bluuebunny/crossref_metadata_2025 huggingface dataset:
Phospholipid fatty acid composition and stereospecific distribution of soybeans with a wide range of fatty acid composition
Authors: Wang Tong , Hammond Earl G. , Fehr Walter R.
Published: May 2007

Phospholipid (PL) fatty acid composition and stereospecific distribution of 25 genetically modified soybean lines with a wide range of compositions were determined by gas chromatography and phospholipase A2 hydrolysis. Pl contained an average of 55.3% phosphatidylcholine, 26.3% phosphatidylethanolamine, and 18.4% phosphatidylinositol. PL class proportions were affected by changes in overall fatty acid composition. PL fatty acid composition changed with oil fatty acid modification, especially for palmitate, stearate, and linolenate. Stereospecific analysis showed that saturated fatty acids were primarily located at the sn‐1 position of all PL, and changes of the saturates in PL were largely reflected on this position. Oleate was distributed relatively equally between the sn‐1 and sn‐2 positions. Linoleate was much more concentrated on sn‐2 than on sn‐1 position for all PL. Linolenate was distributed relatively equally at low concentration but preferred sn‐2 position at high concentration.
Determination of the fatty acid composition of the oil in intact‐seed mustard by near‐infrared reflectance spectroscopy
Authors: Velasco L. , Fernández‐Martínez J. M. , De Haro A.
Published: May 2007

Near‐infrared reflectance spectroscopy (NIRS) was used to estimate the fatty acid composition of the oil in intact‐seed samples of Ethiopian mustard (Brassica carinata Braun) within a mutation breeding program that produced seeds with variable fatty acid compositions. Five populations, from 1992 to 1996 crops, were included in this study; and NIRS calibration equations for major fatty acids (palmitic, stearic, oleic, linoleic, linolenic, eicosenoic, and erucic) were developed within each single population. Furthermore, global calibration equations, including samples from the five populations, were developed. After external validation, the NIRS technique permitted us to obtain a reliable and accurate nondestructive estimation of the fatty acid composition of the oil, especially for the major acids—oleic, linoleic, linolenic, and erucic. For these, the r2 in external validation was higher than 0.95 by using both single‐and multipopulation equations, and higher than 0.85 for the remaining fatty acids. Moreover, the multipopulation equations provided an accurate estimation of samples from a population not represented in the calibration data set, with values of coefficient of determination in validation (r2) from 0.80 (palmitic and eicosenoic acids) to 0.97 (erucic acid). The ability of NIRS to discriminate among different fatty acid profiles was mainly due to changes within six spectral regions, 1140–1240, 1350–1400, 1650–1800, 1880–1920, 2140–2200, and 2240–2380 nm, all of them associated with fatty acid absorbers. Thus, NIRS can be used to estimate the fatty acid composition of Ethiopian mustard seeds with a high degree of accuracy, provided that calibration equations be developed from calibration sets that include large variability for the fatty acid composition of the oil.
Tocopherol and fatty acid composition of some Indian pulses
Authors: Gopala Krishna A. G. , Prabhakar J. V. , Aitzetmüller K.
Published: May 2007

The tocopherol and tocotrienol composition of the Indian pulses Bengal gram (Cicer arietinum L.), blackgram (Vigna mungo L.), green gram (Vigna radiata L.), and horse gram (Dolichos biflorus L.) were studied. The total tocopherol content ranged from 230 to 1567 mg/100 g fat, while the tocopherol content of the pulses as a whole ranged from 6.76 to 12.54 mg/100 g seed. Presence of such a high amount of tocopherol, both in the oil fraction of Indian pulses and in an oil fraction of a food material, is being reported for the first time. The fatty acid composition of the fat extracted from these pulses showed substantial amounts of unsaturated fatty acids (Bengal gram, 88.7%; black gram, 82.9%; green gram, 64.3%; and horse gram, 66.9%). These pulses contained 3.8 to 49.1% linolenic acid in the fat.
Optimizing headspace sampling temperature and time for analysis of volatile oxidation products in fish oil
Authors: Rørbæk Karen , Jensen Benny
Published: May 2007

Headspace‐gas chromatography (HS‐GC), based on adsorption to Tenax GR®, thermal desorption and GC, has been used for analysis of volatiles in fish oil. To optimize sampling conditions, the effect of heating the fish oil at various temperatures and times was evaluated from anisidine values (AV) and HS‐GC. AV indicated sample degradations at 90°C but only small alterations between 60 and 75°C. HS‐GC showed increasing response with temperature and time. Purging at 75°C for 45 min was selected as the preferred sampling condition for oxidized fish oil.
Oxidative stability of conjugated linoleic acids relative to other polyunsaturated fatty acids
Authors: Zhang A. , Chen Z. Y.
Published: May 2007

Contrary to current opinion, conjugated linoleic acids (CLA) as a mixture of several isomers have been previously shown to function as prooxidants in the form of free fatty acids and methyl esters in heated canola oil. Furthermore, CLA oxidizes considerably faster than linoleic acid. However, stability of CLA relative to other polyunsaturated fatty acids remains undetermined. The present study was therefore undertaken to examine the relative oxidation rate of CLA compared with that of linolenic acid (LNA), arachidonic acid (AA), and docosahexaenoic acid (DHA) in air at 90°C. CLA, both in the form of free fatty acids and triacylglycerols, were extremely unstable to the same extent as DHA, but they oxidized considerably faster than LNA and AA. The mechanism by which CLA were readily decomposed was probably due to formation of the unstable free‐radical intermediate.
Fatty methyl ester hydrogenation to fatty alcohol part II: Process issues
Authors: Rieke Ross D. , Thakur Deepak S. , Roberts Brian D. , White Geoffrey T.
Published: May 2007

