bluuebunny/crossref_metadata_2025 huggingface dataset:
Partial hydrogenation of polyunsaturated fatty materials
Authors: Draguez de Hault E. , Demoulin A.
Published: July 2007

For many applications involving the use of polyunsaturated triglycerides such as soybean oil, a liquid product having an improved stability to oxidation is required. The partial hydrogenation of soybean oil into a liquid product containing less oxidizable materials can be achieved with selective nickel catalysts. A soybean oil containing ca. 5% solid matter at 10 C, 1% linolenic acid and 0.5% conjugated dienes is obtained with a nickel/titanium oxide catalyst or with nickel‐zirconium oxide/kieselguhr catalyst treated wity fatty amines such as lauric or coco primary amines. In the frame of this work, ca. 100 heterogenous Ni catalysts have been tested under standard operating conditions for the partial hydrogenation of soybean oil.
Influence of various catalyst poisons and other impurities on fatty acid hydrogenation
Authors: Klimmek Helmut
Published: July 2007

The effect of various impurities which reduce the activity of nickel catalysts during fatty acid hydrogenation has been studied. It is here proposed to divide the compounds which negatively influence the nickel‐based fatty acid hydrogenation process into three categories, namely, catalyst poisons, inhibitors and deactivators, each group acting according to a different mechanis. The deleterious effect of typical catalyst poisons, such as S, N, P or Cl, is more or less independent of the chemical nature of the individual organic compounds containing these elements. There is good correlation between these element contents and the required nickel catalyst loading level. Other typical impurities present in technical fatty acids, such as oxidized fatty acids, soaps and water, also diminish the catalyst activity considerably. A number of experiments were designed to study the influence of various pretreatments of fatty acids on the catalyst loading levels needed for hydrogenation. In view of the high cost of nickel catalysts, considerable savings can be obtained by pretreatment of fatty acids prior to hydrogenation. Such pretreatment steps may include sulfuric acid washing, application of spent catalysts, and/or distillation. The most economical method will depend on local circumstances.
Fatty acid fractionation by column distillation: Purity, energy consumption and operating conditions
Authors: Stage Hermann
Published: July 2007

This paper discusses the optimal process conditions for production of individual fatty acids of any desired purity up to higher than 99% and describes especially the influences of column internals as well as exchange numbers, reflux ratios and fatty acid residence times at distillation temperatures. The new process conditions are characterized by degasification at low temperatures followed by efficient dehydration together with separation of first cuts at high reflux ratios by short‐time dephlegmation. The design of columns for efficiency and low pressure drop is influenced by the thermal properties of crude acids and the quality demands on distillate fractions. Environmental requirements can be met by working without open steam. Bottom temperatures should not exceed 250 C, to prevent thermal degradation of fatty acids as well as corrosion of stainless steel.
The use of bleaching earth in fatty acid production
Authors: Zschau Werner
Published: July 2007

Pretreatment of crude tallow or fish oil fatty acids with bleaching clays considerably improves the rate of hydrogenation with several different catalysts. Several series of tests were run to demonstrate these effects, and the data are presented.
Supercritical CO2extraction of lipid‐bearing materials and characterization of the products
Authors: Friedrich J. P. , Pryde E. H.
Published: July 2007

Supercritical fluid extraction has recently become a reality in the petroleum, coal and food industries and is rapidly increasing in importance as its advantages become known. Advantages of carbon dioxide as a supercritical fluid include its low toxicity, low cost, lack of flammability, lack of reactivity, wide range of solvent properties at different pressures and temperatures, and improved properties of separated components in certain cases. Disadvantages of such extractions include high capital costs for batch extraction and lack of engineering hardware technology for continuous operation. In the supercritical CO2extraction of oil from soybeans, equilibrium solubility and high flow rates are readily achieved in a short‐path batch reactor. The oil has a lighter color, less iron and ca. 1/10 of the phosphorus contained in hexane‐extracted oil. The lower phosphorus content results in lower refining losses. During extraction, some fractionation is observed to take place, with some more polar and/or higher molecular weight compounds having a tendency to increase in the later fractions. In a long cylindrical batch extractor, the flakes perform much like the stationary phase of a chromatographic column. The same advantages that result from extraction of soybeans also apply to the extraction of oil from cottonseed and corn germ. Cottonseed oil obtained by supercritical CO2extraction has a lower gossypol content and requires less alkali for refining. In the extraction of wheat germ and bran, the oil has a lighter color, a milder odor and less unsaponifiables than that obtained by hexane. Free fatty acid contents were comparable, but tocopherol was higher in the supercritical CO2extract.
New developments in the fatty acid industry in America
Authors: Sonntag Norman O. V.
Published: July 2007

