mass (mouse, rat, rabbit, sheep and cattle) and their fatty acid composition was determined. In heart, skeletal muscle and kidney cortex, there were significant allometric decreases in the Unsaturation Index (UI; average number of double bonds per 100 fatty acid molecules) with increasing body mass. There were significant inverse allometric relationships between body mass and the proportion of docosahexaenoic acid (22:6 omega 3) in heart and skeletal muscle. In heart, skeletal muscle and kidney cortex, larger mammals also had shorter fatty acid chains in their phospholipids and a higher proportion of monounsaturates. In liver, smaller mammals had a higher UI than larger mammals (except the rabbit, which had the lowest UI and very low proportions of omega 3 fatty acids). The brain of all mammals maintained a high UI with similar levels of polyunsaturated fatty acids, especially 22:6 omega 3. Our results suggest that in heart, skeletal muscle and kidney cortex the activity of the elongases and desaturases are reduced in large mammals compared to small mammals. The allometric trends in membrane composition may be involved in modifying membrane permeability. It is proposed that the elevated degree of polyunsaturation in the membranes of several tissues from small mammals is related to their higher metabolic activity.

Red blood cell membrane dynamics in schizophrenia. II. Fatty acid composition

Fatty acid compositions were determined in red blood cell (RBC) ghost membranes of schizophrenic patients before and after haloperidol withdrawal, as well as with age-matched normal male control subjects ( n=22). Patients on haloperidol (HD) received treatment in doses between 5 and 20 mg/day for at least 5 weeks ( n=24). Drug-free patients ( n=19) were free of all psychotropic medications for an average of 40 days. A highly significant decrease in the levels (nmol/ml packed RBC) of polyunsaturated fatty acids (PUFAs), particularly 18:2( n−6) and 20:4( n−6), was found in both HD-treated and drug-free patients. This decrease remained in those patients who had withdrawn from HD for more than 5 weeks ( n=10). Concomitantly, the percentage of saturated and monoenoic fatty acids to total fatty acids increased significantly in schizophrenic patients. The resultant fatty acid profile consequently lowers the unsaturation index (UI), which represents the average number of double bonds per fatty acid molecule, in RBC ghost membranes of schizophrenic patients. Furthermore, the decreases in UI were significantly correlated to the increases in “structure order” of RBC ghost membranes as measured by the steady-state fluorescence anisotropy ( r s) in normal control and drug-free schizophrenic subjects. Therefore, it is likely that decreased levels of PUFAs in schizophrenic patients might result from a defective uptake of 18:2( n−6) into RBC membrane phospholipids. Since fatty acid composition of membrane phospholipids affects the relative degree of membrane fluidity, the present results lend further support that RBC membrane dynamics are altered in schizophrenia.

Changes in Membrane Fatty Acid Composition and Δ12‐Desaturase Activity during Growth of Acanthamoeba castellanii in Batch Culture

ABSTRACT. Growth of Acanthamoeba castellanii in batch culture at 30° C was associated with marked changes in cellular fatty acid composition. The largest change occurred in the linoleate to oleate ratio, which was maximal in early‐ to mid‐exponential phase cultures but decreased approximately 10‐fold as cells approached stationary phase. The higher degree of lipid unsaturation in young cultures was accentuated by a greater proportion of 20‐carbon polyunsaturated fatty acids than in stationary phase cultures. The unsaturation index (average number of double bonds per fatty acid) was maximal in mid‐exponential phase cultures after 24 hours growth. Incorporation of [1‐14C]acetate into polyunsaturated fatty acids in short‐term (2 hour) experiments was high in 12 and 24 hour old cultures, where linoleate and eicosadienoate accounted for up to 26% of total labelled fatty acids. Incorporation of [1‐14CJacetate into these fatty acids was negligible in stationary phase cultures. These results were correlated with changes in the specific activity of the Δ12‐desaturase. Δ12‐Desaturase activity was greatest in microsomal membranes isolated from early‐ to mid‐exponential phase cells, but declined by approximately 50% as cultures progressed towards stationary phase. Membrane fractionation studies revealed that although some differences in fatty acid composition between plasma‐membrane, mitochondrial (enriched), and microsomal membrane fractions were evident, the large changes in lipid unsaturation in whole cells of A. castellanii could not be accounted for by differential development of particular subcellular membranes.

