Fats, autoxidation

Buttery, R.G. and Teranishi, R. (1963) Measurement of fat autoxidation and browning aldehydes in food vapors by direct vapor injection gas-liquid chromatography. Agricultural and Food Chemistry, 11, 504-7. 

Chemical Antioxidant Systems. The antioxidant activity of tea extracts and tea polyphenols have been determined using in vitro model systems which are based on hydroxyl-, peroxyl-, superoxide-, hydrogen peroxide-, and oxygen-induced oxidation reactions (109—113). The effectiveness of purified tea polyphenols and cmde tea extracts as antioxidants against the autoxidation of fats has been studied using the standard Rancimat system, an assay based on air oxidation of fats or oils. A direct correlation between the antioxidant index of a tea extract and the concentration of epigallocatechin gallate in the extract was found (107). 

Interestingly, early examples of carotenoid autoxidation in the literature described the influence of lipids and other antioxidants on the autoxidation of carotenoids." " In a stndy by Budowski et al.," the influence of fat was fonnd to be prooxidant. The oxidation of carotenoids was probably not only cansed by molecnlar oxygen bnt also by lipid oxidation products. This now well-known phenomenon called co-oxidation has been stndied in lipid solntions, in aqueons solntions catalyzed by enzymes," and even in food systems in relation to carotenoid oxida-tion." The inflnence of a-tocopherol on the antoxidation of carotenoids was also stndied by Takahashi et al. ° who showed that carotene oxidation was snppressed as... 

Budowski, P. and A. Bondi (1960). Autoxidation of carotene and vitamin A. Influence of fat and antioxidants. Arch. Biochem. Biophys. 89 66-73. 

Autoxidation is responsible for the development of the rancidity that occurs when fats and oils spoil and for the spontaneous combustion of oily rags left open to the air. 

Oxidative rancidity is not necessarily a problem unless a polyunsaturated fat such as sunflower oil has been used. Where such a fat is used oxidative rancidity can occur and, as autoxidation occurs where the reaction becomes self-catalysing as oxygen free radicals react, some very unpleasant tastes can appear very quickly. In general, the effect of oxidation on biscuits at the end of their shelf life is that a cardboard taste starts to appear. 

Autoxidation. Self-catalyzed oxidation in the presence of air. Autoxidation can be initiated by heat, light, or a catalyst. The commercial production of phenol and acetone from cumene is autoxidation. Other examples include the degradation of polymers exposed to sunlight for long periods of time gum formation in lubricating oils and gasoline and the spoilage of fats. 

The slow spontaneous oxidation of compounds in the presence of oxygen is termed autoxidation (autooxidation). This radical process is responsible for a variety of transformations, such as the drying of paints and varnishes, the development of rancidity in foodstuff fats and oils, the perishing of rabber, air oxidation of aldehydes to acids, and the formation of peroxides in ethers. 

Oxygen-mediated autoxidation can occur with unsaturated acid components of fats and oils, which are esters of fatty acids with glycerol (see Box 7.16). This leads initially to hydroperoxides that decompose further to produce... 

A widespread method for determining the induction period for autoxidation of oils and fats consists of passing a continuous stream of air through the heated sample and collecting the volatile acids evolved in a water trap, where they are determined on a real time basis. The time plot usually presents a flat appearance for a certain period and then takes off in an accelerated manner. This test is the basis of several national and international standards (e.g. AOCS Cd 12b-92—oil stability index" ISO 6886—accelerated oxidation test for oxidative stability of fats and oils ) and the design of the Rancimat equipment, where the end determination is based on conductivity measurements . In addition to oxidation stability as determined by the Rancimat method and POV, which negatively affects virgin olive oil stability, other nonstandard properties were proposed for better assessment of the quality of this oil, namely LC determination of Vitamin E (21), colorimetric determination of total polar phenols and UVD of total chlorophyll. ... 

Deep fat frying, oil autoxidation, 623, 662 Deflagration, peroxides, 617 Degradation... 

Tphe major objective of this work was to understand better the effect - of heavy metals in autoxidation reactions in view of the importance of trace metals in oils, fats, rubber, plastics, and other materials. Because of our interest in the stability of polyolefins such as polyethylene and polypropylene the major model substance used was 2,6,10,14-tetramethyl-pentadecane. With its four tertiary C—H bonds it is a suitable model for either polypropylene or branched polyethylene. Hexadec-l-ene was also used since its mono-olefinic character could be typical of some residual unsaturation in polyethylene. N-alkylamides served as model substances for polyamides, and a few experiments were also carried out with methyl linoleate. While studying the causes of initiation of the autoxidation of these substances we observed that certain compounds were catalysts at low concentrations but became inhibitors at higher concentrations. The phenomenon was called catalyst-inhibitor conversion. ... 

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. 

Day, E. A. and Lillard, D. A. 1960. Autoxidation of milk lipids. I. Identification of volatile monocarbonyl compounds from autoxidized milk fat. J. Dairy Sci. 43, 585-597. 

Prolonged storage of ice cream and exposure to severe temperature fluctuation commonly causes shrinkage, which is a defect due to partial thawing and loss of moisture and air. An additional defect common to ice cream after prolonged storage is oxidized flavor, which is caused by autoxidation of milk fat. This defect is especially important in ice cream products that contain frozen or dried milk ingredients. 

The intensity of undesirable sensory notes has been positively correlated with the content of carbonyl compounds formed through lipid autoxidation reactions. In general, the carbonyl compounds present have the greatest impact on flavor owing to their low flavor thresholds in comparison with hydrocarbons, substituted furans, and alcohols. Aldehydes are major contributors to the loss of desirable flavor in meats because of their rate of formation during lipid oxidation and low flavor threshold. Thus, an alternative approach for monitoring the extent of lipid oxidation in fats and oils is to measure... 

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