Although acquisition, divestiture and other organizational changes within the American oleochemical industry are still the most startling and attention‐attracting, the development of new technology continues to be of paramount scientific interest. Noteworthy among the new developments are (a) the continuing development of new vegetable oil raw materials like 90% erucic acid rapeseed oil and 80% oleic acid sunflower; (b) the intense process development under way in some areas for the minimization of thermal energy requirements of certain reactions like polymerization (dimer acids), glycerolysis (mono‐ and diglycerides) and fat splitting; (c) the ever‐increasing substitution of methyl esters for fatty acids in the production of a whole series of oleochemicals; (d) development of new esterification catalysts; (e) lipase catalysis of interesterification; (f) development of new corrosion‐resistant materials of construction; (g) the use of irradition sulfoxylation as a preferred production route to randomly sulfonated methyl esters; and (h) superemulsification as an aid to hydrophobic/hydrophilic liquid chemical reactions. Continued attention to alternative feedstocks, biotechnology, microprocessor technology, pollution control and lower energy consumption are certain to receive considerable attention for the next several years.
The chemistry of dibasic and polybasic fatty acids
Authors: Johnson R. W.
Published: July 2007

Current processes to produce dibasic and polybasic fatty acids including azelaic, sebacic, dodecanedioic, C21diacid, fatty dimer and trimer acids are discussed. A number of alternative routes to produce azelaic, sebacic and fatty dimers are also discussed, includeding the preparation of azelaic and sebacic acids from butadiene and sebacic acid from adipic acid. Physical properties of the various dibasic acids are compared. Preparation of important derivatives and their applications is discussed, including: (a) esters and polyesters as vinyl plasticizers and as base stocks for synthetic lubricants; (b) polyamide resins in coatings, fibres, inks and adhesives; (c) salts as surfactants; and (d) amido amines and imidazolines as corrosion inhibitors. Dimer acids have found application in the petroleum industry as drilling mud thickeners in oil recovery.
Fatty acid derivatives: Important surfactants for household, cosmetic and industrial purposes
Authors: Maag H.
Published: July 2007

This paper reviews selected surfactants obtained from fatty acids. Because of their indispensible properties, some of these surfactants have already been in use for a long time, whereas others, such as sucrose esters or ester sulfonates, are only beginning to be used. However, all these surfactants have in common the fact that they are highly acceptable to the environment, characterized by their skin tolerance, good biological degradability and low toxicity. With consumer awareness becoming more and more apparent, these are noteworthy properties from which we can expect that surfactants prepared from fats will increase in importance in the future.
Fats and oils as feedstocks for oleochemicals
Authors: Gander K. F.
Published: July 2007

The approximate quantity of 3 million tons estimated to be required at present for the production of oleochemicals is to be covered from a total production of more than 60 million tons of vegetable and animal fats. While the quantity of eleochemicals produced has nearly doubled in recent years, vegetable oil production alone has increased from 25 to 40 million tons in the same period. More than half the feedstocks required for oleochemicals are acid oils and other fats and oils which are unsuitable for human food. The demand for fats and oils for oleochemicals will certainly grow for price and technological reasons, but only the use of large quantities of oils and fats for diesel engines could shift this balance drastically and endanger the world supply of edible fats. A bottleneck may arise in the supply of fatty acids of medium chain length, although the use of coconut and palm kernel oil by the food industry in the highly developed countries has been on the decline. The green revolution goes on and the fat supply grows faster than the population. In addition, new approaches to plant breeding and agriculture, and biochemical processes as well, might help circumvent any conceivable shortage in the supply of oils and fats in general, and in the supply of special fatty acids in particular.
Future of petrochemical raw materials in oleochemical markets
Authors: Haupt D. E. , Drinkard G. , Pierce H. F.
Published: July 2007

The petrochemical industry (PCI) has undergone profound changes during the last decade and is continuing to adjust to changing world economic conditions. One of the most important of these is the price of crude oil. Although an equilibrated pricing structure remains to be demonstrated, anticipated adequacy of supply and versatile, innovative methods of converting crude and natural gas to high valued products assures it a vital and healthy future. The product areas in which the PCI and the oleochemical industry (OCI) overlap are actually quite small in terms of the total capacity. In those limited areas of overlap, we expect the role of the PCI during the next several years to continue to be cone of a complementary nature. By providing security of supply at competitive prices, it will create confidence and reliability which will benefit both the petrochemical and oleochemical industries. And most significantly, the resources of the petrochemical industry will also allow it to respond to new market conditions, particularly those of accelerated volume needs and specific performance, with the flexibility and creativity which have been its hallmarks.
Biotechnology and oleochemicals: Changing patterns
Authors: Neidleman S. L. , Geigert J.
Published: July 2007

