Showing papers in "Journal of the American Oil Chemists' Society in 1964"
TL;DR: Examples of data obtained with purified triglycerides indicate that the specific action of pancreatic lipase for the 1,3 ester groups is nearly absolute and the technique may be used as a criterion of purity of di- and tri-acid triglycerides.
Abstract: Procedures are described for rapid lipase hydrolysis of triglycerides, isolation of the hydrolytic products by TLC and their conversion to methyl esters and fatty acid analysis by GLC. The techniques are applicable to a few mg of triglycerides or fats. Examples of data obtained with purified triglycerides indicate that the specific action of pancreatic lipase for the 1,3 ester groups is nearly absolute and the technique may be used as a criterion of purity of di- and tri-acid triglycerides. Ca. 83% of the palmitic but only 10~12% of stearic and C18 unsaturated acids of commercial lard occur in 2-position.
439 citations
TL;DR: In this article, the relative responses for flame ionization detectors in the analysis of the longer chain fatty acid methyl esters are shown to correlate with the theoretical responses based on weight percent content of active carbon.
Abstract: The relative responses for flame ionization detectors in the analysis of the longer chain fatty acid methyl esters are shown to correlate with the theoretical responses based on weight percent content of “active” carbon. While particularly affecting estimation of the shorter chain length saturated fatty acids, these corrections have a less marked effect on the estimation of unsaturated fatty acids.
242 citations
TL;DR: The precision of the method is demonstrated on model mixtures of mono, di-and triglycerides, neural and phospholipids and C14 labeled lipids, compared closely to those obtained by silicic acid column chromatography.
Abstract: A procedure is described for the quantitative analysis of neutral and phospholipids by thinlayer chromatography (TLC) employing densitometry. The chromatophates are prepared with the usual solvent systems. The spots are charred under standard conditions and analyzed with a Photovolt Corp. densitometer equipped with a special stage designed for holding 20×20 cm chromatoplates. Each spot on the chromatoplate gives a peak of density values which is used for quantitative analysis.
227 citations
TL;DR: Using diethylaminoethyl cellulose column chromatography followed by thin layer chromatography for the fractionation of complex lipid mixtures with results obtained with beef brain and beef heart mitochondrial lipids is described.
Abstract: A quantitative chromatographic procedure for the fractionation of complex lipid mixtures is described. The method utilizes diethylaminoethyl (DEAE) cellulose column chromatography followed by thin layer chromatography (TLC). Spots produced in TLC are charred with sulfuric acid-potassium dichromate and heat and are then measured by quantitative densitometry. Results obtained with beef brain and beef heart mitochondrial lipids are presented, and the close correspondence between column isolation procedures and the new procedure is demonstrated. Methods utilizing only column chromatography, column chromatography and TLC, and one- and two-dimensional TLC without column chromatography are compared.
207 citations
TL;DR: The fatty acid composition of body lipids was determined by GLC for 14 species of saltwater fish, three species of freshwater fish and four species of shellfish and significant differences in the amt of particular fatty acids were found in comparing freshwater-fish analyses with analyses for marine fish.
Abstract: The fatty acid composition of body lipids was determined by GLC for 14 species of saltwater fish, three species of freshwater fish and four species of shellfish. In addition, liver lipids of two species and egg lipids of one species were analyzed for comparison with the fish body lipids. The various species ranged from lean to fatty and contained from 0.7~15.5% oil in the tissues. Certain major fatty acids were found to vary widely among the species, as follows: 1.6~8.0% myristic, 9.5~33.4% palmitic, 2.0~11.2% palmitoleic, 5.2~29.1% oleic, 0.7~10.5% eicosenoic, 5.0~21.5% eicosapentaenoic, 0.2~11.6% docosenoic and 5.9~26.2% docosahexaenoic acids. Analyses of two separate mullet-oil samples illustrated the wide differences that are possible for a single species caught during different seasons. Significant differences in the amt of particular fatty acids were found in comparing freshwater-fish analyses with analyses for marine fish. Oysters and scallops showed large amt of pentaenoic and hexaenoic acids in their oils.
197 citations
TL;DR: Observations indicated that eicosenoic and erucic acids were formed by a genetically controlled carbon chain lengthening system operating by the addi-tion of acetate molecules to the carboxyl end of oleic acid.
