Pilot plant extraction of oil fromVernonia galamensis seed

Vernonia galamensis seed containing 40–42% oil and 30–34% epoxy acid, (cis-12,13-epoxy-cis-9-octadecenoic) was processed to oil and meal. Seed conditioning, pressing and solvent extraction research were conducted in pilot facilities at the French Oil Mill Machinery Co. (Piqua, OH). The robust lipase system was successfully inactivated by treating 200 lb. batches ofV. galamensis seed in a cooker/conditioner at 195–200°F and >10% moisture. Conditioned seed was mechanically pressed and the press discharge cone setting was varied during operation from 1/32″ to 3/32″ to demonstrate the feasibility of both full pressing and prepressing. Prepressing successfully reduced oil level in the press cake to ca. 20%. Press cake was extracted with hexane in a 1.5-ft³ batch-type, four-stage percolation unit with a 6″ square extraction cross section. Solvent extraction reduced oil level in the defatted meal to 1–2%. The defatted meal was desolventized and toasted. Excessive foaming of the vernonia oil extract made complete solvent stripping in the oil stripping unit difficult.     

Enzymatic synthesis and spectroscopic characterization of 1,3-divernoloyl glycerol fromVernonia galamensis seed oil

cis-12,13-Epoxy-cis-octadecenoic (vernolic) acid occurs in triglycerides of the seed oil ofVernonia galamensis. The seeds also contain a lipase capable of hydrolyzing the triglycerides. Previous investigators incubated the seed ofVernonia anthelmintica and isolated 5.6% yield of 1,3-divernoloyl glycerol. We used crude lipase extract fromV. galamensis seed to synthesize 1,3-divernoloyl glycerol from vernonia oil in pentane at 40% yield. A 94% conversion of the 1,3-divernoloyl glycerol to pure vernolic acid (5.34% oxirane = 98.9% purity) was achieved by a low-energy saponification process. The carbon-13 nuclear magnetic resonance (NMR) spectrum of the 1,3-divernoloyl glyceride indicates a potential for using carbon-13 NMR spectroscopy in the identification of isomeric diglycerides. Thus the paper describes the synthesis, spectroscopic and chemical characterization of 1,3-divernoloyl glycerol, in addition to providing quantitative carbon-13 NMR studies ofV. galamensis oil.     

Synthesis of azelaic acid and suberic acid fromVernonia galamensis oil

We have demonstrated the potential ofVernonia galamensis seed oil as a source of dibasic acids. Reaction of nitric acid withV. galamensis oil afforded a homologous series of dibasic acids that include butanedioic acid, pentanedioic acid, hexanedioic acid (adipic), heptanedioic acid (pimelic), octanedioic acid (suberic), nonanedioic acid (azelaic), decanedioic acid (sebacic), and undecanedioic acid. Using a combination of chloroform extraction and subsequent water crystallizations, we have isolated suberic acid (∼95% purity by GC) and azelaic acid (∼95% purity by GC). The isolated yield of suberic acid is 15% and of azelaic acid is 11%. Reported reaction of nitric acid with ricinoleic acid (from castor oil) gave 8.8% suberic acid and 7.2% of a mixture of suberic and azelaic acids.     

Synthesis and isolation of epoxy secondary amidesvia direct amidation ofVernonia galamensis seed oil

Vernonia galamensis oil, containing naturally epoxidized triglycerides, was reacted withn-butylamine,n-pentylamine andn-hexylamine to afford high yields of epoxidized secondary amides. Three reaction conditions were investigated: (i) reflux with amines as solvents, (ii) reflux with hexane as the solvent and (iii) room temperature with the amines as solvents. Reactions with amines as refluxing solvents were completed in 1–5 h, while those with hexane went to completion within 2 to 5 d. Room temperature reactions were onlyca. 80% complete after several days. Reactivity was increased with higher amine homologs at both reflux and room temperature reaction conditions. Isolated yields of epoxy-containing amides were about 80% with purity exceeding 96% in all cases. Spectroscopic characterization of the previously unreported alkyl-vernolamides is provided.     

