Unsaturated fat

An unsaturated fat is a fat or fatty acid in which there is at least one double bond within the fatty acid chain. A fatty acid chain is monounsaturated if it contains one double bond, and polyunsaturated if it contains more than one double bond.

Where double bonds are formed, hydrogen atoms are subtracted from the carbon chain. Thus, a saturated fat has no double bonds, has the maximum number of hydrogens bonded to the carbons, and therefore is "saturated" with hydrogen atoms. In cellular metabolism, unsaturated fat molecules contain somewhat less energy (i.e., fewer calories) than an equivalent amount of saturated fat. The greater the degree of unsaturation in a fatty acid (i.e., the more double bonds in the fatty acid) the more vulnerable it is to lipid peroxidation (rancidity). Antioxidants can protect unsaturated fat from lipid peroxidation.

Chemistry and nutrition

Amounts of fat types in selected foods

Double bonds may be in either a cis or a trans isomer, depending on the geometry of the double bond. In the cis isomer, hydrogen atoms are on the same side of the double bond; whereas in the trans isomer, they are on opposite sides of the double bond (see trans fat). Saturated fats are useful in processed foods because saturated fats are less vulnerable to rancidity and usually more solid at room temperature than unsaturated fats. Unsaturated chains have a lower melting point, hence these molecules increase the fluidity of cell membranes.

Although both monounsaturated and polyunsaturated fats can replace saturated fat in the diet, trans unsaturated fats should not. Replacing saturated fats with unsaturated fats helps lower levels of total cholesterol and LDL cholesterol in the blood.[1] Trans unsaturated fats are an exception because the double bond stereochemistry predisposes the carbon chains to assume a linear conformation, which conforms to rigid packing as in plaque formation. The geometry of the cis double bond induces a bend in the molecule, thereby precluding rigid formations (see Trans fat § Chemistry links above for drawings that illustrate this). Natural sources of fatty acids (see above) are rich in the cis isomer.

Although polyunsaturated fats are protective against cardiac arrhythmias, a study of post-menopauseal women with a relatively low fat intake showed that polyunsaturated fat is positively associated with progression of coronary atherosclerosis, whereas monounsaturated fat is not.[2] This probably is an indication of the greater vulnerability of polyunsaturated fats to lipid peroxidation, against which vitamin E has been shown to be protective.[3]

Examples of unsaturated fatty acids are palmitoleic acid, oleic acid, myristoleic acid, linoleic acid, and arachidonic acid. Foods containing unsaturated fats include avocado, nuts, olive oils, and vegetable oils such as canola. Meat products contain both saturated and unsaturated fats.

Although unsaturated fats are conventionally regarded as 'healthier' than saturated fats,[4] the United States Food and Drug Administration (FDA) recommendation stated that the amount of unsaturated fat consumed should not exceed 30% of one's daily caloric intake. Most foods contain both unsaturated and saturated fats. Marketers advertise only one or the other, depending on which one makes up the majority. Thus, various unsaturated fat vegetable oils, such as olive oils, also contain saturated fat.[5]

In chemical analysis, fatty acids are separated by gas chromatography of methyl esters;[6] additionally, a separation of unsaturated isomers is possible by argentation thin-layer chromatography.[7]

Role of dietary fats in insulin resistance

Incidence of insulin resistance is lowered with diets higher in monounsaturated fats (especially oleic acid), while the opposite is true for diets high in polyunsaturated fats (especially large amounts of arachidonic acid) as well as saturated fats (such as arachidic acid). These ratios can be indexed in the phospholipids of human skeletal muscle and in other tissues as well. This relationship between dietary fats and insulin resistance is presumed secondary to the relationship between insulin resistance and inflammation, which is partially modulated by dietary fat ratios (Omega-3/6/9) with both omega 3 and 9 thought to be anti-inflammatory, and omega 6 pro-inflammatory (as well as by numerous other dietary components, particularly polyphenols and exercise, with both of these anti-inflammatory). Although both pro- and anti-inflammatory types of fat are biologically necessary, fat dietary ratios in most US diets are skewed towards Omega 6, with subsequent disinhibition of inflammation and potentiation of insulin resistance.[5] But this is contrary to the suggestion of more recent studies, in which polyunsaturated fats are shown as protective against insulin resistance.

Membrane composition as a metabolic pacemaker

Studies on the cell membranes of mammals and reptiles discovered that mammalian cell membranes are composed of a higher proportion of polyunsaturated fatty acids (DHA, omega-3 fatty acid) than reptiles.[20] Studies on bird fatty acid composition have noted similar proportions to mammals but with 1/3rd less omega-3 fatty acids as compared to omega-6 for a given body size.[21] This fatty acid composition results in a more fluid cell membrane but also one that is permeable to various ions (H+ & Na+), resulting in cell membranes that are more costly to maintain. This maintenance cost has been argued to be one of the key causes for the high metabolic rates and concomitant warm-bloodedness of mammals and birds.[20] However polyunsaturation of cell membranes may also occur in response to chronic cold temperatures as well. In fish increasingly cold environments lead to increasingly high cell membrane content of both monounsaturated and polyunsaturated fatty acids, to maintain greater membrane fluidity (and functionality) at the lower temperatures.[22][23]

See also

• Iodine value – a chemical analysis method to determine the proportion of unsaturated fat.
• List of unsaturated fatty acids

References

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2. Mozaffarian D, Rimm EB, Herrington DM (November 2004). "Dietary fats, carbohydrate, and progression of coronary atherosclerosis in postmenopausal women". The American Journal of Clinical Nutrition. 80 (5): 1175–84. doi:10.1093/ajcn/80.5.1175. PMC 1270002. PMID 15531663.
3. Leibovitz B, Hu ML, Tappel AL (January 1990). "Dietary supplements of vitamin E, beta-carotene, coenzyme Q10 and selenium protect tissues against lipid peroxidation in rat tissue slices". The Journal of Nutrition. 120 (1): 97–104. doi:10.1093/jn/120.1.97. PMID 2303916.
4. Fats and sugars. BBC Health, retrieved 2013-04-07
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6. Aizpurua-Olaizola O, Ormazabal M, Vallejo A, Olivares M, Navarro P, Etxebarria N, et al. (January 2015). "Optimization of supercritical fluid consecutive extractions of fatty acids and polyphenols from Vitis vinifera grape wastes". Journal of Food Science. 80 (1): E101-7. doi:10.1111/1750-3841.12715. PMID 25471637.
7. Breuer B, Stuhlfauth T, Fock HP (July 1987). "Separation of fatty acids or methyl esters including positional and geometric isomers by alumina argentation thin-layer chromatography". Journal of Chromatographic Science. 25 (7): 302–6. doi:10.1093/chromsci/25.7.302. PMID 3611285.
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21. Hulbert AJ, Faulks S, Buttemer WA, Else PL (November 2002). "Acyl composition of muscle membranes varies with body size in birds". The Journal of Experimental Biology. 205 (Pt 22): 3561–9. PMID 12364409.
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23. Raynard RS, Cossins AR (May 1991). "Homeoviscous adaptation and thermal compensation of sodium pump of trout erythrocytes". The American Journal of Physiology. 260 (5 Pt 2): R916–24. doi:10.1152/ajpregu.1991.260.5.R916. PMID 2035703.