12/14/2023 Dr.Shaymaa Galal lecturer of Biochemistry Dr. Shaymaa Galal lecturer of Biochemistry LIPIDS (Greek: lipos, means fat or lard) ❑ The lipids are a heterogeneous group of compounds, including fats, oils, steroids, waxes, and related compounds, that are related more by their physical than by their chemical properties (have a distinguished functional group or structural features). ❑ Lipids are insoluble in water and highly soluble in one or more of the solvents: ether, chloroform, benzene and acetone. This property sets them apart from proteins, carbohydrates,, nucleic acids and other biomolecules. ❑ Lipids are important feature in cell membranes, fatsteroid hormones. soluble vitamins, and Hydrophobic in nature! Main Composition ⚫Mainly contains C, H & O atoms. ⚫Constituents of: ⚫Cell membranes of animal & plant cells ⚫Food storage molecules ⚫Intermediaries in signaling pathways ⚫Vitamins A, D, E and K ⚫Cholestrol , ❑Make up 18–25% of body mass in lean adults. ❑Formed of long-chain hydrocarbon groups, also contain oxygen, phosphorus, nitrogen and sulfur. Properties of Lipids ❑Insoluble in water, but soluble in organic solvent. ❑Actually or potentially related to fatty acids. ❑It can be used as a source of energy by animals. Functions and Biological Importance of Lipids ❑ ❑ ❑ ❑ ❑ ❑ Storage form of energy and acts as fuel to the body (9 kcal/gm) Important dietary components because of their high energy value and also because of the fat-soluble vitamins and the essential fatty acids contained in the fat of natural foods. Structural components of biomembranes. Serve as thermal insulators in the subcutaneous tissues and around certain organs. The Nervous system is particularly rich in lipids. Nonpolar lipids act as electrical insulators, allowing rapid propagation of waves and depolarization along myelinated nerves. Provide shape and contour to the body. Functions and Biological Importance of Lipids Source of energy/Fuel to body Lipoproteins/Phospholi pids Bile salts Importance of LIPIDS Protection & Paddling of internal Organs Thermal & Electrical insulator Prostaglandins Vitamins Building materials(Hormones) CLASSIFICATION OF LIPIDS 1.Simple lipids: Esters of fatty acids with various alcohols. a)Triacylglycerols/Triglycerides • Fats: Esters of short or medium chain fatty acids with glycerol. Eg.triolein, tripalmitin. ▪ Oils are fats in the liquid state. Eg.- corn, groundnut oil. b)Waxes: ▪ True Waxes: Esters of fatty acids (C14 – 36) with higher molecular weight monohydric long chain alcohols (C16 - 30). e.g. Bees wax, lanolin, spermaceti oil. ▪ Other waxes: cholesterol ester, Vit. A ester, Vit. D ester. Fats & Oils – Triglycerides Synthesis (Dehydration synthesis) ⚫Two kinds of molecules ⚫Glycerol ⚫Fatty acids 2. Complex/Compound lipids: Esters of fatty acids containing groups in addition to an alcohol and a fatty acid. a) Phospholipids: Lipids containing, in addition to fatty acids and an alcohol, a phosphoric acid residue. They frequently have nitrogen- containing bases and other substituents, eg, in i)Glycerophospholipids: the alcohol is glycerol ii)Sphingophospholipids: the alcohol is sphingosine. b) Glycolipids (glycosphingolipids): Lipids containing a fatty acid, sphingosine, and carbohydrate. –Cerebosides – Gangliosides c)Lipoproteins: macromolecular complexes of lipids with proteins. d) Other complex lipids: Lipids such as sulfolipids, aminolipids and Lipopolysachharides may also be placed in this category. 3. Derived and Precursor lipids: Derived from simple lipids or complex lipids on hydrolysis. These include o Fatty acids and Glycerol, Monoacyl and Diacylglycerols Steroids lipids with cyclopentanoperhydrophenanthrene (steroid) ring. e.g. cholesterol and its derivatives- bile acids, hormones, Ergosterol. o Lipid-soluble vitamins, eicosanoids-arachidonic acid derivativesPG,TXA2, 4.Miscellaneous lipids: These include a large number of compounds possessing the characteristics of lipids e.g., carotenoids, squalene, hydrocarbons such as pentacosane (in bees wax), terpenes etc. ➢ Neutral Lipids: the lipids which are uncharged are referred to as neutral lipids. These are mono, di, and triacylglycerols, cholesterol Fatty acids ▪ Fatty acids are simplest form of lipids. Fatty acids are aliphatic carboxylic acid with hydrocarbon side chain. Have the