Biotechnology will have a broad impact on the oleochemicals industry. Only a narrow range of this interface is discussed: (a) the use of organic solvents in the enzymatic synthesis of lipid derivatives, (b) the effect of the chemical nature of the feedstock on the production of microbial monoesters, and (c) temperature as a determinant of the level of unsaturation in biosynthetic lipids. Interest in running enzymatic reactions in high concentrations of organic solvents is increasing. The implications of such processes for the oleochemical industry is illustrated by examples of ester synthesis and interesterification of oils and fats. The dramatic effect of feedstock chemistry on the final monoester product mix produced byAcinetobacter sp. HO1‐N is also discussed. Products resulting from usingn‐alkanes (C16−C20), acetic and propionic acids and, most recently, ethanol and propanol, are illustrated. They range from a monoester mix resembling sperm oil to one similar to jojoba oil. In general, temperature inversely affects biolipid unsaturation: the low the temperature, the greater the unsaturation. The major function of this response is to preserve fluidity and function in biological membranes. The effect is universal in nature, occurring in animals, plants and microorganisms. Controlled laboratory studies have supported these observations made in nature. We have investigated the effect of temperature on the unsaturation of monoesters produced by the bacterium,Acimetobacter sp. HO1‐N. The inverse relationship between temperature and unsaturation is clearly shown. The enzymatic basis for these results and the possibility of chemical or genetic modification of plants and microorganisms to produce more or less unsaturated lipids is briefly discussed. Organic solvents, feedstock chemistry and temperature stress in biocatalysis are but three of the variables at the interface of biotechnology and the oleochemicals industry that will cause changing patterns.
Handling and transporation of hazardous materials and hazardous wastes: A practical and legal perspective
Authors: Bierlein Lawrence W.
Published: July 2007

An often unavoidable consequence of the manufacture, of valuable products is the creation of hazardous materials and hazardous wastes. By “hazardous material’ is meant the commercial product—a commodity of value which has hazardous properties that may be essential to its effectiveness. “Hazardous wastes’ are byproducts that usually have little or no value to the company that generates them, but that usually result from manufacturing processes and must be managed to prevent injury to the public and the environment. (Of course, through the establishment of waste exchanges, one company's waste may become another company's feedstock, thereby eliminating or at least postponing the disposal problem.) The more stringent individual countries or regional groups of countries become in their regulation of hazardous wastes, the greater the incentive there is in those, countries to export wastes to nations where requirements are less rigorous. Thus, the development of a world policy on hazardous waste appears to be worthwhile, but in considering such a policy, it is essential to learn from the mistakes others have made.
Oleochemicals as a fuel: Mechanical and economic feasibility
Authors: Harwood Henrick J.
Published: July 2007

The status of vegetable oils as diesel fuel substitutes is currently dubious. Although it is fair to consider them as short‐term emergency fuels (or, more desirably, low proportion supplements to diesel fuels), they present mechanical problems in long‐term use that have not yet been solved. It is preferable to use these oils blended in small proportions with diesel fuels. Indirect‐injection diesel engines have had fewer problems than direct‐injection engines, whether the tests were performed with pure vegetable oil fuel or with vegetable oil/diesel fuel blends. The economic prospect for these fuels is not promising. In general, they are not and have not been economical alternatives to diesel fuel. Exceptions appear to have occurred recently in Brazil and the Philippines where low local prices for vegetable oils combined with high petroleum prices encouraged officials to use low proportion vegetable oil/diesel fuel blends. Nonetheless, current and long‐term trends in petroleum and oilseed prices indicate that these fuels will probably not be price competitive within the near future. Emergency disruption of petroleum supplies completely changes the economic situation. Vegetable oils would be worth much more as a fuel during disruptions than otherwise; thus incentives could be strong to include these oils in the fuel supply, diverting them from the food supply.
Worldwide studies of mixed active laundry detergency
Authors: Cox Michael F. , Matson Ted P. , Berna Jose Louis , Moreno Alfonso , Kawakami Shigeru , Suzuki Michio
Published: July 2007

A cooperative study involving laboratories in the United States, Europe and Japan was conducted to investigate the detergency performance of mixed active detergents. Each location tested mixtures commonly manufactured in their region using wash conditions typical of their area. The utility of the data in selecting optimum cost/performance formulations is discussed. Under typical wash conditions found in the United States and Japan, a mixed‐active formulation is not required. In most cases, optimum detergency is obtained by a linear alkylbenzene sulfonate (LAS) based formulation. In Europe, a mixed active detergent is required. Although LAS provides optimum performance, some soap (or soap plus nonionic |NI|) must be added to control foam.
Production of fatty alcohols from fatty acids
Authors: Voeste Theodor , Buchold Henning
Published: July 2007

Detergent‐range alcohols from natural feedstock can be produced by high pressure hydrogenation of either methyl esters or fatty acids. The increasing quantities of fats and oils on the world market secure a reliable and economically priced material. Although fatty acid is an abundant worldwide commodity, most alcohol producers hydrogenate methyl esters, because direct hydrogenation of fatty acids is difficult as the catalyst is sensitive to acid attack. The process described here makes it possible to hydrogenate fatty acids directly to alcohols of high quality without prior esterification. The reaction takes place in the liquid phase over a fine‐grained copper chromite slurry in a single reactor vessel. A special reactor design with an optimum arragement of the feeding nozzles causing an appropriate circulation of the reacting components inside the reactor facilitates the rapid “in situ” esterification reaction. This minimizes the free fatty acid concentration in the reactor to nearly zero. This results in a low consumption of catalyst. The most important advantages of the process are: direct feed of fatty acids of various origins, use of reasonably priced raw materials such as soapstock fatty acids and lower grade tallow acids, no process steps with methanol, and excellent economics. The process is industrially proven.
The analysis of cationic surfactants
Authors: Metcalfe L. D.
Published: July 2007

