Fatty acid

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In chemistry, especially biochemistry, a fatty acid is a carboxylic acid often with a long unbranched aliphatic tail (chain), which is either saturated or unsaturated. Carboxylic acids as short as butyric acid (4 carbon atoms) are considered to be fatty acids, whereas fatty acids derived from natural fats and oils may be assumed to have at least 8 carbon atoms, e.g., caprylic acid (octanoic acid). Most of the natural fatty acids have an even number of carbon atoms, because their biosynthesis involves acetyl-CoA, a coenzyme carrying a two-carbon-atom group (see fatty acid synthesis).

In industry, fatty acids are produced by the hydrolysis of the ester linkages in a fat or biological oil (both of which are triglycerides), with the removal of glycerol. See oleochemicals.

Definition

Fatty acids are aliphatic monocarboxylic acids, derived from, or contained in esterified form in an animal or vegetable fat, oil or wax. Natural fatty acids commonly have a chain of 4 to 28 carbons (usually unbranched and even numbered), which may be saturated or unsaturated. By extension, the term is sometimes used to embrace all acyclic aliphatic carboxylic acids.^[1]

Types

Three dimensional representations of several fatty acids

Fatty acids can be saturated and unsaturated, depending on double bonds. In addition, they also differ in length.

Saturated fatty acids

Saturated fatty acids do not contain any double bonds or other functional groups along the chain. The term "saturated" refers to hydrogen, in that all carbons (apart from the carboxylic acid [-COOH] group) contain as many hydrogens as possible. In other words, the omega (ω) end contains 3 hydrogens (CH₃-), and each carbon within the chain contains 2 hydrogen atoms.

Saturated fatty acids form straight chains and, as a result, can be packed together very tightly, allowing living organisms to store chemical energy very densely. The fatty tissues of animals contain large amounts of long-chain saturated fatty acids. In IUPAC nomenclature, fatty acids have an [-oic acid] suffix. In common nomenclature, the suffix is usually -ic.

The shortest descriptions of fatty acids include only the number of carbon atoms and double bonds in them (e.g., C18:0 or 18:0). C18:0 means that the carbon chain of the fatty acid consists of 18 carbon atoms, and there are no (zero) double bonds in it, whereas C18:1 describes an 18-carbon chain with one double bond in it. Each double bond can be in either a cis- or trans- conformation, and stands in a different position with respect to the ends of the fatty acid; therefore, not all C18:1s (for example) are identical. If there is one or more double bonds in the fatty acid, it is no longer considered saturated, but rather, mono- or polyunsaturated.

Most commonly-occurring saturated fatty acids are of the following varieties:

Unsaturated fatty acids

Unsaturated fatty acids are of similar form, except that one or more alkenyl functional groups exist along the chain, with each alkene substituting a single-bonded " -CH₂-CH₂-" part of the chain with a double-bonded "-CH=CH-" portion (that is, a carbon double-bonded to another carbon).

The two next carbon atoms in the chain that are bound to either side of the double bond can occur in a cis or trans configuration.

cis 

A cis configuration means that adjacent carbon atoms are on the same side of the double bond. The rigidity of the double bond freezes its conformation and, in the case of the cis isomer, causes the chain to bend and restricts the conformational freedom of the fatty acid. The more double bonds the chain has in the cis configuration, the less flexibility it has. When a chain has many cis bonds, it becomes quite curved in its most accessible conformations. For example, oleic acid, with one double bond, has a "kink" in it, whereas linoleic acid, with two double bonds, has a more pronounced bend. Alpha-linolenic acid, with three double bonds, favors a hooked shape. The effect of this is that, in restricted environments, such as when fatty acids are part of a phospholipid in a lipid bilayer, or triglycerides in lipid droplets, cis bonds limit the ability of fatty acids to be closely packed, and therefore could affect the melting temperature of the membrane or of the fat.

trans 

A trans configuration, by contrast, means that the next two carbon atoms are bound to opposite sides of the double bond. As a result, they do not cause the chain to bend much, and their shape is similar to straight saturated fatty acids.

In most naturally-occurring unsaturated fatty acids, each double bond has 3n carbon atoms after it, for some n, and all are cis bonds. Most fatty acids in the trans configuration (trans fats) are not found in nature and are the result of human processing (e.g., hydrogenation).

The differences in geometry between the various types of unsaturated fatty acids, as well as between saturated and unsaturated fatty acids, play an important role in biological processes, and in the construction of biological structures (such as cell membranes).

