Decarboxylation of fatty acids

Carboxylic acids are thermally stable. Decarboxylation of carboxylic acids is observed at 600 K and higher in the absence of dioxygen [4], At the same time, the decarboxylation of fatty acids in oxidized cumene was observed at 350 K [71]. The study of C02 production from oxidized acetic, butanoic, isobutanoic, pentanoic, and stearic acids labeled with 14C in the... 

Recently, researchers have detected 2,5-dimethylfuran and 2-methylfuran and normal alkanes in kerogen of the 2.7 x 109 year old Belingwe, Rhodesia stromatolites, by the method of pyrolysis/ GC/MS [26]. They concluded that although furans could probably be derived from many compounds, their probable origin is in bacterial and algal sugars, and that the alkanes are either products of decarboxylation of fatty acids or unaltered constituents of ancient organisms. 

Aliphatic hydrocarbons such as n-alkanes and n-alkenes have been successfully used to distinguish between algal, bacterial, and terrestrial sources of carbon in estuarine/coastal systems (Yunker et al., 1991, 1993, 1995 Canuel et al., 1997). Saturated aliphatic hydrocarbons are considered to be alkanes (or paraffins) and nonsaturated hydrocarbons which exhibit one or more double bonds are called alkenes (or olefins)—as indicated in the simple structures of hexadecane and 1,3-butadiene, respectively (figure 9.7). It should also be noted that, n-alkanes tend to be odd-numbered as they result from enzymatic decarboxylation of fatty acids. Long-chain n-alkanes (LCH) (e.g., C27, C29, and C31) are generally considered to be terrestrially derived, originating from epicuticular waxes... 

We cannot, however, support the opinion that there is no correlation between the ketones and fatty acids. Analyses made over a one year period seem to indicate that the percentage of macrocyclic ketones is often high when that of the acids is low and vice versa. This would support Stevens hypothesis, which was challenged by Van Dorp et al. (26), that the ketones are formed by cyclization and decarboxylation of fatty acids (25). 

The final and perhaps the most convincing evidence for the elongation-decarboxylation mechanism was provided by the demonstration that cell-free extracts fromi. sativum leaves catalyzed conversion of [9,10,11- H]C32 acid to C31 alkane (Khan and Kolattukudy, 1974). In such preparations both C31 and C30 alkanes were generated from the labeled C32 acid, suggesting that such preparations catalyzed a-oxidation in addition to decarboxylation of fatty acids to alkanes. Imidazole, an inhibitor of a-oxidation (Shine and Stumpf, 1974), inhibited the formation of both /1-C30 and -C3i alkanes from C32 acid, suggesting that an a-oxidation-type reaction was involved in the conversion of C32 acid to C31 alkane (Table VI). In support of this hypothesis... 

Fig. 4.48 Two mechanisms for the decarboxylation of fatty acids to terminal olefins catalyzed by CYP152L1, one involving p-carbon oxidation and the other carboxyl...

Simakova I, Simakova O, Maki-Arvela P, Murzin D. Decarboxylation of fatty acids over Pd supported on mesoporous carbon. Catal. Today 2010 150 28. 

Maki-Arvela P. Kubickova I, Eranen K, Snare M. Murzin D. Catalytic decarboxylation of fatty acids and their derivatives. Energy Fuels 2007 21 30. 

Biodiesel research is an important area to look for information related to decarboxylation. Biodiesel contains fatty acids and fatty acid methyl esters which have undergone further deoxygenation to produce a higher-quality liquid fuel. Pd has been shown to be an active metal for decarboxylation of fatty acids (Maki-Arvela et al., 2007). It was reported that 97% acid conversion to n-heptadecane was obtained with Pd/C. The decarboxylation rate of fatty acids decreased as the fatty acid to metal ratio increased (Simakova et al., 2010). The decarboxylation of stearic acid was also tested using Pd supported on active carbon (Snare et al., 2006) resulting in the conversion of stearic acid to diesel fuel compounds, carbon dioxide, and/or carbon monoxide. The decarboxylation reaction was more prominent over Pd/C catalyst, while... 

The higher fatty acids undergo decarboxylation and other undesirable reactions when heated at their boiling points at atmospheric pressure. Hence they are distilled at reduced pressure (15,16). Methyl esters boil at lower temperatures than acids at the same pressure as the result of the absence of hydrogen bonding (17). A procedure for calculation of the vapor pressures of fatty acids at various temperatures has been described (18). 

Finally, citrate can be exported from the mitochondria and then broken down by ATP-citrate lyase to yield oxaloacetate and acetyl-CoA, a precursor of fatty acids (Figure 20.23). Oxaloacetate produced in this reaction is rapidly reduced to malate, which can then be processed in either of two ways it may be transported into mitochondria, where it is reoxidized to oxaloacetate, or it may be oxidatively decarboxylated to pyruvate by malic enzyme, with subse-... 

Under metabolic conditions associated with a high rate of fatty acid oxidation, the liver produces considerable quantities of acetoacetate and d(—)-3-liydroxyl)utyrate (P-hydroxybutyrate). Acetoacetate continually undergoes spontaneous decarboxylation to yield acetone. These three substances are collectively known as the ketone bodies (also called acetone bodies or [incorrectly ] ketones ) (Figure 22-5). Acetoacetate and 3-hydroxybu-... 