Synthesis of toughened elastomer from vernonia galamensis seed oil

This paper examines the synthesis of a toughened elastomer fromVernonia galamensis seed oil by reacting vernonia oil with vernonia oil-derived suberic acid (octanedioic acid), and cross-linking the pre-polymer in the immediate presence of cross-linked polystyrene preparedin situ. The paper also demonstrates that the progress of reaction can be followed by monitoring the generation of hydroxyl groups using infrared spectroscopy. Analysis of some crystalline material on the cooler parts of the reaction vessels revealed the presence of component fatty acids of vernonia oil. Transmission electron microscopy characterization of the synthesized toughened elastomer suggests that vernonia oil-suberic acid polyester and polystyrene polymer are interpenetrating.     

The purification and specificity of a lipase fromVernonia anthelmintica seed

Acetone powders prepared fromVernonia anthelmintica seed catalyzed the release of 6.4 to 9.6 μ-moles of free fatty acids per milligram of protein when blended with olive oil and phosphate buffer and shaken for 20 min at 43 C. A 20 fold purification was achieved by differential centrifugation of an ammonium hydroxide extract of the acetone powder. Results from Sephadex G-200 chromatography and polyacrylamide gel electrophoresis suggested that the lipase activity was associated with a molecule of molecular weight greater than 200,000. Free fatty acids, 1,2- and 1,3-diglycerides, monoglycerides and glycerol were found in the digestion products. With most substrates the 1,2-to 1,3-diglyceride ratio was approximately 2∶1 and monoglycerides tended to accumulate. Analysis of the digestion products from synthetic triglycerides of known structure indicated that both primary and secondary ester positions of the triglyceride molecule were hydrolyzed and that considerable isomerization of 1,2-diglyceride to 1,3-diglyceride occurred. The monoglyceride was consistently lower than the 1,2-diglyceride and in the majority of cases also lower than the 1,3-diglyceride in the fatty acid originally present in the 2 position of the triglyceride. No fatty acid preference was observed. Scientific contribution No. 316. Presented in part at the AOCS Meeting, Philadelphia, October 1966.     

Utilization of green seed canola oil for in situ epoxidation

Green seed canola oil is underutilized for edible purposes due to its high chlorophyll content, which makes it more susceptible to photo‐oxidation and ultimately reduces the oxidation stability. The present work is an attempt to compare the kinetics of epoxidation of crude green seed canola oil (CGSCO) and treated green seed canola oil (TGSCO) with peroxyacids generated in situ in presence of an Amberlite IR‐120 acidic ion exchange resin (AIER) as catalyst. Among the two oxygen carrier studied, acetic acid was found to be a better carrier than the formic acid, as it gives 8% more conversion of double bond than the formic acid. A detailed process developmental study was then performed with the acetic acid/AIER combination. For the oils under investigation parameters optimized were temperature (55°C), hydrogen peroxide to double bond molar ratio (2.0), acetic acid to double bond molar ratio (0.5), and AIER loading (15%). An iodine conversion of 90.33, 90.20%, and a relative epoxide yield of 90, 88.8% were obtained at the optimum reaction conditions for CGSCO and TGSCO, respectively. The formation of the epoxide product of CGSCO and TGSCO was confirmed by Fourier Transform IR Spectroscopy (FTIR) and NMR (1H NMR) spectral analysis.     

Analysis of lipids containing epoxy groups: The epoxy glycerides ofVernonia anthelmintica seed oil

Picration-TLC analysis ofVernonia anthelmintica seed oil shows that besides the known triglyceride of vernolic acid, it also contains two additional epoxy compounds. These were isolated by column chromatography and have been identified as the monoepoxy and the diepoxy triglycerides of vernolic acid by a rapid transmethylation-GLC micromethod. Lipase hydrolysis of these glycerides has shown that in the monoepoxy triglycerides the vernolic acid has marked preference for the 1,3-positions, while in the diepoxy triglycerides the 2-position is preferred.     

环氧葵花籽油的合成及其在环氧树脂共混物中的应用研究

通过考察催化剂用量、反应温度及反应时间、氧化剂等因素对环氧葵花籽油产率的影响,确定了较适宜的反应条件.在此反应条件下产品产率大于90％.考察了环氧化葵花籽油含量对环氧树脂/环氧葵花籽油共混物冲击强度的影响.结果表明,当环氧化葵花籽油的质量分数为30％时,共混物的冲击强度比纯环氧树脂提高了60％.     