Fatty alcohols are produced by hydrogenating fatty methyl esters in slurry phase in the presence of copper chromite catalyst at temperatures of 250–300°C and hydrogen pressures of 2000–3000 psi. The fatty methyl ester, catalyst, and hydrogen are fed to the reactor cocurrently. The product slurry is passed through gas‐liquid separators and then through a continuous filtration system for removal of the catalyst. A portion of the used catalyst in crude alcohol is recycled to the hydrogenator. The overall efficiency of the process depends upon the intrinsic activity, life, and filterability of the catalyst. The fatty alcohol producer therefore requires a catalyst with high activity, long life, and good separation properties. The main goal of the present laboratory investigation was to develop a superior copper chromite catalyst for the slurry‐phase process. Two copper chromite catalysts, prepared by different procedures, were tested for methyl ester hydrogenolysis activity, reusability, and filtration characteristics. The reaction was carried out in a batch autoclave at 280°C and 2000–3000 psi hydrogen pressure. The reaction rates were calculated by assuming a kinetic mechanism that was first‐order in methyl ester concentration. The catalyst with the narrower particle size distribution was 30% more active, filtered faster, and maintained activity for several more uses than the catalyst with the broader particle size distribution. X‐ray photoelectron spectroscopy data showed higher surface copper concentrations for the former catalyst.
Effect of fatty acid composition of oils on flavor and stability of fried foods
Authors: Warner K. , Orr P. , Glynn M.
Published: May 2007

Effects of fatty acid composition of frying oils on intensities of fried‐food flavor and off‐flavors in potato chips and french‐fried potatoes were determined. Commercially processed cottonseed oil (CSO) and high‐oleic sunflower oil (HOSUN) were blended to produce oils with 12 to 55% linoleic acid and 16 to 78% oleic acid. Analytical sensory panels evaluated french‐fried potatoes and pilot plant‐processed potato chips. Initially, both foods prepared in CSO (16% oleic/55% linoleic acid) had the highest intensities of fried‐food flavor; however, this positive flavor decreased with decreasing levels of linoleic acid. 2,4‐Decadienal in potato chips also decreased with decreasing linoleic acid in the oils. Frying oil stability, measured by total polar compounds (TPC), and oxidative stability of potato chips, measured by volatile compounds, showed that HOSUN (78% oleic acid) produced the lowest levels of TPC and the lowest levels of hexanal and pentanal, indicating greater frying oil stability and oxidative stability of the food. However, fresh potato chips fried in HOSUN had the lowest intensities of fried‐food flavor and lowest overall flavor quality. Fried‐food flavor intensity was the best indicator of overall flavor quality in fresh potato chips. Volatile compounds, TPC, and oxidative stability index directly varied with increasing oleic acid, and were therefore not directly indicative of flavor quality. No oil analysis predicted flavor stability of aged potato chips. Compositions of 16 to 42% oleic acid and 37 to 55% linoleic acid produced fresh fried‐food with moderate fried food flavor intensity, good overall flavor quality, and low to moderate TPC levels (chips only). However, in aged food or food fried in deteriorated oil, compositions of 42 to 63% oleic and 23 to 37% linoleic provided the best flavor stability.
Heated fat‐based oil substitutes, oleic and linoleic acid‐esterified propoxylated glycerol
Authors: Artz William E. , Hansen Steven L. , Myers Michelle R.
Published: May 2007

Four oils [triolein, trilinolein, oleic acid‐esterified propoxylated glycerol (EPG‐08 oleate), and linoleic acid‐esterified propoxylated glycerol (EPG‐08 linoleate)], each without added antioxidants, were heated for 12 h/d at approximately 190°C in a small deep‐fat fryer until the polymer concentration exceeded 20%, as determined by high‐performance size‐exclusion chromatography. Increases in the free fatty acid content, total acid value, food oil sensor value, and p‐anisidine value during heating indicated that significant thermal oxidation had occurred in each oil. Capillary supercritical fluid chromatography (SFC) was used to determine the substrate concentration of each oil after each heating interval. The average, apparent first‐order reaction rate constant (as determined by SFC) for trilinolein was 0.0348±0.0034 h−1, while the rate for EPG‐08 linoleate was 0.0253±0.0032 h−1. The average apparent reaction rate constant for triolein was 0.0256±0.0011 h−1, while the rate for EPG‐08 oleate was 0.0252±0.0008 h−1. Triolein contained >20% polymer after 60 h of heating, EPG‐08 oleate contained >20% polymer after 36 h of heating, and both trilinolein and EPG‐08 linoleate contained >20% polymer after 24 h of heating.
A multivariate study of the correlation between tocopherol content and fatty acid composition in vegetable oils
Authors: Kamal‐Eldin Afaf , Andersson Roger
Published: May 2007

The main biochemical function of the tocopherols is believed to be the protection of polyunsaturated fatty acids (PUFA) against peroxidation. A critical question that must be asked in reference to this is whether there is a biochemical link between the tocopherol levels and the degree of unsaturation in vegetable oils, the main source of dietary PUFA and vitamin E. We used a mathematical approach in an effort to highlight some facts that might help address this question. Literature data on the relative composition of fatty acids (16:0, 16:1, 18:0, 18:1, 18:2, and 18:3) and the contents of tocopherols (α‐, β‐, δ‐, and γ‐tocopherol) in 101 oil samples, including 14 different botanical species, were analyzed by principal‐component analysis and linear regression. There was a negative correlation between α‐ and γ‐tocopherols (r=0.633, P<0.05). Results also showed a positive correlation between linoleic acid (18:2) and α‐tocopherol (r=0.549, P<0.05) and suggested a positive correlation between linolenic acid (18:3) and γ‐tocopherol.
High‐temperature stabilities of oils from soybeans that lack lipoxygenases
Authors: Shen N. , Fehr W. , White P.
Published: May 2007

