Chemical Examination of Iberis odorata Seed Oil

Iberis odorata seeds of cruciferae plant family yield 26.0 percent of fatty oil which has an iodine value 107.5. The oil is investigated for its fatty acid composition by reversed phase partition chromatography. The fatty acids in the seed oil constitute 39.6% erucic, 3.5% eicosenoic and 3.2% docosadienoic acids, in addition to the usual oleic (13.6%), linoleic (25.7%) and linolenic acids (3.1%). Saturated acids (C₁₂) to (C₂₂) amount to 11.3% of the component 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.     

Chemical Investigations of the Sapindus mukorossi Seed Oil

Two lipid fractions ‘A’ and ‘B’ were isolated from Sapindus mukorossi seed oil by preparative TLC. Fraction ‘A’ (70.4%, R_f value 0.76) is a normal triglyceride and its fatty acid compositions was determined by GLC. Fraction ‘B’ (29.6%, R_f value 0.51) shows the presence of nitrogenous constituents. It develops a reddish brown colour in contact with alkali or alkoxide solution. Percentages of individual acids present in fraction ‘A’ were found to be: palmitic, 5.5; stearic, 3.2; oleic, 64.6; linoleic, 2.9; arachidic, 3.1; eicosenoic, 20.1; minor acids, 0.6. Fraction ‘A’ is composed of 0.1,3.6,29.9 and 66.4 percent trisaturated, monounsaturated-disaturated, diunsaturated-monosaturated and triunsaturated glycerides respectively. On GLC analysis, the percentages of individual acids constituting fraction ‘B’ were found to be:palmitic, 3.8; stearic, 1.5; oleic, 33.6; linoleic, 2.9; arachidic, 11.1; eicosenoic, 30.2; behenic, 2.8; docosenoic, 1.4 and two unidentified acids 7.3 and 5.4. Fraction ‘B’ responded to hydrolysis by pancreatic lipase and the product with polarity equivalent to that of 2-mono-glyceride was isolated by TLC and converted to methyl ester. Percentages of individual acids constituting that methyl esters were found to be:palmitic, 11.8; stearic, 4.1; oleic, 12.8; linoleic, 3.7; arachidic, 8.3; eicosenoic, 10.2; behenic, 6.5; docosenoic, 4.2; and two unidentified acids 22.2 and 16.2. This non-glyceridic component of the S. mukorossi seed oil is a cyanolipid, 1-cyano-2-hydroxymethyl prop-1-ene-3-ol. The structure was confirmed by I. R., N.M.R. and Mass spectral-analysis.     

Gas chromatographic-mass spectrometric analysis of isoprenoid hydrocarbons and fatty acids in shark liver oil products

The liver oil from the South American Basking shark has been fractionated by silica gel chromatography and analyzed by the new method of combined gas-chromatography mass spectrometry. The major compounds of the nonsaponifiable fraction are pristane and squalene, which account for 7.6 and 31.3% of the oil. The saponifiable fraction contains normal fatty acids from C₁₄ to C₂₂; the four major components are palmitic, oleic, and the monounsaturated eicosenoic and docosenoic acids. No correlation was observed between the hydrocarbons (essentially all isoprenoid derivatives) and the fatty acids (essentially all normal) of this oil. The same treatment was applied to a sample of commercial pristane which was obtained from Basking shark liver oil. It was found to contain about 1% phytane and small amounts of octadecane, nonadecane, and methyl and ethyl palmitates. Mass spectral data for squalene are presented for the first time along with the low electron energy-mass spectra for pristane and phytane.     

An Unprecedented Occurrence of Δ5,9- and Δ9,15-Dienoic Fatty Acids in Ovaries of the Archaeogastropod Limpet Cellana toreuma

