Vitamin e analytical procedure for cottonseed and its products

Conclusions A procedure for the analysis of cottonseed and its products for Vitamin E has been developed and improved. The present procedure generally gives good checks on duplicate analyses. The Vitamin E content of whole cottonseed is somewhat more a function of variety than of locality. The 1952 crop of cottonseed contained more Vitamin E than the 1951 crop. The two crops averaged 84 g. per ton and 68.5 g. per ton, respectively. Most recent results show that there is no loss of Vitamin E in the storage of cottonseed or during the processing of the seed for its oil and other products. The hexane-soluble portion of a methanol extract of rolled or cooked cottonseed meats contains Vitamin E in concentrations that have exceeded the values reported for wheat germ oil, the present commercial source. A sample of commercial solvent extracted cottonseed meal was found to contain considerably less Vitamin E than hydraulic- or screw-pressed meals. The Vitamin E research described in this writing was conducted as a cooperative project of the Texas Engineering Experiment Station and the Cotton Research Committee of Texas.     

Effect of antioxidants,individually and in combination,on stability of carotene in cottonseed oil

Summary and Conclusions By an accelerated test, l-ascorbyl palmitate, alphatocopherol, hydroquinone, and phospholipids from cottonseed and soybean oil have been evaluated singly and in combinations, for their antioxidant effect on carotene in mineral oil and cottonseed oil solutions. Their effects in retarding the formation of peroxides in the refined cottonseed oil were also determined, and similar studies were made on cottonseed oil after the addition of 1.2 mg. of carotene per gram of oil. In the refined cottonseed oil the formation of peroxides occurred concurrently with the destruction of carotene and was greatly accelerated as the carotene disappeared. In mineral oil solutions, no peroxides were found until after the carotene had become completely decolorized. Although alpha-tocopherol was very effective in stabilizing carotene when added to mineral oil solutions neither the naturally present nor added tocopherol was effective in a more unstable solvent such as refined cottonseed oil. To make the tocopherol effective in such a solvent it is necessary first to stabilize the solvent. When the combination of phospholipid and hydroquinone was added to the refined cottonseed oil, the oil was stabilized and a very marked increase in carotene stability was obtained. While the combinations AH, APH, TAH and TAPH did not stabilize the carotene during the early part of the storage tests, they did become effective after about 20 per cent of the carotene had been destroyed and were as effective as PH and TPH when measured at the 50 per cent point. The reason for this ineffectiveness during the preliminary period of storage is not apparent. This is one of four regional research laboratories operated by the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

The Viscosity of cottonseed oil,fractionation solvents and their solutions

Cold fractionation of cottonseed oil is made difficult by the high viscosity of the oil. This study was aimed at demonstrating the effect of solvents on the viscosity of mixtures between 0°C and 25°C with a view to facilitating the fractionation of refined cottonseed oil. The solvents used were acetone, methylethylketone, methylisobutylketone, hexane and heptane. Measurements of viscosity were carried out by means of a capillary viscometer. The ratio of the viscosity of cottonseed oil to that of pure solvents is of the order of 300. The viscosities of solutions of various ratios of solvent to oil (1/3, 1/1, 3/1) are between those of cottonseed oil and the pure solvents. The effect of the solvent/oil ratio overrides that of solvent nature. The effect of solvent in reducing the viscosity of cottonseed oil is by descending order: acetone, hexane, methylethylketone, heptane, methylisobutylketone.     

Comparison of Soybean and Cottonseed Oils upon Hydrogenation with Nickel,Palladium and Platinum Catalysts

There is current interest in reducing the trans fatty acids (TFA) in hydrogenated vegetable oils because consumption of foods high in TFA has been linked to increased serum cholesterol content. In the interest of understanding the TFA levels, hydrogenation was carried out in this work on soybean oil and cottonseed oil at two pressures (2 and 5 bar) and 100 °C using commercially available Ni, Pd, and Pt catalysts. The TFA levels and the fatty acid profiles were analyzed by gas chromatography. The iodine value of interest is ~70 for all-purpose shortening and 95–110 for pourable oil applications. In all cases, higher hydrogen pressures produced lower levels of TFA. In the range of 70–95 iodine values for the hydrogenated products, the Pt catalyst gave the least TFA, followed closely by Ni, and then Pd, for both oils. For all three catalysts at 2- and 5-bar pressures and 70–95 iodine values, cottonseed oil contained noticeably less TFA than soybean oil; this is probably because cottonseed oil contains a lower total amount of olefin-containing fatty acids relative to soybean oil. Approximate kinetic modeling was also done on the hydrogenation data that provided additional confirmation of data consistency.     

