Polyunsaturated fatty acids peroxidation

PTFE polytetrafluoroethylene PUFA polyunsaturated fatty acid PV peroxide value PVDF polyvinylidene difluoride PVP polyvinylpyrrolidone PVPP polyvinylpolypyrolidone RAS retronasal aroma stimulator RDA recommended dietary allowance RF radio frequency RFI relative fluorescence intensity RI retention index RNU relative nitrogen utilization ROESY rotational nuclear Overhauser enhancement spectroscopy RP-HPLC reversed-phase HPLC RPER relative protein efficiency ratio RS resistant starch RT retention time RVP relative vapor pressure S sieman (unit of conductance)... 

The peroxidative reactions were mediated and sustained by Cu(II) ions in the light. Table IV shows that fatty acids with at least 2 double bonds are necessary for hydrocarbon formation. As Anacystis lacks those fatty acids, no peroxidative volatile hydrocarbons were produced. Spirulina exclusively contains CO-6 fatty acids as endogenous polyunsaturated fatty acids and evolved Cs hydrocarbons only. The third species, Anabaena, whose thylakoids contain co-3 and Co-6 polyunsaturated fatty acids formed C2 and C5 hydrocarbons simultaneously. We conclude that co-3 polyunsaturated fatty acids are the source of ethane and ethylene and that the CO-6 polyunsaturated fatty acids are the source of pentane and pentene in herbicide-induced peroxidation reactions. Furthermore, we obtained evidence that the propane measured with Bumilleriopsis after an 18-h treatment with either 10 >iM oxyfluorfen or 50 jxM Cu(II) originates from a CO-4 polyunsaturated fatty acid. We have recently isolated and identified this acid as 16 3CO4 (Sandmann, Lambert, B5ger in preparation). 

The high stability of the macadamia nut oil may be associated with the storage conditions and the xmsaturated fatty acid profile, which is an important factor since the unsaturations make the oil less susceptible to oxidation. Therefore, macadamia nut oils have high oxidative stability due to the high content of monounsaturated and polyunsaturated fatty acids. Low peroxide and acidity values are also responsible for high oxidative stability since they are associated with the quality standards and conservation of raw materials [28]. 

Peroxidation of lipids containing polyunsaturated fatty acids leads to generation of free radicals that may damage tissues and cause disease. 

The main function of vitamin E is as a chain-breaking, free radical trapping antioxidant in cell membranes and plasma lipoproteins. It reacts with the lipid peroxide radicals formed by peroxidation of polyunsaturated fatty acids before they can establish a chain reaction. The tocopheroxyl free radical product is relatively unreactive and ultimately forms nonradical compounds. Commonly, the tocopheroxyl radical is... 

Corongui, F.P., Poll, G., Diansani, M.U., Cheeseman, K.H. and Slater, T.F. (1986). Lipid peroxidation and molecular damage to polyunsaturated fatty acids in rat liver. Recognition of two classes of hydroperoxides formed under conditions in vivo. Chem. Biol. Interactions 59, 147-155. 

Chamirlitrat, W. and Mason, KP. (1989). Lipid preroxyl radical intermediates in the peroxidation of polyunsaturated fatty acids by lipoxygenase. J. Biol. Chem. 264, 20968—20973. 

Lipid peroxidation is a radical-mediated chain reaction resulting in the degradation of polyunsaturated fatty acids (PUFAs) that contain more than two covalent carbon-carbon double bonds (reviewed by Esterbauer et al., 1992). One of the major carriers of plasma lipids is LDL, a spherical molecule with a molecular weight of 2.5x10 . A single LDL particle contains 1300 PUFA molecules (2700 total fatty-acid molecules) and is... 

It is now widely appreciated that polyunsaturated fatty acids (PUFAs) are highly susceptible to oxidative damage. Indeed, the process of lipid peroxidation was broadly defined as the oxidative deterioration of polyunsaturated lipids by Tappel (1979). The presence of a double... 

Figure 17.2 Lipid peroxidation scheme. LH, a polyunsaturated fatty acid LOOM, lipid hydroperoxide LOH, lipid alcohol L, lipid radical LOO, lipid hydroperoxyl radical LO, lipid alkoxyl radical. Initiation the LH hydrogen is abstracted by reactive oxygen (e.g. lipid alkyl radical, lipid alkoxy radical, lipid hydroperoxyl radical, hydroxy radical, etc.) to produce a new lipid alkyl radical, L. Propagation the lipid alkyl, alkoxyl or hydroperoxyl radical abstracts hydrogen from the neighbouring LH to generate a new L radical.

The stimulus for the recent surge of activity in this previously dormant area of organic chemistry can be traced to the prostaglandin connection . That is to the discovery that saturated bicyclic peroxides are key intermediates in the biosynthesis of prostaglandins and other physiologically active substances by the enzymatic oxygenation of polyunsaturated fatty acids. 

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). 

Oxidative damage to membrane polyunsaturated fatty acids leads to the formation of numerous lipid peroxidation products, some of which can be measured as index of oxidative stress, including hydrocarbons, aldehydes, alcohols, ketones, and short carboxylic acids. 

Pentane and ethane (end products of n-6 and n-3 polyunsaturated fatty acid peroxidation, respectively) in expired air are useful markers of in vivo lipid peroxidation. Nevertheless, when gas chromatography is used to measure hydrocarbons, some technical difficulties may be experienced because chromatographic resolution of pentane from isoprene and isopentane is extremely difficult to achieve. Another possible problem could be the presence of these gases as contaminants in atmosphere. Furthermore, the production of hydrocarbon gases depends on the presence of metal ions to decompose lipid peroxides. If such ions are only available in limited amounts, this index may be inaccurate. 

The brain has a number of characteristics that make it especially susceptible to free- radical-mediated injury. Brain lipids are highly enriched in polyunsaturated fatty acids and many regions of the brain, for example, the substantia nigra and the striatum, have high concentrations of iron. Both these factors increase the susceptibility of brain cell membranes to lipid peroxidation. Because the brain is critically dependent on aerobic metabolism, mitochondrial respiratory activity is higher than in many other tissues, increasing the risk of free radical Teak from mitochondria conversely, free radical damage to mitochondria in brain may be tolerated relatively poorly because of this dependence on aerobic metabolism. 

FIGURE 32-6 Lipid peroxidation leads to fragmentation or oxidation of polyunsaturated fatty acids (PUFA). HO, hydroxyl radical LO, lipid alkoxylradical LOO, lipid peroxyl radical 0 2, superoxide radical O, atomic oxygen radical. (From Hall in [3].)... 

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