A detailed structural diversity of dienoic fatty acids (FA), including non‐methylene‐interrupted dienoic FA, of triacylglycerols and polar lipids in ovaries of Cellana toreuma was clarified for the first time by using capillary gas chromatography–mass spectrometry of their 3‐pyridylcarbinol esters and argentation thin‐layer chromatography. Interestingly, in addition to 5,9‐octadecadienoic (18:2Δ5,9), 5,9‐eicosadienoic (20:2Δ5,9), 5,9‐heneicosadienoic (21:2Δ5,9), 5,9‐docosadienoic (22:2Δ5,9), 5,9‐tricosadienoic (23:2Δ5,9), and 5,9‐tetracosadienoic (24:2Δ5,9) acids, previously identified in ovaries of C. grata, rare FA 5,9‐hexadecadienoic (16:2Δ5,9), 5,9‐nonadecadienoic (19:2Δ5,9), and 21‐methyl‐5,9‐docosadienoic (iso 23:2Δ5,9) were newly recognized in ovaries of C. toreuma. Detectable amounts of four Δ9,15‐dienoic FA were present in the ovary lipids. The FA identified were one novel 9,15‐heneicosadienoic (21:2Δ9,15) acid and known 9,15‐docosadienoic (22:2Δ9,15), 9,15‐tricosadienoic (23:2Δ9,15), and 9,15‐tetracosadienoic (24:2Δ9,15) acids. The findings help to explain the broad evidence of the structural diversity in marine gastropods and suggest biomarkers to evaluate marine food web relations.     

Sperm oil replacements from selectively hydrogenated soybean and linseed esters: Special lubricants

Soybean and linseed oils were selectively hydroenated with copper-on-silica gel catalyst. The linolenate content of the oils was reduced to diene and monoene with no appreciable increase in saturates. Hydrogenated soybean oils contained 68–76% monoene, 11–18% diene, 0% conjugated diene and triene, 1–6% conjugatable diene, 0–0.3% conjugatable triene, and 23–40% isolatedtrans double bonds. Hydrogenated linseed oils contained 44–54% monoene, 35–45% diene, 0% conjugated diene and triene, 0–7% conjugatable diene, 0–02% conjugatable triene, and 44–59% isoaltedtrans double bonds. Esters of fatty acids, derived from these selectively hydrogenated oils, were prepared with trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ethylene glycol, C₁₈ saturated cyclic alcohols, primary C₁₂–C₁₈ saturated (nC₁₂, nC₁₄, nC₁₆, nC₁₈) alcohol, and primary C₁₆–C₁₈ saturated (nC₁₆, nC₁₈) alcohol blends. Measurements of viscosities and of smoke, flash, and fire points indicate that these esters are possible replacements for sperm oil. Certain of them, after sulfurization, also have potential as extreme pressure lubricant additives. Presented at the AOCS meeting in Philadelphia, September 1974.     

Hydrogenation of linolenate. II. Hydrazine reduction

Observations by Aylward and Rao that hydrazine is a reducing agent for a number of unsaturated fatty acids were extended. The hydrazine reaction on linolenic acid was followed by periodic sampling until methyl esters prepared from the reduced acids had an iodine value of 162. These esters were shown by countercurrent distribution to consist of 26% triene, 43% diene, 26% monoene, and 5% stearate and by infrared analysis to contain notrans bonds. Oxidation of the separated monoene and diene fractions by permanganate-periodate mixtures and gas chromatography of the dibasic acids showed that the double bonds were in the original 9, 12, and 15 positions and that the double bonds farthest from the carboxyl were reduced at a slightly faster rate. Gas chromatography of the monoene fraction indicated three components that were identified in the order of elution from the column as 9, 12, and 15 monoenes; in the diene fraction three components were identified in the order of elution as 9,12; 9,15; and 12,15 dienes. After alkali isomerization of this diene fraction, the conjugated material was reacted with maleic anhydride; the unreacted 9,15 diene isomer was separated by distillation. Presented at fall meeting, American Oil Chemists’ Society, New York, October 17–19, 1960. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

TheTrans-6 fatty acids ofPicramnia sellowii seed oil

The C₁₈ monoenoic acids inPicramnia sellowii Planch. seed oil include bothcis-andtrans-6-octadecenoic acids, as well as oleic acid. The hexadecenoic acids are also thecis- andtrans-Δ6-isomers, and the eicosenoic acids have Δ6-unsaturation of undetermined geometric configuration. The C₁₈ polyenoic acids detected are 9,12- and 6,9-octadecadienoic and 9,12,15- and 6,9,12-octadecatrienoic acids. Partial investigation of another species,P. pentandra Sw., revealed its oil to have a similar fatty acid composition. Presented in part at AOCS Meeting, New York, October 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Fatty acids and sterols ofCronartium fusiforme basidiospores

The hydrocarbons, fatty acids, and sterols ofCronartium fusiforme basidiospores were examined by gas chromatography and mass spectrometry. Trace quantities of aliphatic hydrocarbons were detected, but these were probably not fungal products. Principal nonsubstituted fatty acids were palmitic (11.7%), linoleic (17.2%), and linolenic (16.1%) acids; the predominant acid was 9,10-cis-epoxyoctadecanoic acid (40.7%). Four sterols were detected, three of which were identified as stigmast-7-enol (57.6%), stigmasta-5,7-dienol (22.7%), and ergost-7-enol (16.0%). The fourth sterol (4%) is a C₂₈ diene. Lipids of the aeciospores and basidiospores ofC. fusiforme are compared.     

