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17
Lipids
Chapter 17
17-2
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Lipids: a heterogeneous class of naturally occurring organic compounds classified together on the basis of common solubility properties
insoluble in water soluble in aprotic organic solvents including diethyl ether, methylene chloride, and acetone
17 Lipids
Lipids include
triglycerides, phospholipids, prostaglandins, and fatsoluble vitamins cholesterol, steroid hormones, and bile acids
17-3
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Triglycerides
Fatty acid: a long, unbranched chain carboxylic acid, most commonly of 12 - 20 carbons, derived from hydrolysis of animal fats, vegetable oils, or the phospholipids of biological membranes In the shorthand notation for fatty acids
the number of carbons and the number of double bonds in the chain are shown by two numbers, separated by a colon
17 Fatty Acids
17-5
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Fatty Acids
Carbon Atoms/ Double Bonds 12:0 14:0 16:0 18:0 20:0 16:1 18:1 18:2 18:3 20:4 Common Name lauric acid myristic acid palmitic acid stearic acid arachidic acid palmitoleic acid oleic acid linoleic acid linolenic acid arachidonic acid mp (C) 44 58 63 70 77 1 16 -5 -11 -49
17-6
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Unsaturated
Saturated
17 Fatty Acids
17 Fatty Acids
17-8
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Triglycerides
The lower melting points of triglycerides rich in unsaturated fatty acids are related to differences in their three-dimensional shape 17-9
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
A saturated triglyceride
17 Triglycerides
17-10
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Triglycerides
Natural soaps are prepared by boiling lard or other animal fat with NaOH, in a reaction called saponification (Latin, sapo, soap)
O O CH2 O- CR
+
RCO- CH
3 Na OH
saponification CH 2 OH CHOH
+
17-12
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17-13
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Micelle: a spherical arrangement of organic molecules in water clustered so that their hydrophobic parts are buried inside the sphere and their hydrophilic parts are on the surface of the sphere and in contact with water When soap is mixed with water-insoluble grease, oil, and fat stains, the nonpolar parts of the soap micelles dissolve nonpolar dirt molecules and they are carried away in the polar wash water
17-14
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Soaps form water-insoluble salts when used in water containing Ca(II), Mg(II), and Fe(III) ions (hard water)
+ 2+ 2 CH3 ( CH2 ) 1 4 CO2 Na + Ca A sodium soap (soluble in water as micelles)
2+
2 Na
17-15
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Synthetic Detergents
The most widely used synthetic detergents are the linear alkylbenzene sulfonates (LAS)
17-16
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
1 . H2 SO4 2 . Na OH
Na
17-17
Prostaglandins: a family of compounds that have the 20-carbon skeleton of prostanoic acid
9 10 11 12 13 14 15 16 17 18 19 20 7 8 6 5 4 3 2 1
17 Prostaglandins
CO2 H
Prostanoic acid
17-18
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Prostaglandins are not stored in tissues as such, but are synthesized from membrane-bound 20carbon polyunsaturated fatty acids in response to specific physiological triggers one such polyunsaturated fatty acid is 9 8 6 5 arachidonic acid CO2 H
11 12 14
17 Prostaglandins
15
Arachidonic acid
17-19
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Prostaglandins
9
15
HO HO H
PGE2
HO
9
CO2 H HO
11
15
HO H
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
PGF2
17-20
Research on the involvement of PGs in reproductive physiology has produced several clinically useful derivatives
15-Methyl-PGF2 is used as a therapeutic abortifacient
HO
9
17 Prostaglandins
HO
11
15
HO CH 3 15-Methyl-PGF
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17-21
17 Prostaglandins
the PGE1 analog, misoprostol, is used for prevention of ulceration associated with the use of aspirin-like NSAIDs O CO2 H PGE1
15 16
HO O
HO
15
Misoprostol
17-22
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Steroids: a group of plant and animal lipids that have this tetracyclic ring structure
17 Steroids
C A B
17-23
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Common Features
CH 3 H H CH 3 H H
the fusion of rings is trans and each atom or group of atoms at a ring junction is axial the pattern of atoms or groups of atoms along the ring junctions is nearly always trans-anti-trans-anti-trans the steroid system is nearly flat and quite rigid many have axial methyl groups at C-10 and C-13
17-24
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Cholesterol
H3 C H3 C H HO H H
17-25
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Androgens
OH H H3 C H
H3 C H H
17 Anabolic Steroids
OH CH 3
17
H H H
H3 C H3 C N N H A H H H
OH CH3
O Methandrostenolone
H Stanozolol
17-27
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Estrogens
H 3 C C=O H H3 C H O Progesterone
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
H3 C H
H H HO H
Estrone
17-28
17 Synthetic Estrogens
H H H
H Norethindrone
17-29
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Glucorticoid Hormones
synthesized in the adrenal cortex regulate metabolism of carbohydrates decrease inflammation involved in the reaction to stress