Abstract: Isolation of rapeseed plants containing no erucic acid in their seed oil gave simultaneous selection for low eicosenoic acid. Genetic analy-sis of populations segregating for erucic acid content indicated that the synthesis of these fatty acids was controlled, in the developing embryo, by two genes which displayed no domi-nance and acted in an additive manner. As the genetic capacity for erucic acid synthesis de-creased, there was an increase in percentage of oleic acid with no corresponding decrease in total oil content. The percentage of eicosenoic acid re-mained relatively constant with decreasing erucic acid except in the zero erucic acid genotype where only 1% eicosenoic was detected instead of approx 12%. These observations were in-terpreted to mean that eicosenoic and erucic acids were formed by a genetically controlled carbon chain lengthening system operating by the addi-tion of acetate molecules to the carboxyl end of oleic acid. This hypothesis was supported by data obtained from the injection of radioactive sodium acetate into immature rapeseed pods. In the monoene fraction of the oil, eicosenoate had three times the specific activity of oleate and erucate had twice the activity of eicosenoate. On oxidation, the monocarboxylic fragments of these three acids had low and similar specific activities while in the dicarboxylic acids, where chain elongation has presumably taken place, activity increased in the ratio of 1:5:19.
163 citations
108 citations
TL;DR: In this paper, a preparative chromatographic procedure was used to separate monoenecis and trans isomers of fatty esters using a silver-saturated ion exchange resin.
Abstract: Methyl oleate and methyl elaidate, as well as other monoenecis andtrans isomers of fatty esters, can be separated quickly and conveniently by a preparative chromatographic procedure in which a silver-saturated ion-exchange resin is used. Separations are based on differences in stabilites of the silver-olefin complexes. Recoveries of better than 95% were made, and puretrans andcis monoene fractions were collected. This method can be used to separate saturates fromcis andtrans monoenes. Thecis,trans,cis,cis, andtrans,trans-9-12-octadecadienoates were separated. Whilecis,trans andtrans,trans dienes were cluted separately, thecis,cis diene isomer remained on the column.
95 citations
TL;DR: It appears from experiments with mixtures of various aldehydes that in the case of certain ratios a masking effect in odor and taste occurs.
Abstract: The mean threshold values for odor and taste of some aliphatic aldehydes are determined in solutions of paraffin oil. These threshold values lie at low concn and display a distinct alternating effect in the same homologous series. Moreover it appears from experiments with mixtures of various aldehydes that in the case of certain ratios a masking effect in odor and taste occurs.
85 citations
TL;DR: The topics reviewed include structural con-siderations, natural occurrence, influence of oil processing, analytical methods, isolation proce-dures and commercial preparations, various bio-logical effects and stability questions.
Abstract: This review covers the literature on sesamin, sesamolin and related compounds published since 1951. The topics reviewed include structural con-siderations, natural occurrence, influence of oil processing, analytical methods, isolation proce-dures and commercial preparations, various bio-logical effects and stability questions. Recent developments in pyrethrum synergists are discussed at length, since they owe so much to the discovery of the synergistic activities of sesamin and sesamolin.
78 citations
TL;DR: In this paper, the densities of saturated fatty acid methyl esters from acetate to arachidate, methyl oleate, Linoleate, linolenate, and erucate have been prepared in high purity.
Abstract: Saturated fatty acid methyl esters from acetate to arachidate, methyl oleate, linoleate, linolenate, and erucate have been prepared in high purity. Densities, refractive indices, dispersions, ultrasonic sound velocities, and dielectric constants have been measured in the liquid state at 20 and 40C. In this first communication, the densities of the saturated compounds have been correlated with the Smittenberg relation. The following relations were derived: d
20
4
= 0.85407 + 0.18494/ (n + 0.096) and d
40
4
= 0.84225 + 0.12904/(n-0.408). Molar volumes have been computed and checked for additivity.
TL;DR: A processing method for preparing full-fat soybean flours for human consumption by a new extrusion-cooking method was developed in this article, which can be used to produce high nutritive value and good stability.
