Polyunsaturated biosynthesis

Prostaglandins arise from unsaturated C20 carboxylic acids such as arachidonic acid (see Table 26 1) Mammals cannot biosynthesize arachidonic acid directly They obtain Imoleic acid (Table 26 1) from vegetable oils m their diet and extend the car bon chain of Imoleic acid from 18 to 20 carbons while introducing two more double bonds Lmoleic acid is said to be an essential fatty acid, forming part of the dietary requirement of mammals Animals fed on diets that are deficient m Imoleic acid grow poorly and suffer a number of other disorders some of which are reversed on feed mg them vegetable oils rich m Imoleic acid and other polyunsaturated fatty acids One function of these substances is to provide the raw materials for prostaglandin biosynthesis... 

Prostaglandin biosynthesis from C20 polyunsaturated fatty acids occurs by way of the endoperoxides PGG2 and PGH2. 

Figure 23-3. Biosynthesis of the co9, co6,and co3 families of polyunsaturated fatty acids. Each step is catalyzed by the microsomal chain elongation or desaturase system 1,elongase 2,A desaturase 3,A desaturase 4,A desaturase. ( .Inhibition.)...

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. 

Biosynthesis of triene pheromone components with a triene double bond system that is n-3 (3,6,9-) are probably produced from linolenic acid [49]. Moths in the families Geometridae, Arctiidae, and Noctuidae apparently utilize linoleic and linolenic acid as precursors for their pheromones that must be obtained in the diet,since moths can not synthesize these fatty acids [50]. Most of the Type II pheromones are produced by chain elongation and decarboxylation to form hydrocarbons [51]. Oxygen is added to one of the double bonds in the polyunsaturated hydrocarbon to produce an epoxide [49]. 

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. 

Biosynthesis. Almost all of the body s cells form eicosanoids. Membrane phospholipids that contain the polyunsaturated fatty acid arachidonic acid (20 4 see p.48) provide the starting material. 

Biosynthesis of Polyunsaturated Fatty Acids Occurs Mainly in Eukaryotes... 

Chemler JA, Yan Y, Koffas MA. 2006. Biosynthesis of isoprenoids, polyunsaturated fatty acids and flavonoids in Saccharomyces cerevisiae. Microb Cell Fact 5 20-28. 

A6 9-octadecadienoate rather than linoleate. However, animals need linoleate for the biosynthesis of dihomo-y-linolenate (A81114-eicosatrienoate) and arachidonate (A5 81114-eicosatetraenoate), C20 polyunsaturated fatty acid precursors of... 

Major flaxseed sterols are stigmasterol, camp sterol, and 5-5 avenasterol (Daun et al., 2003). Obtusifoliol, gramisterol, and citrostadienol constituted 45%, 22%, and 12%, respectively, of the total 4a-monomethylsterol in flaxseed (Kamm et al., 2001). Squalene content of flaxseed oil was reported as 4 mg/100 g oil, which was significantly lower than olive, corn, and rice bran oils. Squalene content is an intermediate compound of biosynthesis of plant sterols, which may have protective effects on lipid quality. Squalene could act as a peroxy radical scavengers in high polyunsaturated fatty acid oil (Dessi et al., 2002). 

Prostaglandins are cyclopentane derivatives of unsaturated C20-fatty acids. They display hormonal as well as regulatory activities and were detected for the first time in spermatic fluid. They are obviously widely spread in animal tissue. Biosynthesis of prostaglandins involves cyclization of polyunsaturated carboxylic acids, e.g. arachidonic acid [(5Z,8Z,llZ,14Z)-5,8,ll,14-eicosatetraenoic acid] is enzymatically converted directly into prostaglandin PGE2. Prostaglandins stimulate and contract certain smooth muscles. At very low concentrations they lower the blood pressure and influence the heart frequency. Some of them can release labour and... 

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

Certik, M. 2000. Fermentation physiology and regulation of microbial polyunsaturated fatty acid biosynthesis. In Mohan, R. M. (Ed.), Research Advances in Bioscience Bioengineering (1, pp. 45-64). Kerala Global Research Network. 

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