Showing papers in "Journal of the American Oil Chemists' Society in 2002"

Structure Indices in FA Chemistry. How Relevant Is the Iodine Value

Abstract: Most common analytical methods in FA chem- istry can be categorized as yielding either structure or quality indices. Quality indices often describe components in fats and oils arising from processing, storage, and naturally occurring, nonfatty materials. Common structure indices are the iodine value (IV), the saponification value, and the hydroxyl value. Al- though modern analytical methods yield more detailed and re- liable information, structure indices are still widely used. The IV, which indicates total unsaturation, has even been included in some standards for industrial products such as biodiesel. However, the IV index is too general to allow the correlation of physical and chemical properties with FA composition. The IV is treated in a theoretical fashion regarding biodiesel- and ox- idative stability-related issues. That the concept of IV as a struc- ture index is unsatisfactory is shown by the development of a quaternary composition diagram (QCD). The QCD demon- strates the derivation of a specific IV from varying FA composi- tions. Improved correlations are possible among the structure indices. Alternative indices for the IV are developed. Possible alternatives are the allylic position equivalent (APE) and the bis- allylic position equivalent (BAPE), which better relate structure and amount of common component FA in vegetable oils to ob- served properties. The APE and BAPE indices are based on the number of reactive positions in oxidation. Paper no. J10047 in JAOCS 79, 847-854 (September 2002). Analytical indices related to fats and oils can be distinguished as structure or quality indices. Structure indices are the iodine value (IV), a measure of total unsaturation of an oil or fat; the saponification value (SV), an indicator of average M.W.; and the hydroxyl value (HV), which is applicable to fatty com- pounds (or their mixtures) containing hydroxy groups, such

Antioxidant Activity of Phytosterols, Oryzanol, and Other Phytosterol Conjugates

Abstract: Antioxidant activity of phytosterols, oryzanol, ferulic acid ester of sterols, corn fiber oil, and rice bran oil was investigated. Commercial soybean oil and distilled soybean oil FAME were used as substrates for both oxidative stability determination and viscosity analysis after the oil was oxidized. At low concentration, these materials did not improve the oxidative stability of the oil substrates, although the viscosity tended to be reduced slightly. The antipolymerization activity of steryl ferulate was higher at higher concentration than at lower concentration, and steryl ferulate was more effective than oryzanol. Rice bran oil showed very good antioxidant and antipolymerization activities.

Analysis of free and esterified sterols in vegetable oils

Abstract: In vegetable oils, phytosterols occur as free sterols or as steryl esters. Few analytical methods report the quantification of esterified and free sterols in vegetable oils. In this study, esterified and free sterols were separated by silica gel column chromatography upon elution with n-hexane/ethyl acetate (90∶10 vol/vol) followed by n-hexane/diethyl ether/ethanol (25∶25∶50 by vol). Both fractions were saponified separately and the phytosterol content was quantified by GC. The analytical method for the analysis of esterified and free sterols had a relative standard deviation of 1.16% and an accuracy of 93.6–94.1%, which was comparable to the reference method for the total sterol analysis. A large variation in the content and distribution of the sterol fraction between different vegetable oils can be observed. Corn and rapeseed oils were very rich in phytosterols, which mainly occurred as steryl esters (56–60%), whereas the majority of the other vegetable oils (soybean, sunflower, palm oil, etc.) contained a much lower esterified sterol content (25–40%). No difference in the relative proportion of the individual sterols among crude and refined vegetable oils was observed.

Conjugated linoleic acid production from linoleic acid by lactic acid bacteria

Abstract: After screening 14 genera of lactic acid bacteria, Lactobacillus plantarum AKU 1009a was selected as a potential strain for CLA production from linoleic acid. Washed cells of L. plantarum with high levels of CLA production were obtained by cultivation in a nutrient medium with 0.06% (wt/vol) linoleic acid (cis-9,cis-12-octadecadienoic acid). Under the optimal reaction conditions with the free form of linoleic acid as the substrate, washed cells of L. plantarum produced 40 mg CLA/mL reaction mixture (33% molar yield) from 12% (wt/vol) linoleic acid in 108 h. The resulting CLA was a mixture of two CLA isomers, cis-9,trans-11 (or trans-9,cis-11)-octadecadienoic acid (CLA1, 38% of total CLA) and trans-9,trans-11-octadecadienoic acid (CLA2, 62% of total CLA), and accounted for 50% of the total FA obtained. A higher yield (80% molar yield to linoleic acid) was attained with 2.6% (wt/vol) linoleic acid as the substrate in 96 h, resulting in CLA production of 20 mg/mL reaction mixture [consisting of CLA1 (2%) and CLA2 (98%)] and accounting for 80% of total FA obtained. Most of the CLA produced was associated with the cells (ca. 380 mg CLA/g dry cells), mainly as FFA.

