Estolide triglycerides ofTrewia nudiflora seed oil

The seed oil ofTrewia nudiflora is known to contain glycerides of α-kamlolenic (18-hydroxy-cis-9,trans-11,trans-13-octadecatrienoic) acid. We have shown that a large part of these glycerides contain estolides in which the hydroxyl group of α-kamlolenic acid is esterified to a molecule of another acid, either a hydroxy acid or an ordinary fatty acid. By preparative thin layer chromatography, we isolated a series of tri-, tetra-, penta- and hexaacyl glycerols. By lipolysis and gas chromatography-mass spectrometry, we isolated and characterized estolide-linked fatty acids containing two acid moieties.     

Stereospecific analysis of triglycerides fromMonnina emarginata seed oil

InMonnina emarginata seed oil triglycerides, more than two-thirds of theS-coriolic (13l-hydroxy-cis-9,trans-11-octadecadienoic) acid occurs in position 3 (relative tosn-glycerol). All but a trace of the remainder is in position 1. Presented at AOCS Meeting, Houston, May 1971. N. Market. Nutr. Res. Div., ARS, USDA     

Stereospecific analysis ofOnosmodium hispidissimum Mack. seed oil triglycerides

The objective of the study was to determine the fatty acid composition ofOnosmodium hispidissimum Mack. seed oil and the stereospecific distribution of γ-linolenic and stearidonic acids in the seed oil triglycerides. The seed oil contained about 20% γ-linolenic acid and about 8% stearidonic acid. About 90% of both γ-linolenic acid and stearidonic acids were esterified to thesn-2 andsn-3 positions. This paper is NRCC No. 36484.     

Urea-based fractionation of seed oil samples containing fatty acids and acylglycerols of polyunsaturated and hydroxy fatty acids

The selectivity and efficiency of urea complex (UC) formation-based fractionation of free fatty acids (FFA) were examined. A rapid, simple, and inexpensive procedure recently developed for urea fractionation was applied to lipid mixtures containing various polyunsaturated and hydroxy FFA species. Urea treatment proved useful for isolating polyunsaturated FFA (PUFA) from FFA derived from fish, borage, and linseed oils by removal of saturated and monounsaturated FFA, but was not effective for isolating hydroxy FFA from the FFA derived from castor, Lesquerella, and Dimorphotheca oils. In situations where FFA within the crystalline or UC phase were rich in PUFA, the urea/FFA mole ratio of the UC was relatively higher, with lower recovery of FFA in this phase. The distribution of urea between the crystalline phase and the solvent was not significantly affected by the FFA composition of feed nor the overall ratio of FFA to urea. It was strongly dependent on the overall mass fraction of solvent. Phospholipids and mono-, di-, and triacylglycerols were poor templates for UC formation relative to FFA. Their inclusion in acylglycerol mixtures containing FFA reduced UC formation.     

Fatty acid composition of seed oil triglycerides inCoincya (Brassicaceae)

Oil and triglyceride contents and fatty acid composition were determined for seeds in nine taxa belonging to the genusCoincya (Brassicaceae) on the Iberian Peninsula (Spain and Portugal). The oil content ranges from 11.1 to 24.6%, triglycerides from 68.7 to 88.5%. The major fatty acids were erucic (24.6–30.5%), linolenic (17.7–27.7%), linoleic (13.9–24.6%) and oleic acid (12.3–21.8%).     

Water-blown rigid and flexible polyurethane foams containing epoxidized soybean oil triglycerides

Both rigid and flexible water-blown polyurethane foams were made by replacing 0–50% of Voranol® 490 for rigid foams and Voranol® 4701 for flexible foams in the B-side of foam formulation by epoxidized soybean oil. For rigid water-blown polyurethane foams, density, compressive strength, and thermal conductivity were measured. Although there were no significant changes in density, compressive strength decreased and thermal conductivity decreased first and then increased with increasing epoxidized soybean oil. For flexible water-blown polyurethane foams, density, 50% compression force deflection, 50% constant force deflection, and resilience of foams were measured. Density decreased first and then increased, no changes in 50% compression force deflection first and then increased, increasing 50% constant force deflection, and decreasing resilience with increase in epoxidized soybean oil. It appears that up to 20% of Voranol® 490 could be replaced by epoxidized soybean oil in rigid polyurethane foams. When replacing up to 20% of Voranol® 4701 by epoxidized soybean oil in flexible polyurethane foams, density and 50% compression deflection properties were similar or better than control, but resilience and 50% constant deflection compression properties were inferior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Large-scale preparation of linoleic acid-d2-enriched triglycerides fromCrepis alpina seed oil

Catalytic deuteration ofCrepis alpina seed oil provided a convenient one-step method for the direct synthesis of large quantities of triglycerides enriched with deuteriumlabelled linoleic acid.Crepis alpina seed (19 kg) was crushed, and the oil [74% crepenynic acid (cis-9-octadecen-12-ynoic acid)] was extracted with hexane. After purification by column chromatography (silica gel), > 170-g batches of oil were deuterated with Lindlar catalyst and deuterium (D₂) gas. Purification (silica gel) resulted in > 150-g samples of triglyceride containing 74%cis-9,cis-12-octadecadienoic acid-12,13-d₂ (18:2-d₂) and 14% unlabelled linoleic acid. Pure (> 99%) tricrepenynin was recovered by further fractionation of theCrepis alpina triglycerides on silica gel. Deuteration of this sample produced deuteriumlabelled trilinolein containing linoleic acid-d₂ of > 98% isotopic purity.     