Reaction behaviour and kinetic constants for photopolymerizations of multi(meth)acrylate monomers

The polymerization behaviour of a series of multifunctional methacrylate and acrylate monomers was studied using differential scanning calorimetry to characterize the reaction rate profiles. The polymerization rates, double-bond conversion and kinetic constants were determined for each of the monomers, as well as the effects of monomer type, functionality and rates of polymerization on the reaction behaviour. In particular, by quantifying the kinetic constants for termination and propagation, the controlling mechanism for each of these processes was determined as a function of conversion. In contrast to linear polymerizations, the termination mechanism for these reactions proceeded primarily through reaction diffusion. This behaviour was seen as the termination kinetic constant became proportional to the propagation kinetic constant at very low double-bond conversions. In comparing the acrylates to the methacrylates, the increased reactivity of the acrylates was apparent in the greater values (by three orders of magnitude) of both the termination and propagation kinetic constants. Also, as the number of acrylate or methacrylate groups in the monomer was increased, the kinetic constants correspondingly decreased. This decrease resulted mainly from the greater viscosity of the higher-functionality monomers, attributed to their large molecular weights. Finally, with the exception of the trimethacrylate and triacrylate, the average number of double bonds reacted per monomer at the maximum conversion was near unity, independent of the monomer type or functionality.

Fatty acid compositions of arthropod and cephalopod photoreceptors: interspecific, seasonal and developmental studies

Fatty acid compositions of the compound eyes of insects (soldier-bug, Hemiptera, and silk moth, Lepidoptera), crustaceans (crayfish and grapsid crab, Decapoda) and inner and outer segments of visual cells of a squid (Cephalopoda, Mollusca) were analyzed by gaschromatography for interspecific comparison. Fatty acid compositions showed great variation among species. In insect compound eyes, 16:0 and 18:0 were the main saturated fatty acids, and 18:1 was the dominant unsaturated fatty acid. Silk moth eyes contained, in addition, considerable amounts of 18:2 and 20:5. In crustacean compound eyes, the main saturated fatty acids were 16:0 and 18:0, and 14:0 (5.0%) was only detected in grapsid crabs; the main unsaturated fatty acids were 20:4, 20:5 and 22:6. Both whole eyes and rhabdom fraction of crayfish showed similar profiles of fatty acid compositions. Both inner and outer segments of squid retinae were characterized by high amounts of unsaturated fatty acids, especially 22:6. Compound eyes of grapsid crabs were used for the experiments on seasonal changes of fatty acid compositions. UFA/SFA ratios (weight in % of unsaturated fatty acids saturated fatty acids) were lowest (1.0) in July and highest (2.5) in March, and unsaturation indexes (average number of double bonds per molecule) were lowest (1.5) in July and highest (2.3) in March. Fatty acids 18:0 and 20:1 showed a significant correlation with the changes of seasonal temperature. Fatty acid analysis of the developing compound eyes of silk moths during the pupal stage revealed that eicosapentanoic acid (20:5) increased remarkably in parallel with the development of photoreceptive membranes, the rhabdoms. This suggests that eicosapentaenoic acid may play an important role in formation and function of rhabdoms.

