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Lipids
Lipids
Are heterogeneous group of compounds (fats, oils, steroids, waxes and related compounds), that are related more by their physical than by their chemical properties. Common properties
(1)Relatively insoluble in water (2) Soluble in non-polar solvents
Properties of Lipids
Greasy to touch, leaves a permanent oily stain on paper; Lighter than water Soluble in organic solvent, insoluble in water When pure, colorless with bland odor and taste Yellow color in fat is due to carotene (provitamin A) When heated strongly, undergoes decomposition forming acrid flammable vapors and when ignited, they burn with a sooty flame.
LIPIDS
Important dietary constituents
High energy value Contains fat-soluble vitamins and essential fatty acids Essential Fatty Acids (EFAs)
Are necessary fats that humans cannot synthesize, and must be obtained through diet. Are long-chain polyunsaturated fatty acids derived from linolenic, linoleic, and oleic acids
Biomedical Importance
Fat stored in adipose tissue serves as thermal
insulator in the subcutaneous tissues and around certain organs; Nonpolar lipids act as electrical insulator, allowing rapid propagation of depolarization waves along myelinated nerves; Lipoproteins occur in both cell membrane and mitochondria, and also serve to transport lipid in the blood.
Classification of Lipids
Simple lipid
Ester of fatty acid and _______ Fats/fixed oil - ester of fatty acid and _______
Triglycerides - esters of three molecules of fatty acids plus one molecule of glycerol Found in adipose tissue, butterfat, lard, suet, fish oils, olive oil, corn oil
Classification of Lipids
Compound Lipid
Esters of fatty acid, alcohol and another compound. A. PHOSPHOLIPIDS Fatty acid and alcohol plus a _______ residue; Frequently have nitrogen-containing bases and other substituents (glycerophospholipids, the alcohol is ______; sphingophospholipids, the alcohol is __________).
Classification of Lipids
B. GLYCOLIPIDS Glycosphingolipids
fatty acid and sphingosine plus carbohydrate.
Glycerol Steroids Other alcohols Fatty aldehydes Ketone bodies Hydrocarbons, Lipidsoluble vitamins Hormones * Acylglycerols, cholesterol, and
cholesteryl ester are uncharged, so are termed
NEUTRAL LIPIDS
Fatty Acids
Are aliphatic carboxylic acids Occur mainly as esters of natural fats and oils but do occur in the unesterified form as free fatty acids ( transport form found in the plasma) In natural fats, they are usually straight-chain derivatives containing an even number of carbon atoms.
SATURATED no double bonds UNSATURATED containing one or more double bonds
Fatty Acids
Saturated fatty acids: CnH2nO2 Unsaturated fatty acids: CnH2n - (2x #db) O2
trans
The acyl chain is on the opposite side Elaidic acid
NOMENCLATURE
Named after the corresponding hydrocarbons with the same number and arrangement of carbon atoms, with-oic being substituted for the final e :
anoic saturated acid ends (e.g.,octanoic acid) enoic unsaturated acids with double bonds (e.g., octadecenoic acid)
NOMENCLATURE
Adjacent to carboxyl C as 2, 3 and 4 are also known as , , and carbons, respectively Terminal methyl C is known as or n-carbon is used conventionally to indicate the number and position of the double bond, eg., 9, double bond between C-9 and C-10
Acetic
Butyric
2
4
Valeric
Caproic Lauric
5
6 12
certain fats in small amounts (butter) End product of carbohydrate fermentation by rumen organisms Spermaceti, cinnamon, palm kernel, coconut oils, laurels, butter
Myristic
Palmitic
14
16
Stearic
18
PROSTANOIDS
Are part of a family of biologically active lipids derived from the twenty-carbon essential fatty acids or eicosanoids; Relates to the products of the cyclooxygenase pathway Prostanoic acid as the central structural element Three main groups