Isomerization during hydrogenation of soap: II. Potassium elaidate and potassium linoleate

Potassium elaidate in slightly alkaline solution was hydrogenated for up to 7 hr with 1.5% of Rufert nickel catalyst at 150 C and 20 kg/sq cm pressure. Potassium linoleate was similarly hydrogenated with 1.0% catalyst for 7 hr, and the hydrogenation continued for another 7 hr after addition of 0.5% fresh catalyst. Periodic samples from each were analyzed for component acids. The positional isomers in thecis andtrans monoenes, isolated by preparative argentation thin layer (TLC) or column chromatography, were estimated after oxidation to dicarboxylic acids. Some diene fractions were isolated for further examination. In potassium elaidate hydrogenation,cis monoenes were initially produced in considerable amounts, but to a lesser extent thereafter. Positional isomers were similarly distributed in bothcis andtrans monoenes after prolonged hydrogenation. In the hydrogenation of potassium linoleate, a drop in iodine value (IV) of 60 units occurred in the first hour, and 38% oftrans monoenes (in which the 10- and 11-monoenes constitute 32% each) were formed. The IV then fell only slowly, and up to 38% ofcis monoene (mostly 9- and 12-isomers) was formed. Addition of fresh catalyst caused a major shift ofcis monoenes totrans forms. The diene fraction was mostly nonconjugated material with the first double bond at the 9, 8 and 10-positions. Minor amounts of conjugated dienes were present as well as a dimeric product.     

Fatty acids of asparagus seed oil

Summary Asparagus seed, Mary Washington variety, was found to contain 14.7% of glyceride oil having iodine value 135.1, saponification value 185.5, and unsaponifiable matter 1.46%. The oil was converted to methyl esters, and the mixed esters were separated by fractional distillation and low-temperature crystallization. The acids were identified by chemical and physical methods. The % composition of the fatty acids is estimated from the data as follows: palmitic 3, linoleic 57, oleic 27, stearic 2, eicosenoic 1.5, arachidic 0.6, undetermined 9. The oil is somewhat similar to corn oil in composition. It has at least 2% of acids of the C₂₀ series, which have not been reported previously in this plant family (Liliaceae). Presented at the meeting of the American Oil Chemists' Society, Philadelphia, Pa., October 10–12, 1955. Issued as N.R.C. No. 4426.     

Quantitation of estolides by Fourier transform infrared spectroscopy

Estolides were produced from meadowfoam oil fatty acids, oleic, linoleic, petroselinic, andcis-5,cis-13 docosadienoic acids. Estolide reaction mixtures were quantitated by Fourier transform infrared spectroscopy and compared to the area percentages determined by high-performance liquid chromatography. The absorbance frequency of estolide carbonyl (1737 cm⁻¹) is different than the lactone carbonyl (1790 cm⁻¹) and the acid carbonyl (1712 cm⁻¹). Estolide standards were obtained by wiped-film molecular-still distillations and column chromatography.     

The effect of dietary partially hydrogenated marine oils on desaturation of fatty acids in rat liver microsomes

The influence of dietary partially hydrogenated marine oils on distribution of phospholipid fatty acids in rat liver microsomes was studied with particular reference to the metabolism of linoleic acid. Five groups of weanling rats were fed diets containing 20% (w/w) peanut oil (PO), partially hydrogenated peanut oil (HPO), partially hydrogenated Norwegian capelin oil (HCO), partially hydrogenated herring oil (HHO), and rapeseed oil (RSO) for 10 weeks. The partially hydrogenated oils were supplemented with linoleic acid corresponding to 4.6 cal % in the diets. Accumulation of linoleic acid and reduced amount of total linoleic acid metabolites were observed in liver microsomal phospholipids from rats fed partially hydrogenated oils as compared to PO feeding. The most striking effects on the distribution of ω6-polyunsaturated fatty acids was obtained after feeding HHO, a marine oil with a moderate content oftrans fatty acids in comparison with HPO but rich in isomers of eicosenoic and docosenoic acids. Liver microsomal Δ⁶-as well as Δ⁶-desaturase activities as measured in vitro were reduced in rats kept on HHO as compared to PO dietary treatment. The results obtained suggest that the dietary influence of partially hydrogenated marine oils on the metabolism of linoleic acid might be better related to the intake of isomeric eicosenoic and docosenoic acids than to the total intake oftrans fatty acids.     