Thermal properties of fats and oils

Summary 1. The heat content of a quickly chilled sample, and that of a slowly chilled and tempered sample, of almost completely hydrogenated cottonseed oil, has been measured over a temperature range within which there is in each case complete transformation of the oil from a solid to a liquid form. 2. Heat capacity data have been calculated for the liquid oil and for the quickly chilled and the tempered solid oil. Equations expressing the changes in heat capacity with temperature have been derived. A correlation of the heat capacity data on highly hydrogenated cottonseed oil and similar data previously obtained on unhydrogenated cottonseed oil, and on partially hydrogenated oil, in both liquid and solid states, is presented. 3. The heat of fusion calculated for the quickly chilled and for the tempered solid oil is given. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Synthesis,Characterization, and Surface-Active Properties of Carboxylbetaine and Sulfobetaine Surfactants based on Vegetable Oil

A novel series of carboxylbetaine-type and sulfobetaine-type zwitterionic surfactants (castor oil amidoethyl betaine, castor oil amidoethyl sulfobetaine [CAAS], cottonseed oil amidoethyl betaine, and cottonseed oil amidoethyl sulfobetaine [COAS]) were synthesized via the reactions of nonedible vegetable oils (castor oil and cottonseed oil) with dimethylaminoethylamine, followed by the reaction with sodium chloroacetate and sodium 2-hydroxy-3-chloropropane sulfonate, respectively. Their chemical structures were confirmed using the electrospray ionization mass spectrum (ESI-MS) and infrared (IR) spectra. The surface activities of the prepared compounds were measured by surface tension. It was noticed that the sulfobetaine-type surfactants in aqueous solution performed slightly better at reducing surface tension than the carboxylbetaine-type surfactants. Meanwhile, the synthesized surfactants possess a broad range of isoelectric points, superior foam properties, and exhibit some antibacterial activity on Gram-positive and Gram-negative bacteria.     

Isopropanol as a solvent for extraction of cottonseed oil

Phase equilibrium data for the system; cottonseed oil-isopropanol-water were determined at 30°C. and compared with data for the system; cottonseed oilethanol-water. The relative phase distribution of fatty acids and cottonseed oil in mixtures with isopropanol and water was studied under varying conditions of water and fatty acid concentrations. These tests showed the fatty acids to be highly concentrated in the alcohol-water phase. Flaked cottonseed meats were extracted in continuous extraction apparatus with 91% isopropanol, 99% isopropanol, and mixtures of commercial hexane and isopropanol. Analytical data on the extractions show that 91% isopropanol is an efficient solvent for extracting active gossypol along with the oil. Rat and swine feeding tests of the isopropanol extracted meal showed it to be highly superior to hydraulic meal as a source of protein. A method was developed for treatment of the cottonseed-isopropanol miscella by liquid-liquid extraction to separate purified oil and fatty acid fractions from other materials in the extract.     

Color stability of glandless cottonseed oil

The color stability of oil extracted from glandless cottonseed contaminated with various levels of glanded cottonseed was studied. The rate of darkening in bleached color of cottonseed oil during storage was proportional to the original glanded cottonseed or gossypol content in the oil and to time and temperature of storage. Glandless cottonseed with 0–10% glanded seed contamination, as might be expected in commercial production of glandless cotton, yielded oil with equivalent or better color when conventionally refined and bleached after 30 days storage at 25 to 40 C than miscella refined oil from glanded cottonseed. This indicates that new oil mills for extracting glandless cottonseed need not invest in miscella-refining units in order to produce high quality oil.     