Effect of droplet size on lipid oxidation rates of oil-in-water emulsions stabilized by protein

Abstract: In emulsions lipid oxidation is mainly influenced by the properties of the interface. The aim of this work was to investigate the effects of droplet size and interfacial area on lipid oxidation in protein-stabilized emulsions. Emulsions, made of stripped sunflower oil (30% vol/vol) and stabilized by BSA were characterized by surface area values equal to 0.7, 5.1, and 16.3 m2·cm−3 oil. The kinetics of O2 consumption and conjugated diene (CD) formation, performed on emulsions and nonemulsified controls, showed that emulsification prompted oxidation at an early stage. On condition that oxygen concentration was not limiting, the rates of O2 consumption and CD formation were higher when the interfacial area was larger. Protein adsorbed at the interface probably restrained this pro-oxidant effect. Once most of the O2 in the system was consumed (6–8 h), CD remained steady at a level depending directly on the ratio between oxidizable substrate and total amount of oxygen. At this stage of aging, the amounts of primary oxidation products were similar whatever the droplet size of the emulsion. Hexanal and pentane could be detected in the headspace of emulsions only at this stage. They were subsequently produced at rates not depending on oil droplet size and interfacial area.

Effect of oxidation under accelerated conditions on fuel properties of methyl soyate (biodiesel)

Abstract: Biodiesel derived from transesterification of soybean oil and methanol is an attractive alternative fuel for combustion in direct-injection compression ignition (diesel) engines. During long-term storage, oxidation due to contact with air (autoxidation) presents a legitimate concern with respect to maintaining fuel quality of biodiesel. This work examines the effects of oxidation under controlled accelerated conditions on fuel properties of methyl soyate (SME). SME samples from four separate sources with varying storage histories were oxidized at elevated temperature under a 0.5 standard cm3/min air purge and with continuous stirring. Results showed that reaction time significantly affects kinematic viscosity (ν). With respect to increasing reaction temperature, ν, acid value (AV), PV, and specific gravity (SG) increased significantly, whereas cold flow properties were minimally affected for temperatures up to 150°C. Antioxidants TBHQ and α-tocopherol showed beneficial effects on retarding oxidative degradation of SME under conditions of this study. Results indicated that ν and AV have the best potential as parameters for timely and easy monitoring of biodiesel fuel quality during storage.

Enzyme-assisted aqueous extraction of peanut oil

Abstract: Enzyme-assisted aqueous extraction of oil from oilseeds is a relatively recent technique. In the present study, peanut oil was extracted under optimized aqueous extraction conditions using Protizyme™, which is predominantly a mixture of acid, neutral, and alkaline proteases. The optimal conditions were: enzyme concentration of 2.5% (w/w) in 10 g of peanut seeds, pH 4.0, 40°C, and 18 h incubation with constant shaking at 80 rpm. Centrifuging the mixture at 18,000 × g for 20 min separated the oil with a recovery of 86–92%. The merits of this process over existing solvent extraction and/or mechanical pressing methods are discussed.

Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil

Abstract: Mechanical and thermal properties of materials prepared by curing epoxidized soybean oil with various cyclic acid anhydrides in the presence of tertiary amines were investigated by dynamic mechanical thermal analysis and thermogravimetry. All samples presented thermoset material characteristics that were dependent upon the type of anhydride, the anhydride/epoxy molar ratio, and epoxy group content. The thermosets obtained from anhydrides with rigid structures as such phthalic, maleic, and hexahydrophthalic showed higher glass transition temperatures (Tg) and cross-linking densities. As expected, the Tg decreased as the anhydride/epoxy ratio decreased. The influence of the degree of epoxidation of soybean oil on the mechanical properties and Tg was also investigated. It was found that the higher the epoxy group amount, the higher the Tg and hardness. Cured resins exhibited thermal stability up to 300°C, except for those prepared with dodecenyl succinic anhydride, which began to decompose at lower temperature. They presented excellent chemical resistance when immersed in 1% wt/vol NaOH and 3% wt/vol H2SO4 solutions but poor chemical resistance in the presence of organic solvents.