Isolation of a natural isomer of linoleic acid from a seed oil1,2

trans-10-trans-12-Octadecadienoic acid was found to be a component of the glyceride oil of the seeds ofChilopsis linearis (Cav.) Sweet. It was isolated by fractional crystallization of the acids at low temperatures. Identification was made by absorption spectra, by the adduct with maleci anhydride, and by identification of degralative products. The conjugated triene of the oil was also isolated and identified astrans-9-trans-11-cis-13octadecatrienoic acid. in two samples of seed, the diene acid constituted about 9% of the oil and the triene acid 18% and 25%. Presented at the AOCS meeting in Toronto, Canada, 1962. Issued as NRC No. 7592.     

Chemical and nutritional studies on the seed oil ofAcacia arabica

The seeds ofAcacia arabica contain 5.2% oil. Physicochemical constants and fatty acid composition of the refined seed oil were determined. The seed oil was rich in linoleic acid (39.2%) and oleic acid (32.8%). Trace quantities of epoxy and hydroxy fatty acids were present in the seed oil. Nutritional evaluation of the refined seed oil was done by rat bioassay with peanut oil as control. The animals fed 10% seed oil showed poor growth performance and low feed efficiency ratio. The digestibility of the seed oil was 90% compared to 94% for peanut oil. The seed oil in the diet of rats for 4 wk did not produce any abnormal serum lipids or histopathological findings.     

Chemoenzymatic epoxidation of unsaturated fatty acid esters and plant oils

In the presence of an immobilized lipase fromCandida antacrtica (Novozym 435^R) fatty acids are converted to peroxy acids by the reaction with hydrogen peroxide. In a similar reaction, fatty acid esters are perhydrolyzed to peroxy acids. Unsaturated fatty acid esters subsequently epoxidize themselves, and in this way epoxidized plant oils can be prepared with good yields (rapeseed oil 91%, sunflower oil 88%, linseed oil 80%). The hydrolysis of the plant oil to mono- and diglycerides can be suppressed by the addition of a small amount of free fatty acids. Rapeseed oil methyl ester can also be epoxidized; the conversion of C=C-bonds is 95%, and the composition of the epoxy fatty acid methyl esters corresponds to the composition of the unsaturated methyl esters in the substrate. Based partly on a lecture at the 86th AOCS Annual Meeting & Expo, San Antonio, Texas, May 7–11, 1995.     

Processability characteristics and physico‐mechanical properties of natural rubber modified with rubber seed oil and epoxidized rubber seed oil

The processability characteristics and physico‐mechanical properties of natural rubber (NR) modified with raw rubber seed oil and epoxidized rubber seed oil have been studied. The modified mixes showed higher scorch time and lower cure rate, crosslink density, and ultimate state of cure compared to an unmodified mix. The thermal stability of the vulcanizates was practically unaffected by the modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1413–1418, 2000     

The conjugation and epoxidation of fish oil

Wilkinson's catalyst [RhCl(PPh₃)₃] has been used to conjugate fish oils in high yields under very mild reaction conditions. A catalyst load of 0.35 mol% of RhCl(PPh₃)₃, 0.43 mol% of (o-CH₃C₆H₄)₃P, and 0.87 mol% of SnCl₂·2H₂O in ethanol solvent at 60°C for 2 d produces 82% conjugated Norway fish oil affords 90% conjugated fish oil in 93% yield. The Sharpless epoxidation procedure has also been employed to epoxidize fish oils. Using 0.34 mol% of CH₃ReO₃, 8.15 mol% of pyridine, and 1.03 equivalents of aq. 30% hydrogen peroxide in methylene chloride solvent at 25°C for 6 h, the Norway fish oil ethyl ester can be 100% epoxidized in an 86% yield. The Capelin fish oil gives 100% epoxidized fish oil in a 72% yield. Decreasing the amounts of CH₃ReO₃ and pyridine used in the reaction results in partially epoxidized fish oils.     

Chemical characterization of lysyl oxidase inhibitor from avocado seed oil

The active factor of lysyl oxidase inhibition was separated from unsaponifiables of avocado seed oil and characterized by gas chromatography-mass spectrometry. Results indicated the presence of furan-containing lipids in the active factor mixture and also showed a structural difference compared to previously reported furan-containing lipids of avocado which relates to the length of the hydrocarbon chain substituent. Another structural difference evinced was the availability of the hydroxyl group in the aliphatic moiety of the investigated substances. A purified mixture of furan-containing compounds was testedin vitro for inhibitory activity on pure bovine aorta lysyl oxidase. It was shown that mixing furan-containing lipids in Tween 80 reversibly inhibited pure bovine aorta lysyl oxidase activity against tritiated recombinant tropoelastin with the I₅₀ value of inhibition of 105 μM. Thesein vitro studies suggested that the mixture of avocado seed oil furan-containing lipids was not a substrate-specific inhibitor of lysyl oxidase, and it might prove to be useful as a potential antifibrotic drug. Moreover, the unique chemistry of the studied compound for lysyl oxidase inhibition should enable the designing of new probes of the active site of this important enzyme.     

