Fatty acid reduction

FIGURE 25.12 Elongation of fatty acids in mitochondria is initiated by the thiolase reaction. The /3-ketoacyl intermediate thus formed undergoes the same three reactions (in reverse order) that are the basis of /3-oxidation of fatty acids. Reduction of the /3-keto group is followed by dehydration to form a double bond. Reduction of the double bond yields a fatty acyl-CoA that is elongated by two carbons. Note that the reducing coenzyme for the second step is NADH, whereas the reductant for the fourth step is NADPH. 

Eckel, R.H. S. Borra A.H. Lichtenstein S.Y. Yin-Piazza. Understanding the complexity of trans fatty acid reduction in the American diet American heart association tram fat conference 2006 Report of the tram fat conference planning group. Circulation 2007, 115, 2231-2246. 

It is difficult to alter the composition of the brain lipid fatty acids. Reduction of brain EFAs in young animals has been successfully achieved by feeding EFA-deficient diets to the mother during pregnancy. Reduction of brain EFAs using this technique was associated with retardation of brain development (Caldwell Churchill, 1966 Paoletti Galli, 1972 Sinclair Crawford,... 

Steinbusch KJJ, Mamelers HVM, Buisman CJN. 2008. Alcohol production through volatile fatty acids reduction with hydrogen as electron donor by mixed cultures. Water Res. 42 4059-4066. 

Some fairly typical results, obtained by LaMer and co-workers [275] are shown in Fig. IV-24. At the higher film pressures, the reduction in evaporation rate may be 60-90%—a very substantial effect. Similar results have been reported for the various fatty acids and their esters [276,277]. Films of biological materials may offer little resistance, as is the case for cholesterol [278] and dimyristoylphosphatidylcholine (except if present as a bilayer) [279]. 

Eats and oils from a number of animal and vegetable sources are the feedstocks for the manufacture of natural higher alcohols. These materials consist of triglycerides glycerol esterified with three moles of a fatty acid. The alcohol is manufactured by reduction of the fatty acid functional group. A small amount of natural alcohol is also obtained commercially by saponification of natural wax esters of the higher alcohols, such as wool grease. 

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

Fatty acids derived from animal and vegetable sources generally contain an even number of carbon atoms siace they are biochemically derived by condensation of two carbon units through acetyl or malonyl coenzyme A. However, odd-numbered and branched fatty acid chains are observed ia small concentrations ia natural triglycerides, particularly mminant animal fats through propionyl and methylmalonyl coenzyme respectively. The glycerol backbone is derived by biospeciftc reduction of dihydroxyacetone. 

Hydrogenations can be carried out in batch reactors, in continuous slurry reactors, or in fixed-bed reactors. The material of constmetion is usually 316 L stainless steel because of its better corrosion resistance to fatty acids. The hydrogenation reaction is exothermic and provisions must be made for the effective removal or control of the heat a reduction of one IV per g of C g fatty acid releases 7.1 J (1.7 cal), which raises the temperature 1.58°C. This heat of hydrogenation is used to raise the temperature of the fatty acid to the desired reaction temperature and is maintained with cooling water to control the reaction. 

Whereas catabolism is fundamentally an oxidative process, anabolism is, by its contrasting nature, reductive. The biosynthesis of the complex constituents of the cell begins at the level of intermediates derived from the degradative pathways of catabolism or, less commonly, biosynthesis begins with oxidized substances available in the inanimate environment, such as carbon dioxide. When the hydrocarbon chains of fatty acids are assembled from acetyl-CoA units, activated hydrogens are needed to reduce the carbonyl (C=0) carbon of acetyl-CoA into a —CHg— at every other position along the chain. When glucose is... 

The TCA cycle can now be completed by converting succinate to oxaloacetate. This latter process represents a net oxidation. The TCA cycle breaks it down into (consecutively) an oxidation step, a hydration reaction, and a second oxidation step. The oxidation steps are accompanied by the reduction of an [FAD] and an NAD. The reduced coenzymes, [FADHg] and NADH, subsequently provide reducing power in the electron transport chain. (We see in Chapter 24 that virtually the same chemical strategy is used in /3-oxidation of fatty acids.)... 

The coenzyme for the oxidation-reduction reactions of fatty acid synthesis is NADP /NADPH, whereas degradation involves the NAD /NADH couple. 

Fatty Acid Biosynthesis Depends on the Reductive Power of NADPH... 

The next three steps—reduction of the /3-carbonyl group to form a /3-alcohol, followed by dehydration and reduction to saturate the chain (Figure 25.7) — look very similar to the fatty acid degradation pathway in reverse. However, there are two crucial differences between fatty acid biosynthesis and fatty acid oxidation (besides the fact that different enzymes are involved) First, the alcohol formed in the first step has the D configuration rather than the L form seen in catabolism, and, second, the reducing coenzyme is NADPH, although NAD and FAD are the oxidants in the catabolic pathway. 

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