The effect of steam treating waste cooking oil on the yield of methyl ester

Abstract: The effect of steam injection and sedimentation treatment of waste cooking oil on the quality of TG, to be used as a raw material for the production of biodiesel, was investigated. The effect of steam treatment was evaluated in terms of a number of physical and chemical characteristics. Significant decreases in the moisture, FFA, and PV, as well as increased energy value, were observed. GC analysis of the treated materials demonstrated little change in either the overall composition of the oils or the iodine value. The decreases in moisture from 1.4 to 0.4% and in FFA from 6.27 to 4.28% were found to correlate strongly with an increase in yield of ester from 67.5 to 83.5%.

Observations on the estimation of scavenging activity of phenolic compounds using rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH•) tests

Abstract: Rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH•) tests are often applied to classify the scavenging activity of phenolic compounds (AH). Published analytical protocols differ in more than one experimental condition, and results for the relative order or magnitude of activity are often contradictory. In this work, parameters such as duration of test, [AH]/[DPPH•] molar ratio, and solvent effects were examined and discussed. The test duration and the value of the [AH]/[DPPH•] ratio did not influence the order of activity among tested antioxidants. Ethanol, commonly used as solvent in such tests, was compared with acetonitrile and tert-butyl alcohol. Solvent properties such as the ability to form hydrogen bonds with the AH seem to influence the level of the relative activity (%RSA). Higher %RSA values were observed in ethanol. The activity of the most polar compounds was affected the most, and in some cases (caffeic, dihydrocaffeic, and rosmarinic acids) the order of activity was changed owing to different kinetics. Standardization of the analytical protocol should include a 20-min reaction period and a molar ratio that permits attainment of a 60–80% RSA value for the most potent antioxidant. Solvent choice is critical for classifying activity. Safe classification can be based only on results from kinetic studies.

Optimal tocopherol concentrations to inhibit soybean oil oxidation

Abstract: The optimal concentration for tocopherols to inhibit soybean oil oxidation was determined for individual tocopherols (α-, γ-, and δ-tocopherol) and for the natural soybean oil tocopherol mixture (tocopherol ratio of 1∶13∶5 for α-, γ-, and δ-tocopherol, respectively). The concentration of the individual tocopherols influenced oil oxidation rates, and the optimal concentrations were unique for each tocopherol. For example, the optimal concentrations for α-tocopherol and γ-tocopherol were ∼100 and ∼300 ppm, respectively, whereas δ-tocopherol did not exhibit a distinct concentration optimum at the levels studied (P<0.05). The optimal concentration for the natural tocopherol mixture ranged between 340 and 660 ppm tocopherols (P<0.05). The antioxidant activity of the tocopherols diminished when the tocopherol levels exceeded their optimal concentrations. Above their optimal concentrations, the individual tocopherols and the tocopherol mixture exhibited prooxidation behavior that was more pronounced with increasing temperature from 40 to 60°C (P<0.05). A comparison of the antioxidant activity of the individual tocopherols at their optimal concentrations revealed that α-tocopherol (∼100 ppm) was 3–5 times more potent than γ-tocopherol (∼300 ppm) and 16–32 times more potent than δ-tocopherol (∼1900 ppm).

TAG composition and solid fat content of palm oil, sunflower oil, and palm kernel olein belends before and after chemical interesterification

Abstract: Modification of the characteristics of palm oil (PO), sunflower oil, and plam kernel olein (PKOo) according to conventional three-component mixture designs was undertaken by a combination of blending and chemical interesterification (CIE) techniques. TAG composition and solid fat content (SFC) profile of the starting blends were analyzed and compared with those of the interesterified blends. Upon CIE, extensive rearrangement of FA among TAG was evident. Concentrations of several TAG were increased, some were decreased, and several new TAG were formed. The resulting changes in TAG profile were reflected in the SFC of the blends. The SFC values of the chemically interesterified blends, except binary blends of PO/PKOo, revealed that they were softer than their respective starting blends. SFC data also indicated that eutectic interaction occurred between PO and PKOo in the starting blends and that this interaction was diminished after CIE.

