Oxidized fat/oil

Watts, B. M., and Major, R. 1946. Comparison of a simplified, quantitative Kreis test with peroxide values of oxidizing fats. Oil Soap 23, 222. 

In addition to essential fatty acids and vitamin E, dietary protein levels have been shown to play an important role in the toxicity of oxidized fats/oils. Witting et al. (1957), for example, observed an almost total lack of growth in rats fed a diet containing laboratory prepared heated com oil and 10% casein. With 20% casein in the diet, severe growth depression was still seen, but at 30% or more protein in the diet, only a mild effect was observed. While the mechanism of the protective effects of high dietary protein is not yet clear, it may be linked to an enhanced detoxification capability. Long-term feeding of thermally oxidized fats, for example, has been shown to be associated with an induction of hepatic microsomal enzymes (Andia and Street, 1975). 

Fats, Oils, or Fatty Acids. The primary products produced direcdy from fats, oils, or fatty acids without a nitrile iatermediate are the quatemized amidoamines, imidazolines, and ethoxylated derivatives (Fig. 3). Reaction of fatty acids or tallow with various polyamines produces the iatermediate dialkylarnidoarnine. By controlling reaction conditions, dehydration can be continued until the imidazoline is produced. Quaternaries are produced from both amidoamines and imidazolines by reaction with methyl chloride or dimethyl sulfate. The amidoamines can also react with ethylene oxide (qv) to produce ethoxylated amidoamines which are then quaternized. 

Ethylene-propylene (EPDM) Oxidizing agents Dilute acids Amines Water (Mostly any HR fluid) Oils Hot cone, acids Very strong oxidants Fats fatty acids Chlorinated hydrocarbons... 

At present, chlorine dioxide is primarily used as a bleaching chemical in the pulp and paper industry. It is also used in large amounts by the textile industry, as well as for the aching of flour, fats, oils, and waxes. In treating drinking water, chlorine dioxide is used in this country for taste and odor control, decolorization, disinfection, provision of residual disinfectant in water distribution systems, and oxidation of iron, manganese, and organics. The principal use of chlorine dioxide in the United States is for the removal of taste and odor caused by phenolic compounds in raw water supplies. 

Several methods have been introduced which express the degree of oxidation deterioration in terms of hydroperoxides per unit weight of fat. The modified Stamm method (Hamm et at 1965), the most sensitive of the peroxide determinations, is based on the reaction of oxidized fat and 1,5-diphenyl-carbohydrazide to yield a red color. The Lea method (American Oil Chemists Society 1971) depends on the liberation of iodine from potassium iodide, wherein the amount of iodine liberated by the hydroperoxides is used as the measure of the extent of oxidative deterioration. The colorimetric ferric thiocyanate procedure adapted to dairy products by Loftus Hills and Thiel (1946), with modifications by various workers (Pont 1955 Stine et at 1954), involves conversion of the ferrous ion to the ferric state in the presence of ammonium thiocyanate, presumably by the hydroperoxides present, to yield the red pigment ferric thiocyanate. Newstead and Headifen (1981), who reexamined this method, recommend that the extraction of the fat from whole milk powder be carried out in complete darkness to avoid elevated peroxide values. Hamm and Hammond (1967) have shown that the results of these three methods can be interrelated by the use of the proper correction factors. However, those methods based on the direct or indirect determination of hydroperoxides which do not consider previous dismutations of these primary reaction products are not necessarily indicative of the extent of the reaction, nor do they correlate well with the degree of off-flavors in the product (Kliman et at. 1962). 

In addition to the previously mentioned chemical tests, methods based on the carbonyl content of oxidized fats have also been suggested (Henick et al 1954 Lillard and Day 1961) as a measure of oxidative deterioration. The procedures determine the secondary products of autoxidation and have been reported to correlate significantly with the degree of off-flavor in butter oil (Lillard and Day 1961). The methods, however, are cumbersome and are not suited for routine analysis. 