Oils from normal or low‐linolenic acid (18:3) soybeans that lack lipoxygenase (LOX) 2 or LOX 2 plus LOX 3 activities were evaluated for their stability during frying and for oxidative stability in bread cubes stored after frying. Soybean oils were extracted by a pilot‐plant system and were refined, bleached, and deodorized in the laboratory. Citric acid was added to oils during the cool‐down stage of deodorization. Two replications, separated at the point of conditioning, were evaluated for each genotype. Each sample (250 g) was heated to 180±5°C in a minifryer. Bread cubes were fried at the beginning of heating and after 20 h of heating. Heating of the oils was continued for 10 h each day for three consecutive days. Soybean oils with low 18:3 contents were significantly (P ≤ 0.05) more stable, as measured by conjugated dienoic acids and polymer values, than were oils with normal 18:3 contents. Low‐LOX 2 or low‐LOX 2 + 3 activity had no effect on peroxide values of soybean oils extracted from bread cubes. Sensory evaluation did not differentiate between oils that contained low or high 18:3 amounts or among oils from beans that lacked different LOX enzymes.
Gas chromatographic study on high‐temperature thermal degradation products of methyl linoleate hydroperoxides
Authors: Toschi Tullia Gallina , Costa Arianna , Lercker Giovanni
Published: May 2007

Chromatographic techniques were used to separate secondary products generated by thermal degradation of methyl linoleate hydroperoxides (MLHP). The MLHP were obtained by oxidation, selected, and concentrated by solid‐phase extraction (SPE) and thin‐layer chromatography (TLC). The purified MLHP were then thermo‐degraded in the gas‐chromatographic glass liner and analyzed on‐line by gas chromatography‐mass spectrometry (GC‐MS). The MLHP were also thermodegraded and collected in a short silicic acid‐packed column, eluted, separated by TLC, and then analyzed by GC. By considering the elution in TLC, the GC retention times and the GC‐MS analyses, it was possible to characterize the mono‐ and the dioxygenated secondary products, particularly those having a boiling point higher than methyl linoleate. The peaks that corresponded to the mono‐oxygenated products (epoxy, hydroxy, and keto) were identified, and, on the basis of their MS spectra, molecular structures were proposed. A specific elution order was suggested for keto derivatives: 9‐keto,Δ10,12‐ and 13‐keto,Δ9,11‐octadecadienoate. The hydroxy derivatives, which show the typical fragmentations of 9‐hydroxy,Δ10,12‐ and 13‐hydroxy,Δ9,11‐octadecadienoate, were also identified. On the other hand, identification of the di‐oxygenated compounds was more difficult, and, therefore, it was not possible to indicate each positional isomer; however, their elution order could be epoxy‐hydroxy and epoxy‐keto derivatives.
Kinetics of epoxidation of alkyl esters of undecylenic acid: Comparison of traditional routes vs. ishii‐venturello chemistry
Authors: Yadav G. D. , Satoskar D. V.
Published: May 2007

Epoxidation of undecylenic acid and its methyl and ethyl esters with aqueous H2O2 was carried out by using different traditional routes, ion exchange resin, and the newly developed synergistic usage of heteropoly acids and phase transfer catalysis in a biphasic system. The so‐called Ishii‐Venturello chemistry was employed to develop a kinetic model. Interesting selectivities are obtained.
Castor oil dehydration kinetics
Authors: Guner F. Seniha
Published: May 2007

The dehydration reaction kinetics of castor oil was investigated with sodium bisulfate‐sodium bisulfite mixture (SB‐SB) or p‐toluenesulfonic acid as catalyst. Reactions were carried out at 210, 220, and 230°C, and a kinetic model was determined for each case. The reactions with SB‐SB catalyst at 210 and 220°C and with p‐toluenesulfonic acid at 210°C followed second‐order kinetics. A first‐order rate equation showed the best fit to the experimental data for the reaction with SB‐SB at 230°C. p‐Toluenesulfonic acid‐catalyzed reactions at 220 and 230°C were also first‐order reactions. Additionally, some mathematical equations were derived between iodine value, refractive index, viscosity, and reaction time.
Fractionation of squalene from amaranth seed oil
Authors: Sun H. , Wiesenborn D. , Tostenson K. , Gillespie J. , Rayas‐Duarte P.
Published: May 2007

Amaranth seed oil was fractionated in a bench‐scale short‐path distillation unit to obtain fractions rich in squalene. Fractionations were conducted with degummed amaranth oil, alkali‐refined amaranth oil, and simulated amaranth oil. Squalene concentration was increased about sevenfold with a squalene recovery of 76.0% in the distillate when degummed amaranth oil was fractionated at 180°C and 3 mtorr vacuum. Free fatty acids codistilled with squalene, lowering the squalene content of the distillate, and resulted in a semisolid distillate at room temperature. Alkali‐refining was subsequently used to reduce the free fatty acid content before fractionation. A simulated oil (7% squalene/93% soybean oil) and alkali‐refined amaranth oil were fractionated at three temperatures (160, 170, and 180°C) and five vacuum settings (10, 100, 200, 400, and 600 mtorr). The highest squalene recoveries from simulated oil and alkali‐refined amaranth oil were 73.4 and 67.8%, respectively, both at 180°C and 100 mtorr, which translates to 12.1‐and 9.2‐fold increases in squalene concentration, respectively. The squalene recovery of the alkali‐refined amaranth oil at 180°C was not significantly different at 10 mtorr vs. 100 mtorr. The results of this study can be used as a component to assess the economic feasibility of fractionating amaranth seed for starch, oil, meal, and squalene.
Synthesis of structured triglycerides from peanut oil with immobilized lipase
Authors: Soumanou Mohamed M. , Bornscheuer Uwe T. , Menge Ulrich , Schmid Rolf D.
Published: May 2007