Production of Alkyl Ester as Biodiesel from Fractionated Lard and Restaurant Grease

Abstract: Methyl or ethyl esters were produced from lard and restaurant grease by lipase- or base-catalyzed reactions. Before esterifying, some renewable substrates (lard and restaurant grease) should be manipulated through acetone fractionation or on a chromatography column packed with an adsorbent to obtain maximal reaction rate. Because lipase activity was hindered by excess amounts (more than 1 mol) of methanol, each 1 M methanol was added sequentially after 24 h of reaction. Through a three-step reaction, 74% conversion to tallow-methyl ester was obtained. However, a porous substance, such as silica gel, improved the conversion when more than 1 M methanol was used as reaction substrate. When a 1∶3 (fractionated lard/methanol, mole ratio) substrate was used, the conversion rates (i.e., extent of conversion) were 2.7 (24 h) and 2.8% (48 h). However, with 10% silica gel in the reaction mixture, the conversion rates increased to 25 and 58%, respectively. Regenerated restaurant grease (FFA removed through column chromatography) was further converted to esters by alkali-catalyzed methanolysis. After 24 h of reaction, 96% conversion was obtained, while only 25% conversion was observed from crude grease. Alkyl esters produced in this study could be used for fuels, potentially as biodiesel.

Influence of the Vegetable Oil Refining Process on Free and Esterified Sterols

Abstract: The influence of the refining process on the distribution of free and esterified phytosterols in corn, palm, and soybean oil was studied. Water degumming did not affect the phytosterol content or its composition. A slight increase in the content of free sterols was observed during acid degumming and bleaching due to acid-catalyzed hydrolysis of steryl esters. A significant reduction in the content of total sterols during neutralization was observed, which was attributed to a reduction in the free sterol fraction. Free sterols probably form micelles with soaps and are transferred into the soapstock. The steryl ester content remained constant during all neutralization experiments, indicating that hydrolysis of steryl esters did not take place during neutralization. During deodorization, free sterols are distilled from the oil, resulting in a gradual reduction in the total sterol content as a function of the deodorization temperature (220–260°C). A considerable increase in the steryl ester fraction was found during physical refining, probably owing to a heat-promoted esterification reaction between free sterols and FA.

Antiradical activity of extracts of almond and its by-products.

Abstract: Antioxidant activities of ethanolic extracts of whole almond seed, brown skin, and green shell cover were evaluated using different free radical trapping assays. Trolox equivalent antioxidant capacity assay revealed that the total antioxidant capacities of brown skin and green shell cover extracts were 13 and 10 times greater than that of the whole seed extract at the same extract concentration. The free radical-scavenging activity of extracts of brown skin and green shell cover also exceeded that of the whole seed. The scavenging activity of superoxide radical by different almond extracts ranged from 76 to 97% at 100 ppm and 85 to 99% at 200 ppm. The corresponding reduction of hydrogen peroxide concentration was 59–66% (100 ppm) and 86–91% (200 ppm). The hydroxyl radical-scavenging capacities at 100 and 200 ppm were 16 and 42% for whole seed, 57 and 100% for brown skin, and 40 and 56% for green shell extracts, respectively. A 100% scavenging activity of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical was observed for brown skin and green shell extracts at 100 and 200 ppm concentrations, respectively, and whole seed extracts scavenged 21 (at 100 ppm) and 73% (at 200 ppm) of the DPPH radical.