Biophysical and biochemical alterations of renal cortical membranes in diabetic rat

The objective of this study was to determine whether streptozotocin-induced diabetes mellitus in the rat causes alterations in the lipid composition and fluidity of renal brush border membranes (BBM) and basolateral membranes (BLM). Compared to membranes of non-diabetic rats, BBM and BLM of diabetic rats contained 31% and 26%, respectively, less arachidonic acid and 36% and 46%, respectively, more linoleic acid esterfied in phospholipids. These changes were accompanied by a decrease in the average number of double bonds per mole of fatty acid, a measure of fatty acid unsaturation. In diabetic rats BLM had a higher total phospholipid/protein ratio (567 ± 20 vs. 482 ± 15 nmol/mg protein, P < 0.01), less cholesterol (369 ± 30 vs. 512 ± 34 nmol/mg protein, P < 0.01), more phosphatidylcholine (+72%) and less sphingomyelin (−22%) than did BBM. These differences were identical to those observed between BLM and BBM of non-diabetic rats. In control rats BLM was more fluid than BBM as assessed by the steady state fluorescence anisotrophy of diphenylhexatriene and by glycerol permeability. In diabetic rats the fluidity of BLM was not different from that of BBM as assessed by the steady state fluorescence anisotrophy of diphenylhexatriene whereas BLM was slightly more fluid than BBM as assessed by glycerol permeability. By both measures BLM and BBM from diabetic rats were significantly less fluid than BLM and BBM from control rats. Removal of proteins and cholesterol in sequence was accompanied by an increase in membrane fluidity in both groups. However, in no instance did the removal of proteins or cholesterol abolish the difference between the fluidity of diabetic membranes and that of control membranes. From these data we conclude that the reduction in fluidity of renal BLM and BBM in the diabetic rat is due to the change in the composition of fatty acids esterified in membrane phospholipids.

Photooxidation of soybean oils as affected by triacylglycerol composition and structure

The photooxidation of soybean oil was determined and correlated with triacylglycerol composition and structure. Purified triacylglycerols were photooxidized at room temperature under fluorescent light. Rates of peroxide formation and total headspace volatiles were related positively (P&lt;0.5 significance) to oxidizability (r=0.75, r=0.76); content of linolenic acid (r=0.80, r=0.85) and linoleic acid (r=0.61, r=0.57); linoleic acid on carbon 2 (r=0.64, r=0.64); and average number of double bonds (r=0.76, r=0.76). Negative correlations were observed with respect to oleic acid (r=−0.70, r=−0.70). Soybean oil stability was decreased by linolenic acid‐containing triacylglycerols and increased by oleic acid‐containing triacylglycerols. Trilinoleoylglycerol and dilinoleoyl‐oleoylglycerol were the most important oxidation product precursors. However, for high‐linolenic acid soybean oil, dilinoleoyl‐linolenoylglycerol and trilinoleoylglycerol were the most important oxidation product precursors. The most abundant volatile produced from thermal decomposition at 140°C of photooxidized triacylglycerols was 2‐heptenal, except for high‐linolenic acid oils, where the most abundant volatile was propanal. The photooxidative stability of soybean oil triacylglycerols with respect to composition and structure is of interest for the development of soybean varieties with oils of improved odor and flavor stability.

Effect of triacylglycerol composition and structures on oxidative stability of oils from selected soybean germplasm

The oxidative stability of soybean oil triacylglycerols was studied with respect to composition and structure. Crude soybean oils of various fatty acid and triacylglycerol composition, hexane‐extracted from ground beans, were chromatographed to remove non‐triacylglycerol components. Purified triacylglycerols were oxidized at 60°C, in air, in the dark. The oxidative stability or resistance of the substrate to reaction with oxygen was measured by determination of peroxide value and headspace analysis of volatiles of the oxidized triacylglycerols (at less than 1% oxidation). The correlation coefficients (r) for rates of peroxide formation (r=0.85) and total headspace volatiles (r=0.87) were related positively to oxidizability. Rate of peroxide formation showed a positive correlation with average number of double bonds (r=0.81), linoleic acid (r=0.63), linolenic acid (r=0.85). Rate of peroxide formation also showed a positive correlation with linoleic acid (r=0.72) at the 2‐position of the glycerol moiety. A negative correlation was observed between rate of peroxide formation and oleic acid (r=−0.82). Resistance of soybean triacylglycerols to reaction with oxygen was decreased by linolenic (r=0.87) and increased by oleic acid (r=−0.76)‐containing triacylglycerols. Volatile formation was increased by increased concentration of linolenic acid at exterior glycerol carbons 1,3 and by linoleic acid at the interior carbon 2. Headspace analysis of voltiles and high‐performance liquid chromatography of hydroperoxides indicated that as oxidation proceeded there was a slight decrease in the linolenic acid‐derived hydroperoxides and an increase in the linoleic acid‐derived hydroperoxides. The oxidative stability of soybean oil triacylclycerols with respect to composition and structure is of interest to the development of soybean varieties with oils of improved odor and flavor stability.