Nomenclature

There are several different ways to make clear where the double bonds are located in molecules. For example:

• cis/trans-Delta-x or cis/trans-Δ^x: The double bond is located on the xth carbon-carbon bond, counting from the carboxylic acid end. The cis or trans notation indicates whether the molecule is arranged in a cis or trans conformation. In the case of a molecule's having more than one double bond, the notation is, for example, cis,cis-Δ⁹,Δ¹².
• Omega-x or ω-x : A double bond is located on the xth carbon-carbon bond, counting from the ω, (methyl carbon) end of the chain. Sometimes, the symbol ω is replaced with a lowercase letter n.
• In IUPAC nomenclature, a systematic naming system for all chemical compounds, counting begins from the carboxylic acid end and cis double bonds are labelled Z and trans double bonds are labelled E. (See IUPAC nomenclature of organic chemistry for details.)

Examples of unsaturated fatty acids:

Alpha-linolenic, docosahexaenoic, and eicosapentaenoic acids are examples of omega-3 fatty acids. Linoleic acid and arachidonic acid are omega-6 fatty acids. Myristoleic is omega-5 fatty acid, palmitoleic is omega-7 fatty acid, and oleic and erucic acid are omega-9 fatty acids. Stearic and oleic acid are both C18 fatty acids. They differ only in that stearic acid is saturated with hydrogen, whereas oleic acid is an unsaturated fatty acid with two fewer hydrogens.

Essential fatty acids

Main article: Essential fatty acid

The human body can produce all but two of the fatty acids it needs. These two, linoleic acid (LA) and alpha-linolenic acid (ALA), are widely distributed in plant oils. In addition, fish oils contain the longer-chain omega-3 fatty acids eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Other marine oils, such as from seal, also contain significant amounts of docosapentaenoic acid (DPA), which is also an omega-3 fatty acid. Although the body to some extent can convert LA and LNA into these longer-chain omega-3 fatty acids, the omega-3 fatty acids found in marine oils help fulfill the requirement of essential fatty acids (and have been shown to have wholesome properties of their own).

Since they cannot be made in the body from other substrates and must be supplied in food, they are called essential fatty acids. Mammals lack the ability to introduce double bonds in fatty acids beyond carbons 9 and 10. Hence linoleic acid and alpha-linolenic acid are essential fatty acids for humans.

In the body, essential fatty acids are primarily used to produce hormone-like substances that regulate a wide range of functions, including blood pressure, blood clotting, blood lipid levels, the immune response, and the inflammation response to injury infection.

Essential fatty acids are polyunsaturated fatty acids and are the parent compounds of the omega-6 and omega-3 fatty acid series, respectively. They are essential in the human diet because there is no synthetic mechanism for them. Humans can easily make saturated fatty acids or monounsaturated fatty acids with a double bond at the omega-9 position, but do not have the enzymes necessary to introduce a double bond at the omega-3 position or omega-6 position.

The essential fatty acids are important in several human body systems, including the immune system and in blood pressure regulation, since they are used to make compounds such as prostaglandins. The brain has increased amounts of linolenic and alpha-linoleic acid derivatives. Changes in the levels and balance of these fatty acids due to a typical Western diet rich in omega-6 and poor in omega-3 fatty acids is alleged"Study Links Brain Fatty Acid Levels To Depression", ScienceDaily, Bethesda, MD: American Society For Biochemistry And Molecular Biology, 2005-05-25. Retrieved on 2008-01-18.  to be associated with depression and behavioral change, including violence. The actual connection, if any, is still under investigation. Further, changing to a diet richer in omega-3 fatty acids, or consumption of supplements to compensate for a dietary imbalance, has been associated with reduced violent behavior^[2] and increased attention span, but the mechanisms for the effect are still unclear. So far, at least three human studies have shown results that support this: two school studies^{[citation needed][3]} as well as a double blind study in a prison.^[2][4][5]

Fatty acids play an important role in the life and death of cardiac cells because they are essential fuels for mechanical and electrical activities of the heart. ^{[6] [7] [8] [9]}

Trans fatty acids

Main article: Trans fat

A trans fatty acid (commonly shortened to trans fat) is an unsaturated fatty acid molecule that contains a trans double bond between carbon atoms, which makes the molecule less 'kinked' in comparison to fatty acids with cis double bonds. These bonds are characteristically produced during industrial hydrogenation of plant oils. Research suggests that amounts of trans fats correlate with circulatory diseases such as atherosclerosis and coronary heart disease more than the same amount of non-trans fats, for reasons that are not well understood.

Long and short

In addition to saturation, fatty acids are short, medium or long.

• Short chain fatty acids (SCFA) are fatty acids with aliphatic tails of less than eight carbons.
• Medium chain fatty acids (MCFA) are fatty acids with aliphatic tails of 8–14 ^[10] carbons.
  • Long chain fatty acids (LCFA) are fatty acids with aliphatic tails 16 carbons or more^[10].