The Effect of Fatty Acid Composition on the Acrylation Kinetics of Epoxidized Triacylglycerols

Abstract: Epoxidized oils, epoxidized triacylglycerols, and epoxidized fatty acid methyl esters were made by reaction with performic acid formed in situ. The extent of epoxidation was ca. 95% for all of the epoxidized samples, as determined by 1H nuclear magnetic resonance. The epoxidized samples were reacted with an excess of acrylic acid for different reaction times. The acrylation reaction was found to have a first-order dependence on the epoxide concentration for all oils, pure triacylglycerols, and fatty acid methyl esters. However, the rate constant of acrylation was found to depend on the composition of the epoxidized material. The acrylation rate constant for 9,10-epoxystearic acid was 96 L2/(mol2·min). The rate constant of acrylation for the epoxides on 9,10,12,13-diepoxystearic acid was 60 L2/(mol2·min). The acrylation rate constant for the epoxides on 9,10,12,13,15,16-triepoxystearic acid was 50 L2/(mol2·min). Thus, the rate constant of acrylation increased as the number of epoxides per fotty acid decreased. Multiple epoxides per fatty acid decrease the reactivity of the epoxides because of steric hindrance effects, and the oxonium ion, formed as an intermediate during the epoxyacrylic acid reaction, is stabilized by local epoxide groups. These results were used to derive an acrylation kinetic model that predicts rate constants from fatty acid distributions in the oil. The predictions of the model closely match the experimentally determined rate constants.

Supercritical CO2 extraction of flaxseed

Abstract: Extraction of flaxseed oil was performed with supercritical carbon dioxide (SC-CO2). To investigate the effects of pressure and temperature on the solubility of oil and oil yield, three isobaric (21, 35, and 55 MPa) and two isothermal (50 and 70°C) extraction conditions were selected. Although the maximal solubility of flaxseed oil, 11.3 mg oil/g CO2, was obtained at 70°C/55 MPa, the oil yield obtained after 3 h of extraction at this condition was only 25% (g oil/g seed×100), which represented 66% of the total available oil of the flaxseed. Lipid composition and FFA and tocol (tocopherol and tocotrienol) contents of the oils obtained by both SC-CO2 and petroleum ether extraction were determined. The α-linolenic acid content of the SC-CO2-extracted oil was higher than that obtained by solvent extraction.

Extraction and identification of natural antioxidant from the seeds of the Moringa oleifera tree variety of Malawi

Abstract: The oil from the dried seeds of the Moringa oleifera tree (variety of Malawi) was extracted with a mixture of chloroform/methanol (50∶50). The induction period measurements demonstrated a great resistance to oxidative rancidity. After degumming, there was a reduction of 74% in induction periods. The gums produced were extracted with diethylether, n-butanol, and water, yielding four fractions: Fraction 1 (81.8% w/w), Fraction 2 (0.04% w/w), Fraction 3 (0.05% w/w), and Fraction 4 (17.0% w/w). These fractions were tested for their protection of fresh sunflower oil against rancidity, at 50°C, using a UV accelerated method. The oxidation of the sunflower oil was measured using PV; absorbance E 1cm 1% and malondialdehyde concentration were measured by HPLC. The fraction that showed the highest antioxidant activity was further fractionated by HPLC, yielding seven fractions. Fraction HPLC 3 (present in a quantity of 330.8 and 29.11 ppm in gums and oil, respectively) showed the highest antioxidant activity. Its activity was also compared with that of the commonly used antioxidants BHT and α-tocopherol on sunflower oil using the same methods. At the same level of addition (200 ppm), HPLC 3 showed higher antioxidant activity than BHT and α-tocopherol. The identification of HPLC3 was done using 1H NMR, 13C NMR, MS, melting point, and UV absorption spectroscopy and proved to be 3,5,7,3′,4′,5′-hexahydroxyflavone (myricetin).

