Lipids• Group of naturally occurring, non polar, water insoluble and hydrophobic substances found in cells• These are extractible with non polar organic solvents• They have both commercial as well as biological importance
Biological Importance• Lubricants in alimentary canal and other sites of metabolism• Primary transport system for non polar compounds• Important constituents of cell membrane and cell organelles• Good food due to high caloric value• Important for the functioning of nervous system• Essential fatty acids in the diet• Starting materials for other products• Lipids like fat soluble vitamins and hormones are important for normal biological functions
Classification of lipids• Simple lipids – Fats, oils and waxes (esters of alcohol and fatty acids)• Compound lipids (additional moiety other than alcohol and acid) – Phospholipids – Glycolipids – Lipoproteins• Derived lipids (which qualify the general criteria but cant be grouped in above classes) – Steroids and carotenoids
Lipids• Lipids (fixed oils, fats, and waxes) are esters of long-chain fatty acids and alcohols, or of closely related derivatives. The chief difference between these substances is the type of alcohol; in fixed oils and fats, glycerol combines with the fatty acids; in waxes, the alcohol has a higher molecular weight, e.g., cetyl alcohol[CH3(CH2)15OH].
• Fats and oils are made from two kinds of molecules: glycerol (a type of alcohol with a hydroxyl group on each of its three carbons) and three fatty acids joined by dehydration synthesis. Since there are three fatty acids attached, these are known as triglycerides
Triglyceride O H2C O C R O HC O C R O H2C O C R• where R, R, and R" are long alkyl chains; the three fatty acids RCOOH, RCOOH and R"COOH can be all different, all the same, or only two the same.
Structure of Fatty Acids (CH2)6COOH• The “tail” of a fatty acid is a long hydrocarbon chain, making it hydrophobic. The “head” of the molecule is a carboxyl group which is hydrophilic. Fatty acids are the main component of soap, where their tails are soluble in oily dirt and their heads are soluble in water to emulsify and wash away the oily dirt. However, when the head end is attached to glycerol to form a fat, that whole molecule is hydrophobic. H3C Linoleic acid
•The terms saturated, mono-unsaturated, and poly-unsaturatedrefer to the number of hydrogensattached to the hydrocarbon tails ofthe fatty acids as compared to thenumber of double bonds betweencarbon atoms in the tail.• Cyclic acidsThe only known cyclic acid ischaulmoogric acid, which is 13(cyclopentenyl)-tridecanoic acid
• Fats, which are mostly from animal sources, have all single bonds between the carbons in their fatty acid tails, thus all the carbons are also bonded to the maximum number of hydrogens possible.
• Since the fatty acids in these triglycerides contain the maximum possible amount of hydrogens, these would be called saturated fats.• The hydrocarbon chains in these fatty acids are, thus, fairly straight and can pack closely together, making these fats solid at room temperature.
• Oils, mostly from plant sources, have some double bonds between some of the carbons in the hydrocarbon tail, causing bends or “kinks” in the shape of the molecules.• Because some of the carbons share double bonds, they’re not bonded to as many hydrogens as they could if they weren’t double bonded to each other. Therefore these oils are called unsaturated fats.
• Because of the kinks in the hydrocarbon tails, unsaturated fats (or oils) can’t pack as closely together, making them liquid at room temperature.
• In unsaturated fatty acids, there are two ways the pieces of the hydrocarbon tail can be arranged around a C=C double bond (cis and trans).• In cis bonds, the two pieces of the carbon chain on either side of the double bond are either both “up” or both “down,” such that both are on the same side of the molecule.• In trans bonds, the two pieces of the molecule are on opposite sides of the double bond, that is, one “up” and one “down” across from each other.
• Naturally-occurring unsaturated vegetable oils have almost all cis bonds, but using oil for frying causes some of the cis bonds to convert to trans bonds.
• If oil is used only once like when you fry an egg, only a few of the bonds do this so it’s not too bad. However, if oil is constantly reused, like in fast food French fry machines, more and more of the cis bonds are changed to trans until significant numbers of fatty acids with trans bonds build up. The reason for this concern, is that fatty acids with trans bonds are carcinogenic, or cancer-causing.
• Although most vegetable oils are liquid at ordinary temperatures and most animal fats are solid, there are notable exceptions, such as cocoa butter, which is a solid vegetable oil, and cod liver oil, which is a liquid animal fat.
Production of fixed oils and fats• Fixed oils and fats of vegetable origin are obtained by:3. Extraction by pressing Fixed oils are obtained by pressing in hydraulic presses. If the pressing is carried out in the cold, the oil is known as a "virgin oil" or a "cold-pressed oil." In contrast, if the pressing is carried out in heat, the oil is known as a "hot-pressed oil."5. Extraction by solvents Sometimes organic solvents are used for the extraction of oils.
• Animal fats are separated from other tissues by steam, with or without pressure. The heat melts the fat, which rises to the top and may be separated by decantation.
Biosynthesis of lipids• In plants, biosynthesis of saturated and unsaturated fatty acids is from combinations of acetate units (acetate pathway).
Applications of fixed oils and fats1. Soap manufacture2. Suppositories, tablet coating3. Dietary supplements4. Emulsifying agents5. Manufacture of paints, varnishes and lubricants6. Therapeutic uses (castor oil).
Waxes• Like fats, waxes are esters of fatty acids. The alcohol, however, is not glycerol but usually a long-chain, high- molecular weight alcohol.• In plants, waxes are generally found covering the external parts, like the epidermis of leaves and fruits, where their main function is to prevent the loss of water.
• Wax is also produced by insects, e.g. the honeycombs of bees and wasps. USES OF WAX3. Wax is used in pharmacy to make soft ointments harder and to prepare lip salves.4. The technical uses of waxes are substantial, e.g. in shoe polishes and car waxes.
Waxes × fixed oils and fats• Wax has a melting point above approximately 45 °C (113 °F) (which differentiates waxes from fats and oils).• Fats and oils my be saponified by means of either aqueous or alcoholic alkali but waxes are only saponified by alcoholic alkali. (this fact is used for the detection of fats when added as adulterants to waxes).
Chemical properties of fatty acids• Salt Formation• Ester formation• Hydrogenation• Halogenation
• Oxidation – With alkaline KMnO4 (hydroxylation takes place) – With KMnO4 at elevated temperature (after hydroxylation cleavage takes place to produce lower fatty acids) – Ozonolysis (first O3 adds forming ozonoid which then produce mixture of aldehydes) – Autoxidation (epoxides, peroxides which undergo reduction to form alcohols- polymerization to form resins)