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).
Types of fatty acids
Three dimensional representations of several fatty acids
[edit] 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 in either 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 mono- or polyunsaturated.
Most commonly-occurring saturated fatty acids are:
Common name IUPAC name Chemical structure Abbr.
Butyric Butanoic acid CH3(CH2)2COOH C4:0
Caproic Hexanoic acid CH3(CH2)4COOH C6:0
Caprylic Octanoic acid CH3(CH2)6COOH C8:0
Capric Decanoic acid CH3(CH2)8COOH C10:0
Lauric Dodecanoic acid CH3(CH2)10COOH C12:0
Myristic Tetradecanoic acid CH3(CH2)12COOH C14:0
Palmitic Hexadecanoic acid CH3(CH2)14COOH C16:0
Stearic Octadecanoic acid CH3(CH2)16COOH C18:0
Arachidic Eicosanoic acid CH3(CH2)18COOH C20:0
Behenic Docosanoic acid CH3(CH2)20COOH C22:0
[edit] Unsaturated fatty acids
Comparison of the trans isomer (top) and the cis-isomer of oleic acid.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).
[edit] 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-Δx: 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, making it n-6 or n-3.
In IUPAC nomenclature, a systematic naming system for all chemical compounds, counting is 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:
Common name Chemical structure ω Δ Abbr.
Myristoleic acid: CH3(CH2)3CH=CH(CH2)7COOH ω-5 cis-Δ5 C14:1
Palmitoleic acid: CH3(CH2)5CH=CH(CH2)7COOH ω-7 cis-Δ7 C16:1
Oleic acid: CH3(CH2)7CH=CH(CH2)7COOH ω-9 cis-Δ9 C18:1
Linoleic acid: CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH ω-6 cis, cis-Δ6, Δ9 C18:2
Alpha-linolenic acid: CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH ω-3 cis, cis, cis-Δ3, Δ6, Δ9 C18:3
Arachidonic acid CH3(CH2)4CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3COOHNIST ω-6 cis, cis, cis, cis-Δ6, Δ9, Δ12, Δ15 C20:4
Eicosapentaenoic acid CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3COOH ω-3 cis, cis, cis, cis, cis-Δ3, Δ6, Δ9, Δ12, Δ15 C20:5
Erucic acid: CH3(CH2)7CH=CH(CH2)11COOH ω-9 cis-Δ9 C22:1
Docosahexaenoic acid CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)2COOH ω-3 cis, cis, cis, cis, cis, cis-Δ3, Δ6, Δ9, Δ12, Δ15, Δ18 C22:6
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.
[edit] 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 (LNA), 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 fulfil 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 linoleinic 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[citation needed] 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[1] 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][2] as well as a double blind study in a prison.[1][3][4]
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. [5] [6] [7] [8]
[edit] 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.
[edit] 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. 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.
[edit] Fatty acids in dietary fats
The following table gives the fatty acid and cholesterol composition of some common dietary fats.[9] [10]
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
[edit] Acidity
Short chain carboxylic acids such as formic acid and acetic acid are miscible with water and dissociate to form reasonably strong acids (pKa 3.77 and 4.76, respectively). Longer-chain fatty acids do not show a great change in pKa. Nonanoic acid, for example, has a pKa 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 pKa 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.
[edit] 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.
[edit] 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.
Lipids can be broadly defined as any fat-soluble (hydrophobic), naturally-occurring molecules. The term is more-specifically used to refer to fatty-acids and their derivatives (including tri-, di-, and monoglycerides and phospholipids) as well as other fat-soluble sterol-containing metabolites such as cholesterol.
Lipids have many functions in living organisms including nutrients, energy storage, structural components of cell membranes, and important signaling molecules. Although the term lipid is sometimes used as a synonym for fat, fats are in fact a subgroup of lipids called triglycerides and should not be confused with the term fatty acid.
Fatty acids and glycerides
Main article: fatty acid
Chemically, fatty acids can be described as long-chain monocarboxylic acids the saturated examples of which have a general structure of CH3(CH2)nCOOH. The length of the chain usually ranges from 12 to 24, always with an even number of carbon atoms. When the carbon chain contains no double bonds, it is a saturated chain. If it contains one or more such bonds, it is unsaturated. The presence of double bonds reduces the melting point of fatty acids. Furthermore, unsaturated fatty acids can occur either in cis or trans geometric isomers. In naturally occurring fatty acids, the double bonds are in the cis-configuration.
Glycerides are lipids possessing a glycerol (another name for which is propan-1, 2, 3-triol) core structure with one or more fatty acyl groups, which are fatty acid-derived chains attached to the glycerol backbone by ester linkages. Glycerides with three acyl groups (triglycerides or neutral fats) are the main form of fatty energy storage in animals and plants.