Hydrogenation of linolenate. I. Fractionation and characterization studies

Methyl linolenate hydrogenated at 140°C, with 0.5% Ni catalyst and 1.1 mole of hydrogen at atmospheric pressure was separated into octadecenoate, octadecadienoate, and octadecatrienoate fractions by countercurrent distribution. Gas chromatography on a 200-ft. capillary Apiezon L column revealed one component in the triene fraction, four in the diene fraction, and nine in the monoene fraction. These components were partially fractionated by low-temperature crystallization, and their solubilities were correlated with alkali conjugation results, with infrared data forcis andtrans configuration of bonds and with dibasic acids isolated from the fractions after oxidative cleavage. Approximately 45% oftrans acids were present in both the monoene and diene fractions. Considerable migration of double bonds from the original 9, 12, and 15 positions occurred.Cis,cis dienes which could not be conjugated by alkali were formed. Little alteration of the residual methyl linolenate was observed. The results demonstrate the applicability and utility of new techniques of fractionation and analysis to the study of the hydrogenation mechanism. Presented at 51st annual meeting, American Oil Chemists' Society, Dallas, Tex., April 4–6, 1960. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Effect of dietarytrans fatty acids on microsomal enzymes and membranes

Three groups of rats were maintained on diets containing different proportions oftrans fatty acids (0, 18.3 or 36.6% of the total fatty acids) for eight weeks. No differences in body weight were observed among the three groups, but the fat cell size, determined in epididymal fat, differed significantly between the controls and the rats fed diets containingtrans fatty acids. The supernatant obtained by centrifuging homogenates of liver from the rats at 9000×g (S-9 fraction) was used as an activator in a bacterial test for mutagenicity of 2-aminofluorene and aflatoxin B₁ usingSalmonella typhimurium strains TA 98 and TA 100, respectively. The mutagenicities of 2-aminofluorene in strain TA 98 and of aflatoxin B₁ in strain TA 100 were significantly lower with the liver S-9 fraction from rats fed a diet containing 36.6%trans fatty acids than with the liver S-9 fraction from rats fed a control diet with notrans fatty acids.     

Application of Methoxy-Bromomercuric-Adduct Fractionation to the Study of Cyclic Fatty Acid Monomers from a Heated Linseed Oil

A linseed oil was heated at 275° C for 12 hr under nitrogen. The triglycerides were isolated from the polymers by gel permeation chromatography on 2μ-styragel columns using tetrahydrofuran (THF) as solvent. One part of the isolated triglyceride fraction was submitted to HPLC on a C₁₈ reverse phase column. The resulting 8 fractions were transformed into methyl esters and hydrogenated on PtO₂ The content of cyclic fatty acid monomers (CFAM) in the different hydrogenated fractions was determined by gasliquid chromatography (GLC) on a Silar-10 C column. The other part of the isolated triglyceride fraction was submitted to the action of BF₃/MeOH. The resulting methyl esters were fractionated by thin-layer chromatography of the corresponding methoxybromomercuric adducts. Five bands were obtained using a mixture of hexane: dioxane (60:40) as the solvent system. A band between the diene and the triene bands contained 40.6% of the total cyclic fatty acid monomers (CFAM) while the diene and the monoene band contained respectively 38.9 and 11.2% of these cyclic components. The diene band and the band between the diene and the triene bands were hydrogenated on PtO₂ The structures of the resulting hydrogenated cyclic fatty acid monomers were studied using a gas-liquid chromatograph coupled with a mass spectrometer (GC-MS).     