CH2 OH O H3 C H O Cortisone
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
CH2 OH HO H3 C C=O H3 C OH H H H
17-30
H3 C H H
C=O OH
O Cortisol
17 Mineralocorticoid Horm.
OH O H3 C H O Aldosterone H H CH CH2 OH C= O
synthesized in the adrenal cortex regulates blood pressure and volume by stimulating the kidneys to absorb Na+ , Cl-, and HCO3-
17-31
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Bile Acids
synthesized in the liver, stored in the gallbladder, and secreted into the intestine where their function is emulsify dietary fats and aid in their absorption and digestion H3 C
H3 C H H H CO2 H
HO
OH H Cholic acid
17-32
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Biosynthesis of Steroids
all carbon atoms of cholesterol are derived from the two carbon acetyl group of acetyl-CoA cholesterol is, in turn, the starting material for the synthesis of these classes of compounds
bile acids (e.g., cholic acid) Cholesterol sex hormones (e.g., testosterone and estrone) mineralocorticoid homones (e.g., aldosterone) glucocorticoid hormones (e.g., cortisone)
17-33
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Phospholipids are the second most abundant group of naturally occurring lipids
they are found almost exclusively in plant and animal membranes, which typically consist of 40% -50% phospholipids and 50% - 60% proteins the most abundant phospholipids are derived from phosphatidic acid, a molecule in which glycerol is esterified with two molecules of fatty acid and one of phosphoric acid the three most abundant fatty acids in phosphatidic acids are palmitic acid (16:0), stearic acid (18:0), and oleic acid (18:1)
17-34
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Phospholipids
A phosphatidic acid
stearic acid
17 Phospholipids
O CH 2 -O- P- O O OO CH O CH 2 palmitic acid O glycerol
17 Phospholipids
Name and Formula ethanolamine HOCH 2 CH 2 NH 2 choline + HOCH 2 CH 2 N( CH 3 ) 3 serine HOCH 2 CH CO 2 NH 3 inositol HO HO
+
HO
OH
OH phosphatidylinositol
17-36
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
A lecithin
17 Phospholipids
O stearic acid O
2
choline
+
O P OCH 2 CH 2 N( CH 3 ) 3 O CH O CH O CH 2 glycerol
palmitic acid
in aqueous solution, phospholipids spontaneously form into a lipid bilayer, with a back-to-back arrangement of lipid monolayers
17-37
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 A Lecithin
17-38
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Fluid mosaic model: a biological membrane consists of a phospholipid bilayer with proteins, carbohydrates, and other lipids embedded on the surface and in the bilayer
fluid signifies that the protein components of membranes floatin the bilayer and can move freely along the plane of the membrane mosaic signifies that the various components of the membrane exist side-by-side, as discrete units rather than combining to form new molecules and ions
17 Biological Membranes
17-39
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
Vitamins are divided into two broad classes on the basis of their solubility
those that are fat-soluble (and hence classified as lipids those that are water-soluble
17 Fat-Soluble Vitamins
17-40
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Vitamin A
Vitamin A is found in the plant world in the form of a provitamin in a group of pigments called carotenes (tetraterpenes)
enzyme-catalyzed cleavage of b-carotene followed by reduction gives two molecules of vitamin A
17-41
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Vitamin A
CH 3 CH 3 CH 3 b- Carotene CH 3 CH 3
site of cleavage
H3 C H3 C
CH 3
CH 3
CH 3
CH 3
CH 3 CH 2 OH
The best understood role of Vitamin A is its participation in the visual cycle in rod cells
the active molecule is retinal (vitamin A aldehyde), which forms an imine with an -NH2 group of the protein opsin to form the visual pigment called rhodopsin the primary chemical event of vision in rod cells is absorption of light by rhodopsin followed by isomerization of the 11-cis double bond to the 11-trans configuration
17 Vitamin A
17-43
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Vitamin A
CH3 CH3 CH3 H3C CH3
11
12
CH=N-opsin light
CH3
11 12
CH3 CH=N-opsin
17-44
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
A group of structurally related compounds that play a role in the regulation of calcium and phosphorus metabolism
the most abundant form in the circulatory system is vitamin D3
17 Vitamin D
HO Vitamin D 3
17-45
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
17 Vitamin E
In the body, vitamin E functions as an antioxidant; it traps peroxy radicals of the type HOO and ROO formed as a result of oxidation by O2 of unsaturated hydrocarbon chains in membrane phospholipids
17 Vitamin E
17-47
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.
The name of this vitamin comes from the German word Koagulation, signifying its important role in the blood-clotting process
O CH3 3 isoprene units
17 Vitamin K
O Vitamin K1
O CH3 3
17-48
17
Lipids
End Chapter 17
17-49
Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.