Lipids from autoxidation

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. 

The primary products from autoxidation are hydroperoxides, which are often simply referred to as peroxides. Peroxides are odorless and colorless, but are labile species that can undergo both enzymatic and nonenzymatic degradation to produce a complex array of secondary products such as aliphatic aldehydes, alcohols, ketones, and hydrocarbons. Many of these secondary oxidation products are odiferous and impart detrimental sensory attributes to the food product in question. Being able to monitor and semi-quantitate the development of peroxides by objective means (e.g., PV determination) over time is important for food scientists who want to characterize the quality of an oil or a lipid-containing food product, even though the peroxides themselves are not directly related to the actual sensory quality of the product tested. 

E lipid-soluble antioxidant, prevents lipid oxidation of membranes, needed for healthy blood cells and tissues, blocks nitrosamine formation, protects PUFAs from autoxidation, important for normal immune fimction neuromuscular disorders, red blood ceU mpture (both uncommon) reduces risk of chronic disease (cardio-vascular, precancerous lesions, cancer), immunoenhancement, protec-tion from exercise-induced muscle injury, improves metaboHc control, re-duces risk of compHcations in diabetes... 

In aqueous systems containing metals, ascorbic acid may also act as a prooxidant by reducing the metals that become active catalysts of oxidation in their lower valences. However, in the absence of added metals, ascorbic acid is an effective antioxidant at high concentrations. The action of ascorbic acid in lipid autoxidation is dependent on concentration, the presence of metal ions, and other antioxidants. It has been shown that ascorbates can protect plasma and LDL lipids from peroxidative damage, and may inhibit the binding of copper ions to LDL. Mixtures... 

Oxidation of unsaturated acyl chains of lipids is a major route to volatile compounds during cooking of fat-containing food of either animal or vegetable origin. The unsaturated fatty acids, readily susceptible to the attack by oxygen, form hydroperoxides which in themselves are odorless and tasteless. The compounds that influence the flavor of the product result from a further breakdown of these hydroperoxides, and, normally, include saturated and unsaturated aldehydes, alcohols, and ketones. The carbonyl compounds resulting from autoxidation impart specific flavors that are normally detrimental to food products (Table 9.3). It should be pointed out, however, that they may also contribute to the desirable characteristic flavor of foods [48]. 

Volatile decomposition products from autoxidized linoleic acid and methyl linoleate were characterized for their intense aroma and flavor impact by capillary gas chromatography-olfactometry. This technique involves sniffing the gas chromatograph effluent after stepwise dilution of the volatile extract. The most intense volatiles included hexanal, c/ -2-octenal, /ra. s-2-nonenal, l-octene-3-one, 3-octene-2-one and trans-l-ociQmX (Table 4.2). This analytical approach does not, however, consider the effects of complex interactions of volatiles occurring in mixtures produced in oxidized food lipids. 

Frankel, E.N., Neff, W.E. and Selke, E. Analysis of autoxidized fats by gas chromatography-mass spectrometry VII. Volatile thermal decomposition products of pure hydroperoxides from autoxidized and photosensitized oxidized methyl oleate, linoleate, and linolenate. Lipids 16, 279-285 (1981). 

Awl, R. A., Frankel, E. N. and Weisleder, D. Cyclic fatty esters Hydroperoxides from autoxidation of methyl 9-(6-propyl-3-cyclohexenyl)-(Z)-8-Nonenoate. Lipids 22, 721-730 (1987). 

Textbooks often refer to the oxidation of food lipids as autoxidation. The prefix auto is defined as self-acting thus the term, autoxidation has been used to describe the ability of lipids to oxidize by the self perpetuating generation of ftee radicals from unsaturated fatty acids in the presence of oxygen. Unfortunately, the term autoxidation can be misinterpreted as the ability of lipids to oxidize on their own. This is rarely ftie case in foods since there are normally prooxidants present or environmental conditions that cause and accelerate lipid oxidation. 

Lipid components associated with meat fat, especially unsaturated aldehydes, play a significant role in species-characterization flavors. For example, ( ,Z)-2,4-decadienal exhibits the character impact of chicken fat and freshly boiled chicken (66). ( , )-2,6-Nonadienal has been suggested as the component responsible for the tallowy flavor in beef and mutton fat (63). 12-Methyltridecanal was identified as a species-specific odorant of stewed beef and provides a tallowy, beeflike flavor character (67). Aldehydes provide desirable flavor character to cooked meat, but they can contribute rancid and warmed-over flavors at high concentrations, resulting from autoxidation of lipids (68). 

As a reasonable biogenetie pathway for the enzymatic conversion of the polyunsaturated fatty acid 3 into the bicyclic peroxide 4, the free radical mechanism in Equation 3 was postulated 9). That such a free radical process is a viable mechanism has been indicated by model studies in which prostaglandin-like products were obtained from the autoxidation of methyl linolenate 10> and from the treatment of unsaturated lipid hydroperoxides with free radical initiators U). 

The effects of flavonoids on in vitro and in vivo lipid peroxidation have been thoroughly studied [123]. Torel et al. [124] found that the inhibitory effects of flavonoids on autoxidation of linoleic acid increased in the order fustin < catechin < quercetin < rutin = luteolin < kaempferol < morin. Robak and Gryglewski [109] determined /50 values for the inhibition of ascorbate-stimulated lipid peroxidation of boiled rat liver microsomes. All the flavonoids studied were very effective inhibitors of lipid peroxidation in model system, with I50 values changing from 1.4 pmol l-1 for myricetin to 71.9 pmol I 1 for rutin. However, as seen below, these /50 values differed significantly from those determined in other in vitro systems. Terao et al. [125] described the protective effect of epicatechin, epicatechin gallate, and quercetin on lipid peroxidation of phospholipid bilayers. 

Ideally samples from living organisms should be extracted without any delay to prevent autoxidative or enzymic deterioration of their lipid constituents. If this is not feasable the sample should be frozen immediately and stored at — 20 °C in a glass container under nitrogen. Often lipids will be extracted into an organic solvent and during this and subsequent steps in the analytical procedure minimal exposure of the lipids to air, light and heat is very important to prevent oxidation or destruction of the lipids. 

The mechanisms behind lipid oxidation of foods has been the subject of many research projects. One reaction in particular, autoxida-tion, is consistently believed to be the major source of lipid oxidation in foods (Fennema, 1993). Autoxidation involves self-catalytic reactions with molecular oxygen in which free radicals are formed from unsaturated fatty acids (initiation), followed by reaction with oxygen to form peroxy radicals (propagation), and terminated by reactions with other unsaturated molecules to form hydroperoxides (termination O Connor and O Brien, 1994). Additionally, enzymes inherent in the food system can contribute to lipid oxidization. 

Results demonstrate that Mb er se is not the catalyst of lipid oxidation in cooked meat. However, cooking destroys part of the Mb, releasing Fe2+ which then catalyzes the development of WOF. Although the role of grinding in development of WOF was not studied, it seems likely that it also releases Fe2+. It has recently been shown that solubilization of iron from grinding equipment can increase the free iron content of fish meal, which could also be a factor in autoxidation of fresh ground meat (TS). 

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