Abstract: A processing method for preparing full-fat soybean flours for human consumption by a new extrusion-cooking method was developed. Biological evaluations were made of samples produced experimentally by this method to determine the best conditions for preparing a product of maximum nutritive value and stability. Twelve processed full-fat soybean flours, prepared under different conditions, were evaluated by means of chemical analyses, biological assays, available lysine content, organoleptic and bacteriological tests, and oxidative stability storage tests. Flour of high nutritive value and good stability can be prepared by preheating unextracted soybean flakes or grits to 200-212F, premixing and adding sparge steam at 212F to adjust moisture content to 18-21%, extruding for 1-1.5 min with final extrusion temp reaching 250-290F, cooling, drying and grinding. Clinical testing of the flour with infants up to 12 months of age has begun in two Far Eastern countries on a fairly extensive scale, and completed results should be available by late 1964.
TL;DR: In an attempt to account for carbonyls found in oxidized lipid systems, but not theoretically predicted from the decomposition of lipid hydroperoxides, a member from each of the monocarbonyl classes commonly observed in oxidizing lipids was oxidized at 45C in a Warburg apparatus and the carbonyl products studied as mentioned in this paper.
Abstract: In an attempt to account for carbonyls found in oxidized lipid systems, but not theoretically predicted from the decomposition of lipid hydroperoxides, a member from each of the monocarbonyl classes commonly observed in oxidizing lipids was oxidized at 45C in a Warburg apparatus and the carbonyl products studied. The carbonyl compounds used weren-nonanal,n-non-2-enal,n-hepta-2,4-dienal andn-oct-1-en-3-one. Nonanal was relatively stable to oxidation and was oxidized to nonanoic acid. Oct-1-en-3-one did not absorb oxygen during a 52-hr period; however, the unsaturated aldehydes oxidized at faster rates than methyl linoleate or linolenate. Non-2-enal upon absorption of 0.5 mole of oxygen was oxidized almost quantitatively to non-2-enoic acid. Hepta-2,4-dienal was polymerized at 0.5 mole of oxygen uptake. In addition both of the unsaturated aldehydes produced shorter chain mono- and dicarbonyls as oxidative degradation products. The identification of these compounds helps to explain the presence of carbonyls in oxidizing lipids and model systems that are not accountable through the decomposition of theoretically predictable isomeric hydroperoxide esters. The relatively large yield of malonaldehyde from the oxidized dienal suggests that these carbonyls may serve as a major source of malonaldehyde in oxidizing diene esters. Significant quantities of malonaldehyde are not observed in methyl linoleate until late stages of oxidation, and the dienals formed through degradation of primary hydroperoxides may in turn oxidize to give malonaldehyde.
TL;DR: Carbon numbers have been determined for all the 17 isomeric methyl hydroxy- and acetoxystearates and 15 of the 16 methyl oxostearates using silicone SE-30, silicone QF-1, and ethylene glycol succinate (EGS) as liquid phases.
Abstract: Carbon numbers have been determined for all the 17 isomeric methyl hydroxy- and acetoxystearates and for 15 of the 16 isomeric methyl oxostearates using silicone SE-30, silicone QF-1, and ethylene glycol succinate (EGS) as liquid phases. The carbon numbers of the isomers increase with increasing distance of the point of substitution from the carboxyl end of the fatty acid chain (the increases for the 4- and 5-hydroxy esters are unexpectedly large). The change in carbon number from one isomer to the next is greatest when the substituents are attached near either end of the chain. The best separation of isomers with the substituent near the carboxyl end is obtained for oxo esters using the QF-1 column, and that of isomers substituted near the methyl end is obtained for acetoxy esters using the EGS column. Isomers with substituents at carbons 9<13 are not distinguishable on any of the columns used, but the other isomers are partly or completely separated. The quantitative aspects of the separations have not been investigated.
TL;DR: Analysis of seed oils from 29 species of the family Boraginaceae revealed widespread occur-rence of 6,9,12-octadecatrienoic and C18 noncon-jugated tetraenoic acids in addition to linolenic and other common C16 and C 18 acids.
Abstract: Analysis of seed oils from 29 species of the family Boraginaceae revealed widespread occur-rence of 6,9,12-octadecatrienoic and C18 noncon-jugated tetraenoic acids in addition to linolenic and other common C16 and C18 acids. The 6,9,12-octadecatrienoic acid ranged in amount from 0-27%, tetraene from 0-17%, and linolenic acid from 0.3-50%. Iodine values of the oils ranged from 88-225.