Chemical and nutritional evaluation of chili (Capsicum annum) seed oil

Alkali-refined red chili (Capsicum annum) seed oil was analyzed for free fatty acids, iodine value, saponification value, peroxide value and fatty acid composition, and the values were found to be close to those of edible oils. The alkali-refined chili oil (5% of diet), alcohol-treated chili oil (5%) and a mixture of alcohol-treated chili oil and peanut oil (5%+5%) were fed to adult male albino rats in natural diets for eight weeks. Digestibility was normal in all experimental animals and was on par with the peanut oil control. Serum lipid levels in the group fed alcohol-treated chili oil were slightly high compared to those in groups fed alkali-refined chili oil and peanut oil. Liver structure revealed no abnormalities.     

Mesua ferrea L. seed oil based highly branched polyester/epoxy blends and their nanocomposites

Mesua ferrea L. seed oil based highly branched polyester and epoxy resins blends were prepared by mechanical mixing at different weight ratios. The best performing blend was used as the matrix for the preparation of nanocomposites with different dose levels of organophilic montmorillonite (OMMT) nanoclay. The prepared nanocomposites were characterized by X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Data resulting from the mechanical and thermal studies of the blends and nanocomposites indicated improvements in the tensile strength and thermal stability to appreciable extents for the nanocomposites with OMMT loading. The nanocomposites were characterized as well‐dispersed, partially exfoliated structures with good interfacial interactions. From the X‐ray diffraction analysis, the absence of d₀₀₁ reflections of the OMMT clay in the cured nanocomposites indicated the development of an exfoliated clay structure, which was confirmed by transmission electron microscopy. The homogeneous morphologies of the pure polyester/epoxy blend and clay hybrid systems were ascertained with scanning electron microscopy. The tensile strength of the 5 wt % clay‐filled blend nanocomposite system was increased by 2.4 times compared to that of the pure blend resin system. The results suggest that the prepared nanocomposites have the potential to be used as active thin films for different applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characteristics of tea seed oil in comparison with sunflower and olive oils and its effect as a natural antioxidant

A comparison of iodine values showed that the degree of saturation of tea seed oil (Lahjan variety) was intermediate between the oils of sunflowerseed (Fars variety) and olive (Gilezeytoon variety), and the saponification values of these three oils were similar. Tea seed oil consisted of 56% oleic acid (C18∶1), 22% linoleic acid (C18∶2), 0.3% linolenic acid (C18∶3), and therefore, on the basis of oleic acid, occupied a place between sunflower and olive oil. In studies at 63°C, the shelf life of tea seed oil was higher than that of sunflower oil and similar to olive oil. Tea seed oil was found to have a natural antioxidant effect, and it enhanced the shelf life of sunflower oil at a 5% level. In this study, tea seed oil was found to be a stable oil, to have suitable nutritional properties (high-oleic, medium-linoleic, and lowlinolenic acid contents), and to be useful in human foods.     

Kinetic parameters of a two-phase model forin situ epoxidation of soybean oil

The process ofin situ epoxidation consists of a two-phase system that involves reactions in both phases, mass transfer between phases, and thermodynamic driving forces for the mass transfer. In this paper, we present a model that treats the process as a two-phase system and uses local phase concentrations to calculate reaction and mass transfer rates. The process ofin situ epoxidation has been broken down into a set of systematic steps, and rate constants for each step have been determined. A conventional stirred tank reactor, equipped with cooling coils, eliminated the heat and mass transfer limitations so that the true kinetics ofin situ epoxidation were observed. It is shown that significantly larger rates (larger by factors of 2–10) are obtained when heat and mass transfer limitations are removed. The two-phase model adequately predicts the epoxidation kinetics over a wide range of temperatures (50–90°C). In addition, the model also correctly predicts the effect of adding an inert solvent.