Professional Documents
Culture Documents
Chapter 26
26-1
Lipids
Lipids:
A heterogeneous class of naturally occurring organic compounds classified together on the basis of common solubility properties.
They are insoluble in water but soluble in aprotic organic solvents, including diethyl ether, methylene chloride, and acetone.
Lipids
include:
triglycerides, phospholipids, prostaglandins, prostacyclins, and fat-soluble vitamins. cholesterol, steroid hormones, and bile acids.
26-2
Triglycerides
Triglyceride:
acids.
Saponification
O O CH2 OCR R'COCH O CH2 OCR'' A triglyceride
1 . NaOH, H2 O 2 . HCl, H2 O
RCOOH
+
26-3
Fatty Acids
Fatty
acid: A carboxylic acid derived from hydrolysis of animal fats, vegetable oils, or membrane phospholipids.
Nearly all have an even number of carbon atoms, most between 12 and 20, in an unbranched chain. The three most abundant are palmitic (16:0), stearic (18:0), and oleic acid (18:1), where the first number is the number of carbons and the second is the number of double bonds in the hydrocarbon chain. In most unsaturated fatty acids, the cis isomer predominates; the trans isomer is rare. Unsaturated fatty acids have lower melting points than their saturated counterparts; the greater the degree of unsaturation, the lower the melting point. 26-4
Fatty Acids
The
Higher mp
12:0 14:0 16:0 18:0 20:0 16:1 18:1 18:2 18:3 20:4
Lauric acid Myristic acid Palmitic acid Ste aric acid Arachidic acid Palmitoleic acid Oleic acid Linole ic acid Linole nic acid Arachidonic acid
Lower mp
26-5
Triglycerides
Physical
26-6
Triglycerides
example: a triglyceride derived from one molecule each of palmitic acid, oleic acid, and stearic acid, the three most abundant fatty acids in the biological world.
p almitate (16:0) O oleate (18:1) O CH2 OC(CH2 ) 1 4 CH3 stearate (18:0) CH3 ( CH2 ) 7 CH=CH(CH2 ) 7 COCH O CH2 OC(CH2 ) 1 6 CH3
26-7
Triglycerides
The
lower melting points of triglycerides rich in unsaturated fatty acids are related to differences in their three-dimensional shape.
Hydrocarbon chains of saturated fatty acids can lie parallel with strong dispersion forces between their chains; they pack into well-ordered, compact crystalline forms and melt above room temperature. Because of the cis configuration of the double bonds in unsaturated fatty acids, their hydrocarbon chains have a less ordered structure and dispersion forces between them are weaker; these triglycerides have melting points below room temperature.
26-8
soaps are prepared by boiling lard or other animal fat with NaOH, in a reaction called saponification (Latin, sapo, soap).
O O CH2 OCR saponification + 3 N aOH RCOCH O CH2 OCR A triglyce ride (a trie ste r of glycerol) CH2 OH CHOH
+
COO Na
26-9
Their long hydrophobic hydrocarbon chains are insoluble in water and tend to cluster in such a way as to minimize their contact with water. Their polar hydrophilic carboxylate groups, on the other hand, tend to remain in contact with the surrounding water molecules. Driven by these two forces, soap molecules spontaneously cluster into micelles.
26-10
26-11
26-12
form water-insoluble salts when used in water containing Ca(II), Mg(II), and Fe(III) ions (hard water).
2 CH3 ( CH2 ) 1 4 COO Na
+ +
Ca
2+
A s odium soap (s oluble in water as micelles) [ CH3 ( CH2 ) 1 4 COO ] 2 Ca Calciu m salt of a fatty acid (insoluble in water)
2+ +
2 Na
26-13
Synthetic Detergents
The
a long hydrocarbon tail of 12 to 20 carbons. a polar head group that does not form insoluble salts with Ca(II), Mg(II), or Fe(III) ions.
The
most widely used synthetic detergents are the linear alkylbenzenesulfonates (LAS).
26-14
Synthetic Detergents
CH 3 ( CH2 ) 1 0 CH 2 Dodecylbenzen e CH 3 ( CH2 ) 1 0 CH 2 SO 3
-
1 . H2 SO 4 2 . Na OH
Na
Prostaglandins
Prostaglandins:
COOH
26-16
Prostaglandins, origin
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 arachidonic acid (notice the all cis configurations).
9 8 6 5
COOH
11 12
14
15
Arachidonic acid
26-17
Prostaglandins, examples
Among the prostaglandins synthesized biochemically from arachidonic acid are:
O
9
PGE2
11 15
COOH HO HO H HO
9
PGF2
11 15
COOH HO HO H
PGE2 generated in macrophages of the liver and lungs triggers the earliest phase of fever following any infection
26-18
Prostaglandins
Research
on the involvement of PGs in reproductive physiology has produced several clinically useful derivatives.
(15S)-15-methyl-PGF2 is used as a therapeutic abortifacient.
HO
9
HO
26-19
Prostaglandins
The PGE1 analog, misoprostol, is used to prevent the ulceration associated with the use of aspirin.