Structured triglycerides (ST) that contain medium‐ and long‐chain fatty acids were synthesized by lipase‐catalyzed interesterification between tricaprylin and peanut oil. To select appropriate enzymes, we investigated nine commercial lipase preparations for their ability to hydrolyze pure triglycerides as well as natural oils. Three microbial lipases from Rhizomucor miehei (RML), Candida sp. (CSL), and Chromobacterium viscosum (CVL) gave good results, and immobilized preparations were used in the interesterification. RML gave the highest yields of ST (73%, 40°C), although its hydrolytic activity toward triolein was low. As the temperature was raised to 50°C, the yield of ST increased to 79%. After 120 h reaction time, remaining activities were high for CSL (71%), moderate for CVL (48%), and low for RML (20%).
Stereoselective acylation of Dl‐menthol in organic solvents by an immobilized lipase from Pseudomonas cepacia with vinyl propionate
Authors: Wu Wen‐Hsin , Akoh Casimir C. , Phillips Robert S.
Published: May 2007

An effective lipase‐catalyzed stereoselective transesterification of (±)‐menthol in organic solvent with vinyl propionate as acylating agent is described. Immobilization by adsorption and the presence of molecular sieves improved the formation of (±)‐menthyl propionate by lipase (PS‐30) from Pseudomonas cepacia. The reaction time course, mole ratio of substrates, temperature, amount of enzyme, as well as the effect of various organic solvents, were examined for their influence on the enzymatic stereoselective formation of (−)‐menthyl propionate. Among the parameters studied, the stereospecificity toward (−)‐menthol decreased significantly as temperature increased but the yields of both enantiomers increased. Organic solvents with log P (partition coefficient) values above 3.5 gave higher yield and stereoselectivity than solvents with lower log P values.
Cold‐active enzymes from cold‐adapted bacteria
Authors: Morita Yasutaka , Nakamura Tetsuya , Hasan Quamrul , Murakami Yuji , Yokoyama Kenji , Tamiya Eiichi
Published: May 2007

The properties of amylase, lipase and protease, excreted by newly isolated bacteria from snow‐covered soil, salmon intestine and crab intestine, have been investigated. One amylase, one lipase, and three proteases have been characterized by shifts in their apparent optimal activities toward low temperatures and by reductions in their activation energy values. The discovered enzymes were rapidly inactivated at temperatures above the optimum (30 to 40°C). These results suggest that the enzymes are cold‐active. The best cold‐active protease producer, isolated from salmon intestine, has been identified as Flavobacterium balustinum by the analysis of 16S rRNA. The optimal growth temperature of this bacterium was 20°C, but a higher amount of protease activity was present at 10°C.
Repeated use of immobilized lipase for monoacylglycerol production by solid‐phase glycerolysis of olive oil
Authors: Rosu Roxana , Uozaki Yuki , Iwasaki Yugo , Yamane Tsuneo
Published: May 2007

By using immobilized lipase for production of monoacylglycerol (MAG) by solid‐phase glycerolysis of fats and oils, the enzyme could be recovered easily from the reaction mixture and recycled to reduce the cost of the catalyst. Several support materials (CaCO3, CaSO4·2H2O, Ca2P2O7, and Celite) were screened for immobilization of Pseudomonas sp. lipase by adsorption and tested for solid‐phase glycerolysis of olive oil. Immobilization made the reuse of enzyme feasible. CaCO3 proved to be the best support: 90% MAG (wt% in the glycerolfree reaction mixture after 72 h of reaction time) was obtained until the fifth use, 80% after the seventh use, and 60% after the tenth use. The same support was found suitable for immobilization of two other bacterial lipases from Chromobacterium viscosum and Pseudomonas pseudoalkali.
Lipolytic activity in free and immobilized cells of Phoma glomerata
Authors: Pollero Ricardo , Gaspar María , Cabello Marta
Published: May 2007

The lipolytic activity of free and immobilized whole cells of the pathogenic fungus Phoma glomerata was demonstrated, and several properties of the lipase involved were determined. Free fungal cells and small pieces of immobilized cells, prepared by spontaneous colonization on a solid surface or entrapped in calcium alginate, were incubated with triolein in buffered medium. Different incubation conditions were assayed to optimize the reaction, to determine the effects of heating and time on stability of the immobilized preparations and the time course of the reactions. Although the enzyme cleaves all ester bonds of triolein, it shows some preference for the outer bonds. An optimal pH of 7.5–8.0, optimal temperature of 45°C for free and 50°C for immobilized cell preparations, the necessity for substrate emulsifiers, and reaction independence from calcium and magnesium were demonstrated. Results suggest that immobilized whole cells of P. glomerata would be a suitable tool to study its lipid physiology and to explore further the possible biotechnological use of its lipase activity.
Production of 8,11,14,17‐cis‐eicosatetraenoic acid by Δ5 desaturase‐defective mutants of an arachidonic acid‐producing fungus, Mortierella alpina
Authors: Kawashima Hiroshi , Kamada Nozomu , Sakuradani Eiji , Jareonkitmongkol Saeree , Akimoto Kengo , Shimizu Sakayu
Published: May 2007

