Linoleic acid double carbon bond

Mammals cannot synthesize unsaturated fatty acids having double bonds further than 9 carbons from the carboxyl group. Thus, mammals can synthesize oleic acid and palmitoleic acid (double bonds at carbon 9), but not linoleic acid (double bons at carbons 9 and 12) or linolenic acid (double bonds at carbons 9,12, and 15). As a result, fatty acids such as linoleic acid and linolenic acid are called essential fatty acids because they must be present in the diet. Figure 18.33 shows how linoleic acid is converted to arachidonic acid, an important precursor to the prostaglandins and thromboxanes. 

Mammals cannot synthesize double bonds in fatty acids beyond the ninth carbon, so linoleic acid (double bonds at carbons 9 and 12) and linolenic Acid (double bonds at carbons 9,12, and 15) must be provided in mammalian diets. 

Mammals can add additional double bonds to unsaturated fatty acids in their diets. Their ability to make arachidonic acid from linoleic acid is one example (Figure 25.15). This fatty acid is the precursor for prostaglandins and other biologically active derivatives such as leukotrienes. Synthesis involves formation of a linoleoyl ester of CoA from dietary linoleic acid, followed by introduction of a double bond at the 6-position. The triply unsaturated product is then elongated (by malonyl-CoA with a decarboxylation step) to yield a 20-carbon fatty acid with double bonds at the 8-, 11-, and 14-positions. A second desaturation reaction at the 5-position followed by an acyl-CoA synthetase reaction (Chapter 24) liberates the product, a 20-carbon fatty acid with double bonds at the 5-, 8-, IT, and ITpositions. 

Most moth sex pheromones that are straight chain hydrocarbons also usually have an odd number of carbons. Most of these are polyunsaturated with double bonds in the 3,6,9- or 6,9-positions, indicating that they are derived from linolenic or linoleic acid, respectively [49,51]. Iinolenic and linoleic acid cannot be biosynthesized by moths so they must be obtained from the diet [75]. A few even chain-length hydrocarbon sex pheromones have been identified that also have 3,6,9- or 6,9-double bond configurations [49], indicating they too are derived from linolenic or linoleic acids however, it is not known how these even chain hydrocarbons are formed. 

Odor and color stability problems were also related to the alkyl chains used for SAI. These could be traced to the oxidation of unsaturated carbons, such as oleic acid (Ci8 fatty acid with a single double bond between carbon 9 and 10, i.e. bond position 9 counted from the carboxyl carbon), linoleic acid (Cis fatty acid with two double bonds at position 9 and 12), and linolenic acid (Cis fatty acid with three double bonds at position 9, 12, and 15). Natural coconut fatty acid contains about 6% oleic acid, about 3% linoleic acid, and less than 1% linolenic acid. Tallow fatty acid contains nearly 44% oleic and about 6% of other unsaturates [20]. Partial hydrogenation of the coconut fatty acid used in the manufacture of SCI served to eliminate linoleic and linolenic acids for improved odor stability, while not eliminating oleic acid, which is important for good lather. 

The common fatty acids have a linear chain containing an even number of carbon atoms, which reflects that the fatty acid chain is built up two carbon atoms at a time during biosynthesis. The structures and common names for several common fatty acids are provided in table 18.1. Fatty acids such as palmitic and stearic acids contain only carbon-carbon single bonds and are termed saturated. Other fatty acids such as oleic acid contain a single carbon-carbon double bond and are termed monounsaturated. Note that the geometry around this bond is cis, not trans. Oleic acid is found in high concentration in olive oil, which is low in saturated fatty acids. In fact, about 83% of all fatty acids in olive oil is oleic acid. Another 7% is linoleic acid. The remainder, only 10%, is saturated fatty acids. Butter, in contrast, contains about 25% oleic acid and more than 35% saturated fatty acids. 

