Linoleic acid, conversion

With the resting cells suspension, the ratio of products, lO-HOA lO-KOA was 97 3. Less 10-KOA was produced in comparison with that of growing cells. The cells were disrupted with ultrasonic oscillation and centrifuged to obtain cell-free crude extract. The linoleic acid conversion enzyme(s) resided in the cell-free crude extract, and only lO-HOA was produced from linoleic acid. 

FIGURE 21-12 Routes of synthesis of other fatty acids. Palmitate is the precursor of stearate and ionger-chain saturated fatty acids, as well as the monounsaturated acids palmitoleate and oleate. Mammals cannot convert oleate to linoleate or a-linolenate (shaded pink), which are therefore required in the diet as essential fatty acids. Conversion of linoleate to other polyunsaturated fatty acids and eicosanoids is outlined. Unsaturated fatty acids are symbolized by indicating the number of carbons and the number and position of the double bonds, as in Table 10-1. 

The conversion of oleoyl-CoA to linoleoyl-CoA is accomplished by some insects118 but does not take place in most animals. As a result of this biosynthetic deficiency, polyunsaturated fatty acids such as linoleic, linolenic, and the C20 arachidonic acid are necessary in the diet (Box 21-B). One essential function of linoleic acid is to serve as a precursor of prostaglandins and related prostanoids (Section D). Dietary linoleate is converted to its Co A derivative and then by sequential A6 desaturation,119 elongation, and then A5 desaturation, to the 20 4 (A5 8 11 14) arachidonoyl-CoA (Fig. 21-2, lower right). These acids are referred to as 0)6 because of the position of the last double bond. Linolenic acid can be converted in an analogous fashion to the CoA derivative of the 20 5 (A5 8 11 14 17 co6) eicosapentaenoic acid (EPA). The 22 6 docasahexaenoic acid (DHA Fig. 21-2) is apparently formed by elongation of the 22 5 acyl-CoA to 24 5, desaturation, transfer to a peroxisome or mitochondrion, and p oxidation to shorten the chain.953... 

Enzyme complexes occur in the endoplasmic reticulum of animal cells that desaturate at A5 if there is a double bond at the A8 position, or at A6 if there is a double bond at the A9 position. These enzymes are different from each other and from the A9-desaturase discussed in the previous section, but the A5 and A6 desaturases do appear to utilize the same cytochrome b5 reductase and cytochrome b5 mentioned previously. Also present in the endoplasmic reticulum are enzymes that elongate saturated and unsaturated fatty acids by two carbons. As in the biosynthesis of palmitic acid, the fatty acid elongation system uses malonyl-CoA as a donor of the two-carbon unit. A combination of the desaturation and elongation enzymes allows for the biosynthesis of arachidonic acid and docosahexaenoic acid in the mammalian liver. As an example, the pathway by which linoleic acid is converted to arachidonic acid is shown in figure 18.17. Interestingly, cats are unable to synthesize arachidonic acid from linoleic acid. This may be why cats are carnivores and depend on other animals to make arachidonic acid for them. Also note that the elongation system in the endoplasmic reticulum is important for the conversion of palmitoyl-CoA to stearoyl-CoA. 

Hussein, N., Ah-Sing, E., Wilkinson, P., Leach, C., Griffin, B.A., and Millward, D.J. 2005. Long-chain conversion of [13C] linoleic acid and a-linolenic acid in response to marked changes in their dietary intake in men. J. Lipid Res. 46, 269-280. 

I Average conversion yield Linolenic acid methyl ester Linoleic acid methyl ester Oleic acid methyl ester... 

Reaction temperature and time were significant operating parameters, which are closely related to the energy costs, of the biodiesel production process. Figure 7 shows the effect of reaction time on the transesterification of rapeseed oil at a catalyst concentration of 1%, molar ratio of 1 6, and 60°C. Within 5 min, the reaction was rapid. Rapeseed oil was converted to above 85% within 5 min and reached equilibrium state after about 10 min. Several researchers reported that the conversion of vegetable oils to FAME was achieved above 80% within 5 min with a sufficient molar ratio (8,11). For a reaction time of 60 min, linoleic acid methyl ester was produced at a low conversion rate, whereas oleic and linolenic methyl ester were rapidly produced. 

A quantitative conversion has been described within 4 h with 40 bar of pressure and at 100°C. The polyunsaturated fatty acids like linoleic acid were hydroformylated manifold. If RhC P O is employed, soybean oil cannot be hydroformylated because only the isomerization of conjugated fatty acids is obtained [24]. The direct processing of a fat without cleavage of the triglyceride is attractive for several applications. 

FIGURE 26.2 Metabolic conversion of linoleic acid and a-linolenic acid to longer chain, more unsaturated fatty acids. 

Nugteren, D.H. and Kivits, G.A.A., Conversion of linoleic acid and arachidonic acid by skin epidermal lipoxygenases, Biochim. Biophys. Acta, 921, 135, 1987. 

In humans, the conversion of ALA to EPA and DHA is extremely slow, with only about 15% and 5% of ALA converted to EPA and DHA, respectively (Cunnane, 1995). This conversion appears to be affected by a number of dietary factors. For example, a diet rich in linoleic acid has been found to reduce this conversion by as much as 40% (Emken, 1995). In addition, saturated and lruns fatty acids also interfere with ALA desaturation and elongation steps (Ackman and Cunnane, 1992 HouwelingenandHornstra, 1994). DHA can be reconverted back to EPA, although in humans it appears to be a very minor pathway (Brossard et al., 1996). DHA appears to play an important in the brain and retina and was found to be incorporated during the last trimester of pregnancy and the first year of life. Visual acuity was shown to develop much faster in preterm infants fed formulas rich in DHA compared with standard infant formulas low in long chain n-3 fatty acids (Jorgensen et al., 1996). 

Emken, E.A. (1995) Influence of linoleic acid on conversion of linolenic acid to omega-3 fatty acids in humans, in Proceedings from the Scientific Conference on Omega-3 Fatty Acids in Nutrition, Vascular Biology, and Medicine. American Heart Association, Dallas, Texas, USA, pp. 9-18. 

Question What are the steps involved in the conversion of linoleic acid to arachidonic acid ... 

Conversely, SFME exhibited relatively poor improvement in oxidative stability with the use of antioxidants, presumably due to the higher concentrations of linoleic acid methyl esters in sunflower oil in comparison to the other biodiesel samples evaluated by the authors. Therefore, a good correlation was found between the improvement in oxidative stability as measured by OSI when antioxidants are used and the fatty acid composition of the biodiesel sample (Mittelbach and Schober, 2003). 

According to the reports describing metabolic pathways involved in the conversion of linoleic acid to trihydroxy fatty acids, several intermediate reaction products, such as trihydroxy-, hydroperoxy-, dihydroxy-, and hydroxyepoxy-octadecenoate, were involved (Kato et al., 1984,1986). Those metabolites of linoleic acid showed distinct biological functions according to their intermediate structures, including mono-, di-, trihydroxy-octadecenoic acid, and hydroperoxy-, epoxy-forms (Kato et al., 1984 Blair, 2001 Gobel et al., 2002 Hou and Forman, 2000). In an effort to understand the overall mechanism involved in the varied biological functions of the complicated reaction metabolites of bio-converted polyunsaturated fatty acids, Kim et al. (2006) studied the oxidative activities on fish oil, of crude extracts produced by PR3 from... 

Dix,T. A., and Marnett, L. J. 1985. Conversion of linoleic acid hydroperoxide to hydroxy, keto, epoxyhydroxy, and trihydroxy fatty acids by hematin. J. Biol. Chem., 260, 5351-5357. 

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