Δ5 Desaturase‐defective mutants of an arachidonic acid‐producing fungus, Mortierella alpina 1S‐4, accumulate large amounts of 8,11,14,17‐cis‐eicosatetraenoic acid (20:4ω3) when grown with linseed oil. One of the mutants, the S14 strain, produced 1.65 mg of 20:4ω3 per mL of culture medium (corresponding to 66.0 mg/g dry mycelia and 11.6% of total cellular fatty acids) when grown in a medium containing 1% glucose, 1% yeast extract, and 4% linseed oil methyl ester at 28°C for 2 d, and then at 16°C for 7 d. In a bench‐scale fermentation in a 5‐L jar fermenter, 20:4ω3 production reached 1.60 g/L of culture medium on the eighth day (corresponding to 77.3 mg/g dry mycelia and 26.0% of total cellular fatty acids). The cellular lipids of the S14 strain comprised 75.8% triacylglycerol (TG), 6.7% diacylglycerol, and 13.3% phospholipids (PL). The percentage of 20:4ω3 was higher in PL than in TG, and highest in phosphatidylcholine (32.6%).
Nonpolar‐volatile lipids from soy protein isolates and hexane‐defatted flakes
Authors: Boatright W. L. , Crum A. D.
Published: May 2007

Lipid extracts from two samples of commercial soy protein isolates (SPI) and two samples of commercial hexane‐defatted flakes were fractionated by silici acid‐column chromatography. The material eluted with 100% chloroform was collected, further fractionated by silica solid‐phase extractions, and analyzed by gas chromatography‐mass spectroscopy by using mass spectra, retention times of authentic standards, and Kovats indices for identification. Thirty‐eight compounds were identified and quantitated in the lipid fractions from soy protein isolates (SPI); 23 of these are reported for the first time as components of SPI. An additional 13 compounds are reported for the first time as components of hexane‐defatted soybean flakes. The major classes of compounds reported for the first time associated with SPI include: butyl, methyl, and ethyl esters of fatty acids; phenols, diphenyls and phenyl esters; and abietic acid derivatives. Dehydroabietinal at 0.180 to 0.191 ppm of the protein isolates was the most abundant aldehyde in the SPI lipid extracts. The third most abundant aldehyde found in SPI after dehydroabietinal and hexanal was 2‐butyl‐2‐octenal (0.065 to 0.086 ppm). Dehydroabietic acid methyl ester was present in SPI (0.309 to 0.459 ppm). Dehydroabietene (0.628 ppm) and abietatriene (0.396 ppm) were tentatively identified in one sample of hexane‐defatted flakes.
Detection of hydrocarbons in irradiated and roasted sesame seeds
Authors: Choi C. R. , Hwang K. T.
Published: May 2007

Hydrocarbons produced by γ‐radiation of sesame seed were analyzed to determine the relation of irradiation dose to the production of hydrocarbons and to eventually use them as markers for identifying post‐irradiated sesame seed. Hydrocarbons in sesame seed were determined by a sequential procedure of lipid extraction by hexane, Florisil column chromatography, and gas chromatography. 16:2, 16:3, 17:1, and 17:2 were prominently detected in irradiated sesame seed, 17:2 was detected in seed irradiated at 0.1 kGy or higher, and the others were detected at 0.5 kGy or higher. These hydrocarbons were not detected in unirradiated sesame seeds that were raw, roasted, whole, ground, or stored.
Optimization of the sulfuric acid‐catalyzed estolide synthesis from oleic acid
Authors: Isbell Terry A. , Frykman Hans B. , Abbott Thomas P. , Lohr Joseph É. , Drozd Joseph C.
Published: May 2007

The production of estolide from oleic acid with sulfuric acid as a catalyst was optimized for minimal acid concentration and temperature. Commercial oleic acid forms estolide optimally when reacted at 55°C with 5% vol/vol concentrated sulfuric acid for 24 h under vacuum. The extent of oligomerization was 1.2 estolide units under these reaction conditions. Temperature plays a critical role in the rate of estolide formation as well as in the overall yield, with higher temperatures providing faster rates but lower yields. The ratio of sulfuric acid to oleic acid equivalents also plays a role, where higher acid concentrations gave faster rates and higher yields of estolide. Vacuum had a minor effect on oligomerization and estolide yield.
Structure of an antioxidant from fermented soybeans (tempeh)
Authors: Hoppe Markus B. , Jha Hem Chandra , Egge Heinz
Published: May 2007

In an exhaustive investigation of the antioxidative properties of tempeh constituents, the substance at Rf 0.58 (cyclohexane/ethyl ether, 9:1) was isolated and purified. Until now, only the ultraviolet and fluorescence data of the substance were known, and the presence of an OH group was indicated. In the present paper, the structure of the substance at Rf 0.58 was elucidated by the application of spectroscopic methods and found to be 5‐(δ‐tocopheroxy)‐δ‐tocopherol. That previous researchers did not confirm antioxidant activity in tempeh oil has been related to the way the tempeh oil was prepared. Previous suggestions regarding the substance at Rf 0.58 as being one of the main tempeh antioxidants could not be proved. The antioxidative effect of tempeh oil seems to be the result of a synergistic effect of tocopherols (present in the soybeans) and amino acids (liberated during the fermentation process with Rhizopus oligosporus).
Permeability changes caused by surfactants in liposomes that model the stratum corneum lipid composition
Authors: de la Maza A. , Coderch L. , Lopez O. , Baucells J. , Parra J. L.
Published: May 2007