Long‐chain cationic surfactants have become a very important class of industrial chemicals. These useful oleochemicals are usually based on vegetable oils and animal fats. They have many applications which include fabric softeners, antistatic agents, organo clays, emulsifiers, germicides, flotation, chemicals, corrosion inhibitors and foam depresents. The fatty quaternary ammonium compounds (quats) are by far the most important of this group of the commerical compounds. However, the fatty amine salts and amine oxides must also be classified as cationic surfactants. Although not as widely used as quats, they have special properties and uses which are often unique and useful. The various analytical methods used for these chemicals serves several objectives, including routine quality control, identification and characterization, determination in mixtures and formulations, determination at use level, and determination in the environment. In general, the objective of the analysis will determine what method will be used. Routine quality control procedures will most often use wet methods or some simple instrumental techniques. Identification and characterization of unknown cationic samples often require the most sophisticated of instrumental and chromatographic methods. Use level and environmental samples usually must be analyzed using the most sensitive methods. Often, colorimetric analysis is adequate. These samples often must undergo rigorous separation and celan‐up techniques before the method of choice can be used. The methodology for the analysis of fatty amines, amine oxides and quaternary ammonium compounds is reviewed with the various analytical objectives in mind. However, the main emphasis is placed on the quats.
Ecological behavior of cationic surfactants from fabric softeners in the aquatic environment
Authors: Huber L. H.
Published: July 2007

The use of cationic surfactants in fabric softeners has reached considerable proportions in the Western industrialized nations during the last 10 years. In the Federal Republic of Germany alone, some 22,000 ton of cationic surfactants were marketed in 1981 for this specific purpose. The considerable share (12%) of total consumption which this class of surfactants accounts for is equivalent to a theoretical wastewater concentration of ca. 5 mg/L. Consequently, it raises questions concerning environmental behavior of this class of substances. The following factors are of substantial importance in this regard: acute and chronic toxicity in the aquatic environment; biodegradability under aerobic and anaerobic conditions; and the possibility of bioaccumulation in the aquatic organisms, particularly in fish. Basically, the ecological behavior of cationic surfactants, like that of distearyl dimethyl ammonium chloride (DSDMAC) and dialkyl imidazolinium salts (DAIC) which are mostly used, is determined markedly by their physicochemical properties, above all their strong adsorption on surfaces, e.g., on clay minerals or on activated sludge, thus leading to their elimination in water treatment plants and water courses. Of far‐reaching consequence from the toxicological aspect is the fact that they form neutral salts with the anionic surfactants present in excess in domestic wastewater, thus leading to a considerable decrease in toxicity. Although adsorption and ion‐exchange processes are primarily effective in climination of cationic surfactants of the DSDMAC and DAIC types in wastewater treatment, there are significant indications on the basis of experiments that these substances are subject to extensive aerobic biochemical degradation. However, it appears that anaerobic degradation does not take place. Tests conducted so far on the bioaccumulation behavior, particularly on a laboratory scale, indicate that these substances practically do not accumulate in the edible parts of fish and thus no risks are being discerned at present as regards the residue situation.
Organoclay rheological additives: Past, present and future
Authors: Mardis Wilbur S.
Published: July 2007

Rheological or flow properties have important implications in many and diverse applications. Often, an additive is used to impart the desired flow behavior. Among these, organoclay products, formed by the reaction of organic cations with smectite clays, are the most widely used additives for solvent‐based coatings. The cation— usually a quaternary ammonium salt—used will influence the performance of the resultant organoclay. Criteria to consider in the choice of a cation are molecular size, compatibility with the fluid in which the organoclay is to be used, stability and reactivity. To form a stable organoclay product, the organic cation must contain at least one long‐chain alkyl group. Othr groups attached to the cation may be divided into two categories: “filler” groups serve to complete the tetrahedron around the nitrogen, whereas “active” groups contribute beneficially to the performance of the organoclay. Our study of the structure/property relationships has led to the development of new additives described here. These are superior, particularly in terms of use, while providing the same excellent rheological control offered by earlier additives.
Advances in quaternary ammonium biocides
Authors: Schaeufele Peter J.
Published: July 2007

Several generations of structurally variable quaternary ammonium biocides were developed from approximately 1935 until the present. Demand for products with improved microbiological performance guided each successive step of development. Commercial availability of dialkyl dimethyl ammonium chlorides in 1965 set the stage for significant advances in quaternary biocide practices in the USA and Europe. This trend is continuing today with development of new, fourth‐generation quaternary biocides. Regulatory requirements by the US Environmental Protection Agency (organic soil tolerance) and specific consumer/marketing demands (hard water tolerance) provided a renewed challenge for quaternaries meeting those requirements. Development and properties of new, fourth‐generation quaternary biocides meeting those challenges are discussed. Some of the functional advantages of quaternaries are outlined. Development of the fourth‐generation quaternary biocides has led to products demonstrating significantly superior broad spectrum biocidal activity, specifically designed to meet the new challenges of organic soil and hard water contamination. Strong market gains, made by quaternary biocides over the recent past, have been primarily as a result of the type of work described herein, but some of the gains in quaternary usage can be ascribed to concern over adverse toxicological and environmental impact of other traditional biocides such as phenolics and aldehydes. The outlook for a continued increase in the use of modern‐day quaternary biocides is encouraging.
Oleochemical base fluid development
Authors: Struyck W. J. A.
Published: July 2007

