The storage of cottonseed. IX. Behavior of cottonseed during storage under mill conditions

Summary The production of heat and the rate of formation of free fatty acids in 20- to 40-ton lots of cottonseed have been found to be dependent on the initial moisture and free fatty acids contents of the seed. Even though sustained aeration controlled the temperature of the seed and reduced the moisture content appreciably, the rate of formation of free fatty acids was rapid in all the tests except those involving seed of initially low or medium moisture and low free fatty acids contents. Losses in oil content proportional to the storage interval occurred. Presented at the 41st Annual Meeting of the American Oil Chemists' Society, Atlanta, Ga., May 1–3, 1950. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture. This work was conducted with these companies under an informal memorandum of understanding with the Bureau of Agricultural and Industrial Chemistry.     

Polyamides from polymeric fat acids

Summary The preparation and properties of various polyamides, copolyamides, and modified polyamides, of polymeric fat acids have been described. These polymers are of interest because of their unusual properties and because of the unsaturation and relatively high molecular weight of the polybasic acids involved. Despite the presence of tribasic acids in polymeric fat acids, ungelled polymers having molecular weights of 3,000 to 5,000 are obtainable. A brief discussion has been given concerning the application of theoretical principles of polymerization to the preparation of these polymers. Possible industrial uses for the polyamides are indicated. This is one of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Comparison of fat-splitting reagents in the twitchell process

Summary Commercial petroleum sulfonic acid reagents have been compared with Twitchell reagents, alkylarylsulfonic acids, and sulfoarylstearic acids as fat-splitting reagents in the hydrolysis of lard oil, tallow, cotton-seed oil, garbage grease, and inedible grease. The best reagents were made from commercial wetting agents of the alkylarylsulfonate type. Sulfoxylylstearic acid, seven petroleum sulfonic acids, and four Twitchell reagents followed in decreasing order. Observations have been made on the distribution of the fat-splitting reagent between phases, the necessity of removing the sweet water after a certain degree of hydrolysis, and the effect of the fat-splitting reagent upon the color of the crude fat acids. This is one of four Regional Research Laboratories operated by the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Norelac — A proposed new synthetic coating material

Summary A new protective coating material, Norelac, the ethylene diamine polyamide of polymeric fat acids has been described. A preliminary report on its properties indicates that it may prove to be a superior protective coating for wood, metal, and other materials, and an adhesive for heat-sealing and laminating of paper, cellophane, glassine, and other packaging materials. The solubility characteristics of Norelac show that solvation probably occurs in compounds containing electron-acceptor groups, such as alcohols, amines, acids, and chloroform. The Northern Regional Research Laboratory is one of four Regional Laboratories authorized by Congress in the Agricultural Research Act of 1938 for the purpose of conducting research to develop new uses and outlets for agricultural commodities. These Laboratories are operated by the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Buckwheat leaf meal fat. II. Composition of the fatty acids

Summary The composition of fatty acids of the saponified fat of buckwheat leaf meal was investigated. The mixed fatty acids amounted to 49.6% of the composition of the fat. The chief organic acids found were: linolenic, 15.1%; oleic, 13.1%; linoleic, 8.5%; and palmitic, 8.0%. Less than 1% each of such acids as formic, lactic, stearic, arachidic, hexacosanoic, and octacosanoic, and only traces of acetic, lignoceric, and tricontanoic (or higher) acids were found. The so-called “insoluble acids” of the saponified fat, less the unsaponifiable matter, contained 28.5% (18.5% based on the original fat) of material identified as red pigment and probably a mixture of chlorophyll degradation compounds, chiefly phylloerythrin. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Synthetic oils from residual dimerized fat acids

Summary Synthetic oils have been prepared from residual dimerized fat acids with soybean and linseed fat acids by esterification with polyalcohols, and with or without maleic anhydride or phthalic anhydride. Preliminary evaluation indicates that these oils give films which dry faster and are more resistant to water and alkali than linseed oil films. This enhancement of water and alkali resistance may result from an increase in C-C bonds present in the films. Ester gum varnishes made from these oils were not markedly superior to similar varnishes made from linseed oil. The Northern Regional Research Laboratory is one of four Regional Laboratories authorized by Congress in the Agricultural Research Act of 1938 for the purpose of conducting research to develop new uses and outlets for agricultural commodities. These Laboratories are administered and operated by the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

The fatty acids of dormant tung buds

Conclusions and Summary The methyl esters of the fatty acids in the wax of dormant tung buds were prepared and fractionated in a column packed with a spiral screen. Myristic, palmitic, linoleic, oleic, and stearic acids were identified in some of the fractions by the saponification equivalents and by the melting points of the p-bromophenacyl derivatives of the saturated acids and the hydroxy derivatives of the unsaturated acids. The identification of these acids proved the presence of some of the higher fatty acid radicals similar to those found in Crisco and lanolin. It is believed that the mutual solubility of these fatty acids may have facilitated penetration of the alpha-naphthalenacetic or indole-3-acetic acid in Crisco and lanolin emulsions, into the bud tissue and in this way increased their effectiveness in prolonging dormancy. Associate chemist (resigned) and associate plant physiologist, respectively, Division of Fruit and Vegetable Crops and Diseases, Bureau of Plant Industry, Soils, and Agricultural Engineering, Agricultural Research Administration, United States Department of Agriculture     