Characterization and supercritical carbon dioxide extraction of Walnut oil

Abstract: Walnut (Juglans regia L.) oil was extracted with compressed carbon dioxide (CO 2 ) in the temperature range of 308 to 321 K and in the pressure range of 18 to 23.4 MPa. The influence of particle size was also studied at a superficial veloc- ity of 0.068 cm/s, within a tubular extractor of 0.2 L capacity (cross-sectional area of 16.4 cm 2 ). FFA, sterol, TAG, and to- copherol compositions were not different from those of oil ob- tained with n-hexane. The main FA was linoleic acid (56.5%), followed by oleic acid (21.2%) and linolenic acid (13.2%). The main TAG was LLL (linoleic, linoleic, linoleic) (24.4%), fol- lowed by OLL (oleic, linoleic, linoleic) (19.6%) and LLLn (linoleic, linoleic, linolenic) (18.4%). The main component of sterols was β-sitosterol (85.16%), followed by campesterol (5.06%). The amount of cholesterol was low (0.31 and 0.16% for oils extracted by n-hexane and supercritical fluid extraction, respectively. The CO 2 -extracted oil presented a larger amount of tocopherols (405.7 µg/g oil) when compared with 303.2 µg/g oil obtained with n-hexane. Oxidative stability determined by PV and the Rancimat method revealed that walnut oil was read- ily oxidized. Oil extracted by supercritical CO 2 was clearer than that extracted by n-hexane, showing some refining. A central composite, nonfactorial design was used to optimize the extrac- tion conditions using the software Statistica, Version 5. The best results were found at 22 MPa, 308 K, and particle diameter (Dp) = 0.1 mm. Paper no. J9865 in JAOCS 79, 225-230 (March 2002).

One-step methodology for the synthesis of FA Picolinyl esters from intact lipids

Abstract: Picolinyl derivatives are used for structural determination of FA by GC-MS. Although they provide reliable diagnostic fragments, the usual multistep methodologies applied for their preparation require TAG hydrolysis or acid chloride formation prior to picolinyl synthesis. These reaction conditions may result in the presence of artifact molecules in the samples and thus compromise analytical quality and accuracy. To address these problems, a rapid, simple and quantitative methodology for the synthesis of FA picolinyl esters from intact lipids was developed. It involves their transesterification under basecatalyzed conditions using 3-potassiooxamethylpyridine in methylene chloride. The catalyst was prepared by proton exchange between potassium tert-butoxide and anhydrous 3-hydroxymethylpyridine. Mild reaction conditions allowed complete derivatization of TAG and phospholipids in 2 min at room temperature, and of FAME in 15 min at 45°C. The proposed procedure, which can be used on a routine basis, was applied to Ipomoae imperialis seed lipids and used to confirm occurrence of γ-linoleic acid at a level of 0.9%.

Formation of 4-hydroxynonenal, a toxic aldehyde, in soybean oil at frying temperature

Abstract: The formation of 4-hydroxy-2-trans-nonenal (HNE), a mutagenic and cytotoxic product of the peroxidation of linoleic acid, was monitored in soybean oil that was heated at 185°C for 2, 4, 6, 8, and 10 h. Unheated soybean oil contained no HNE and a relatively low concentration of polar lipophilic secondary oxidation products (aldehydes and related carbonyl compounds), measured as 2,4-dinitrophenylhydrazine derivatives by HPLC. An increase in the concentration of both HNE and total lipophilic polar oxidation products was observed with increased exposure to frying temperature. A considerable concentration of HNE had already formed at 2 h and the concentration continued to increase at 4 and 6 h of heating. After 6 h the concentration of HNE decreased, possibly due to degradation of the aldehyde with further exposure to high temperature. The loss of endogenous tocopherols was also monitored in the heated oil, and the tocopherol concentration decreased as the secondary lipid oxidation products increased.

Relationship between crystallization behavior, microstructure, and mechanical properties in a palm oil-based shortening

Abstract: In this study, the effects of cooling rate, degree of supercooling, and storage time on the microstructure and rheological properties of a vegetable shortening composed of soybean and palm oils were examined. The solid fat content vs. temperature profile displayed two distinct regions: from 5 to 25°C, and from 25°C to the end of melt at 45–50°C. A peak melting temperature of 42.7°C was determined by DSC. Discontinuity in the crystallization induction time (determined by pulsed NMR) vs. temperature plot at 27°C also suggested the existence of two separate groups of crystallizing material. Isothermal crystallization kinetics were characterized using the Avrami and Fisher-Turnbull models. In using DSC and powder X-ray diffraction, the α polymorph formed upon fast cooling (>5°C/min), and the β′ form predominated at lower cooling rates (<1°C/min). An α to β′ transition took place upon storage. Fractal dimensions (D f ) obtained by microscopy and image analysis showed no dependence on the degree of supercooling since D f remained constant (∼1.89) at crystallization temperatures of 5, 22, and 27°C. Crystallization at 22°C at 1°C/min and 15°C/min yielded D f values of 1.98 and 1.93, respectively. Differences in microstructure were observed, and changes in particle properties increased the parameter λ at higher degrees of supercooling.