RP-HPLC with nonaqueous solvents and UVD at 246 nm was developed for the determination of low level POVs of vegetable oils. These measurements are specific for conjugated diene peroxides derived from vegetable oils with relatively high linoleic acid content. These measurements may be supplemented by nonspecific UVD at 210 nm and ELSD for detection of all eluted species. The elution sequence of the triglycerides in a nonaqueous RP-HPLC is linearly dependent on the partition number of each species, Vp, which is defined as = Nq — 2Ni, where Nq is the carbon number and is the double bond number. In the case of hydroperoxides = Nq — 2Nd — Vhpo, where Vhpo is the number of hydroperoxyl groups in the molecule (usually 1 for incipient POV). For... 

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. 

About 40 different fatty acids occur naturally. Palmitic acid (Ci6) and stearic acid (Cis) are the most abundant saturated acids oleic and linoleic acids (both G ) are the most abundant unsaturated ones. Oleic acid is monounsaturated because it has only one double bond, but linoleic and linolenic acids are polyunsaturated fatty acids (called PUFAs) because they have more than one carbon-carbon double bond. Although the reasons are not yet clear, it appears that a diet rich in saturated fats leads to a higher level of blood cholesterol and consequent higher risk of heart attack than a diet rich in unsaturated fats. 

The reaction mechanism for the selective hydrogenation of edible oils is very complex. Figure 14.1 illustrates a reaction scheme for linoleic acid. In this scheme, (n m) is used to represent an oil with n carbon atoms and m double bonds. There are several parallel, consecutive, and side reactions. Oleic acid (cis 18 1) is the desired product when the reaction starts with linolenic (all-cis 18 3) or linoleic acid (cis, cis 18 2). In the hydrogenation of linolenic and linoleic acid, elaidic acid (trans 18 1) is formed in a cisjtrans isomerization reaction. From the viewpoint of dietics, elaidic acid is an undesirable product however, its presence increases the melting point of the product in a desirable way. Stearic acid (18 0) is formed in a consecutive reaction, but direct formation from linoleic acid is also possible. 

Important essential fatty acids in the diet are linoleic acid (cis,cis-9,12-octadecadienoic acid, 18 2d9,12) and a-linolenic acid (all-cis-9,12,15-octadecatrienoic acid 18 3d9,12,15). The numbering in this conventional system begins with the carboxyl group. The "short hand," for example 18 2d9,12, indicates 18 carbon atoms, with two double bonds located between carbon atoms 9 and 10 and 12 and 13. There is an alternative system of numbering in which fatty acids are numbered from the methyl (or a>) terminal. In this case, linoleic acid is designated a>-6,9-octadecadienoic acid (18 2ft)6), and a-linolenic acid is o>-3,6,9-octadecatrienoic acid (18 3ft)3). This serves to designate two unsaturated fatty acid families, the ft)6 and the a families. 

See Fig. 13-9. The carbon chain of linoleic acid is desaturated at position 6. y-Linolenic acid is elongated by two carbon units, and then another double bond is introduced in the C2o chain at position 5. 

What is important though is that the double bonds are separated by one and only one single bond. Remember the unsaturated fatty acid, linoleic acid, that you met in Chapter 3 Another fatty acid with even more unsaturation is arachidonic acid. None of the four double bonds in this structure are conjugated since in between any two double bonds there is an sp3 carbon. This means there is no p orbital available to overlap with the ones from the double bonds. The saturated carbon atoms insulate the double bonds from each other. 

The products obtained from the co-6 fatty acids (linoleic acid, y-linolenic acid, and arachidonic acid) by in vivo reactions with strain ALA2 contain diepoxy bicyclic structures, tetrahydrofuranyl rings, and/or trihydroxy groups in their molecules. In contrast to these co-6 PUFAs, substrates classified as co-3 PUFAs (a-linolenic acid, EPA, and DHA) are only converted to hydroxyl THFAs by strain ALA2 with no diepoxy bicyclic or trihydroxy derivatives uncovered to date. Both the hydroxyl groups and cyclic structures derived there from appear to be placed at the same positions on the substrates from the co-carbon termini within each PUFA class, despite differences in carbon chain length and the number of double bonds in the specific PUFA substrates. 

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