4-hydroxy-3-methoxycinnamate esters of milkweed oil: Synthesis and characterization

The common milkweed (Asclepias syriaca L.) is a new industrial crop. Its seed oil (TAG) is highly polyunsaturated. In the search for novel applications for milkweed seed oil, the olefinic groups in the TAG were oxidized to polyhydroxy TAG via epoxidation and subsequent epoxy ring-opening reactions. These polyhydroxy TAG exhibit unique industrially desirable emulsoid properties in water. Esterification of the secondary polyhydroxy functionalities of the TAG derivatives of the oil with trans-4-hydroxy-3-methoxycinnamic acid (ferulic acid) has resulted in the development of novel cinnamate esters of milkweed oil. These cinnamates are also obtainable via direct ring-opening of the epoxy TAG intermediate with ferulic acid. Among the interesting characteristics of the ester derivatives is their UV radiation-absorbing property.     

Phase equilibrium data pertaining to the extraction of cottonseed oil with ethanol and 2-propanol

Summary Basic phase relation data have been obtained relative to the extraction of cottonseed oil with ethanol and 2-propanol, especially as affected by water in the solvent. Mutual solubility diagrams have been constructed for cottonseed oil with ethanol and 2-propanol of various aqueous concentrations. Tie-line data at 30° C. have been obtained for the ternary ethanol-cotton-seed oil-water and 2-propanol-cottonseed oil-water systems. These combined data will be of assistance in the selection of the most desirable temperatures and moisture concentrations in the solvent extraction of cottonseed with these alcohols. Comparison with results previously published for soybean oil suggests that the mutual solubility data for cottonseed oil and aqueous ethanols are applicable to other vegetable oils over a wide range of iodine values. In general, the results indicate that 2-propanol is the more desirable solvent since complete miscibility with the oil can be attained at temperatures below its normal boiling point even at moisture contents as high as 10% by weight whereas ethanol can tolerate only about 1.5% of water. High moisture contents result in more effective separation of the oil from the solvent when the miscella is cooled after extraction. Constant boiling aqueous ethanol and 2-propanol present the disadvantage of requiring greater than atmospheric pressure during extraction in order to attain complete miscibility with the oil. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

A simplified process for the elimination of the halphen-test response in cottonseed oils

Since certain biological effects have been ascribed to the cyclopropenoids that give a positive response to the Halphen test, processes were explored to eliminate this response from cottonseed oils. Heating alkali-refined, Halphen-positive cottonseed oils in a modified laboratory deodorizer in the presence of cottonseed oil fatty acids, capric acid, citric acid, or phosphoric acid was found to be an effective method of eliminating this response. These treated, Halphen-negative cottonseed oils, the untreated Halphen-positive cottonseed oil, and a corn oil control were incorporated into rations fed to different groups of laying hens. Hens that ingested either the Halphen-negative cottonseed oil or the corn control produced normal eggs, whereas hens fed the Halphen-positive cottonseed oil produced eggs with pink whites, decreased pH of whites, and increased pH of yolks on storage, and lower ratios of oleic acid to stearic acid in the yolk lipids. The simple processes presented—particularly the use of cottonseed oil fatty acids—appear to offer a practical means of inactivating the cyclo-propenoids in cottonseed oil and thus eliminating the biological effects attributed to them. Presented at AOCS Meeting in Houston, 1965. Honorable Mention, Bond Award Competition. So. Utiliz. Res. Dev. Div., ARS, USDA.     

A new method for determining gossypol in cottonseed oil by FTIR spectroscopy

A new method was developed to determine the gossypol content in cottonseed oil using FTIR spectroscopy with a NaCl transmission cell. The wavelengths used were selected by spiking clean cottonseed oil to gossypol concentrations of 0–5% and noting the regions of maximal absorbance. Transmittance values from the wavelength regions 3600–2520 and 1900–800 cm⁻¹ and a partial least squares (PLS) method were used to derive FTIR spectroscopic calibration models for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils. The coefficients of determination (R ²) for the models were computed by comparing the results from the FTIR spectroscopy against those obtained by AOCS method Ba 8-78. The R ² were 0.9511, 0.9116, and 0.9363 for crude cottonseed, semirefined cottonseed, and gossypol-spiked cottonseed oils, respectively. The SE of calibration were 0.042, 0.009, and 0.060, respectively. The calibration models were cross-validated within the same set of oil samples. The SD of the difference for repeatability and accuracy of the FTIR method were better than those for the chemical method. With its speed (ca. 2 min) and ease of data manipulation, FTIR spectroscopy is a useful alternative to standard wet chemical methods for rapid and routine determination of gossypol in process and/or quality control for cottonseed oil.     