Effect of FA composition on epoxidation kinetics of TAG

Abstract: The rate constants of epoxidation were determined by reacting formic acid with a number of oils, pure TAG, and pure FAME. These results showed that FA composition had a significant effect on the value of the rate constant. In TAG, the double bonds of oleic acid and linoleic acid were equally reactive, and the double bonds of linolenic acid were approximately three times more reactive than oleic and linoleic acids. For FAME, the rate constants of epoxidation increased as the level of unsaturation increased. Furthermore, the rate constants of epoxidation for the FAME were higher than their respective TAG. We conclude that steric and electronic effects caused FA with different levels of unsaturation to have different reactivities. These results were used to derive a model that predicts the epoxidation kinetics of oils from their FA composition. The predictions of the model closely match the experimentally determined rate constants.

Camelina oil and its unusual cholesterol content

Abstract: The oil in Camelina sativa L. Crantz has a combined linolenic and linoleic acid content that is greater than 50% and a relatively low saturated FA content (∼10%). Although the FA composition has been reported, no information is available on the sterol composition of camelina oil. The derivatized plant sterols were separated and quantified with capillary GC and their identity confirmed with GC-MS. The refined camelina oil sample contained approximately 0.54 wt% unsaponifiables, and over 80% of the unsaponifiables were desmethylsterols. Perhaps the most unusual characteristic of camelina oil is its relatively high content of cholesterol, particularly for a vegetable oil, since it contains several times the cholesterol found in other “high-cholesterol” vegetable oils. Camelina oil also contains relatively large amounts of another unusual sterol, brassicasterol. The major sterols identified in the camelina oil included cholesterol (188 ppm), brassicasterol (133 ppm), campesterol (893 ppm), stigmasterol (103 ppm), sitosterol (1,884 ppm), and Δ5-avenasterol (393 ppm).

Effect of roasting temperature and time on the chemical composition of rice germ oil

Abstract: Compositional changes of rice germ oils prepared at different roasting temperatures (160–180°C) and times (5–15 min) from rice germ were evaluated and compared with those of unroasted rice germ oil. The color development and phosphorus content of oils increased significantly as roasting temperature and time increased, whereas the FA compositions of rice germ oils did not change with roasting temperature and time. Four phospholipid classes, i.e., PE, PI, PA and PC, were identified. PE had the lowest stability under roasting conditions. There were no significant differences in γ-oryzanol levels of rice germ oils prepared at different roasting temperatures and times. Four tocopherol isomers (α−, β−, γ−, and δ-tocopherol) and three tocotrienol isomers (α−, γ−, and δ-tocotrienol) were identified, but no β-tocotrienol was detectable. The content of α− and γ−tocopherol in rice germ oil gradually increased as roasting temperature and time increased.

Study of TAG ethanolysis to 2-MAG by immobilized Candida antarctica lipase and synthesis of symmetrically structured TAG

Abstract: Regiospecific ethanolysis of homogenous TAG with immobilized Candida antarctica lipase (Novozym 435) was studied using trioleoylglycerol (TO) as a model substrate. Optimization of the reactant weight ratio revealed that the 2-MAG reaction yield increased when a larger amount of ethanol was used. These results suggested that Novozym 435 showed strict regiospecificity in an excess amount of ethanol. The process optimization (reaction temperature and reactant molar ratio) and a study of lipase specificity for various substrates were performed. Under the optimized conditions (ethanol/TO molar ratio=77∶1 and 25°C), 2-monooleoylglycerol (2-MO) was obtained in more than 98% content among glycerides of the reaction mixture and approximately 88% reaction yield in 4 h. The above reaction conditions were applied for ethanolysis of tridocosahexaenoylglycerol, trieicosapentaenoylglycerol, triarachidonoylglycerol, tri-α-linolenoylglycerol, and trilinoleoylglycerol. Reaction yields ranging from 71.9 to 93.7% were obtained in short reaction times (2.5 to 8 h). Purified (>98%) 2-MO and 2-monodocosahexaenoylglycerol (2-MD) were reesterified with caprylic acid by immobilized Rhizomucor miehei lipase (Lipozyme IM) to afford symmetrical structured TAG. At a stoichiometric ratio of 2-MAG/caprylic acid, 25°C and 2–5 mm Hg vacuum, the glyceride composition of the esterification mixture was approximately 95% 1,3-dicapryloyl-2-oleoylglycerol (COC) at 4 h, and 96% 1,3-dicapryloyl-2-docosahexaenoylglycerol (CDC) at 4 h, and 96% 1,3-dicapryloyl-2-docosahexaenoylglycerol (CDC) at 8 h. The regioisomeric purity of both COC and CDC was 100%.