For over a decade, synthetic lubricants have been identified as a true field of growth and opportunities. An attempt will be made to demonstrate to what extent the actual developments followed market‐research predictions. The path to a commercially successful base fluid is lengthy, risky and costly. A summary is given on the business environment in which developments take place as well as internal and external pressures on such development activities. Although the oleochemical industry provides essential “chemical backbones” for lubricant base esters, compounds of petrochemical origin are needed to design the proper molecule. Moreover, the petrochemical industry provides its own versions of synthetic base fluids. A picture is drawn on the relative position of oleochemical‐versus petrochemical‐derived base fluids.
Utilization of Malaysian palm oil and palm kernel oil for fatty acids and derivatives
Authors: de Vries Roy J.
Published: July 2007

Malaysia produces ca. 65% of the world's palm oil, or (in 1982) ca. 3,500,000 metric tons. By 1985, this will increase to 80% of world production, or ca. 4,800,000 metric tons. Palm oil products are refined, bleached and deodorized oil for edible purposes, palm olein for edible use, palm stearin for edible or industrial use, and the acid oil or fatty acid distillate for industrial uses. The Malaysian processors naturally want to upgrade the products as much as possible.
Structural determination and uses of jojoba oil
Authors: Miwa Thomas K.
Published: July 2007

The predominating molecular species in jojoba oil iscis‐13‐docosenylcis‐11‐eicosenoate (erucyl jojobenoate), ranging from 31% to 45% of the extracted seed oil. Other alcohol/acid combinations contribute to the C42 molecular chain length so that this fraction constitutes a low of 41% to a high of 57% of the total wax esters. The positions of the exclusivelycis ethylenic bonds in the alcohol and acid moieties of the wax esters are 99% ω‐9 and 1% ω‐7. Only 2% of the alcohol and acid moieties were saturated when analyzed after saponification of the oil. Triglycerides were detected by gas chromatography in all of the more than 200 natural jojoba oil samples tested, a few of which had substantially more than the normal 1%. Among the many uses of jojoba oil cited here, the two most promising are the sulfurized oil as extreme‐pressure/extreme‐temperature lubricant additive and the natural or refined oil formulated into cosmetic products.
Fatty oxazolines and imidazolines
Authors: Linfield Warner M.
Published: July 2007

Fatty acids are converted, almost quantitatively, into oxazolines by reaction with 2‐methyl‐2‐aminopropanol. These oxazolines are of high purity. They can be reacted further with paraformaldehyde to yield a mixture of mono‐ andbis‐methylol derivatives in the α‐position. Heating causes dehydration to form α‐methylene oxazolines, which on hydrolysis provide good overall yields of α‐alkylacrylic acids. Substituted anilides of the acrylic acids possess substantial antibacterial properties against Gram‐positive microorganisms. The reaction of two moles of fatty acid with one of diethylenetriamine yields a primary amine with the structure of RCON(CH2CH2NH2)CH2CH2NHCOR, instead of a secondary amine as reported in the literature. Imidazoline is also formed. Removal of water by vacuum results in almost quantitative ring closure. The unquaternized imidazolines are highly unstable to hydrolysis and will revert to the above diamido amine at room temperature. Open‐chain compounds are more water repellent than the imidazolines. Repellency of the saturated fatty acid derivatives increases with increasing molecular weight. Unsaturation decreases repellency, particularly for thecis derivative, whereas thetrans derivative (from elaidic acid) possesses better repellent properties. Branching of the alkyl chains is also detrimental to water repellency. Application of repellents to soil dramatically reduces water absorption and seed germination.
Reaction of oxygen and unsaturated fatty acids
Authors: Gunstone F. D.
Published: July 2007

Oxygen reacts readily with unsaturated fatty acids so that every time these compounds are handled there is a danger they will become contaminated with oxidation products. The products formed first are allylic hydroperoxides which are labile molecules that change rapidly to other compounds, some of which are highly flavorous. Sometimes these changes are desirable and may be promoted: frequently they are not and have to be inhibited. Instrumental procedures recently introduced—especially separation by high performance liquid chromatography and identification by1H and13C nuclear magnetic resonance spectroscopy—have led to a renewed interest in this subject. For the nonenzymic processes of autoxidation and photooxygenation we now have a better understanding of the routes leading to the first‐formed allylic hydroperoxides and an improved appreciation of the structure of further oxidation products including dihydroperoxides and hydroperoxides which also contain one or more cyclic peroxide units. Direct chemical routes to several of these compounds have also been developed. Oxidation of linoleic acid by plant‐derived lipoxygenases gives diene hydroperoxides similar to those produced by autoxidation, except that the former are optically active and the latter racemic. Enzymic oxidation of arachidonic acid and certain related C20 acids in animal systems produces a wide variety of prostaglandins, physiological properties. These compounds have been described as “tomorrow's drugs”.
Neo acids chemistry and applications
Authors: Fefer M. , Rutkowski A. J.
Published: July 2007