Preparation of hydroxy acids by sulfation of oleic and linoleic acids

Summary Monohydroxystearic acids were prepared by sulfation and subsequent hydrolysis of oleic acid, and the effect of reaction conditions on yield was studied. Monohydroxystearic acids were obtained from commercial oleic acid in 72% yield and from pure oleic acid in 86% yield. Conditions for the best yields apparently gave increased amounts of isomeric hydroxy acids. Hydroxy acids prepared by the sulfation and subsequent hydrolysis of linoleic acid were converted to methyl esters, and purified by fractional distillation and low temperature crystallization. Experimental evidence indicates that sulfuric acid reacts with one double bond of linoleic acid to form isomeric monohydroxyoleic acids and with both double bonds to form dihydroxystearic acids. The by-products formed by the sulfation of linoleic acid include both ester-type polymers and additional polymeric material which cannot be converted to monomers by alkaline saponification. When commercial oleic acid is sulfated and subsequently hydrolyzed, the monohydroxystearic acid thus obtained presumably contains monohydroxyoleic acids and dihydroxystearic acids resulting from the linoleic acid present in the starting material. The formation of an unsaponifiable polymer during the sulfation of linoleic acid accounts in part for the lower yield of hydroxy acids obtained from commercial oleic acid, as compared with that of purified oleic acid. One of the laboratories of the Bureau of Agricultural and Industrial Ohemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

A note on the composition of wheat-germ oil

Preliminary to an exploration of the possibilities for the increased industrial utilization of wheat oils, the proximate analysis of a commercially available wheat-germ oil has been repeated in the light of present conceptions of the significance of the analytical constants of the unsaturated fatty acids. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Spectrophotometric determination of small proportions of polyunsaturated constituents in fatty materials

Summary Existing ultraviolet spectrophotometric methods have been modified for application primarily to the detection and estimation of low proportions of conjugated and nonconjugated unsaturated constituents in fats, oils, and soaps. The method is applicable also to fatty materials having high proportions of these constituents. Modifications include corrections for absorption by interfering substances, use of alkaline glycerol as an isomerization medium in the analytical procedure, and correction of absorption data on the isomerized product for absorption by conjugated constituents in the material before isomerization. The presence of small proportions of highly unsaturated conjugated and nonconjugated compounds is established in lards, tallows, tallow soaps, and highly purified esters and acids. Tall oil fatty acids are shown to contain approximately 10% of conjugated diene acids and a small amount of linolenic acid. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

The hydrolysis of fatty acid chlorides

Summary Fatty acid chlorides of octanoic, decanoic, lauric, myristic, palmitic, stearic, oleic, elaidic, and linoleic acids were hydrolyzed at 25° C, in water and the amounts of unchanged acid chlorides determined after different periods of reaction. Contrary to expectations, the chlorides of the longer chain fatty acids, palmitic and stearic, reacted at a more rapid rate than the chlorides of the shorter chain fatty acids. Lauryl chloride appears to be more resist-ant to hydrolysis than either the chlorides of the lower molecular weight octanoic and decanoic acids or the chlorides of the higher molecular weight myristic to stearic acids. The chlorides of the unsaturated acids, oleic, elaidic, and linoleic, are hydrolyzed less rapidly than stearyl chloride. However, elaidyl and myristyl chlorides exhibit the same relative rates of hydrolysis during the first two hours of reaction. Myristyl chloride hydrolyzes more rapidly than elaidyl chloride after the first two hours. The addition of either hydrochloric acid or free fatty acids to the reaction mixture was found to have no pronounced effect on the hydrolysis of the acid chlorides. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Allylic esters of polymeric fat acids

Summary 1. Allyl, β-methallyl, and β-chlorallyl esters have been prepared from polymeric soybean fat acids by direct esterification and from dilinoleic acid by transesterification of methyl dilinoleate. 2. The method of polymerizing the esters and the properties of the polymers are described. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

The occurrence of higher fatty acids in corn pollen

Summary The methyl esters of the fatty acids of corn pollen were prepared and fractionated through a Stedman column. Palmitic, stearic, oleic, linoleic, and linolenic acids were identified by the melting points of thep-bromophenacyl esters of the saturated acids and the hydroxy and bromine addition compounds of the unsaturated acids. This investigation was supported by a grant from the National Science Foundation. Journal Article No. 2139 of the Michigan Agricultural Experiment Station.     

Oil from calabash seed,Crescentia cujete L.

