Polyunsaturated fatty acids products

Certik, M., and Shimizu, S. 1999a. Biosynthesis and regulation of microbial polyunsaturated fatty acid production. /. Biosci. Bioeng., 87,1-14. 

EN] POLYUNSATURATED FATTY ACID PRODUCTION IN HETEROLOGOUS ORGANISMS USING PUFA POLYKETIDE SYNTHASE SYSTEMS... 

Tonon, T., Harvey, D., Larson, T. R., Graham, I. A. (2002). Long chain polyunsaturated fatty acid production and partitioning to triacylglycerols in four microalgae. Phytochemistry, 67(1), 15-24. 

Hofiinaim, M. Wagner, M. Abbadi, A. Fulda, M. Feussner I metabolic engineering of omega-3-very long chain polyunsaturated fatty acid production by an exclusively acyl-coA-dependent pathway. JBiol Chem 2008,283 22352-22362. 

Kamlangdee, N. and Fan, K.W. (2003) Polyunsaturated fatty acids production by Schyzochytrium sp. isolated from mangrove, Songklaruikarin J. Scl Technol, 25, 643-650. 

Polyunsaturated fatty acids in vegetable oils, particularly finolenic esters in soybean oil, are especially sensitive to oxidation. Even a slight degree of oxidation, commonly referred to as flavor reversion, results in undesirable flavors, eg, beany, grassy, painty, or fishy. Oxidation is controlled by the exclusion of metal contaminants, eg, iron and copper addition of metal inactivators such as citric acid minimum exposure to air, protection from light, and selective hydrogenation to decrease the finolenate content to ca 3% (74). Careful quality control is essential for the production of acceptable edible soybean oil products (75). 

Polyunsaturated fatty acids pose a slightly more complicated situation for the cell. Consider, for example, the case of linoleic acid shown in Figure 24.24. As with oleic acid, /3-oxidation proceeds through three cycles, and enoyl-CoA isomerase converts the cA-A double bond to a trans-b double bond to permit one more round of /3-oxidation. What results this time, however, is a cA-A enoyl-CoA, which is converted normally by acyl-CoA dehydrogenase to a trans-b, cis-b species. This, however, is a poor substrate for the enoyl-CoA hydratase. This problem is solved by 2,4-dienoyl-CoA reductase, the product of which depends on the organism. The mammalian form of this enzyme produces a trans-b enoyl product, as shown in Figure 24.24, which can be converted by an enoyl-CoA isomerase to the trans-b enoyl-CoA, which can then proceed normally through the /3-oxidation pathway. Escherichia coli possesses a... 

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... 

Interaction of lipid oxidation products and amino compounds. Amino acids and primary amines may be involved in other reactions which could lead to the formation of compounds having the potential to undergo N-nitrosation. Malonaldehyde, produced as a result of oxidation of lipids, particularly polyunsaturated fatty acids, has been shown to react with amino acids to produce... 

Problems resembling the first example, but much more complex, are often studied in industry. For instance in the agro-food industry linear programming is a current tool to optimize the blending of raw materials (e.g. oils) in order to obtain the wanted composition (amount of saturated, monounsaturated and polyunsaturated fatty acids) or property of the final product at the best possible price. Here linear programming is repeatedly applied each time when the price of raw materials is adapted by changing markets. 

Lipoxygenase (EC 1.13.11.12, nonheme iron dioxygenase), the substrate (polyunsaturated fatty acid) is poorly water soluble and the product (hydroperoxy-fatty acid) is hydrophilic. The reaction occurs in the aqueous phase [85,86]. 

The lipase-catalyzed fatty acid ester hydrolysis and the lipoxygenation of free polyunsaturated fatty acids are involved in the same lipid degradation pathway. They are respectively the first and second reaction in the lipoxygenase pathway (Fig. 3) [87-91]. The pathway produces volatile products of considerable importance in food technology including Cg[92, 93] or Cg- 94—96 aldehydes and alcohols from polyunsaturated fatty... 

As mentioned earlier, both MCTs and LCTs are used in tube feeding products. Corn, soy, and safflower oils have been the mainstay sources of fat in these products, providing mainly co-6 polyunsaturated fatty acids (PUFAs). On the other hand, some newer EN products contain higher quantities of co-3 PUFAs from sources such as fish oil [i.e., docosahexenoic acid (DHA) and eicosapentenoic acid or (EPA)]. Still other formulas contain higher quantities of monounsaturated fatty acids from canola oil and high-oleic safflower or sunflower oils. The essential fatty acid (EFA) content (mainly linoleic acid) of EN... 

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). 

Chilliard Y, Ferlay A and Doreau M (2001), Effects of different types of forages, animal fat or marine oils in cow s diet on milk fat secretion and composition, especially conjugated linoleic acid (CLA) and polyunsaturated fatty acids , Livestock Production Science, 70, 31-48. 

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. 

FIGURE 3-7 Pathways for the interconversion of brain fatty acids. Palmitic acid (16 0) is the main end product of brain fatty acid synthesis. It may then be elongated, desaturated, and/or P-oxidized to form different long chain fatty acids. The monoenes (18 1 A7, 18 1 A9, 24 1 A15) are the main unsaturated fatty acids formed de novo by A9 desaturation and chain elongation. As shown, the very long chain fatty acids are a-oxidized to form a-hydroxy and odd numbered fatty acids. The polyunsaturated fatty acids are formed mainly from exogenous dietary fatty acids, such as linoleic (18 2, n-6) and a-linoleic (18 2, n-3) acids by chain elongation and desaturation at A5 and A6, as shown. A A4 desaturase has also been proposed, but its existence has been questioned. Instead, it has been shown that unsaturation at the A4 position is effected by retroconversion i.e. A6 unsaturation in the endoplasmic reticulum, followed by one cycle of P-oxidation (-C2) in peroxisomes [11], This is illustrated in the biosynthesis of DHA (22 6, n-3) above. In severe essential fatty acid deficiency, the abnormal polyenes, such as 20 3, n-9 are also synthesized de novo to substitute for the normal polyunsaturated acids. 

Nitric oxide and peroxynitrite contribute to oxidative damage 569 Production of eicosanoids from polyunsaturated fatty acids such as arachidonic acid may generate reactive oxygen species 570 Brain antioxidant defenses modify ischemia-reperfusion injury 570 Reactive oxygen species may modify both the excitotoxic and the apoptotic components of ischemic brain damage 570... 

Free arachidonic acid, along with diacylglycerols and free docosahexaenoic acid, is a product of membrane lipid breakdown at the onset of cerebral ischemia, seizures and other forms of brain trauma. Because polyunsaturated fatty acids are the predominant FFA pool components that accumulate under these conditions, this further supports the notion that fatty acids released from the C2 position of membrane phospholipids are major contributors to the FFA pool, implicating PLA2 activation as the critical step in FFA release [1,2] (Fig. 33-6). 

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