The alterations caused by different surfactants in the permeability of liposomes formed by a lipid mixture that models the stratum corneum (SC) composition (40% ceramides, 25% cholesterol, 25% palmitic acid, and 10% cholesteryl sulfate) were investigated. The surfactant/lipid molar ratios (Re) and the bilayer/aqueous phase surfactant partition coefficients (K) were determined at two sublytic levels. The selected surfactant were sodium dodecyl sulfate (SDS); sodium dodecyl ether sulfate (SDES) to assess the influence of the ethylene oxide groups on the anionic surfactant’s behavior; Triton X‐100 (OP‐10EO) and dodecyl betaine (D‐Bet) as representatives of nonionic and amphoteric surfactants. Permeability alterations were determined by monitoring the increase in the fluorescence intensity of liposomes due to the 5(6) carboxyfluorescein (CF) released from the interior of vesicles. The SC liposomes/surfactant sublytic interactions were mainly ruled by the action of surfactant monomers. OP‐10EO showed the highest ability to alter the permeability of bilayers and the highest affinity with these structures, whereas D‐Bet showed the lowest tendencies. Although SDS and SDES exhibited similar activity at 50% CF release (similar Re values), SDES appeared to be more active at 100% CF release, its affinity with bilayers being also increased. The different ability exhibited by SDS, SDES, and D‐Bet (same alkyl chainlength) to alter the permeability of SC liposomes emphasizes the role played by the polar part of these surfactants in this interaction. Different trends in the evolution of Re and K were observed when comparing the results with those reported for phosphatidylcholine (PC) liposomes. Thus, whereas SC liposomes appeared to be more resistant to the action of surfactants, the surfactant affinity with SC bilayers was always greater than that reported for PC bilayers.
Changes in phospholipid bilayers caused by sodium dodecyl sulfate/nonionic surfactant mixtures
Authors: de la Maza Alfonso , Parra Jose Luis
Published: May 2007

The interaction of mixtures of sodium dodecyl sulfate (SDS) and oxyethylenated nonylphenol (30 mol of ethylene oxide) [NP(EO)30] with phosphatidylcholine liposomes was investigated. Permeability alterations were detected as a change in 5(6)‐carboxyfluorescein (CF) released from the interior of vesicles, and bilayer solubilization was measured as a decrease in the static light scattered by liposome suspensions. Three parameters were described as the effective surfactant/lipid molar ratios (Re) at which the surfactant system: (i) resulted in 50% CF release (Re50%CF); (ii) saturated the liposomes (ReSAT); (iii) led to complete solubilization of these structures (ReSOL). The corresponding surfactant partition coefficients (K50%CF, KSAT, and KSOL) were determined from these parameters. The free surfactant concentrations SW were lower than the mixed surfactant critical micellar concentration at subsolubilizing levels, whereas they remained similar to these values during saturation and solubilization of bilayers. Although the Re values increased linearly as the mole fraction of the SDS rose (XSDS), the K parameters showed maximum values at XSDS 0.6 for K50%CF and approximately at XSDS 0.2 for KSAT and KSOL, respectively. Thus, the lower the surfactant contribution in the surfactant/lipid system, the higher the XSDS at which the maximum bilayer/water partitioning of added mixed surfactant systems occurred. As a consequence, the influence of SDS in this partition appears to be more significant at the sublytic level (monomeric effect), whereas the influence of NP(EO)30 seems to be greater during saturation and solubilization of liposomes via formation of mixed micelles.
Direct ethoxylation of fatty methyl ester over Al‐Mg composite oxide catalyst
Authors: Hama I. , Okamoto T. , Hidai E. , Yamada K.
Published: May 2007

For the purpose of estimating the reaction mechanism of the direct ethoxylation of a fatty ester in the presence of an Al‐Mg composite oxide catalyst, a labeled fatty methyl ester C11H23CO18OCH3 containing 18O isotope was synthesized and directly ethoxylated. The product was evaluated by gas chromatography‐mass spectrometry (GC‐MS). The GC‐MS spectra showed that the 18O isotope label was present only in the methoxy group at the molecular end of the ethoxylated fatty methyl ester. This supports the reaction mechanism of coordination anionic polymerization where the bond between the acyl and methoxy groups of the fatty methyl ester molecule was broken, caused by the bifunctional effect of the acid‐base active sites; an intermediate chemisorption species was formed; and then ethylene oxide was addition‐polymerized sequentially, in parallel.
Alcohol ethoxycarboxylates—Mild, high‐foaming surfactants for personal‐care products
Authors: Schmidt W. W. , Durante D. R. , Gingell R. , Harbell J. W.
Published: May 2007

Alcohol ethoxycarboxylates (AEC) may be derived from alcohol ethoxylates (AEO) either by reaction of the nonionic surfactant with monochloroacetic acid (MCAA) or by oxidation. If MCAA is used, a ‐CH2COOH unit is added to the AEO. When an AEO is oxidized, the terminal ‐CH2OH group is selectively converted to ‐COOH. By use of proprietary carefully controlled oxidation technology, a variety of AEC surfactants have been synthesized. These surfactants exhibit good foaming and excellent line soap dispersion, and they allow formulation of high‐quality personal‐care products. Starter formulations have been investigated with AEC, both in shampoos and liquid hand cleaners. These formulations had the viscosity and foaming found in a survey of commercially available products. A shampoo and a liquid soap formulation with AEC were subjected to in‐vitro assays to assess the potential for irritation to the skin or eyes. The assay results predict these formulations to cause minimal irritation, similar to commercial products.
Synthesis and surface properties of chemodegradable anionic surfactants: Sodium (2‐n‐alkyl‐1,3‐dioxan‐5‐yl)sulfates
Authors: Piasecki Andrzej , Sokołowski Adam , Burczyk Bogdan , Kotlewska Urszula
Published: May 2007

In the reaction of cis‐ and trans‐2‐n‐alky‐5‐hydroxyl‐1,3‐dioxane mixtures with SO3 · pyridine complex, followed by neutralization with sodium hydroxide or sodium carbonate, a new group of anionic surfactants, i.e., sodium cis‐ and trans‐(2‐n‐alkyl‐1,3‐dioxan‐5‐yl)sulfates were obtained. The hydrophobic intermediates used in the sulfation reaction were obtained in high yields from four‐component glycerol acetals by the process of transacetalization and selective crystallization of 1,3‐dioxane derivatives. The physical data of the new compounds and some of their surface properties, such as critical micelle concentration (CMC), effectiveness of water surface tension reduction πCMC, standard free energies of adsorption and micellization, ΔGadso and ΔGCMCo, surface excess concentration, ΓCMC, and the surface area demand per molecule, ACMC, were determined. It was shown that the surface activity of the standard anionic surfactant sodium dodecyl sulfate should be similar to the surface activity of sodium (2‐n‐decyl‐1,3‐dioxan‐5‐yl)sulfate.
Glucoside ester synthesis in microemulsions catalyzed by Candida antarctica component B lipase
Authors: Skagerlind Peter , Larsson Karin , Barfoed Martin , Hult Karl
Published: May 2007