general formula R-(CH2)n-COOH where, R -Alkyl / hydrocarbon chain and COOH- Carboxyl end. Occurrence: ▪ They occur mainly as esters in natural fats and oils but do occur in the unesterified form as free fatty acids (Free fatty acids are formed only during metabolism), a transport form found in the plasma. ▪ Fatty acids that occur in natural fats are usually straight-chain derivatives containing an even number of carbon atoms. Even and odd carbon fatty acids: ❑ Most of the Fatty acids that occur in natural lipids are of even carbons (usually 14C – 20C). This is due to biosynthesis of fatty acids mainly occurs with the sequential addition of 2 carbon units. Palmitic acid (16C) and Stearic acid (18C) are most common. Propionic acid (3C) and valeric acid (5C) are common odd chain fatty acids. Nomenclature: ➢ It is based on hydrocarbon from which it is derived. After the name of the parent hydrocarbon with suffix –anoic acid for saturated fatty acid, –enoic acid for unsaturated fatty acid. 8 7 6 5 4 3 2 1 CH3-CH2-CH2-CH2-CH2-CH2-CH2-COOH Carboxyl group Hydrocarbon chain Octane + acid = Octanoic acid Common name – Caprylic acid ➢ For example, the C18 saturated fatty acid is called octadecanoic acid because the parent hydrocarbon is octadecane. ➢ A C18 fatty acid with one double bond is called octadecenoic acid; with two double bonds, octadecadienoic acid; and with three double bonds, octadecatrienoic acid. ❑The notation 18:0 denotes a C18 fatty acid with no double bonds, whereas 18:2 signifies that there are two double bonds. ❑ The Carbon atoms are numbered from COOH group as 1. The carbons adjacent to this are 2,3,4 etc or α, β, γ. ❑ Carboxyl group carbon is C1, next carbon atom is C2/ α-carbon, next is β and so on. ❑ The position of a double bond is represented by the symbol ∆ followed by a superscript number counting from carboxyl group end. eg, ∆ 9 indicates a double bond between carbons 9 and 10 of the fatty acid. ❑ Alternatively, the position of a double bond can be denoted by counting from the distal end, with the ω- carbon atom (the methyl carbon) as number 1. ➢ ω9 indicates a double bond on the ninth carbon counting from the ωcarbon. ❑ In animals, additional double bonds are introduced only between the existing double bond (eg, 9, 6, or 3) and the carboxyl carbon, leading to three series of fatty acids known as the ω9, ω6, and ω3 families, respectively. CH3 – CH2 - CH2 - COOH 1 Butyric acid (Arabic numbers) 4 3 2 (Greek alphabetical numbers) ω1 ω2 ω3 (Omega numbers) Polyunsaturated fatty acid of ω6 family E.g., linoleic acid (18: 2 ; Δ9,12 ) ω6. 12 9 CH3 - (CH2)4 - CH = CH - CH2- CH = CH - (CH2)7 – COOH In (18: 2 ; Δ9,12 ) ω6 or Δ6. where, 18= total no of carbon atom, 2= no of double bonds, (Δ 9,12) OR 9,12= first carbon position of double bonds, starting from the carboxyl end, ➢ ω6 = first carbon position of double bonds starting from terminal methyl group (ω,omega carbon) Poly-unsaturated Essential Fatty acids α-Linolenic ALA) EPA DHA nuts - flaxseed oil soybean and canola oil- fatty fish (tuna & salmon) Omega-3 Fatty acids Omega-6 Fatty acids Linoleic (18:2) Arachidonic (2o:4) corn oil - sunflower oilsafflower, soybean meat, eggs 12/14/2023 Dr.Shaymaa Galal lecturer of Biochemistry General structure of Fatty Acid: ❑ Fatty acids are amphipathi molecules composed of a hydrophilic (polar, ionized) head (formed by the carboxyl group) and a hydrophobic (non-polar, non-ionized) tail (formed by the hydrocarbon chain). ❑ -The degree of solubility of a fatty acid depends on the length of the hydrocarbon chain. H+ CH3 – (CH2)n –COOH Ionization (at pH:7) CH3 – (CH2)n –COO- Classification of fatty acids: 1. According to chain length: short, medium and long 2. According to degree of saturation: saturated & unsaturated 3. According to chain type: branched and cyclic. 