Four commercial neo acids (synthetic trialkylacetic acids) C5, C7, C10, and C13 are synthesized employing an olefin, carbon monoxide, and acidic catalyst and possess the hindered neo configuration around the alpha carbon. Esterification using simple alcohols and polyols, and preparation of peroxyesters and metal salts using neo acids as well as toxicity,LD50 values of the acids, are discussed. Hydrolytic stability of the esters, and possible end use applications are described.
Synthetic fatty acids in Eastern Europe
Authors: Zilch Karl T.
Published: July 2007

For over a century various investigators have studied the air oxidation of paraffinic hydrocarbons to produce synthetic fatty acids. Today in the socialistic countries there are six to eight plants manufacturing these acids to replace in soaps tallow fatty acids which are needed as a source of food.

The principal technological advances in air oxidation, prior to World War II, were made by Germany while more recently Russia and its satellite countries have made the major contributions. Although the oxidation involves a multitude of chemical reactions taking place consecutively and simultaneously, it has been fairly well established that the alkylhydroperoxide precursors are converted to alcohols and then further oxidized to carboxylic acids.

The cost of manufacturing synthetic fatty acids in Eastern Europe ranges between 8–12¢ per pound depending upon the raw material, processing costs and by‐products.
Hepatic metabolism of 1‐14C octanoic and 1‐14C palmitic acids
Authors: Scheig Robert , Klatskin Gerald
Published: July 2007

The hepatic metabolism of 1−14C octanoic acid was compared with that of 1−14C palmitic acid in male rats which were fed. After intraportal injection only 1/6 to 1/18 as much octanoic acid as palmitic acid was incorporated into hepatic lipids. In contrast, octanoic acid yielded two to four times as much water‐soluble product as did palmitic acid. Similar, but even more impressive, differences between the incorporation of these fatty acids into hepatic lipids were observed in liver slices incubated with14C octanoate and14C palmitate. The oxidation of octanoate to CO2 was more than 10 times as great as that of palmitate. With both substrates, triglycerides comprised almost half the labeled lipid recovered. However octanoate yielded a higher proportion of labeled, unesterified fatty acids and a lower proportion of labeled phospholipid and monoglycerides than did palmitate. Most of the14C recovered in hepatic lipids after incubation with 1−14C octanoate was found in the carboxyl groups of long‐chain fatty acids, suggesting that the latter had been synthesized from 2‐carbon fragments formed from the oxidation of octanoate. In contrast, only a small fraction of the palmitate was elongated.

The similarities and differences between the metabolism of octanoic and palmitic acid in liver and intestine, and the possible nutritional significance of octanoic acid are discussed.
Surface activity of sodium salts of alpha‐sulfo fatty esters: The air‐water interface
Authors: Boucher E. A. , Grinchuk T. M. , Zettlemoyer A. C.
Published: July 2007

Adsorption at the air‐water interface of sodium hexyl α‐sulfopelargonate, sodium heptyl α‐sulfopelargonate, sodium methyl α‐sulfomyristate, and sodium methyl α‐sulfopalmitate has been investigated.

The amount of surfactant adsorbed at the interface has been obtained by the application of a simple form of the Gibbs equation to surface tensions of aqueous solutions of varying surfactant ion concentration but at constant counterion (Na+) concentration. Surface tensions were determined by using the drop‐volume method. Counterion concentrations of 0.01 and 0.04N were used. Cross‐sectional areas for the surfactant anions are in the range 44 to 59Å2 (independent of concentration) and are consistent with close packing in which the carbon chains are perpendicular to the interface.

For each surfactant, increase in counterion concentration from 0.01 to 0.04N results in a surface‐tension decrease of about 7.5 dyne/cm. This effect can be predicted by using bulk activity coefficients from the Debye‐Hückel theory.

Dependence of surface tension on carbon chain length indicates that the carbon chains of the four compounds behave similarly at the air‐water interface.
Determination of fat composition
Authors: Dutton H. J.
Published: July 2007

A revolution has taken place in the analysis of fats. Physical methods, both rapid and accurate, have replaced laborious chemical procedures. The timehonored saponification equivalents and iodine values now are calculated from Chromatographic and nuclear magnetic resonance spectroscopic data. Differential migration processes such as countercurrent distribution, liquid‐liquid chromatography, and gas chromatography have supplanted the classical distillation and crystallization procedures for analysis and preparation.