An important type of glyceride-based molecule found in biological membranes, such as the cell's plasma membrane and the intracellular membranes of organelles, are the phosphoglycerides or glycerophospholipids. These are phospholipids that contain a glycerol core linked to two fatty acid-derived "tails" by ester or, more rarely, ether linkages and to one "head" group by a phosphate ester linkage. The head groups of the phospholipids found in biological membranes are phosphatidylcholine (also known as PC, and lecithin), phosphatidylethanolamine (PE), phosphatidylserine and phosphatidylinositol (PI). These phospholipids are subject to a variety of functions in the cell: for instance, the lipophilic and polar ends can be released from particular phospholipids through enzyme-catalysed hydrolysis to generate secondary messengers involved in signal transduction. In the case of phosphatidylinositol, the head group can be enzymatically modified by the addition of one, two or three phosphate groups, this constituting another mechanism of cell signalling. While phospholipids are the major component of biological membranes, other non-glyceride lipid components like sphingolipids and sterols (such as cholesterol in animal cell membranes) are also found in biological membranes.
A biological membrane is a form of lipid bilayer, as is a liposome. The formation of lipid bilayers is an energetically-preferred process when the glycerophospholipids described above are in an aqueous environment. In an aqueous system, the polar heads of lipids orientate towards the polar, aqueous environment, while the hydrophobic tails minimise their contact with water. The lipophilic tails of lipids (U) tend to cluster together, forming a lipid bilayer (1) or a micelle (2). Other aggregations are also observed and form part of the polymorphism of amphiphile (lipid) behaviour. The polar heads (P) face the aqueous environment, curving away from the water. Phase behaviour is a complicated area within biophysics and is the subject of current academic research.
Micelles and bilayers form in the polar medium by a process known as the lipophilic effect. When dissolving a lipophilic or amphiphilic substance in a polar environment, the polar molecules (i.e. water in an aqueous solution) become more ordered around the dissolved lipophilic substance, since the polar molecules cannot form hydrogen bonds to the lipophilic areas of the amphiphile. So in an aqueous environment the water molecules form an ordered "clathrate" cage around the dissolved lipophilic molecule.
Figure 2: Self-organization of phospholipids. A lipid bilayer is shown on the left and a micelle on the right.The self-organisation depends on the concentration of the lipid present in solution. Below the critical micelle concentration, the lipids form a single layer on the liquid surface and are (sparingly) dispersed in the solution. At the first critical micelle concentration (CMC-I), the lipids organise in spherical micelles, at given points above this concentration, other phases are observed (see lipid polymorphism).
[edit] Nutrition and health
Lipids play diverse and important roles in nutrition and health. Many lipids are absolutely essential for life, however, there is also considerable awareness that abnormal levels of certain lipids, particularly cholesterol (in hypercholesterolemia) and, more recently, fatty acids with trans fatty acids, are risk factors for heart disease amongst others. We need fats in our bodies and certain types in our diet. Animals in general use fat for energy storage because fat stores 9 KCal/g of energy. Plants, which do not require energy for movement, can afford to store food for energy in a less compact but more easily accessible form, so they have evolved to use starch, a carbohydrate, (not a lipid) for energy storage. Carbohydrates and proteins store only 4 KCal/g of energy, so fat stores over twice as much energy/gram as other sources of energy. Furthermore, lipids can be stored in an anhydrous form whereas carbohydrates typically cannot, which means that anhydrous lipid stores about 6 times as much energy per weight as hydrated carbohydrates. As an example, a typical 70 kg man would have to weigh approximately 125 kg if his energy stores were converted from triacylglycerol to glycogen.
The baby formula brands Enfamil and Similac offer versions with lipids (DHA and ARA) added to the base formula.
[edit] Types of Lipids
Fat - Fats consist of a wide group of compounds that are generally soluble in organic solvents and largely insoluble in water. Chemically, fats are generally triesters of glycerol and fatty acids. Fats may be either solid or liquid at normal room temperature, depending on their structure and composition. Although the words "oils", "fats" and "lipids" are all used to refer to fats, "oils" is usually used to refer to fats that are liquids at normal room temperature, while "fats" is usually used to refer to fats that are solids at normal room temperature. "Lipids" is used to refer to both liquid and solid fats. The word "oil" is used for any substance that does not mix with water and has a greasy feel, such as petroleum (or crude oil) and heating oil, regardless of its chemical structure.
Phospholipid are a class of lipids, and a major component of all biological membranes, along with glycolipids, cholesterol and proteins. Understanding of the aggregation properties of these molecules is known as lipid polymorphism and forms part of current academic research.
Steroids - A steroid is a terpenoid lipid characterized by a carbon skeleton with four fused rings, generally arranged in a 6-6-6-5 fashion.
2007-10-15 16:02:34
·
answer #7
·
answered by wierdos!!! 4
·
1⤊
0⤋