Lipid

Lipids are a broad group of organic compounds that include fats, waxes, sterols, fat-soluble vitamins, monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include storing energy, signaling, and acting as structural components of cell membranes. Lipids have applications in the cosmetic and food industries, and in nanotechnology.

Lipids are a broad group of organic compounds that include fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include storing energy, signaling, and acting as structural components of cell membranes.[3][4] Lipids have applications in the cosmetic and food industries, and in nanotechnology.[5]

Lipids are broadly defined as hydrophobic or amphiphilic small molecules; the amphiphilic nature of some lipids allows them to form structures such as vesicles, multilamellar/unilamellar liposomes, or membranes in an aqueous environment. Biological lipids originate entirely or in part from two distinct types of biochemical subunits or "building-blocks": ketoacyl and isoprene groups.[3] Using this approach, lipids may be divided into eight categories: fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, saccharolipids, and polyketides (derived from condensation of ketoacyl subunits); and sterol lipids and prenol lipids (derived from condensation of isoprene subunits).[3]

Although the term lipid is sometimes used as a synonym for fats, fats are a subgroup of lipids called triglycerides. Lipids also encompass molecules such as fatty acids and their derivatives (including tri-, di-, and monoglycerides, and phospholipids), as well as other sterol-containing metabolites such as cholesterol.[6] Although humans and other mammals use various biosynthetic pathways both to break down and to synthesize lipids, some essential lipids cannot be made this way and must be obtained from the diet.

History

In 1815, Henri Braconnot classified lipids (graisses) into two categories, suifs (solid greases or tallow) and huiles (fluid oils).[7] In 1823, Michel Eugène Chevreul developed a more detailed classification, including oils, greases, tallow, waxes, resins, balsams and volatile oils (or essential oils).[8][9][10] In 1827, William Prout recognized fat ("oily" alimentary matters), along with protein ("albuminous") and carbohydrate ("saccharine"), as an important nutrient for humans and animals.[11][12]

The first synthetic triglyceride was reported by Théophile-Jules Pelouze in 1844, when he produced tributyrin by treating butyric acid with glycerin in the presence of concentrated sulfuric acid.[13] Several years later, Marcellin Berthelot, one of Pelouze's students, synthesized tristearin and tripalmitin by reaction of the analogous fatty acids with glycerin in the presence of gaseous hydrogen chloride at high temperature.[14]

For a century, chemists regarded "fats" as only simple lipids made of fatty acids and glycerol (glycerides), but new forms were described later. Theodore Gobley (1847) discovered phospholipids in mammalian brain and hen egg, called by him as "lecithins". Thudichum discovered in the human brain some phospholipids (cephalin), glycolipids (cerebroside) and sphingolipids (sphingomyelin).[9]

The terms lipoid, lipin, lipide and lipid have been used with varied meanings from author to author.[15] In 1912, Rosenbloom and Gies proposed the substitution of "lipoid" by "lipin".[16] In 1920, Bloor introduced a new classification for "lipoids": simple lipoids (greases and waxes), compound lipoids (phospholipoids and glycolipoids), and the derived lipoids (fatty acids, alcohols, sterols).[17][18]

The word lipide, which stems etymologically from Greek λίπος, lipos 'fat', was introduced in 1923 by the French pharmacologist Gabriel Bertrand.[19] Bertrand included in the concept not only the traditional fats (glycerides), but also the "lipoids", with a complex constitution.[9] The word lipide was unanimously approved by the international commission of the Société de Chimie Biologique during the plenary session on July 3, 1923. The word lipide was later anglicized as lipid because of its pronunciation ('lɪpɪd). In French, the suffix -ide, from Ancient Greek -ίδης (meaning 'son of' or 'descendant of'), is always pronounced (ɪd).

In 1947, T. P. Hilditch defined "simple lipids" as greases and waxes (true waxes, sterols, alcohols).[20][page needed]

Categories

Lipids have been classified into eight categories by the Lipid MAPS consortium[3] as follows:

Fatty acids

Fatty acyls, a generic term for describing fatty acids, their conjugates and derivatives, are a diverse group of molecules synthesized by chain-elongation of an acetyl-CoA primer with malonyl-CoA or methylmalonyl-CoA groups in a process called fatty acid synthesis.[21][22] They are made of a hydrocarbon chain that terminates with a carboxylic acid group; this arrangement confers the molecule with a polar, hydrophilic end, and a nonpolar, hydrophobic end that is insoluble in water. The fatty acid structure is one of the most fundamental categories of biological lipids and is commonly used as a building-block of more structurally complex lipids. The carbon chain, typically between four and 24 carbons long,[23] may be saturated or unsaturated, and may be attached to functional groups containing oxygen, halogens, nitrogen, and sulfur. If a fatty acid contains a double bond, there is the possibility of either a cis or trans geometric isomerism, which significantly affects the molecule's configuration. Cis-double bonds cause the fatty acid chain to bend, an effect that is compounded with more double bonds in the chain. Three double bonds in 18-carbon linolenic acid, the most abundant fatty-acyl chains of plant thylakoid membranes, render these membranes highly fluid despite environmental low-temperatures,[24] and also makes linolenic acid give dominating sharp peaks in high resolution 13-C NMR spectra of chloroplasts. This in turn plays an important role in the structure and function of cell membranes.[25]: 193–5  Most naturally occurring fatty acids are of the cis configuration, although the trans form does exist in some natural and partially hydrogenated fats and oils.[26]

Examples of biologically important fatty acids include the eicosanoids, derived primarily from arachidonic acid and eicosapentaenoic acid, that include prostaglandins, leukotrienes, and thromboxanes. Docosahexaenoic acid is also important in biological systems, particularly with respect to sight.[27][28] Other major lipid classes in the fatty acid category are the fatty esters and fatty amides. Fatty esters include important biochemical intermediates such as wax esters, fatty acid thioester coenzyme A derivatives, fatty acid thioester ACP derivatives and fatty acid carnitines. The fatty amides include N-acyl ethanolamines, such as the cannabinoid neurotransmitter anandamide.[29]

Glycerolipids

Glycerolipids are composed of mono-, di-, and tri-substituted glycerols,[30] the best-known being the fatty acid triesters of glycerol, called triglycerides. The word "triacylglycerol" is sometimes used synonymously with "triglyceride". In these compounds, the three hydroxyl groups of glycerol are each esterified, typically by different fatty acids. Because they function as an energy store, these lipids comprise the bulk of storage fat in animal tissues. The hydrolysis of the ester bonds of triglycerides and the release of glycerol and fatty acids from adipose tissue are the initial steps in metabolizing fat.[31]: 630–1 

Additional subclasses of glycerolipids are represented by glycosylglycerols, which are characterized by the presence of one or more sugar residues attached to glycerol via a glycosidic linkage. Examples of structures in this category are the digalactosyldiacylglycerols found in plant membranes[32] and seminolipid from mammalian sperm cells.[33]

Glycerophospholipids

Glycerophospholipids, usually referred to as phospholipids (though sphingomyelins are also classified as phospholipids), are ubiquitous in nature and are key components of the lipid bilayer of cells,[34] as well as being involved in metabolism and cell signaling.[35] Neural tissue (including the brain) contains relatively high amounts of glycerophospholipids, and alterations in their composition has been implicated in various neurological disorders.[36] Glycerophospholipids may be subdivided into distinct classes, based on the nature of the polar headgroup at the sn-3 position of the glycerol backbone in eukaryotes and eubacteria, or the sn-1 position in the case of archaebacteria.[37]

Examples of glycerophospholipids found in biological membranes are phosphatidylcholine (also known as PC, GPCho or lecithin), phosphatidylethanolamine (PE or GPEtn) and phosphatidylserine (PS or GPSer). In addition to serving as a primary component of cellular membranes and binding sites for intra- and intercellular proteins, some glycerophospholipids in eukaryotic cells, such as phosphatidylinositols and phosphatidic acids are either precursors of or, themselves, membrane-derived second messengers.[31]: 844  Typically, one or both of these hydroxyl groups are acylated with long-chain fatty acids, but there are also alkyl-linked and 1Z-alkenyl-linked (plasmalogen) glycerophospholipids, as well as dialkylether variants in archaebacteria.[38]

Sphingolipids

Sphingolipids are a complicated family of compounds[39] that share a common structural feature, a sphingoid base backbone that is synthesized de novo from the amino acid serine and a long-chain fatty acyl CoA, then converted into ceramides, phosphosphingolipids, glycosphingolipids and other compounds. The major sphingoid base of mammals is commonly referred to as sphingosine. Ceramides (N-acyl-sphingoid bases) are a major subclass of sphingoid base derivatives with an amide-linked fatty acid. The fatty acids are typically saturated or mono-unsaturated with chain lengths from 16 to 26 carbon atoms.[25]: 421–2 

The major phosphosphingolipids of mammals are sphingomyelins (ceramide phosphocholines),[40] whereas insects contain mainly ceramide phosphoethanolamines[41] and fungi have phytoceramide phosphoinositols and mannose-containing headgroups.[42] The glycosphingolipids are a diverse family of molecules composed of one or more sugar residues linked via a glycosidic bond to the sphingoid base. Examples of these are the simple and complex glycosphingolipids such as cerebrosides and gangliosides.