Aerobic living features metabolize sugars and fatty acids to carbon dioxide. Accordingly, there are some kinds of decarboxylation reactions. TPP-mediated decarboxylation of pyruvic acid to acetaldehyde is one of the most important steps of the metabolism of sugar compounds (Fig. 1). When the intermediate reacts with lipoic acid instead of a proton, pyruvic acid is converted to acetylcoenzyme A, which is introduced to TCA cycle (Fig. 2). 

The tricarboxylic acid cycle was therefore validated, having been tested not only in pigeon-breast muscle but also with brain, testis, liver, and kidney. The nature of the carbohydrate fragment entering the cycle was still uncertain. The possibility that pyruvate and oxaloacetate condensed to give a 7C derivative which would be decarboxy-lated to citrate, was dismissed partly because the postulated compound was oxidized at a very low rate. Further, work on the oxidation of fatty acids (see Chapter 7) had already established that a 2C fragment like acetate was produced by fatty acid oxidation, en route for carbon dioxide and water. It therefore seemed likely that a similar 2C compound might arise by decarboxylation of pyruvate, and thus condense with oxaloacetate. For some considerable time articles and textbooks referred to this unknown 2C compound as active acetate. ... 

The tricarboxylic acid cycle not only takes up acetyl CoA from fatty acid degradation, but also supplies the material for the biosynthesis of fatty acids and isoprenoids. Acetyl CoA, which is formed in the matrix space of mitochondria by pyruvate dehydrogenase (see p. 134), is not capable of passing through the inner mitochondrial membrane. The acetyl residue is therefore condensed with oxaloacetate by mitochondrial citrate synthase to form citrate. This then leaves the mitochondria by antiport with malate (right see p. 212). In the cytoplasm, it is cleaved again by ATP-dependent citrate lyase [4] into acetyl-CoA and oxaloacetate. The oxaloacetate formed is reduced by a cytoplasmic malate dehydrogenase to malate [2], which then returns to the mitochondrion via the antiport already mentioned. Alternatively, the malate can be oxidized by malic enzyme" [5], with decarboxylation, to pyruvate. The NADPH+H formed in this process is also used for fatty acid biosynthesis. 

A number of the reactions in which HOCl and O2 might participate to kill bacteria and to attack biological molecules have been documented. These include the halogenation of tyrosines, the formation of aldehydes and chloramines, the attack of Oj on unsaturated bonds in fatty acids, and decarboxylation of amino acids. The experimental basis for these reactions has been reviewed by Klebanoff and Clark... 

Individuals with either type of diabetes are unable to take up glucose efficiently from the blood recall that insulin triggers the movement of GLUT4 glucose transporters to the plasma membrane of muscle and adipose tissue (see Fig. 12-8). Another characteristic metabolic change in diabetes is excessive but incomplete oxidation of fatty acids in the liver. The acetyl-CoA produced by JS oxidation cannot be completely oxidized by the citric acid cycle, because the high [NADH]/[NAD+] ratio produced by JS oxidation inhibits the cycle (recall that three steps convert NAD+ to NADH). Accumulation of acetyl-CoA leads to overproduction of the ketone bodies acetoacetate and /3-hydroxybutyrate, which cannot be used by extrahepatic tissues as fast as they are made in the liver. In addition to /3-hydroxybutyrate and acetoacetate, the blood of diabetics also contains acetone, which results from the spontaneous decarboxylation of acetoacetate ... 

It is an acyl-CoA of the type mentioned in Section 1 and can also be formed from acetate, ATP, and coenzyme A. Although the human diet contains some acetic acid, the two major sources of acetyl-CoA in our bodies are the oxidative decarboxylation of pyruvate (Eq. 10-6) and the breakdown of fatty acid chains. Let us consider the latter process before examining the further metabolism of acetyl-CoA. 

Fatty acid chains are taken apart two carbon atoms at a time by (3 oxidation. Biosynthesis of fatty acids reverses this process by using the two-carbon acetyl unit of acetyl-CoA as a starting material. The coupling of ATP cleavage to this process by a carboxylation-decarboxylation sequence, the role of acyl carrier protein (Section H,4), and the use of NADPH as a reductant (Section I) have been discussed and are summarized in Fig. 17-12, which gives the complete sequence of... 

In the synthesis of fatty acids the acetyl irnits are condensed and then are reduced to form straight hydrocarbon chains. In the oxo-acid chain elongation mechanism, the acetyl unit is introduced but is later decarboxylated. Tlius, the chain is increased in length by one carbon atom at a time. These two mechanisms account for a great deal of the biosynthesis by chain extension. However, there are other variations. For example, glycine (a carboxylated methylamine), under the influence of pyridoxal phosphate and with accompanying decarboxylation, condenses with succinyl-CoA (Eq. 14-32) to extend the carbon chain and at the same time to introduce an amino group. Likewise, serine (a carboxylated ethanolamine) condenses with... 

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