4.According to Biological value: essential & non-essential Classification of fatty acids: 1. According to chain length: short, medium and long A)Low or short chain fatty acids: Contain 8 carbon atoms or less (from 2- 8) Acetic acid (2 C): CH3-COOH Butyric (4 C): CH3-CH2-CH2-COOH B)Medium-chain fatty acids: Contain from 10-12 carbon atoms C)High or Long chain fatty acids: Contain more than 12 carbon atoms Palmitic (16 C): CH3-(CH2)14-COOH Stearic (18 C): CH3-(CH2)16-COOH Lignoceric (24 C): CH3-(CH2)22COOH 2. According to degree of saturation: saturated & unsaturated A) Saturated Fatty Acids: They do not contain double bonds ❑ Saturated fatty acids may be envisaged as based on acetic acid (CH3 —COOH) as the first member of the series in which — CH2— is progressively added between the terminal CH3 — and — COOH groups. ❑ Fatty acids in biological systems usually contain an even number of carbon atoms, typically between 14 and 24. The 16and 18-carbon fatty acids are most common. ❑ The hydrocarbon chain is almost invariably unbranched in animal fatty acids. A few branched-chain fatty acids have also been isolated from both plant and animal sources. Palmitic acid (16 C) CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH [ CH3-(CH2)14-COOH ] Stearic acid (18 C) CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2 CH2-CH2-CH2-CH2-COOH [ CH3-(CH2)16-COOH ] Number of C atoms Common Name Systemic Name Formula 2 Acetic acid Ethanoic acid CH3COOH 4 Butyric acid Butanoic acid CH3(CH2)2COOH 6 Caproic acid Hexanoic acid CH3(CH2)4COOH 8 Caprylic acid Octanoic acid CH3(CH2)6COOH 10 Capric acid Decanoic acid CH3(CH2)8COOH 12 Lauric acid Dodecanoic acid CH3(CH2)10COOH 14 Myristic acid Tetradecanoic acid CH3(CH2)12COOH 16 Palmitic acid CH3(CH2)14COOH 18 Stearic acid 20 Arachidic acid Hexadecanoic acid Octadecanoic acid Eicosanoic acid 22 Behenic acid DocBoiosaenostriycfoarceiddics CH3(CH2)16COOH CH3(CH2)18COOH C6/H29/2(0C12H) COOH 3 2 20 A) Unsaturated Fatty Acids: They contain one or more double bonds They are named by adding suffix “enoic” (1)Monounsaturated (monoethenoid, monoenoic) acids, containing one double bond. e.g. Oleic acid (18: 1; 9 )ω9 or Δ9 CH3-(CH2)7-CH = CH-(CH2)7-COOH In (18: 1; 9 ) ω9 , 18= total no of carbon atom, 1= no of double bonds, 9= first carbon position of double bonds, starting from the carboxyl end, ω9/ Δ9 = first carbon position of double bonds starting from terminal methyl group (ω,omega carbon) (2) Polyunsaturated (polyethenoid, polyenoic) acids, containing two or more double bonds. The configuration of the double bonds in most unsaturated fatty acids is cis. The double bonds in polyunsaturated fatty acids are separated by at least one methylene group. Nuts contain high content of PUFA, low saturated fats and high conte of vitamin E. e.g. peanuts, almonds and cashews 1. Dienoic fatty acids (contain 2 double bonds) • e.g. linoleic acid (18: 2 ; 9,12 ) ω6. 12 9 CH3 - (CH2)4 - CH = CH - CH2- CH = CH - (CH2)7 – COOH 2. Trienoic fatty acids (contain 3 double bonds) e.g. α-Linolenic acid (18: 3; 9,12, 15) ω3 9 15 12 CH3 - CH2 - CH = CH - CH2 - CH = CH - CH2 - CH = CH - (CH2)7 -COOH CH3 - (CH2 - CH = CH)3 - (CH2)7 - COOH 3. Tetraenoic fatty acids (contain 4 double bonds) e.g. Arachidonic acid (20: 4; 5, 8, 11, 14) ω6 CH3 - (CH2)3 - (CH2 - CH = CH)4 - (CH2)3 - COOH Polyunsaturated fatty acid of ω3 & ω6 family 4. According to Biological value: essential & non-essential Essential Fatty Acids ▪ The Fatty Acids that cannot be synthesized by the body, should be supplied through diet known as essential fatty acids. They are polyunsaturated fatty acids, linoleic acid and linolenic acid. ▪ Mammals can synthesize saturated fatty acids (FAs) and monounsaturated FAs, but they are unable to synthesize FAs containing more than one double bond because they lack the enzyme system that is responsible for introduction of more than one double bond. ▪ Arachidonic acid is synthesized in the body from linoleic acid, so it is a nonessential fatty acid. ▪ It is also found in animal fats and peanut oil. ▪ Arachidonic acid becomes essential if its precursor, linoleic acid, is missing in the Significanceof Essential Fatty Acids ❑ Components of cell membranes, structural elements of membrane. ❑ Required for brain growth and development gonads. ❑ Precursors for synthesis of Eicosanoids ❑ They have a cardio protective role- Lower serum cholesterol and increase HDL levels through cholesterol esterification. ➢ Deficiencies of essential polyunsaturated fatty acids may cause a wide variety of symptoms, including retarded growth in children, reduced fertility and pathologic changes in the skin. Non Essential Fatty Acids ▪ They can be synthesized by mammals, so it is not essential to take them in diet. ▪ They include saturated fatty acids and mono- unsaturated fatty acids.