    When discussing essential fatty acids, (EFA) a slightly different terminology applies. Short-chain EFA are 18 carbons long; long-chain EFA have 20 or more carbons.^[11]

    Free fatty acids

    Fatty acids can be bound or attached to other molecules, such as in triglycerides or phospholipids. When they are not attached to other molecules, they are known as "free" fatty acids.

    The uncombined fatty acids or free fatty acids may come from the breakdown of a triglyceride into its components (fatty acids and glycerol). However as fats are insoluble in water they must be bound to appropriate regions in the plasma protein albumin for transport around the body. The levels of "free fatty acid" in the blood are limited by the number of albumin binding sites available.

    Free fatty acids are an important source of fuel for many tissues since they can yield relatively large quantities of ATP. Many cell types can use either glucose or fatty acids for this purpose. In particular, heart and skeletal muscle prefer fatty acids. The brain cannot use fatty acids as a source of fuel; it relies on glucose, or on ketone bodies. Ketone bodies are produced in the liver by fatty acid metabolism during starvation, or during periods of low carbohydrate intake.

    Fatty acids in dietary fats

    The following table gives the fatty acid, vitamin E and cholesterol composition of some common dietary fats.^{[12] [13]}

    	Saturated	Monounsaturated	Polyunsaturated	Cholesterol	Vitamin E
    	g/100g	g/100g	g/100g	mg/100g	mg/100g
    Animal fats
    Lard	40.8	43.8	9.6	93	0.00
    Butter	54.0	19.8	2.6	230	2.00
    Vegetable fats
    Coconut oil	85.2	6.6	1.7	0	.66
    Palm oil	45.3	41.6	8.3	0	33.12
    Cottonseed oil	25.5	21.3	48.1	0	42.77
    Wheat germ oil	18.8	15.9	60.7	0	136.65
    Soya oil	14.5	23.2	56.5	0	16.29
    Olive oil	14.0	69.7	11.2	0	5.10
    Corn oil	12.7	24.7	57.8	0	17.24
    Sunflower oil	11.9	20.2	63.0	0	49.0
    Safflower oil	10.2	12.6	72.1	0	40.68
    Rapeseed/Canola oil	5.3	64.3	24.8	0	22.21

    Acidity

    Short chain carboxylic acids such as formic acid and acetic acid are miscible with water and dissociate to form reasonably strong acids (pK_a 3.77 and 4.76, respectively). Longer-chain fatty acids do not show a great change in pK_a. Nonanoic acid, for example, has a pK_a of 4.96. However, as the chain length increases the solubility of the fatty acids in water decreases very rapidly, so that the longer-chain fatty acids have very little effect on the pH of a solution. The significance of their pK_a values therefore has relevance only to the types of reactions in which they can take part.

    Even those fatty acids that are insoluble in water will dissolve in warm ethanol, and can be titrated with sodium hydroxide solution using phenolphthalein as an indicator to a pale-pink endpoint. This analysis is used to determine the free fatty acid content of fats, i.e., the proportion of the triglycerides that have been hydrolyzed.

    Reaction of fatty acids

    Fatty acids react just like any other carboxylic acid, which means they can undergo esterification and acid-base reactions. Reduction of fatty acids yields fatty alcohols. Unsaturated fatty acids can also undergo addition reactions, most commonly hydrogenation, which is used to convert vegetable oils into margarine. With partial hydrogenation, unsaturated fatty acids can be isomerized from cis to trans configuration. In the Varrentrapp reaction certain unsaturated fatty acids are cleaved in molten alkali, a reaction at one time of relevance to structure elucidation.

    Auto-oxidation and rancidity

    Main article: Rancidification

    Fatty acids at room temperature undergo a chemical change known as auto-oxidation. The fatty acid breaks down into hydrocarbons, ketones, aldehydes, and smaller amounts of epoxides and alcohols. Heavy metals present at low levels in fats and oils promote auto-oxidation. Fats and oils often are treated with chelating agents such as citric acid.

    Circulation

    Digestion and intake

    Main article: Digestion#Fat digestion

    Short- and medium chain fatty acids are absorbed directly into the blood via intestine capillaries and travel through the portal vein just as other absorbed nutrients do. However, long chain fatty acids are too large to be directly released into the tiny intestine capillaries. Instead they are absorbed into the fatty walls of the intestine villi and reassembled again into triglycerides. The triglycerides are coated with cholesterol and protein (protein coat) into a compound called a chylomicron.

    Within the villi, the chylomicron enters a lymphatic capillary called a lacteal, which merges into larger lymphatic vessels. It is transported via the lymphatic system and the thoracic duct up to a location near the heart (where the arteries and veins are larger). The thoracic duct empties the chylomicrons into the bloodstream via the left subclavian vein. At this point the chylomicrons can transport the triglycerides to where they are needed.