Synthesis of some new diarylsulphides and diarylsulphones containing a quinazol-4-one moiety

4-Amino-4′-nitrodiphenylsulphide and 4-amino-2′-nitrodiphenyl sulphide ( I ) were smoothly condensed with 2-methyl-3,1-benzoxazin-4-one ( II ) to produce the corresponding 2-methyl-3-diphenylsulphidoquinazol-4-ones ( III ). 2-Styryl-3-diphenylsulphidoquinazol-4-ones ( IV ) were prepared by heating III with the appropriate aromatic aldehydes using piperidine as a basic catalyst. Compounds IV oxidised easily in a hydrogen peroxide-glacial acetic acid mixture to produce the corresponding sulphones ( V ). The constitution of some of the prepared products is discussed in the light of their infrared and ultraviolet spectra. The biological activities of some of these compounds were tested.     

Synthesis and properties of a new crosslinkable polymer containing benzoxazine moiety in the main chain

Using difunctional phenolic and amine compounds, a new polymer with benzoxazine groups in the main chain has been synthesized through the Mannich reaction of a phenol, formaldehyde, and an amine. ¹H and ¹³C nuclear magnetic resonance spectroscopies, Fourier transform infrared spectroscopy, size exclusion chromatography, and elemental analysis are used to characterize the resulting polymer. Polymer with molecular weight of approximately 10,000 Da is obtained. The resultant polymer has a moderately broad polydispersity index. The thermal properties of the polymer have also been studied by differential scanning calorimetry and thermogravimetric analysis.     

Western Australian sandalwood seed oil: new opportunities

Western Australian Sandalwood (Santalum spicatum R.Br.) is an economically important timber crop. Sandalwood seeds have been identified as a potential secondary source of income prior to harvesting the tree. Chemical and toxicological studies of the seed have found that the kernels contain nearly 50% of a drying oil. This oil is comprised mainly of unsaturated fatty acids. The presence of an unusual acetylenic fatty acid has been confirmed. The oil was found to cause no pathological abnormalities in mice but reduced fat deposition. Acetylenic fatty acids are known to inhibit eicosanoids and stimulate certain enzymes, even though dietary consumption is yet to be trialled. The oil has potential uses in cosmetic and external pharmaceutical applications. Vegetable oils used in pharmaceutical and cosmetic formulations require high oxidation stability and antioxidant activity and benefit from the presence of other compounds such as sterols and tocopherols. This article summarises the research conducted over a half a century on sandalwood seeds and considers suitable uses and the future research needed to commercialise this oil.     

Vicinally unsaturated hydroxy acids in seed oils

Summary The interference of certain unsaturated hydroxy acids in the Durbetaki method of epoxide determination has been demonstrated. The concentrations of these constituents were determined concurrently with those of epoxy components by measurement of the near infrared spectra of samples before and after treatment with anhydrous ethereal hydrogen chloride. The individual hydroxy esters were separated and isolated from samples of mixed esters by thinlayer chromatography. GLC of these esters resulted in their alteration to conjugated trienoates and gave proof of their conjugated diene hydroxyl structure. Thin-layer chromatographic and infrared studies verified theTrans-trans diene unsaturation of the acid fromDimorphotheca aurantiaca oil and showed that the other hydroxy compounds examined have acistrans diene system. These data suggest that the seed oils ofArtemisia absinthium, Calliandra eriophylla, Balanites aegyptica, Cosmos bipinnatus, and Helianthus annuus contain 9-hydroxy-trans-10-cis-12- and 13-hydroxy-cis-9-trans-11-octadecadienoic acids. Supported by grants from The Hormel Foundation and the National Institutes of Health (Research Grant No. H-3559), and presented in part at the 33rd fall meeting, American Oil Chemists’ Society, Los Angeles, Calif., September 28–30, 1959. Fulbright Scholar to the Hormel Institute, 1958–1960.     