Influence of moisture content and cooking on screw pressing of crambe seed

Abstract: The cooking and drying conditions for oilseeds preparatory to screw pressing are some of the most important factors that influence screw-press performance. Screw-press oil recovery, residual oil, pressing rate, and oil sediment content were measured for uncooked crambe seed and crambe seed cooked at 100°C for 10 min, pressed at six moisture contents ranging from 9.2 to 3.6% dry basis. Oil recovery significantly increased (P≤0.01) from 69 to 80.9% and 67.7 to 78.9% for cooked and uncooked seeds, respectively, as moisture content decreased. Residual oil significantly decreased (P≤0.01) from 16.3 to 11.1% and 16.9 to 11.9%, respectively, as moisture content decreased. The reduced oil loss due to only drying the seed from 9.2 to 3.6% was 32% for cooked seed, whereas cooking contributed only 3.6 to 7% reduced oil loss. Pressing rate decreased from 5.81 to 5.17 kg/h and 6.09 to 5.19 kg/h for cooked and uncooked seeds, respectively, whereas sediment content increased from 0.9 to 7.8% and 1.1 to 5.4%, respectively, as moisture content decreased. The effects of moisture content on pressing rate and sediment content were significant at P≤0.05. All relationships of screw-press performance to moisture content were fitted to a second-order polynomial.

Epoxidation of soybean oil by the methyltrioxorhenium‐CH2Cl2/H2O2 catalytic biphasic system

Abstract: We studied the methyltrioxorhenium (MTO)-CH2Cl2/H2O2 biphasic system for epoxidizing soybean oil. The reactions were optimized (reactant ratio, time, and temperature), which resulted in a better performance (higher conversion and selectivity) than those described in the literature. Total doublebond conversion and 95% selectivity were obtained in 2 h at room temperature. Furthermore, it was possible to reach desired epoxidation degrees by changing the oxidant and MTO amounts. The rhenium-epoxidized soybean oil remained stable in the absence of stabilizers for up to 30 d when stored at mild conditions.

Plasticization of soy protein polymer by polyol-based plasticizers

Abstract: Soy protein isolate (SPI) was mixed with four polyol-based plasticizers and molded into plastics using a hot press. The plasticized SPI powder was evaluated for denaturation temperatures and denaturation enthalpies. The SPI plastics were studied for mechanical properties, glass transition temperatures, storage modulus, morphology, and water absorption. Thermal properties of the SPI plastics with propylene glycol were depressed to the largest degree, and the plastics with glycerol showed the largest strain at break, whereas plastics with 1,3-butanediol gave the highest tensile strength. The morphology of the fractured surface on the SPI plastics changed from brittle fracture for the unplasticized SPI to ductile fracture for the plasticized SPI. Water absorption of all the plasticized SPI plastics was lower than that of the unplasticized SPI plastics.

Variables affecting the yields of methyl esters derived from in situ esterification of rice bran oil

Abstract: The influence of specific factors on in situ methanolic esterification of rice bran oil (RBO) using sulfuric acid catalyst was investigated. using high-FFA rice bran was found to be the most effective means to increase methyl ester yields. The ester content of the extract increased about 67% when the FFA content of oil was increased from 16.6 to 84.5%. Increasing the reaction time beyond 30 min did not affect yields. Increasing the temperature from 20 to 65°C elevated the FAME yield by about 30%, but increasing the amount of acid catalyst above 5 mL did not enhance yield, and increasing the methanol dose from 200 to 250 mL had a negligible effect.