TL;DR: Seed oils from five species ofCuphea show three distinct patterns of fatty acid composition as mentioned in this paper : C. hookeriana and C. painteri oils contain ca. 70% caprylic acid, C. ignea and c.llavea oils have over 80% capric acid, andC. carthagenensis oil contains 57% lauric and 18% ca.
Abstract: Seed oils from five species ofCuphea show three distinct patterns of fatty acid composition.C. hookeriana andC. painteri oils contain ca. 70% caprylic acid,C. ignea and C.llavea oils have over 80% capric acid, andC. carthagenensis oil contains 57% lauric and 18% capric acids.
TL;DR: The triglycerides of Cuphea llavia var.miniata seed fat were separated according to the number of double bonds/molecule using preparative thin layer chromatography (TLC) on silicic acid impregnated with silver ion.
Abstract: The triglycerides ofCuphea llavia var.miniata seed fat were separated according to the number of double bonds/molecule using preparative thin layer chromatography (TLC) on silicic acid impregnated with silver ion. The recovered frac-tions were quantitated by the chromotropic acid technique. Each fraction was then separated ac-cording to mol wt using gas-liquid chromatog-raphy (GLC). This multiple chromatography procedure resolvedC. llavia triglycerides into 17 different components. The triglyceride composition ofC. llavia seed fat was calculated from the above results. Since the fat contains 91.2 mole % decanoic acid, it was expected that each triglyceride molecule would contain at least two molecules of decanoic acid. Results showed this to be generally true, but sev-eral minor component triglycerides not conform-ing to this pattern were found.
TL;DR: In this article, a method was developed to determine the concn of polyoxyethylene nonionic surfactant (PNS) in the parts/million concn range in a water-bacteria medium.
Abstract: A method has been developed to determine the concn of polyoxyethylene nonionic surfactant (PNS) in the parts/million concn range in a water-bacteria medium. The method has successfully determined the concn of PNS during the course of biodegradation studies using either activated sludge or river water as the bacterial source. The nonionic surfactant was removed from the water solution by continuous ether extraction. Detection and measurement of the PNS was accomplished using cobalt thiocyanate and measuring the absorbance of the blue cobalt-PNS complex at 620 m.03 in a five-cm absorption cell. Optimum extraction conditions required a neutral pH and a low ionic strength. The colorimetric step required that each molecule of PNS contain at least six ethylene oxide units for color development, and since the absorbance varies with the length of the polyoxyethylene chain, the method must be standardized using the particular compound under investigation.
TL;DR: The major component acid,cis-5-eicosenoic, ranged 52-77% of the acids present in all species examined and one species also yielded a small amount of oxazolidinethione-like compound of the type associated with enzyme-treated rapeseed meal as discussed by the authors.
Abstract: Seed oils from most of the known species and varieties ofLimnanthes were analyzed for their fatty acid content. Each contained at least 95% acids with more than 18 carbon atoms. The major component acid,cis-5-eicosenoic, ranged 52–77% of the acids present. Seeds of all species examined contained thioglucosidic precursors of volatile isothiocyanates, liberated by the action of mustard seed enzymes on the meal. One species also yielded a small amount of an oxazolidinethione-like compound of the type associated with enzyme-treated rapeseed meal.
TL;DR: Iso-lation analysis of the fatty acids showed no evidence that linoelaidic acid was converted to higher polyunsaturated fatty acids in the EFA-deficient rat.
Abstract: Male weanling rats of the Sprague-Dawley strain were made essential fatty acid (EFA)-deficient by feeding them a fat-free diet for five months. The animals were then fed a supple-ment of methyltrans-9,trans-12-octadecadienoate (methyl linoelaidate), as 5% of the dietary calo-ries (approximately 400 mg/animal/day) for 19 days, and killed by exsanguination. The com-position of the liver, kidney, epididymal and plasma lipids was determined and compared with that obtained from EPA-deficient rats given oral supplements of methylcis-9,cis-12-octadeca-dienoate (linoleate) and methylcis-9,trans-12- octadecadienoate. Linoelaidic acid was depos-ited in the phospholipids, sterol esters and tri-glycerides in all of the tissues examined. Iso-lation analysis of the fatty acids showed no evidence that linoelaidic acid was converted to higher polyunsaturated fatty acids in the EFA-deficient rat.