Solvent Interesterification of Vegetable Oils III

Directed interesterification reaction in solvents of cottonseed, peanut and cottonseed containing peanut, sesame and safflower oils was investigated with special reference to the influence of amount of sodium methoxide catalyst, oil content in solvent, temperature during the reaction and the nature of solvent on the characteristics of the reaction. The parameters were first studied with cottonseed oil and the conditions that favoured the reaction were adopted for peanut oil and cottonseed oil mixtures.     

棉籽油制备生物柴油的研究概况

我国棉籽油原料充足,由棉籽油制备生物柴油具有广阔的发展前景。文章综述了酯交换反应中的酸、碱、酶、超临界法在棉籽油制备生物柴油中的研究概况。     

Influence of lauroyl and myristoyl peroxides and oxidized cottonseed oil on depot fat and liver lipid composition

In view of the interest in the biological properties of products of fat oxidation, lauroyl and myristoyl peroxides were fed and their nutritional effects compared with those of autoxidized cottonseed oil, which had been analyzed for its composition. Purified diets containing no fat +2% of linoleic acid, 5% lauroyl or myristol peroxide, or 10% oxidized cottonseed oil were fed to weanling male albino rats for 73 to 98 days, after which they were killed and their organs weighed. Their sera, livers, and testicular fat bodies were used for lipid analysis. With peroxides, growth was significantly depressed but not as much as when oxidized cottonseed oil was fed. Analysis of organ weight data showed that peroxides and oxidized cottonseed oil differed in their effects. Animals fed the latter had significantly heavier livers, kidneys, and hearts. The rats fed peroxides were also different from those fed the fat-free diet and those kept on restricted food intake. Gas chromatographic analysis of the testicular fat bodies revealed a greater deposition of oleate in the animals fed oxidized cottonseed oil, which suggested that these animals were unable to use the oxidized oil for depot fat formation. In the anials fed lauroyl and myristoyl peroxides, appreciable amounts of laurate and myristate, respectively, were found. The composition of the liver neutral fat of the animals fed peroxides was similar to that of the animals fed the low-fat diet +2%, linoleic acid. Serum cholesterol levels of the rats fed peroxides were about 70 mg. %, and of those fed oxidized cottonseed oil, 53 mg. %. The groups fed peroxides also had significantly higher liver cholesterol levels, which suggests that peroxides and oxidized cottonseed oil differed in their effects on cholesterol formation and transport. Aided by Grant A-1654 from the United States Public Health Service. Presented at the 34th fall meeting of the American Oil Chemists’ Society.     

Studies in the Glyceride Composition of Partially Hydrogenated Rearranged Glycerides of Cottonseed Oil

The directed rearrangement reaction in solvents of partially hydrogenated cottonseed oil was investigated with special reference to the influence of polarity of solvents and amount of trisaturated glycerides formed. The results as obtained by selective enzymatic hydrolysis, gas liquid chromatography and infrared spectrophotometry of the whole fat triglycerides and of the corresponding monoglycerides of cottonseed oil and partially hydrogenated cottonseed oil, before and after directed interesterification, indicate a general trend of the increase of the saturated fatty acyl radicals in the 2-position of the glyceride moiety with the corresponding decrease of the unsaturated acids. The considerable decrease in the concentration of cis unsaturated acid in the 2-position of the triglycerides of partially hydrogenated cottonseed oil has been observed after the directed rearrangement reaction with the simultaneous enrichment of trans unsaturated acid. It was also observed that cottonseed oil does not show any plasticity, whereas after directed interesterification it shows remarkable plasticity. The plasticity of partially hydrogenated cottonseed oil is further diminished after directed rearrangement reaction.     

Sterol content of some plant oils; Further observations on fast-reacting sterols

Total and free sterols were measured by a modified Sperry-Webb procedure in raw and refined corn, cottonseed, safflower seed, linseed, soybean and wheat germ oils. Wheat germ and safflower seed oil sterols were relatively rich in fastreacting sterols, which predominated in the sterol ester fraction. Photometric constants following color reaction were obtained for cholesterol and plant sterols and applied to a procedure for analysis of cholesterol and plant sterols in mixtures thereof.     