What have been referred to as “gadgets” are now the stock‐in‐trade of the analytical lipid chemist. Mass, infrared, ultraviolet, and nuclear magnetic resonance spectrometers are the accepted tools for organic characterization. Recording detectors and computer processing of data reduce the labor of analysis and improve its quantitation. Today's methodology stands at the verge of specifying fatty acid composition of even so complex lipids as hydrogenated fats in terms of the amounts, the positions, and geometric configurations of its individual component fatty acids.
An exploratory study of the addition reactions of ethyleneglycol, 2‐chloroethanol and 1,3‐dichloro‐2‐propanol to 1‐dodecene
Authors: Bakker P. M. , Borstlap C.
Published: July 2007

sec‐Dodecyl ethers of ethyleneglycol, 2‐chloroethanol, and 1,3‐dichloro‐2‐propanol have been prepared by reacting 1‐dodecene with the corresponding substituted alcohol in the presence of BF3 as a catalyst.

The addition of ethyleneglycol to 1‐dodecene proceeds best in the presence of a reaction solvent (e.g., nitromethane), which suppresses side reactions. The resulting ethers consist almost exclusively of the mono‐sec‐dodecyl derivatives. The maximum yield was about 50 mol% on dodecene intake and 75%m on converted ethyleneglycol.

The addition of 2‐chloroethanol and 1,3‐dichloro‐2‐propanol to dodecene can easily be conducted without a reaction solvent; yields are 77 and 67 mol% respectively on 1‐dodecene intake. A reaction scheme for the addition of ethyleneglycol to 1‐dodecene is proposed.
Ether alcohol sulfates from oleyl alcohol
Authors: Weil J. K. , Stirton A. J. , Leardi Eileen B.
Published: July 2007

Oleyl alcohol was caused to react with ethylene oxide, propylene oxide, and 1,2‐butylene oxide in the presence of an alkaline catalyst. The first and second derivatives from each reaction were isolated by fractional distillation. Sulfation with dioxane‐SO3 gave high‐purity oleyl ether sulfates, easily soluble, with good detergent and lime soap‐dispersing properties.

The use of chlorosulfonic acid or sulfuric acid as the sulfating agent for oleyl ether alcohols resulted in about 60% retention of the double bond, compared with oleyl alcohol, which under the same conditions retained only about 25% unsaturation. Oleyl ether alcohols sulfated with chlorosulfuric acid or sulfuric acid are easily sobuble and have good lime soap‐dispersing properties. They are able to solubilize less soluble soaps and saturated ether alcohol sulfates.
Detergent alcohols. I. The effect of alcohol structure and molecular weight on surfactant properties
Authors: Finger B. M. , Gillies G. A. , Hartwig G. M. , Ryder E. E. , Sawyer W. M.
Published: July 2007

A large number of aliphatic alcohols have been studied to relate performance of the derived surfactants to structure and molecular weight. The alcohols were examined as sulfates, ethoxylates, and ethoxysulfates in heavy‐and light‐duty compositions. Clear points and surface tensions of aqueous solutions were determined. Cotton detergency was evaluated in a bench‐scale test by using artificially soiled test cloths. Foam performance was measured in a soil titration test. In general, excellent performance is observed with derivatives which have 70% or greater n‐primary alcohol content. The odd‐numbered alcohol derivatives contribute significantly to optimum performance.
Lactones in autoxidized vegetable oils
Authors: Fioriti J. A. , Krampl V. , Sims R. J.
Published: July 2007

It was demonstrated that bothgamma anddelta saturated lactones are present in highly peroxidized vegetable oils. In the oils which were investigated thegamma isomers are predominant. Additional lactones also form when the hydroperoxides are reduced. Although no lactones were detectable in fresh, refined soybean oil, considerable amounts of bothgamma anddelta lactones were found to be present in highly peroxidized samples of cottonseed and soybean oils.

The lactones in the peroxidized oils were concentrated by column chromatography on silica gel and by vacuum distillation. Gas‐liquid chromatography was used for separation and identification. This has been supplemented by thin‐layer chromatography, infrared spectrophotometry, and nuclear‐magnetic‐resonance spectrometry.
The use of fatty chemicals as flotation reagents
Authors: Agar G. E.
Published: July 2007

Fatty chemicals are widely used as flotation collectors in the mineral‐processing industry and, even though this application is quite old, improvements are being made with regard to both application and utilization. Most of the fatty chemicals that are used in flotation are used in the processing of industrial minerals such as phosphate, potash, iron ore, cement rock, and feldspar.

The understanding of the functioning of collectors is not complete, and only recently have concerted efforts been made in researching this area with tools such as electrokinetics, radiotracers, infrared spectroscopy, and adsorption measurements. It appears that a thorough knowledge of the behavior of inorganic solids in aqueous solutions will be required before a full appreciation of collector behavior can be made.
Contributions of walter A. Pons, to development of methodology for mycotoxins
Authors: Lee L. S. , Goldblatt L. A.
Published: July 2007