TL;DR: Oleic, linoleic, and linolenic esters and olive, sunflower, linseed, rapeseed, hydrogenated rape-seed, and coriander oils have been oxidized by the permanganate-periodate reagent as discussed by the authors.
Abstract: Oleic, linoleic, and linolenic esters and olive, sunflower, linseed, rapeseed, hydrogenated rape-seed, and coriander oils have been oxidized by the permanganate-periodate reagent. The relative amounts of the dibasic acids and of the mono-basic acids produced were determined by gas liquid chromatography (GLC). These results were used in combination with the compositions of the oils, also found by GLC, to calculate the positions of the double bonds in the unsaturated fatty acids of the oils. Evidence for the presence of small amounts of 11-octadecenoic acid and other unusual isomers was obtained.
TL;DR: This reaction of sulfhydryl groups with the cyclopropene ring may have its counterpart in the animal’s body, and could be the cause of the physiological effects that are observed when cycloprostene derivatives are fed to laying hens.
Abstract: Lipids that contain a cyclopropene ring have been found to be biologically active when incorporated into the diet of laying hens. Methyl sterculate and sterculene (1,2-di-n-octylcyclopropene) are examples of these compounds. When added to dilute solutions of methyl mercaptan and β-mercaptopropionic acid, the sulfhydryl group added to the double bond of the cyclopropene ring. The cyclopropyl methyl and 2-carboxyethyl derivatives were isolated and their structure established. This reaction of sulfhydryl groups with the cyclopropene ring may have its counterpart in the animal’s body, and could be the cause of the physiological effects that are observed when cyclopropene derivatives are fed to laying hens.
TL;DR: In this paper, it was shown that the structure of the conjugated 10-trans, 12-trans linoleate (250C, 5 hr) is similar to the Diels-Alder reaction between two molecules of monomer.
Abstract: Thermal dimerization of the conjugated 10-trans, 12-trans linoleate (250C, 5 hr) produced a dimer whose structure is shown to be that of the Diels-Alder reaction between two molecules of monomer, with one molecule acting as diene, and either one of the two double bonds of the second molecule acting as dieneophile. This produces four skeletal isomers of a tetrasubstituted (1,2,3,4) cyclohexene structure with α-β unsaturation on one chain. The isomers formed depend on whether the 10 or the 12 double bond acts as dieneophile, and whether the monomers add “head to head” or “head to tail.” Evidences for the structures include chemical analyses, ozonolysis, nuclear magnetic resonance, IR and UV spectrometry and particularly mass spectrometry of the distilled dimer, of the completely hydrogenated dimer, and of the aromatized dimer formed by catalytic dehydrogenation. The hydrogenated dimer can be separated into two components by TLC. These are probably related to “head to head” vs. “head to tail” addition.
TL;DR: In this paper, the dehydro-dimer of methyl oleate was prepared and its structure determined as a model of a non-ring dimer for reference in studying the structure of other fatty dimer acids.
Abstract: The dehydro-dimer of methyl oleate was prepared and its structure determined as a model of a non-ring dimer for reference in studying the structure of other fatty dimer acids.
TL;DR: The results show that the proximal structure has greater influence than the terminal structure on the biosynthesis of unsaturated odd-numbered acids, and chain lengths of 17 and 18 carbon atoms with double bonds in position 9 are crucial for synthesis of the polyenoic C19 and C20 acids.
Abstract: Mullet oil contains more than 25% straight-chain odd-numbered fatty acids. Odd- and even-numbered components of chain lengths C15 to C20 were isolated and their structures determined. The vinylmethane rhythm prevails in all polyun-saturated acids. Numerous homologs have their double bonds in identical positions, relative to the carboxyl group, as for example, ‡9,12- and ‡6,9,12-C15, -C16, -C17 and -C18 acids. The terminal structures which are characteristic for oleic, linoleic, etc., families are not found in the unsaturated odd-numbered acids. The results show: that the proximal structure has greater influence than the terminal structure on the biosynthesis of unsaturated odd-numbered acids ; that chain lengths of 17 and 18 carbon atoms with double bonds in position 9 are crucial for synthesis of the polyenoic C19 and C20 acids; that chain lengths C15 and C16 with double bonds in position 9 are suitable for desaturation but that they are not suitable for desaturation after elongation. These specifications bring all acids of mullet into a rational order and reflect their possible interconversions. Presently, such classification has only limited predictive value in regard to the physiological properties of polyunsaturated acids. However, the new definitions for grouping the polyunsaturated fatty acids lead to interesting working hypotheses.