Summary The composition and characteristics of calabash,Crescentia cujete L., seed and oil have been determined. The oil was found to have the following composition calculated from the iodine and thiocyanogen values, and saturated acid content of mixed fatty acids: saturated acids 19.7%, oleic acid 59.4%, linoleic acid 19.3%, and linolenic acid 1.6%. Comparison of the composition and characteristics of calabash seed oil with those for peanut and olive oil indicate that, except for the presence of a small amount of linolenic acid in the former, the oils are similar. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

A method for the determination of linoleic acid and conjugated dienoic acids in materials containing eleostearic acids

Summary A procedure has been described which extends the scope of the spectrophotometric method for polyun-saturated acids to the determination of linoleic and conjugated acids in the presence of large quantities of conjugated trienoic acids. Basis for the proposed method rests on equations which are offered to correct the “end” or “back-ground” absorption of the highly absorbing triene conjugated acids at 233 mμ, the position of maximum absorption of conjugated dienoic acids and alkali isomerized linoleic acids. The method is limited to samples which do not contain nonconjugated trienoic acids (linolenic acids). The method has been tested by the analysis of several mixtures of cottonseed and dehydrated castor oils of known composition, to which varying amounts of alpha, beta, and mixtures of alpha- and beta-eleostearic acids have been added. These samples have been used to demonstrate the application of the proposed method for the determination of dienoic conjugated acids, alpha-eleostearic acid, beta-eleostearic acid linoleic acid, oleic acid, and total saturated fatty acids. Comparisons of the results obtained with similar values, calculated from the known composition of the mixtures, prove that the proposed method gives reasonable results. Standard deviations between determined and calculated results vary from 0.36 for diene conjugated acids to 1.40 for oleic acid. The method has been applied to the analysis of foreign and domestic tung oils. Presented before the American Oil Chemists' Society, Cincinnati, O., Oct. 20–22, 1952. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

The identification of the fatty acids of the fat from a North American black bear

Summary A study has been made of the identification of the fatty acids of the fat from a North American black bear. The methyl esters of the fatty acids from the fat were prepared and fractionated through a Stedman Column. Myristie, palmitic, stearic, oleic, palmitoleic, and linoleic acids were identified by the melting points of the p-bromophenacyl ester of the saturated acids and the hydroxy and bromine addition compounds of the unsaturated acids. Published with the approval of the Director of the Michigan Agricultural Experimental Station as Journal article No. 970 (new series).     

Amino acids of citrus seed meal

Defatted seed meal from oranges and grapefruit contained more sulfur amino acids but less lysine than some common oilseed proteins. Grapefruit seed meal had less tryptophan and more sulfur amino acids than orange seed meal. Probable annual yields of Florida citrus seed oil, meal and hulls are 17, 23 and 13 million lb, respectively. Florida Agricultural Experiment Station Journal Series No. 4313.     

Buckwheat leaf meal fat. I. Its physical and chemical characteristics and the constituents of the water-soluble and unsaponifiable fractions of the saponified fat

Summary The leaf meal fat of the Japanese buckwheat plant has been prepared, and its physical and chemical characteristics have been determined. Spectrophotometric analysis of the fat of this variety indicates that in composition it is similar to the fat of the Tartary variety, the one now preferably used for manufacture of rutin. The large quantity of unsaponifiable matter is unusual. This fraction contains carotene, xanthophylls, phytol, β-sitosterol, and an eicosanol. Also of interest is the presence in the fat of significant quantities of lecithin when isopropanol is used for extraction. The water-soluble acidic constituents of the saponified fat consist of the organic acids formic, acetic, and lactic, and the inorganic acids phosphoric, nitric, sulfuric, and hydrochloric. Ammonia was present in the alcohol distillate collected after saponification, and glycerol was identified in the water-soluble acid fraction. Quantitative values are given for formic and lactic acids and for ammonia. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

Application of urea complexes in the purification of fatty acids,esters, and alcohols. III. Concentrates of natural linoleic and linolenic acids

Summary Concentrates of natural linoleic acid (linoleic acid content, 85–95%) have been prepared in 50–72% yields from corn oil fatty acids by preferential precipitation of the saturated and monounsaturated fatty acids at room temperature as their urea complexes. By a similar procedure, concentrates of natural linolenic acid (linolenic acid content, 87–89%) have been prepared in 55–61% yields from perilla oil fatty acids by preferential precipitation of the saturated, monounsaturated, and diunsaturated fatty acids. Although concentrates of natural linolenic acid containing only 66–70% linolenic acid were obtained from linseed oil fatty acids, yields were 87–90%. A levelling-off effect has been observed in the use of the preferential precipitation technique in raising the purity of concentrates of linoleic and linolenic acid. This parallels the experience in the purification of these acids by low-temperature crystallization. The preceding papers in this series are references 12 and 13. Presented at the Fall Meeting of the American Oil Chemists' Society, Cincinnati, O., Oct. 20–22, 1952. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Degradation of polysaccharides in alkaline solution to organic acids: Product characterization and identification

Agricultural products have considerable potential for conversion to valuable oxychemicals. Analyses by ether extraction, titration, and anion-exchange classification of the alkaline degradation products of totally converted starch and cellulosics showed that the product compounds are mainly organic acids. Almost all the organic acids are monocarboxylic in nature, with an average equivalent weight in the range 76–84. The organic acids identified thus far by HPLC and GC are formic, acetic, glycolic, lactic, 2-hydroxybutyric, 2-hydroxyisobutyric, and 2-hydroxyvaleric acids. Together, these compounds represent 41–46% of the starting material weight.