    Distribution

    Main article: Blood fatty acids

    Blood fatty acids are in different forms in different stages in the blood circulation. They are taken in through the intestine in chylomicrons, but also exist in very low density lipoproteins (VLDL) and low density lipoproteins (LDL) after processing in the liver. In addition, when released from adipocytes, fatty acids exist in the blood as free fatty acids.

    References

    1. ^ (1997) The Gold Book, 2nd, IUPAC Compendium of Chemical Terminology, International Union of Pure and Applied Chemistry. Retrieved on 2007-10-31. 
    2. ^ ^{a b} C. Bernard Gesch, CQSW Sean M. Hammond, PhD Sarah E. Hampson, PhD Anita Eves, PhD Martin J. Crowder, PhD (2002). "Influence of supplementary vitamins, minerals and essential fatty acids on the antisocial behavior of young adult prisoners". The British Journal of Psychiatry 181: 22-28. Retrieved on 2006-06-27. 
    3. ^ Alexandra J. Richardson and Paul Montgomery (2005). "The Oxford-Durham study: a randomized controlled trial of dietary supplementation with fatty acids in children with developmental coordination disorder". Pediatrics 115 (5): 1360 - 1366. doi:10.1542/peds.2004-2164. Retrieved on 2006-06-27. 
    4. ^ Lawrence, Felicity (2004). in Kate Barker: Not on the Label. Penguin, 213. ISBN 0-14-101566-7. 
    5. ^ Using Fatty Acids for Enhancing Classroom Achievement. Retrieved on January, 2004.
    6. ^ E Honoré, J Barhanin, B Attali, F Lesage, and M Lazdunski (1994 March 1). "External blockade of the major cardiac delayed-rectifier K+ channel (Kv1.5) by polyunsaturated fatty acids.". Proc Natl Acad Sci U S A 91(5): 1937–1941. Retrieved on 2007-01-18.  - see page 1 of this link
    7. ^ Reiffel JA, McDonald A (2006). "Antiarrhythmic effects of omega-3 fatty acids". Am. J. Cardiol. 98 (4A): 50i–60i. doi:10.1016/j.amjcard.2005.12.027. PMID 16919517. Retrieved on 2007-12-04. 
    8. ^ Landmark K, Alm CS (2006). "Alpha-linolenic acid, cardiovascular disease and sudden death" (in Norwegian). Tidsskr. Nor. Laegeforen. 126 (21): 2792–4. PMID 17086218. Retrieved on 2007-12-04. 
    9. ^ Herbaut C (2006). "Omega-3 and health" (in French). Rev Med Brux 27 (4): S355–60. PMID 17091903. Retrieved on 2007-12-04. 
    10. ^ ^{a b} Short term effects of dietary medium-chain fatty acids and n-3 long-chain polyunsaturated fatty acids on the fat metabolism of healthy volunteers Christopher Beermann1 , J Jelinek1 , T Reinecker2 , A Hauenschild2 , G Boehm1 and H-U Klör2
    11. ^ Health Facts About Good Fats : The Basics : Omega-3s, Mono & Polyunsaturated Fatty Acids. Fats of Life Newsletter. Retrieved on 2007-12-12.
    12. ^ Food Standards Agency (1991). "Fats and Oils", McCance & Widdowson's The Composition of Foods. Royal Society of Chemistry. 
    13. ^ Ted Altar. More Than You Wanted To Know About Fats/Oils. Sundance Natural Foods Online. Retrieved on 2006-08-31.

    
    

    See also

    

    Wikimedia Commons has media related to:

    Fatty acids
    • Essential fatty acid
    • Saturated fat
    • Unsaturated fat
    • Fatty acid synthase
    • Fatty acid metabolism
    • Vegetable oils

    External links

    • Lipid Library
    • Chemical Structure of Fats and Fatty Acids
    • Plant Oils and Fats, from the Cyberlipid Center Web site
    • Prostaglandins, Leukotrienes & Essential Fatty Acids Journal
    • Fat content and fatty acid composition of seed oils. Retrieved on 2006-10-07. From Udo Erasmus' book, Fats that Heal Fats that Kill

    v • d • e Lipids: fatty acids
    Saturated	Butyric - Hexanoic - Caprylic - Decanoic - Lauric - Myristic - Palmitic - Stearic - Arachidic - Behenic - Lignoceric
    Omega-3 fatty acid	Alpha-linolenic - Stearidonic acid - Eicosapentaenoic acid - Docosahexaenoic acid
    Omega-6 fatty acid	Linoleic - Gamma-Linolenic acid - Dihomo-gamma-linolenic acid - Arachidonic
    Omega-9 fatty acid	Oleic - Erucic

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