Polyunsaturated fatty acids oxidation susceptibility

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... 

Lipids are susceptible to oxidation and, therefore, analytical protocols are required to measure their quality. Not all lipids have the same degree of susceptibility to oxidation. Many factors are responsible for a lipid s tendency to oxidize, including the presence of catalysts, oxidative enzymes, radiation, and a lipid-air interface, as well as the oxygen partial pressure, the incorporation of oxygen into the product, and the presence of metal ions. The most important factor is the degree of unsaturation of the lipid itself. The majority of a food product s polyunsaturated fatty acids (PUFAs) are generally contained in phospholipids, which are consequently more prone to autoxi-dation than the triacylglycerol fraction. 

Such imbalanced antioxidant systems in schizophrenia could lead to oxidative stress- and ROS-mediated injury as supported by increased lipid peroxidation products and reduced membrane polyunsaturated fatty acids (PUFAs). Decrease in membrane phospholipids in blood cells of psychotic patients (Keshavan et al., 1993 Reddy et al., 2004) and fibroblasts from drug-naive patients (Mahadik et al., 1994) as well as in postmortem brains (Horrobin et al., 1991) have indeed been reported. It has also been suggested that peripheral membrane anomalies correlate with abnormal central phospholipid metabolism in first-episode and chronic schizophrenia patients (Pettegrewet al., 1991 Yao et al., 2002). Recently, a microarray and proteomic study on postmortem brain showed anomalies of mitochondrial function and oxidative stress pathways in schizophrenia (Prabakaran et al., 2004). Mitochondrial dysfunction in schizophrenia has also been observed by Ben-Shachar (2002) and Altar et al. (2005). As main ROS producers, mitochondria are particularly susceptible to oxidative damage. Thus, a deficit in glutathione (GSH) or immobilization stress induce greater increase in lipid peroxidation and protein oxidation in mitochondrial rather than in cytosolic fractions of cerebral cortex (Liu et al., 1996). 

Effect of monounsaturated and polyunsaturated fatty acids on the susceptibility of plasma LDL to oxidative modification... 

The high concentration of polyunsaturated fatty acids in cellular and subcellular membranes makes them particularly susceptible to free radical damage. In addition, mitochondrial membranes contain flavins as a part of their basic structure, potentially contributing C>2 resulting in free radical damage. The process of uncontrolled lipid peroxidation can result in the loss of essential polyunsaturated fatty acids, and the formation of toxic hydroperoxides and other secondary products. The loss of essential fatty acids may then result in loss of membrane integrity and loss of function. Extensive oxidation can also lead to rupture of... 

Lipid peroxidation is a free radical-mediated, chain reaction resulting in the oxidative deterioration of polyunsaturated fatty acids (PUFAs) defined for this purpose as fatty acids that contain more than two double covalent carbon-carbon bonds. Singlet oxygen can produce lipid hydroperoxides in unsaturated lipids by non-radical processes (Pryor and Castle, 1984), but the reaction usually requires a radical mechanism (Porter, 1984). Polyunsaturated fatty acids are particularly susceptible to attack by free radicals. Lipid peroxidation is a complex process, and three distinct phases are recognized (a) initiation, (b) propagation and (c) termination (see Fig. 2.10). 

In addition to modifying the rheological properties of butter, blends of milk fat and vegetable oils can be produced at a reduced cost (depending on the price paid for milk fat) and have an increased content of polyunsaturated fatty acids, which probably has a nutritional advantage. Oils rich in CO-3 fatty acids, which are considered to have desirable nutritional properties, may be included in the blend, although these oils may be susceptible to oxidative rancidity. 

It is largely accepted that a high dietary intake of poly-unsaturated fatty adds (PUFA) in the a>-3 series has beneficial effects. Recently, cellular lipid metabolism has been suggested as a target for cancer therapy. Cancer cells, compared with normal cells, seem to be vulnerable to exposure of certain polyunsaturated fatty acids (PUFAs), especially those in the o -3 series. Characteristic for these compounds are their poor abihty to be oxidized in the cell due to multiple double bonds. They are however likely to be ester-rfied to oflier Upids, and their incorporation into membrane phosphohpids will influence membrane properties such as fluidity, protein interactions and susceptibility to lipid peroxidation. The hypohpidemic properties of some (0-3 fatty acids, such as EPA, are probably e lained by an induction of mitochondrial P -oxidation that is not found after adrninistration of the non-hypolipidemic (o-3 PUFA docosahexaenoic acid (DHA)." However, both eicosapentaenoic acid (EPA) and DHA cause increased peroxisomal... 

Antixmdants The direct action of oxygen in the air is the chief cause of the destruction of the fats in food. Carbon-carbon double bonds in polyunsaturated fatty acids are particularly susceptible. Oxidation produces a complex mixture of volatile aldehydes, ketones, and acids that causes a rancid odor and taste. Foods kept wrapped, cold, and dry are relatively protected from air oxidation. The most common antioxidant food additives are butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), which act by releasing a hydrogen atom from their — OH groups as a free radical (H ). 

---