The surfactant, ethyl 6‐O‐decanoyl glucoside, was synthesized in microemulsion systems by lipase catalysis. The microemulsions were based on the two substrates for the reaction, ethyl glucoside and fatty acid, and either the sodium salt of the fatty acid or the glucoside ester was used as surfactant. The lipase used was component B from Candida antarctica. Reduced pressure was employed to eliminate the water of condensation. The reaction yield was good, with conversion of fatty acid and ethyl glucoside reaching 77 and 96%, respectively.
Hydrolysis of nonionic ester surfactants facilitated by potassium β‐glycyrrhizinate: Implication of catalytic functions played by the carboxyl groups
Authors: Koide Misao , Ukawa Jinta , Tagaki Waichiro , Tamagaki Seizo
Published: May 2007

Two different types of methyl esters of β‐glycyrrhizinate (GK2) have been prepared to delineate the mechanism of the catalytic action of each carboxyl group of GK2 in the hydrolysis of nonionic fatty acid surfactants. In the acidic pH region of less than 4, the hydrolysis is catalyzed by the carboxyl groups of the sugar moiety, while in the close‐to‐neutral acidic region, the carboxyl group at the hydrophobic triterpenoid end becomes important in catalysis.
Poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblock copolymer as a sustained‐release carrier for perfume compounds
Authors: Suzuki Katsumasa , Saito Yoshihiro , Tokuoka Yoshikazu , Abe Masahiko , Sato Takatoshi
Published: May 2007

The volatility behavior of perfume compounds in poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) copolymer was investigated by means of dynamic and static headspace analyses. Suppression of the volatility of perfume compounds by EO105PO27EO105 copolymer was markedly greater than by polyethyleneglycol. This suppressive effect may be due to micelle and gel formation of EO105PO27EO105 copolymer. EO105PO27EO105 copolymer is expected to be useful as a novel sustained‐release carrier that maintains constant release rates for the volatility of perfume compounds over a wide temperature range.
Thermal reactions of fatty acids with diethylene triamine
Authors: Wu Yinqiu , Herrington Philip R.
Published: May 2007

The relative reactivities of the primary and secondary amino groups of diethylene triamine with fatty acids depend on the thermal reaction conditions. Without solvents, the primary amines are more reactive than the secondary amine for steric reasons, and the reaction results mainly in the 1,3‐diamide. However, in dilute solution, the secondary amine shows higher reactivity than the primary amines, and the reaction proceeds probably by way of the 1,2‐diamide, which forms imidazolines under much milder conditions than from the 1,3‐diamide. The hydrolysis of imidazoline to the 1,2‐diamide as the major product confirmed the higher reactivity of the secondary amine.
Kinetics of hydrogen peroxide oxidation of alkyl dimethyl amines
Authors: Gee J. C. , Williamson R. C.
Published: May 2007

We measured the absolute rate constants for the hydrogen peroxide oxidation of two different octyl dimethyl amines in isopropanol/water mixtures at 23°C. The amines were 1‐octyl dimethyl amine (1) and 2‐ethylhexyl dimethyl amine (2); their structures were analogous to those most often encountered in commercial alkyl dimethyl amine oxide production. The observed first‐order rate constants for the disappearance of amine across a range of H2O2 concentrations (0.5–8 M) indicated that the overall rate was first‐order in amine and 3/2‐order in H2O2. Calculations showed k1=0.16 M−1h−1, k2=0.046 M−1h−1, and k1/k2=3.5. The rates appeared to decrease with increasing steric hindrance around the nitrogen atom. We also investigated the effect of water on the reaction rates. When [H2O]<∼4.5 M in isopropanol, the rates increased with increasing [H2O]; for [H2O]>∼4.5 M, the rates were insensitive to [H2O].
Effect of drying methods on molecular properties and functionalities of disulfide bond‐cleaved soy proteins
Authors: Kalapathy U. , Hettiarachchy N. S. , Rhee K. C.
Published: May 2007

Effects of drying methods on hydrophobicity, solubility, water hydration capacity, viscosity, and adhesive strength of soy protein isolates treated with Na2SO3(disulfide bond‐cleaving agent) were investigated. Treatment with 0.1 M Na2SO3resulted in 28% decrease in disulfide linkages in soy proteins. While hydrophobicity and solubility increased, waterholding capacity of soy proteins decreased due to the treatment. Spray‐dried product had higher hydrophobicity, solubility, water hydration capacity, and viscosity compared to freeze‐dried product. Adhesive strength on wood increased due to modification; however, the drying process had no significant effect on this property. Viscosities of spray‐dried product, freeze‐dried product, and unmodified soy proteins were 2,200, 100, and 240 cP, respectively. Fluorescence spectra of spray‐dried and freezedried products indicated a partial folding of molecules around tryptophan. High‐performance liquid chromatographic elution profiles showed no significant differences in molecular sizes of unfolded molecules of spray‐dried and freeze‐dried proteins.
Pilot‐scale two‐phase extraction of canola
Authors: Thobani Mahmood , Diosady Levente L.
Published: May 2007