Polyunsaturated aliphatic alkohols, aldehydes, ketones, and esters occur as fragrance components in fats, oils, fruits and plants 158). As an example the synthesis of ethyl (2 ,4Z)-2,4-decadienoate (232, pear ester ), which is responsible for the aroma of bartlett pears 161) is given. 2,4-Diunsaturated ester 232 may be obtained by a number of highly stereoselective syntheses, a lot of them making use of the Wittig reaction. Ohloff and Pawlak condensed 4,5-epoxy-( )-2-pentenal 228 with the ylide generated from 229 (butyllithium/ether) to the alkadiene epoxide 230 which was oxidized with periodic acid to the 2,4-decadienal 231. 231 is subsequently converted with MnOj/NaCN in ethanol to the pear ester 232162) [75 % (Z)-amount of the C-4 double bond] (Scheme 44). 

If more than one species of fatty acid is present, its relative location on the glycerol may be important to its functionality, enzyme susceptibility, and oxidation stability of the fat/oil. Several conventions have been developed to specify arrangements of fatty acids on the glycerol molecule (if known). To avoid confusion from inversion of the 1 and 3 carbon positions, hierarchies have been established to designate the number 1 carbon under... 

Peroxide value. The oxidation of oils and fats leads to the formation of hydroperoxides. The hydroperoxides readily decompose to produce aldehydes, ketones, and other volatile products, which are characteristic of oxidation rancidity. The method for determination of peroxide concentration is based on the reduction of the hydroperoxide group with HI (or KI) to liberate free iodine, which may be titrated. The... 

Ferric Ion Complexes Other chemical methods based on the oxidation of ferrous ion (Fe ) to ferric ion (Fe ) in an acidic medium and the formation of iron complexes have also been widely accepted. These methods spectrophotometri-cally measure the abihty of lipid hydroperoxides to oxidize ferrous ions to ferric ions, which are complexed by either thiocyanate or xylenol orange (23, 28, 29). Ferric thiocyanate is a red-violet complex that shows strong absorption at 500-510 nm (8). The method of determining PV by coloremetric detection of ferric thiocyanate is simple, reproducible, and more sensitive than the standard iodometric assay, and has been used to measure hpid oxidation in milk products, fats, oils, and liposomes (8, 23). 

Carbonyl compounds in oxidized fats and oils are the secondary oxidation products that originate from decomposition of hydroperoxides. They usually have low threshold values and hence are responsible for off-flavor development in oxidized oils. Therefore, content of carbonyl compounds corresponds with sensory data. 

Oxidation. Oxidation of oils and fats is due to prolonged exposure to air. By virtue of the low polyunsaturated fatty acid content, palm oil is relatively more stable to oxidative deterioration than the polyunsaturated vegetable oils. However, in the presence of trace metals such as iron and copper, excessive oxidation at the olefin bonds of the oleic and linoleic acids can occur, resulting in rancidity. Highly oxidized crude palm oil is known to have poor bleachability and thus requires more bleaching earth and more severe refining conditions, and the final product will likely be of poor stability (44, 45, 68). 

AAFCO Definitions—Chemical Preservatives (Antioxidants). Antioxidants are used to retard oxidation of unsaturated fatty acids in fats, oils, and fish and meat meals, and to slow the destruction of fat-soluble vitamins, especially vitamin E. Their presence must be identified on the label when used. Use of the following compounds is permitted alone or in combination at levels not to exceed 0.02% of the fat present. 

Oxidative stability index (hrs) Time (in hours induction period) for fats/oils to begin to undergo rapid acceleration in oxidation Cd 12b-92... 

Peroxide value Measures peroxides (oxidation of Kl => I2) in fats/oils Cd 8-53 ... 

Review of Ascorbic Acid Mechanisms of Action. Ascorbic acid and AP have antioxidant activity in fats, oils, vitamin A, and carotenoids. In these systems AP is a better antioxidant than are the phenolic antioxidants BHT and BHA, both from these data and others (29,35). Ascorbic acid protects against oxidation of flavor compounds in wine, beer, fruits, artichokes, and cauliflower (29) presumably by oxygen scavenging. The well-known formation of nitric oxide from nitrites by ascorbic acid is used not only for inhibition of nitrosamine fortnation, but also to promote... 

Pure crystalline vitamin A occurs as pale yellow plates or crystals. It melts at 63 to 64°C and is insoluble in water but soluble in alcohol, the usual oiganic. solvents, and the fixed oil.s. It is unstable in the presence of light and oxygen and in oxidized or readily oxidized fats and oils. It can be protected by the exclusion of air and light and by the presence of antioxidants. 

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