Chemical Composition and Characteristics of <Emphasis Type="Italic">Commiphora wightii</Emphasis> (Arnott) Bhandari Seed Oil

The seeds of Commiphora wightii (Arnott) Bhandari contain 9.8 ± 0.7% oil. The fatty acid composition and chemical properties of the extracted oil were determined. Gas liquid chromatography of the methyl esters of the fatty acids shows the presence of 46.62% saturated fatty acids and 51.40% unsaturated fatty acids. The fatty acid composition is as follows: capric acid 3.50%, myristic acid 14.51%, palmitic acid 6.68%, stearic acid 4.70%, arachidic acid 3.18%, behenic acid 14.05%, myristoleic acid 1.34%, palmitoleic acid 12.07%, oleic acid 14.15%, eicosenoic acid 0.11%, linoleic acid 22.34% and alpha linoleic acid 1.37%.     

Monohydroxylation of unsaturated oils: I. Sulfation-hydrolysis and sultone-formation

Hydroxy unsaturated glycerides were sought from safflower and linseed oils by partial sulfation with sulfuric acid, followed by hydrolysis of sulfate to hydroxy groups. Sulfation of oleicrich oils or their fatty acids and subsequent hydrolysis (effected conveniently with acidified barium chloride) yielded hydroxy products corresponding to 50–70% of the monoene content. Sulfation of a mixture of methyl oleate and linoleate with 78% w/w of sulfuric acid was directed mainly at the oleate component. Safflower oil was partially sulfated without side reactions using 78% or 79% w/w of sulfuric acid, the hydrolyzed products showing hydroxyl value (HV) of about 35 for a loss of 13 units of iodine value (IV). Use of more concentrated sulfuric acid, and subsequent hydrolysis, led to sulfur-containing products which include sultones. Treatment of atrans,trans, but not of acis,trans conjugated diene with sulfuric acid led to sultone formation. It is postulated that when linoleate is sulfated with strong acids, acidisomerization to atrans,trans conjugated diene occurs, probably followed by 1,4-addition of -OH and -SO₃H and quick dehydration of these moieties to give a 1,4-sultone. Linseed oil was apparently sulfated without side reactions using 80% w/w sulfuric acid at 0–5 C and then hydrolyzed to a product of HV 77 and IV 159.     

Impact fracture behavior of PP/EPDM/glass bead ternary composites

The effects of glass bead filler content and surface treatment of the glass with a silane coupling agent on the room temperature impact fracture behavior of polypropylene (PP)/ethylene‐propylene‐diene monomer copolymer (EPDM)/glass bead(GB) ternary composites were determined. The volume fraction of EPDM was kept constant at 10%. The impact fracture energy and impact strength of the composites increased with increasing volume fraction of glass beads (?_g). Surface pretreatment of the glass beads had an insignificant effect on the impact behavior. For a fixed filler content, the best impact strength was achieved when untreated glass beads and a maleic anhydride modified EPDM were used. The impact strength exhibited a maximum value at ?_g=15%. Morphology/impact property relationships and an explanation of the toughening mechanisms were developed by comparing the impact properties with scanning electron micrographs of fracture surfaces.     

Jojoba oil wax esters and derived fatty acids and alcohols: Gas chromatographic analyses

HCl-catalyzed ethanolysis followed by saponification readily surmounts the resistance of long chain wax esters to direct hydrolysis by alkali. Additionally, choosing ethyl instead of methyl esters allows baseline separations between long-chain alcohols and corresponding esters in gas liquid chromatographic (GLC) analysis of total alcohol and acid components before saponification. Liquid wax esters were analyzed on a temperature-programmed 3% OV-1 silicone column. Geographical and genetic effects on the variability of jojoba oil composition were investigated with five different seed samples. Major constituents in jojoba seed oil from shrubs in the Arizona deserts, as indicated by GLC analyses of oil, ethanolysis product, isolated fatty alcohols and methyl esters of isolated fatty acids, were C₄₀ wax ester 30%, C₄₂ wax ester 50% and C₄₄ wax ester 10%; octadecenoic acid 6%; eicosenoic acid 35%, docosenoic acid 7%, eicosenol 22%, docosenol 21% and tetracosenol 4%. Oil from smaller leaved prostrate plants growing along California’s oceanside showed a slight tendency toward higher molecular size than oils from the California desert and Arizona specimens. The wax esters are made up of a dispro-portionately large amount of docosenyl eicosenoate and are not a random combination of constituent acids and alcohols.Lunaria annua synthetic wax ester oil was used as a model for evaluating the analytical procedures. Presented at the AOCS Meeting, Chicago, September 1970 No. Utiliz, Res. Dev. Div., ARS, USDA.