Triglyceride composition of olive oil,cottonseed oil and their mixtures by low temperature crystallization and gas liquid chromatography

Crystallization and gas liquid chromatography (GLC) have been used to characterize the triglyceride composition of olive and cottonseed oil and their precipitates from acetone or methanol/acetone (10:90, v/v) at −2 C. The precipitate obtained after a 24 hr crystallization of a 5% (w/v) solution of the sample in acetone or methanol/acetone (10:90, v/v) at −2 C was named Precipitate I (P-I); that isolated after 2 successive crystallizations under identical conditions was named Precipitate II (P-II). In each case, the ratio of oleic to linoleic acid (O/L) was calculated and proved to be a useful index for detecting adulteration of olive oil with cottonseed oil. In olive oil, the ratio O/L increased from the original sample to its precipitates, whereas in cottonseed oil and the adulterated samples the ratio O/L was lower in the precipitates than in the original sample. For olive oil P-II, the lowest value of the ratio O/L was 8.4; for the adulterated samples it was 7.6. On the basis of this index, adulteration of olive with cottonseed oil as low as 10% can be detected. Hydrolysis of P-1 by porcine pancreatic lipase and analysis of the fatty acids of the sn-2 position showed that the enrichment factor of linoleic acid varied between 1.11–1.30 for olive oil and between 1.55–1.90 for the adulterated samples. Even for adulteration with 5% cottonseed oil, the enrichment factor appears to increase (1.55–1.57) and can be used as a criterion for adulteration.     

Tocol-derived minor constituents in selected plant seed oils

Various crude and processed seed oils were analyzed for tocopherols (T) and tocotrienols (T₃) by reversed-phase HPLC with fluorescence detection (FL). The oils included processed canola oil, crude corn oil, crude milkweed oil, crude palm oil, crude/processed rice bran oils, crude/processed soybean oil, crude/processed sunflower oil, and related modified oil, crude/processed sunflower oil, and related modified oil varieties. The HPLC system consisted of a pentafluorophenylsilica (PFPS) column and a mobile phase of methanol and water. The results of comparative methodological studies with rice bran oils and milkweed oils indicated that the reversed-phase PEPS-HPLC method in conjunction with the use of less hazardous solvents proved to be superior and a viable alternative to the conventional normal-phase HPLC method. Unlike the traditional nonpolar octadecylsilica phase, which fails to resolve β-γ pairs of T and T₃, HPLC with the unique polar PFPS column enables separations of all compounds of interest. Except for palm oil, βT and γT were detected in all other crude oils. Although most milkweed oils contained moderale levels of βT and γT, the βT species was present in relatively low abundance in edible oils despite the observation of fairly high concentrations of γT in the latter oils. βT₃ and γT₃ were detected along with αT₃ and σT₃ only in palm and rice bran oils. Tocolderived antioxidant distribution data for zero-time processed oils provided potential utility in correlation studies of frying quality and stability. The variable distribution data for crude oils shed some light on market profitability of oilseeds with rich sources of vitamin E-related minor constituents.     

Synthesis and Characterization of the Intrinsic Properties of Milkweed Polyhydroxy Fatty Acids

Seed oils consist mainly of triglycerides, that is, they comprise a unit of glycerol backbone esterified with three acyl groups (usually but not limited to C16–C18) which may be saturated or unsaturated with one or more olefinic functionalities per acyl group. Very rarely do seed oils contain additional functional groups, such as hydroxyls as in castor and lesquerella seeds. Milkweed seed oil follows the natural triglyceride patterns, but with a difference in being highly poly olefinic. This character allows for the introduction of different reactive groupings into the structure of the oil so as to be amenable to tailoring to a variety of uses. Synthesis of the milkweed polyhydroxy triglyceride (MWPHTG) from the polyoxirane triglyceride derivative of milkweed oil using in situ peroxy acid epoxidation of the oil was previously reported. Subsequent acidolysis of the epoxy derivative gave the MWPHTG. Here the polyhydroxy triglyceride was saponified for glycerol removal thus generating the polyhydroxy fatty acids of milkweed oil. Studies of the physical characteristics, flow and stability of the resulting hydroxylated fatty acids using FTIR, NMR, DSC, Rheometry and TGA indicate a stable material with unique properties that would be useful as additives in many applications such as pharmaceuticals.