TL;DR: In this article, the ultrasonic sound velocity of unsaturated fatty acid methyl esters from acetate to nonadecanoate, methyl oleate, Linoleate, linolenate, and erucate have been measured at 20C and 40C in the liquid state.
Abstract: The ultrasonic sound velocity of the unsaturated fatty acid methyl esters from acetate to nonadecanoate, methyl oleate, linoleate, linolenate, and erucate have been measured at 20C and 40C in the liquid state. Data of the saturated compounds were correlated with the Smittenberg relation and a reasonable fit was noted. The molar sound velocity according to Rao was computed from the observed values and increments for the CH2 group and for the double bond are presented.
TL;DR: In this paper, the authors show that the removal of the LAS by biodegradation is paralleled by removal of toxicity and there is no indication that toxic intermediates accumulate during the biodegrading process.
Abstract: Linear alkylate sulfonates (LAS) are relatively toxic to fish when tested under static conditions by standard bioassay techniques, the median tolerance limit (TLm) being around 3 mg/liter and 0.6 mg/liter for the C12 and C14 homologs, respectively. However, these materials are so readily degraded by bacterial attack that bluegill fingerlings live with no trouble in effluents from laboratory continuous flow activated sludge units being fed 100 mg/liter or more of either product. No effects on the fish were noticeable in exposures of 96 hr or more, except for slight alterations in the microscopic appearance of the gill tissue. Thus, the removal of the LAS by biodegradation is paralleled by the removal of toxicity and there is no indication that toxic intermediates accumulate during the biodegradation process. This conclusion is substantiated by the observation of a much lower degree of toxicity (TLm 75 mg/liter) for sulfophenylundecanoic acid disodium salt (mixed isomers), synthesized as a model of an intermediate degradation product. Characterization, gas chromatography and methylene blue analysis of this product are also discussed.
TL;DR: Gas-liquid chromatographic analysis of methyl esters of two samples of castor oil gave the following (as wt %): palmitate 1.2, 0.9; stearate 0.7, 1.3; linoleate 3.4, 3.2; hexadecenoate0.2.
Abstract: Gas-liquid chromatographic analysis of methyl esters of two samples of castor oil gave the following (as wt %): palmitate 1.2, 0.9; stearate 0.7, 1.2; arachidate 0.3, 0.2; hexadecenoate 0.2, 0.2; oleate 3.2, 3.3; linoleate 3.4, 3.7; linolenate 0.2, 0.2; ricinolE'ate 89.4, 89.0; and dihydroxystearate 1.4, 1.3. Oxidative cleavage of purified methyl ricinoleate indicated that the double bond was exclusively in the 9–10 position.
TL;DR: A modified thiobarbituric acid test has been devised for the determination of certain components of oxidized fat as discussed by the authors, which is carried out in a single phase solvent designed to eliminate the color extraction or fat removal steps of other TBA tests.
Abstract: A modified thiobarbituric acid test has been devised for the determination of certain components of oxidized fat. The reaction was carried out in a single phase solvent designed to eliminate the color extraction or fat removal steps of other TBA tests. A moderate temperature of 60C, with no added acid, was used to minimize breakdown of hydroperoxides and TBA. Under certain reaction conditions, temperature, sunlight, ferric ion, and oxygen can influence results. Of the aldehydes examined, the TBA reaction products of dienals showed an absorption peak at 532 m dm only, while the TBA reaction products of the saturated aldehydes showed a peak at 452 mμ only. The spectral behavior of TBA reaction products of monoenals was found to vary with the location of the double bond. Fat samples, aged at either 60C or 37.8C, were examined organoleptically and by the modified TBA test. The 452 mμ peak was of value in assessing the flavor of beef fat, cottonseed oil, and used frying fat, whereas the 532 mμ wavelength was of value in assessing the flavor of soybean oil, used frying fat, and pork fat.