An extraction process was developed in our laboratory for rapeseed (canola) with 10% (w/w) ammonia in methanol, containing 5% (vol/vol) water, and hexane to simultaneously produce an improved meal and a high‐quality oil. To remove the hazards associated with the use of ammonia, a two‐phase solvent extraction, with 0.08% (w/w) sodium hydroxide replacing the ammonia, was tested on a semipilot scale with a Szego mill and a Karr reciprocating‐plate extraction column. Flooding curves and appropriate agitation parameters were examined for this system. Then, the effects of polar solvent‐to‐seed ratio, slurry‐to‐hexane flow ratio, plate amplitude and plate agitation frequency on extraction efficiency were investigated. The process is technically viable for industrial application. A meal that contained 0.9% residual oil, 44.4% protein and 2.79 mmol/kg glucosinolates (moisture and oil‐free basis) and a miscella with 19.5% oil were obtained.
Two‐phase solvent extraction of canola
Authors: Thobani Mahmood , Diosady Levente L.
Published: May 2007

The equilibrium relationships in the extraction process that was developed in our research laboratory for the treatment of canola were studied. In the process, hexane is used as well as CH3OH that contains 5% (vol/vol) H2O and 0.08% (w/w) NaOH to simultaneously produce improved meal and high‐quality oil. Equilibrium data for canola oil in the hexane‐CH3OH/H2o/NaOH, meal‐hexane, and meal‐CH3OH/H2O/NaOH‐hexane systems are reported. A high partition coefficient for oil between hexane and the polar phase provided a large driving force for mass transfer. The presence of the CH3OH phase improved oil extraction, probably by rupturing the cell structure. The process proved to be a somewhat less desirable replacement for CH3OH/H2O/NH3 extraction and recovered 93.5% of the oil and 91.8% of the protein in the seed, while with CH3OH/H2O/NH3, the oil and protein recoveries were 96.8 and 94.0%, respectively. The NaOH treatment removed only 50.2% of the glucosinolates, and some of the oil was hydrolyzed by the NaOH, making the process less effective, despite its simplicity.
Effects of processing on oxidative stability of sesame oil extracted from intact and dehulled seeds
Authors: Abou‐Gharbia H. A. , Shahidi F. , Adel A. , Shehata Y. , Youssef M. M.
Published: May 2007

Oxidative stability of oils extracted from intact and dehulled sesame seeds was determined by monitoring changes in fatty acid composition, iodine value (IV), peroxide value (PV), conjugated diene (CD), para‐anisidine value (p‐AV), and 2‐thiobarbituric acid (TBA) value and by nuclear magnetic resonance spectroscopy after storage under Schaal oven conditions at 65°C for up to 35 d. The oils from coated seeds were more stable, as reflected in PV, CD, p‐AV and TBA values, than those extracted from dehulled seeds after roasting at 200°C, steaming at 100°C, roasting at 200°C plus steaming, or microwaving at 2450 MHz, except for TBA values of oil from microwaved seeds. After 35 d of storage at 65°C, the CD, p‐AV, and TBA values of extracted oil from dehulled microwaved seeds were 17.72, 10.20, and 1.22, respectively, while those of their coated counterparts were significantly (P<0.05) different at 14.20, 16.47, and 1.26, respectively. Few significant changes were evident in the fatty acid composition of oil obtained from either coated and dehulled seeds subjected to different treatments. Nuclear magnetic resonance analyses found that Rao (aliphatic to olefinic protons) and Rad (aliphatic to diallylmethylene protons) ratios increased steadily over the entire storage period, which indicated progressive oxidation of unsaturated fatty acids.
Preparation and characterization of methyl 11‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate and methyl 8‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate
Authors: Herron Barry F. , Bagby Marvin O. , Isbell Terry A. , Byrdwell Wm. Craig , Plattner Ron , Weisleder David
Published: May 2007

Allylic amination of methyl oleate with bis(N‐p‐toluenesulfonyl) sulfodiimide results in a mixture of methyl 11‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate and methyl 8‐amino‐(N‐p‐toluenesulfonyl)‐9‐E‐octadecenoate in 58% yield. These novel products were isolated and characterized by nuclear magnetic resonance, infrared spectroscopy, mass spectrometry, and melting point. The reaction was analyzed by highperformance liquid chromatography and thin‐layer chromatography.
Synthesis of alkyloxy (di)alkylamino propanols, hydroxy alkyloxy (di)alkylamino propanols, and the dimer compounds for use as fuel additives
Authors: de Caro Pascale Satgé , Mouloungui Zéphirin , Gaset Antoine
Published: May 2007

Alkyl glycidyl ethers and bis glycidyl ethers, synthesized in a heterogeneous weakly hydrous medium, were condensed with primary or secondary amines to obtain 3‐alkyloxy propanolamines or bis alkyloxy propanolamines in a regioselective manner. The compounds were characterized by conventional spectroscopic methods, and complete nuclear magnetic resonance data are given. Their high‐temperature stability, their good emulsifying power, their oxidation, and corrosion inhibition make these compounds suitable for solubilizing ethanol‐diesel fuel blends.
Synthesis of derivatives of alkylamino alkyloxy propanol structures by N‐alkylation, acylation, and nitration. Application as fuel additives
Authors: de Caro Pascale Satgé , Mouloungui Zéphirin , Gaset Antoine
Published: May 2007

Polyfunctional compounds were prepared by alkylation, acylation, and nitration of hydroxyl and amine functions of the following alkanolamine ether structures: (di)alkylamino alkyloxy propanol, hydroxy alkyloxy (di)alkylamino propanol, and their dimer compounds. The resulting compounds were characterized by conventional spectroscopic methods, and complete nuclear magnetic resonance data are given. These reactions extented the application of these propanic compounds to use as multipurpose fuel additives. In particular, they enhance phase stability and improve the cetane number in ethanol‐diesel fuel blends.