(S)-1,2-diacyl-3-acetins: Optically active triglycerides fromEuonymus verrucosus seed oil

The seed oil ofEuonymus verrucosus Scop., family Celastraceae, contains more than 90% 1,2-diacyl-3-acetins (monoacetotriglycerides). The constituent triglyceride acids, other than acetic, are the usual long-chain fatty acids. Thin-layer chromatography (TLC), infrared (IR) and hydrolysis with pancreatic lipase indicate that the acetic acid is esterified exclusively on the outer glycerol carbon atoms. The isolated mixed monoacetotriglycerides exhibit optical rotation caused by asymmetry of the central glycerol carbon atom. Comparison with synthetic products of known configuration shows that the natural material is essentially all (S)-1,2-diacyl-3-acetin. IR, TLC and GLC analyses indicate the presence of monoacetotriglycerides in seven other species of Celastraceae and five species in three other plant families in amounts from 13 to 98%. Presented at the AOCS Meeting in Los Angeles, April 1967, under the title “Optically Active Acetotriglycerides ofEuonymus verrucosus.” No. Utiliz. Res. Dev. Div., ARS, USDA.     

Glyceride structure ofErlangea tomentosa seed oil,a new source of vernolic acid

(+)-Methyl vernolate constitutes 52% of the methyl esters formed by transmethylating the oil ofErlangea tomentosa seed. Thin layer chromatography fractionated the oil into trivernolin, divernolins, monovernolins and nonvernolate glycerides. Pancreatic lipolyses of the monovernolins and the divernolins followed by transmethylation of the monoglycerides indicated the presence of 34 vernolate glycerides above the 0.1% level, grouped as follows: α-monovernolins, 15%; β-monovernolins, 3%; α,α′-divernolins, 10%; α,β-divernolins, 37%; trivernolin, 16%; and nonvernolate glycerides, 19%. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Stereospecific analysis of triglycerides from apple seed endosperm

Triglyceride composition and stereospecific distribution of fatty acids in apple seed oil are reported. Results are compared with proposed distribution theories.     

Polygala virgata seed oil—A new source of acetotriglycerides

The seed oil ofPolygala virgata (family Polygalaceae) contains 74% of monoacetotriglycerides, the first found in nature with the acetate group in position 2 ofsn-glycerol. Naturally occurring triglycerides characterized previously all have the acetate at position 3. The configuration of the acetoglyceride fromP. virgata was established by a combination of thin layer chromatography, optical rotatory dispersion, and nuclear magnetic resonance. Presented at AOCS Meeting, New York, May 1977.     

Synthesis and characterization of new C60-PPV dyads containing carbazole moiety

New C₆₀ covalently linked PPV derivatives containing carbazole moiety poly{(2,5-di-pentoxyl-phenylene)-1,4-diylvinylene-3,6-[9-(1-azafulleroid-propyl)carbazolenevinylene]} (PPV-AFCAR) were synthesized and characterized. The polymers containing different percentage of C₆₀ were obtained through the percentage of azido unit being controlled by the initial feed ratio. Cyclic voltametric analysis showed that the electronic characteristic remained while it covalently attached to polymer by the cycloaddition reaction. The fluorescences of PPV moieties were strongly quenched due to the presence of fullerene.     

Synthesis and characterization of new unsaturated polyesters containing cyclopentapyrazoline moiety in the main chain

3‐p‐Hydroxyphenyl‐6‐p‐hydroxybenzylidene cyclopentapyrazoline (III) and 3‐vanillyl‐7‐vanillylidene cyclopentapyrazoline (IV) were used as new starting materials for preparing new unsaturated polyesters. The polyesters were prepared by reacting (III) or (IV) with adipoyl, sebacoyl, isophthaloyl, and terephthaloyl dichlorides utilizing the interfacial polycondensation technique. The polyester samples have been characterized by elemental and spectral analyses. The polyesters have inherent viscosities of 0.55–0.97 dL/g. All the polyesters are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in concentrated sulfuric acid. Their glass transition temperatures (T_g) range from 103.34 to 208.81°C, and the temperatures of 10% weight loss as high as 190 to 260°C in air, indicating that these aromatic polyesters have high T_g and excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced dark brown colored semiconductive polymers with a maximum conductivity in the order of 3.1 × 10^?7 Ω^?1 cm^?1. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydroxymethylation and polymerization of plant oil triglycerides

The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free‐radical–initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by ¹H‐NMR, ¹³C‐NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass‐transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybean‐based polymer and 30°C for sunflower‐based polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4037–4046, 2004     

Characterization of triglycerides isolated from jojoba oil

Triglyceride compounds isolated from jojoba seed oil by column chromatography were composed predominantly of C_18′ C_20′ C_22′ and C₂₄ n−9 fatty acids with minor amounts of saturated C₁₆. Chain length and double-bond positions were determined by gas-liquid chromatography and gas-liquid chromatography-mass spectrometry of the corresponding methyl ester and picolinyl ester derivatives. Triglyceride structures were analyzed directly by ion trap mass spectrometry. The analysis of minor compounds, can provide highly specific information about the identity of an oil.