Analysis of north atlantic and baltic fish oil triacylglycerols by high‐performance liquid chromatography with a silver ion column

AbstractTriacylglycerols from Atlantic herring (Clupea harengus), sandeel (Ammodytes sp.) and Baltic herring (Clupea harengus membras) have been fractionated by silver ion high‐performance liquid chromatography. An ion exchange column loaded with silver ions was the stationary phase, and a gradient in the mobile phase from 1,2‐dichloroethane/dichloromethane (1∶1, v/v) to acetone and then to acetone/acetonitrile (2∶1, v/v) was used to effect the separation with light‐scattering (i.e., mass) detection. Fractions were collected via a streamsplitter, and fatty acid methyl esters were prepared by transesterification in the presence of an internal standard for identification and quantification by gas liquid chromatography. Triacylglycerols were separated according to the number of double bonds in the fatty acyl residues. Resolution was excellent at first, when the least unsaturated molecules eluted (trisaturated to dimonoene‐monodiene fractions). Base‐line resolution could no longer be achieved when molecules containing trienoic or more highly‐unsaturated fatty acids began to elute because of overlapping components. Nonetheless, some valuable separations of species containing two saturated and/or monoenoic fatty acids and one polyenoic fatty acid were achieved. Double bond indices (average number of double bonds in each triacylglycerol molecule) were calculated to estimate the separations possible. Fractions containing at least 11–14 double bonds per molecule were obtained.

Diurnal Variation in Membrane Lipid Composition of Sonoran Desert Teleosts

ABSTRACT Phospholipid molecular species and headgroup compositions were determined for sarcoplasmic reticular and microsomal membranes in two species of Sonoran desert cyprinid fish (Agosia chrysogaster Girard and Notropis lutrensis Girard) trapped in an isolated pool of a desert stream. Fish populations were sampled in the cool of the morning (water temperature 21–21·9°C for Agosia and 22–26°C for Notropis) and 7–11 h later in the heat of the afternoon (water temperature 34·2°C) to determine whether membrane lipid composition varied with sampling time and thermal exposure. The composition of sarcoplasmic reticular membranes did not vary significantly through the day. In contrast, the molecular species composition of muscle microsomes (a mixture of endoplasmic reticulum and plasma membranes) changed markedly from the cool of the morning to the heat of the afternoon in both species. Adjustments were particularly striking in phosphate dylcholine (PC). For example, in Agosia, the ratio of saturated-to-unsaturated species of PC, the unsaturation index (the average number of double bonds per molecular species) and the proportion of diunsaturated molecular species decreased from 7·48 to 0·77, from 1·36 to 0·35 and from 7·23% to 2·46%, respectively, between the morning and afternoon samples. Similar, but less dramatic, changes were noted for phosphatidylethanolamine (PE) in both species, and for phosphatidylinositol (PI) in Notropis. In addition, microsomal membranes of Agosia exhibited a significant reduction in the proportion of PE (from 12·1 to 2·7 %) and a corresponding increase in the proportion of PC between the morning and afternoon samples. These patterns of change in membrane lipid composition are in a direction consistent with thermal compensation of membrane function and suggest that rapid adjustments in the lipid composition of biological membranes may stabilize membrane structure against substantial diurnal fluctuations in temperature.

