Fatty acid

2007 Schools Wikipedia Selection. Related subjects: Food and agriculture; Health and medicine

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, while 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.

Industrially, 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.

Types of fatty acids

Several fatty acid molecules

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

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 either in a cis- or trans- conformation and 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, rather it makes it mono- or polyunsaturated.

Most commonly occurring saturated fatty acids are:

This is a computer generated image of Dodecanoic Acid, a fatty acid.

• Butyric (butanoic acid): CH₃(CH₂)₂COOH or C4:0
• Caproic (hexanoic acid): CH₃(CH₂)₄COOH or C6:0
• Caprylic (octanoic acid): CH₃(CH₂)₆COOH or C8:0
• Capric (decanoic acid): CH₃(CH₂)₈COOH or C10:0
• Lauric (dodecanoic acid): CH₃(CH₂)₁₀COOH or C12:0
• Myristic (tetradecanoic acid): CH₃(CH₂)₁₂COOH or C14:0
• Palmitic (hexadecanoic acid): CH₃(CH₂)₁₄COOH or C16:0
• Stearic (octadecanoic acid): CH₃(CH₂)₁₆COOH or C18:0
• Arachidic (eicosanoic acid): CH₃(CH₂)₁₈COOH or C20:0
• Behenic (docosanoic acid): CH₃(CH₂)₂₀COOH or C22:0

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 singly- bonded " -CH₂-CH₂-" part of the chain with a doubly-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 the two carbons 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, while 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 don't 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 (eg, 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 is biological processes, and in the construction of biological structures (such as cell membranes).

Nomenclature

There are two 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 carboxyl terminus. The cis or trans notation indicates whether the molecule is arranged in a cis or trans conformation. In the case of a molecule 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 substituted with a lowercase letter n, making it n-6 or n-3.

Examples of unsaturated fatty acids:

• Oleic acid: CH₃(CH₂)₇CH=CH(CH₂)₇COOH or cis-Δ⁹ C18:1
• Linoleic acid: CH₃(CH₂)₄CH=CHCH₂CH=CH(CH₂)₇COOH or C18:2
• Alpha-linolenic acid: CH₃CH₂CH=CHCH₂CH=CHCH₂CH=CH(CH₂)₇COOH or C18:3
• Arachidonic acid CH₃(CH₂)₄CH=CHCH₂CH=CHCH₂CH=CHCH₂CH=CH(CH₂)₃COOH ^NIST or C20:4
• Eicosapentaenoic acid or C20:5
• Docosahexaenoic acid or C22:6
• Erucic acid: CH₃(CH₂)₇CH=CH(CH₂)₁₁COOH or C22:1

Alpha-linolenic, docosahexaenoic, and eicosapentaenoic acids are examples of omega-3 fatty acids. Linoleic acid and arachidonic acid are omega-6 fatty acids. Oleic and erucic acid are omega-9 fatty acids. Stearic and oleic acid are both 18 C fatty acids. They differ only in that stearic acid is saturated with hydrogen, while oleic acid is an unsaturated fatty acid with two fewer hydrogens.

Essential fatty acids

The human body can produce all but two of the fatty acids it needs. These two, linoleic acid and alpha-linolenic acid, are widely distributed in plant and fish oils. Since they cannot be made in the body from other substrates and must be supplied in food, they are called essential fatty acids. 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 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 to be associated with depression and behavioral change, including violence. The actual connection, if any, is still under investigation. Further, changing to a more natural diet, or consumption of supplements to compensate for a dietary imbalance, has been associated with reduced violent behaviour 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 as well as a double blind study in a prison.

Trans fatty acids

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 increasing amounts of trans fats are, for causal reasons not well understood, correlate with circulatory diseases such as atherosclerosis and coronary heart disease, than the same amount of non-trans fats.

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).

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. However, heart and skeletal muscle prefer fatty acids. On the other hand, the brain cannot use fatty acids as a source of fuel, relying instead on glucose, or on ketone bodies produced by the liver from fatty acid metabolism during starvation, or periods of low carbohydrate intake.

Fatty acids in dietary fats

The following table gives the fatty acid and cholesterol composition of some common dietary fats.

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 only has relevance 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 additionally 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.

Auto-oxidation and rancidity

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.