Walter Pons began work on mycotoxins in 1963, well prepared by 20 years’ experience in the Analytical Section of the SURDD, USDA. His first paper on aflatoxin methodology, presented at the fall meeting of the AOCS in 1964, was rated as one of the 3 best. In this paper, he introduced acetone as the extraction solvent for aflatoxins, moved away from the lengthy, exhaustive Soxhlet extraction to the far more rapid equilibrium shaker extraction and introduced lead acetate to precipitate major interfering impurities. He early saw the need for the calibration of reference aflatoxin standards and for their availability. He prepared and supplied more than 3,000 aflatoxin standards, used worldwide, as a public service of USDA before such standards were available commercially. Walter Pons pioneered in every aspect of development of analytical methodology for aflatoxins. He was instrumental in development of objective densitometric methods for determination of aflatoxins in diverse commodities, including milk, eggs and mixed feeds; in multimycotoxin methodology; in application of minicolumns for the rapid estimation of aflatoxins in various agricultural commodities; and, most recently, in application of high pressure liquid chromatography to the precise objective determination of aflatoxins. Many of Walter's contributions resulted from the generous gift of his time. He organized symposia, presented seminars, participated in workshops and responded freely and enthusiastically to numerous requests from analysts for assistance.
Rapid analysis for aflatoxins in cottonseed products with silica gel cartridge clean‐ up
Authors: Mckinney J. D.
Published: July 2007

A proposed rapid and versatile method of analysis for aflatoxins in cottonseed products using Waters Associates’ Sep‐ Pak silica cartridge clean‐ up is presented. Samples are extracted with acetonitrile/ water azeotrope and a filtered aliquot is evaporated to dryness. A toluene/acetonitrile (96:4) solution of the dry extract is applied to a Sep‐ Pak column. Gossypol derivatives and other artifacts are eluted with chloroform/ethyl ether (1:4). The Sep‐ Pak is then mated with either a Romer minicolumn for rapid minicolumn application or a small column of acid alumina deactivated with 4% water to produce a clean extract for quantitation by thin layer chromatography or high pressure liquid chromatography.
Replacement of benzene as a solvent for aflatoxin standards
Authors: Velasco J.
Published: July 2007

Cyclohexane, heptane and toluene were evaluated for possible replacement of benzene in the preparation of aflatoxin standard solutions. The results of a 6‐month study showed that these solvents can be substituted for benzene, provided they are not unduly exposed to light. The superiority of benzene as a solvent for aflatoxin standards was clearly demonstrated in a test in which these solvent systems containing 5μg B1 /mL, were exposed to daily lighting in the laboratory for 3 months. Complete photodegradation of aflatoxin B1 occurred in the cyclohexane, heptane and toluene systems whereas only a 15% B1 decrease occurred in the benzene system.
Enzyme‐linked immunosorbent assay for T‐2 toxin
Authors: Pestka J. J. , Lee S. C. , Lau H. P. , Chu F. S.
Published: July 2007

An enzyme‐linked immunosorbent assay (ELISA) was developed for the rapid quantitation of T‐2 toxin, a tricothecene mycotoxin produced by members of the genusFusarium. T‐2 toxin was first converted to the T‐2 hemisuccinate (T‐2 HS) and then conjugated by the water‐soluble carbodiimide method to either bovine serum albumin for use as an immunogen or to horseradish peroxidase for use as an enzyme marker. T‐2 antiserum was air‐dried onto polystyrene microtissue culture plates and the ELISA conducted by simultaneously incubating standards of T‐2 toxin and the T‐2 HS‐peroxidase conjugate. Competition curves were prepared by determining total bound enzyme. The ELISA took about 2 hr to complete and allowed minimal detection of T‐2 at levels of 2.5 pg/assay. Average recoveries from samples of wheat flour spiked with T‐2 toxin in the 1.0‐30 ppb range were 95 ± 25% and those for corn meal spiked in the 5.0‐30 ppb range were 98 ± 19%. The results suggested the ELISA is a simple and convenient alternative for the screening of T‐2 toxin in food and feeds.
Confirmation of identity of aflatoxins
Authors: Nesheim S. , Brumley W. C.
Published: July 2007

Aflatoxins are detected and determined by analytical procedures based on physical and chemical properties, e.g., ultraviolet absorbance, fluorescence, solubility and Chromatographie retention times during thin layer (TLC) or liquid chromatography. For acceptance of analytical results based on these properties, especially for regulatory purposes, proof of identity of the compound being measured is essential. Numerous tests have been devised for confirmation of identity. Included are tests based on toxicological effects observed in the duckling, zebrafish, chick embryo,Bacillus megaterium and many other species; chemical tests based on formation of derivatives such as the acetates and water adducts; and tests based on color changes of TLC spots after contact with spray reagents, e.g., sulfuric acid. All of the foregoing have inherent uncertainties in interpretation of identity. On the other hand, mass spectrometry (MS) is one of the most specific methods of identification available; however, it has been difficult to apply at the low concentrations at which aflatoxins are routinely detected. In this paper, the confirmation techniques for aflatoxins are placed in historical perspective and are reviewed and evaluated A recently developed procedure for the application of negative ionization MS for the confirmation of identity of aflatoxins in foods or feeds at concentrations as low as 10 ng/g is described. This procedure consists of isolation of the aflatoxin by Association of Official Analytical Chemists’ methods, purification by preparatory 2‐dimensional TLC, in situ elution of the aflatoxin TLC spot and analysis of the sample by negative ion chemical ionization MS using a direct insertion probe.