Membrane lipid composition ofBetula pubescens(Ehrh.) andBetula tortuosa(Ledeb.)

The lipid composition of the two closely related birches Betula pubescens and Betula tortuosa was investigated. The total amount of lipids and the lipid composition was strikingly similar. The glycolipid content on a chlorophyll basis was high in both birches. A comparison of the. acyl groups revealed a small difference in 16:3 in monogalactosyl diacylglycerol, but the total amount of trienoic acids was similar. The acyl group composition in the nonplastid lipid phosphatidyl choline differed between the birches and B. tortuosa had a higher average number of double bonds. The observations on galactolipid and phospholipid could not explain the earlier stated higher tolerance of B. tortuosa to the freezing of its leaves

Membrane lipids in Ceratodon purpureus protonemata grown at high and low temperatures

Ceratodon purpureus (Hedw.) Brid. was grown at two temperatures, 20 and 4°C. The protonemata grown at 4°C fixed more CO2 at low temperatures; but their frost tolerance, tested as the recovery of photosynthesis after frost treatment, was not better than in the protonemata grown at 20°C. The effects of the growth temperature were studied on the membrane lipids of intact protonemata and on the lipid and protein contents of isolated thylakoid membranes. A large proportion, 70 to 90%, of the thylakoid membrane lipids was lost unless precautions were taken to inhibit the lipid‐degrading enzyme activities. The lipid content of the thylakoid membranes of protonemata grown at 20 and 4°C was 3.9 and 4.8 mol (mol chlorophyll)−1, respectively. Only minor differences were found in the lipid class composition. Monogalactosyldi‐acylglycerol constituted more than 50 mol‐% of the thylakoid membrane lipids at both 20 and 4°C. However, each lipid class had a higher average number of double bonds per lipid molecule in cold growth conditions. The protein content of the thylakoid membranes was low at both 20 and 4°C. These characteristics of the thylakoid membranes may be a prerequisite for the observed ability of protonemata to photosynthesize even at subzero temperatures.

Adriamycin transport and sensitivity in fatty acid-modified leukemia cells

The membrane phospholipids of L1210 murine leukemia cells were modified by supplementing the growth medium with micromolar concentrations of polyunsaturated or monounsaturated fatty acids. This procedure results in enrichment of cellular phospholipids by the supplemented fatty acid. Enrichment with polyunsaturated fatty acids resulted in a marked increase in sensitivity to adriamycin as compared to enrichment with monounsaturated fatty acids. The increased cytotoxicity was directly proportional to the extent of unsaturation of the inserted fatty acid, but there was no difference in cells enriched with n − 3 compared with n − 6 family fatty acids. To explore the mechanism of this observation, we examined whether augmented uptake of the drug might explain the increased cytotoxicity. The uptake of [ 14C]adriamycin, which was approximately linear at later time points, was only partially temperature dependent and never reached a steady state. Initial uptake at time points prior to 60 s could not be measured due to high and variable rapid membrane adsorption. Cellular accumulation of drug was greater in the docosahexaenoate 22:6-enriched L1210 cells as compared to oleate 18:1-enriched cells and was about 32% greater after 20 min. When L1210 cells were enriched with six fatty acids of variable degrees of unsaturation, the accumulation of adriamycin was directly correlated with the average number of double bonds in the fatty acids contained in cellular phospholipids. There was no difference in efflux of drug from cells pre-loaded with adriamycin. We conclude that the greater accumulation of adriamycin by the polyunsaturated fatty acid-enriched L1210 cells likely explains the increased sensitivity of these cells to adriamycin compared to 18:1-enriched cells.