Prostaglandins (PGs) Prostacyclins (PGIs) Thromboxanes (TXs)
PROSTAglandins
Acts as local hormones Synthesized from eicosanoic polyunsaturated fatty acids (arachidonic acid) to form cyclopentane ring PG1, PG2, and PG3 numbers are based on the double bonds in the side chain The letter component identifies the functional groups of the cyclopentane ring
PGE keto group in 9 position PGF hydroxyl group in 9 position
THROMBOXANES
Cyclopentane ring interrupted with an oxygen atom; The two major thromboxanes are thromboxane A2 and thromboxane B2 Its role is in clot formation (thrombosis)
TRIACYLGLYCEROLS (TRIGLYCERIDES)
Main storage forms of fatty acids They are formed by esterification of glycerol with three fatty acids Depending on the content of unsaturated fatty acids, triglycerides can be solids (fats) or liquids (oils)
Oils have highly unsaturated fatty acid chains and are liquid at room temperature
Main lipid constituents of membrane Derivatives of phosphatidic acid Phosphate is esterified with the OH of a suitable alcohol Phosphatidic acid intermediate in the synthesis of triacylglycerols
PHOSPHATIDYLCHOLINE (Lecithin)
Phosphoacylglycerol containing choline Most abundant phospholipids of the cell membrane and represent a large proportion of the bodys store of choline CHOLINE important in nervous transmission, as acetylcholine, and as a store of labile methyl group
DIPALMITOYL LECITHIN
Major constituent of the surfactant preventing adherence, due to surface tension, of the inner surfaces of the lungs. Absence from the lungs of premature infants causes respiratory distress syndrome
PHOSPHATIDYLETHANOLAMINE (Cephalin)
Ethanolamine replaces choline A lipid found in biological membranes Cephalin is found particularly in nervous tissue such as the white matter of brain, nerves, neural tissue, and in spinal cord Cephalin is the principal phospholipid in bacteria.
PHOSPHATIDYLSERINE
Serine replaces choline Found in most tissues US-FDA qualified claim states that;
"Consumption of phosphatidylserine may reduce the risk of dementia in the elderly" and; "Consumption of phosphatidylserine may reduce the risk of cognitive dysfunction in the elderly".
PHOSPHATIDYLINOSITOL
Precursor of second messenger Inositol is present as stereoisomer, myoinositol Phosphatidylinositol 4,5-biphosphate important constituent of the cell membrane phospholipids and cleaved into diacylglycerol and inositol triphosphate (internal signals or second messenger)
CARDIOLIPIN
bisphosphatidyl glycerol Is an important component of the inner mitochondrial membrane, where it constitutes about 20% of the total lipid It serves as an insulator and stabilizes the activity of protein complexes important to the electron transport chain
LYSOPHOSPHOLIPIDS
Are intermediates in the metabolism of phosphoglycerols Important in the metabolism and interconversions of phospholipids (lysophosphatidylcholine) Found in oxidized lipoproteins and can promote atheroschlerosis
PLASMALOGENS
10% of the phospholipids of the brain and muscle Resemble phosphatidylethanolamine (ether linked) Alkyl radical is an unsaturated alcohol Choline, serine or inositol ---- may be substituted for ethanolamine
SPHINGOMYELINS
Found in large quantities in brain and nerve tissues Yields fatty acid, phosphoric acid, choline, and a complex amino alcohol, sphingosine
CERAMIDE
Sphingosine plus amino acid Structure found in glycosphingolipids
GLYCOLIPIDS (GLYCOSPHINGOLIPIDS)
Distributed in every tissue of the body
Nervous tissues (brain) Plasma membrane cell surface carbohydrates
Glycosphingolipids
Major glycolipids in animal tissues Ceramide + sugar
GALACTOSYLCERAMIDE
Major sphingolipid of brain & other nervous tissue, C24 fatty acids
GLYCOLIPIDS (GLYCOSPHINGOLIPIDS)
GANGLIOSIDES