O COOH PGE 1
15 16
HO O Misopros tol
HO H
COOCH 3 HO HO
15 16
CH3
26-20
Eicosanoids
The
prostaglandins are members of an even larger family of compounds called eicosanoids, all of which contain 20 carbons and are derived from polyunsaturated fatty acids.
1
HOOC
9 8 1
5 6
O
11
COOH
12 13 15 14 20
O H
7 9 8 11 13
14 15
20
26-21
Eicosanoids
Leukotrienes
cells.
One function is constriction of smooth muscles, especially those of the lungs.
HO
11 20 14 9 7 6 5 1
HN
26-22
Steroids
Steroids:
A group of plant and animal lipids that have this tetracyclic ring structure.
C A B D
The
features common to the ring system of most naturally occurring steroids are illustrated next.
26-23
Steroids
The fusion of rings is trans and each atom or group at a ring junction is axial. The pattern of atoms or groups along the ring junctions is nearly always trans-anti-trans-anti-trans. The steroid system is nearly flat and quite rigid. Most have have axial methyl groups at C-10 and C-13.
CH3
CH3
H H
26-24
Cholesterol
H3 C H3 C H HO H H
26-25
Androgens
Androgens
OH H H3 C H HO
H3 C H H
Androste rone
26-26
H3 C H3 C
CH3
OH
H H
H H
Meth enolone H3 C O
O OC(CH2 ) 8 CH3 H3 C H O
H H
26-27
Generic Name: methandrostenolone Danabol / Dianabol has always been one of the most popular anabolic steroids available. Danabol / Dianabol's popularity stems from it's almost immediate and very strong anabolic effects. 4-5 tablets a day is enough to give almost anybody dramatic results. It is usually stacked with deca durabolin and testosterone enanthate. Along with strong anabolic effects comes the usual androgen side effects, users often report an overall sense of well being. Danabol / Dianabol is a strong anabolic and androgenic product. It most often produced dramatic gains in size and strength. Danabol / Dianabol was also shown to increase endurance and glycogen retention. The down side is that this drug is responsible for a number of side effects. It is an alpha alkylated 17 compound, which is quite toxic to the liver. Average dosages for Danabol / Dianabol have been in the range of 15mg to 30mg a day oral or 50mg to 100mg a week by injection. Regarded by many athletes as being one of the most effective oral steroids ever produced. It was not known as the "Breakfast of Champions" for nothing. Danabol / Dianabol is still one of the most effective strength and size building oral steroids probably second only to Anadrol 50 but it is not as harsh on the system as Anadrol 50 is.
26-28
Estrogens
Estrogens
H3 C H O
Progesteron e
H3 C H3 C H O Tes tos terone H
Androste rone
26-29
Synthetic Estrogens
Progesterone-like
contraceptives.
"Nor" refers to the abs ence of a methyl group here. The methyl group is pres ent in ethin drone O Norethindrone
26-30
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 Cortis one H3 C H H O Cortis ol C= O OH HO H3 C H H3 C H H CH2 OH C= O OH
26-31
Mineralocorticoid Hormones
Synthesized in the adrenal cortex. Regulate blood pressure and volume by stimulating the kidneys to absorb Na+, Cl-, and HCO3-.
OH O H3 C H O Aldosterone H H CH CH2 OH C=O
26-32
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.
OH H H H OH COOH
HO H
26-33
Biosynthesis of Steroids
The
building block from which all carbon atoms of steroids are derived is the two carbon acetyl group of acetyl-CoA
Stage 1: synthesis of isopentenyl pyrophosphate from three molecules of acetyl-CoA. Stage 2: synthesis of cholesterol. Stage 3: conversion of cholesterol to other steroids.
bile acids (e.g., cholic acid) se x hormones (e .g., te stos terone and estrone ) mineralocorticoid hormones (e .g., aldosterone) glucocorticoid hormon es (e.g., cortis one)
choles terol
26-34
Vitamin E
OH Four isoprene units, join ed head-to-tail, beginning here and ending at the aromatic ring
26-35
Phospholipids
Phospholipids
26-36
phosphatidic acid
Phospholipids
Among the most common of these low-molecularweight alcohols are:
26-38
Phospholipids, an example
A
lecithin
In aqueous solution, phospholipids spontaneously form into a lipid bilayer, with a back-to-back arrangement of lipid monolayers.
26-39
Biological Membranes
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 float in 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.
26-40
Biological Membranes
Fluid-mosaic model of a biological membrane showing the lipid bilayer and membrane proteins on the inner and outer surfaces of the membrane and penetrating the thickness of the membrane.
26-41
Fat-Soluble Vitamins
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.
The
26-42
Vitamin A
Occurs only in the animal world. Found in the plant world in the form of a provitamin in a group of pigments called carotenes.
26-43
Vitamin A
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.
26-44
26-45
Vitamin D
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.
26-47
Vitamin E
Vitamin
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.
26-48
Vitamin K
The
name of this vitamin comes from the German word Koagulation, signifying its important role in the blood-clotting process.
26-49