Polyunsaturated fatty acyl residues of galactolipids are involved in the control of bilayer/non-bilayer lipid transitions in higher plant chloroplasts

Total polar lipid extracts of chloroplasts isolated from broad beans ( Vicia faba) tend to form non-bilayer structures when dispersed in dilute salt solutions. Monoglactosyldiacylglycerol is shown to play a dominant role in this process. The tendency of this lipid to form non-bilayer structures when dispersed alone in water was found to depend upon the degree of unsaturation of its associated fatty acyl chains. Highly unsaturated lipids (average number of double bonds per lipid molecule greater than about 5.0) form inverted hexagonal (Hex II) structures in water at 20°C, whilst more saturated lipids (average number of double bonds per lipid molecule less than about 4.5) form lamellar sheets. Wide-angle X-ray diffraction and differential scanning calorimetry measurements indicate that these lamellae consist of gel-phase lipid that can adopt either of two structures depending on the thermal history of the sample. Freeze-fracture studies performed on total polar lipid extracts that have been hydrogenated using Adams' catalyst, and reconstituted extracts in which monogalactosyldiacylglycerol has been selectively hydrogenated, show that the degree of unsaturation of this lipid is a key factor in determining whether or not non-bilayer structures are formed in such extracts. Increasing the extent of saturation of the acyl residues of monogalactosyldiacylglycerol reduces the tendency to form non-bilayer structures. Similar effects are observed on lowering the temperature of the dispersions. Fluorescence polarisation measurements using 1,6-diphenyl-1,3,5-hexatriene indicate that the disappearance of non-bilayer structures is accompanied by a marked decrease in the fluidity of the lipid matrix. The possible significance of these observations is discussed in terms of the thermal adaptation and chilling sensitivity of plant membranes.

Distribution of double bonds in thermally degraded polyisobutylene

The distribution of double bonds in thermally degraded polyisobutylene was determined quantitatively by using pulsed Fourier transform 1H n.m.r. spectroscopic analysis. The double bonds in the degraded polymer did not exist in the interior but at the terminal positions of the polymer chain. These olefins were of the terminal trisubstituted and terminal vinylidene types. The content of the former was much greater than that of the latter. This shows that radical chain transfer predominantly occurs at the methylene hydrogen rather than at the methyl groups of the polymer chain. The average number of double bonds per molecule, f, was greater than 1 and tended to be near 2. Thereby most of the degraded polyisobutylene was shown to have two terminal unsaturations per molecule.

Fatty acids in phospholipids isolated from human red cells

Total lipids of packed erythrocytes from healthy men 22 to 25 years old were extracted with chloroform-methanol mixture. Phospholipid classes were separated from neutral lipids and pigments on a silicic acid column. Phosphatidyl inositol (PI) was freed of its contaminants phosphatidyl ethanolamine (PE) and phosphatidyl serine (PS) on an aluminum oxide column. Additional silicic acid columns with modified solvent systems were needed for complete separation of other overlapped phospholipid classes. The identification of phospholipids in each eluted fraction was accomplished by TLC, using the appropriate spray tests and reference compounds, and confirmed on each of the isolated phospholipids by IR spectrophotometry.The total content of phospholipids as determined by phosphorus analysis was found to be 2.63 mg/ml of packed cells. These phospholipids were found to have the following composition (in per cent of total phospholipid): PI, 2.3; PE, 13.4; ethanolamine plasmalogen (EP), 14.5; PS, 3.9; lecithin (L), 34.2; choline plasmalogen (CP), 1.4; sphingomyelin (Sph), 28.4 and lysolecithin (LL), 1.7. The fatty acid composition of each phospholipid was determined by GLC. The average number of double bonds per fatty acid in the isolated phospholipids was found to be as follows: PI, 1.5; PE, 1.9; EP, 3.6; PS, 2.1; L, 1.0; CP, 2.0; Sph, 0.2 and LL, 0.5. The positional distribution of fatty acids in both L and PE was ascertained by selective enzymatic hydrolysis with phospholipase A. Saturated fatty acids of L were esterified predominantly in the alpha'-position, whereas in PE only 63.9 mole per cent of the saturated fatty acids were found in this position.