Are complex glycosphingolipids derived from glucosylceramide that contain in addition one or more molecules of a sialic acid
NEURAMINIC ACID principal sialic acid found in human tissues. GM3 contains ceramide, one molecule of glucose, one molecule of galactose and one molecule of NeuAc
The simplest gangliosides in tissues
STEROIDS
Phenanthrene rings
Cyclopentane ring
This nucleus, partially or completely hydrogenated, is generally substituted by methyl groups at C10 and C13. A chemical group (ketone, hydroxyl...) or an alkyl side-chain may also be present at C17
47
Steroids
The carbon skeleton of steroids is bent to form 4 fused rings
Cholesterol
Cholesterol is the base steroid from which your body produces other steroids
Estrogen Testosterone
CHOLESTEROL
Associated with atherosclerosis & heart disease Biochemical significance
Precursor of bile acids, adrenocortical hormones, sex hormones, Vit. D, cardiac glycosides, sitosterols and alkaloids
Major constituent of the plasma membrane and of plasma lipoproteins Cholesteryl ester
OH at 3 position is esterified with long chain fatty acid Occurs in animals but not in bacteria
ERGOSTEROL
Precursor of vitamin D2 Occurs in plants and yeast It is turned into viosterol by UV light, and is then converted into ergocalciferol (a form of Vitamin D) Acquires antirachitic properties when irradiated with UV light A component of fungal cell membranes, serving the same function that cholesterol serves in animal cells
POLYPRENOIDS
Not steroids, but synthesized like cholesterol UBIQUINONE- participates in respiratory chain in mitochondrion DOLICHOL - takes part in glycoprotein synthesis by transferring carbohydrate residues to asparagine residues of polypeptide ISOPRENOID rubber, camphor, fat solubleVit A, D, E & K and -carotene (provitamin A)
LIPID PEROXIDATION
Lipids exposed to oxygen (Auto-oxidation) A chain reaction providing a continuous supply of free radicals Effects of peroxidation include:
deterioration of food (rancidity) damage of tissue (cancer, inflammation, atheroschlerosis and aging) caused by free radicals containing methylene-interrupted double bonds
PEROXIDATION
Catalyzed in vivo by heme compounds and by lipoxygenases (platelets and leukocytes) Other products of auto-oxidation (or enzymatic oxidation) of physiologic importance include;
Oxysterols formed from cholesterol Isoprostanes - prostanoids
ANTIOXIDANTS
Control and reduce lipid peroxidation Antioxidants for food are propyl gallate, BHA, BHT Naturally occuring antioxidants include;
Vitamin E (tocopherol) is lipid soluble Vitamin C and urate are water soluble Beta-carotene
CLASSES OF ANTIOXIDANTS
i. Preventive antioxidants reduce the rate of chain initiation
Catalases and Peroxidases - gluthathione peroxidase (reacts with ROOH) Selenium EDTA, DTPA (Chelators of metal ions)
AMPHIPHATIC LIPIDS
Contain predominantly nonpolar groups plus a polar group Molecule is partly hydrophobic and hydrophilic Include fatty acids, phospholipids, sphingolipids, bile salts, and cholesterol Oriented at oil:water interfaces with the polar group in water phase and the nonpolar group in the oil phase Basic structure of biologic membranes (bilayer)
AMPHIPHATIC LIPIDS
MICELLES
Formed when critical concentration of amphiphatic lipids is present in aqueous medium Formed by sonicating an amphiphatic lipid in an aqueous medium Useful as carriers of drugs in circulation, targeted to specific organs, eg, in cancer therapy Also used for gene transfer into vascular cells Carriers for topical and transdermal delivery of drugs and cosmetics
LIPOSOMES
3 1
Triacylglycerols (fats)
Esterification Lipolysis
Steroids
Steroidogenesis
Fatty acids
-oxidation Lipogenesis
Cholesterol
Cholesterologenesis
Carbohydrates
Acetyl CoA
Amino acids
Ketogenesis
CO2
Ketone bodies