Lipids

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: An ester of glycerol with three fatty

acids.
Saponification
O
O CH2OCR
R'COCH O
CH2OCR''
A triglyceride

1. NaOH, H2 O
2. HCl, H2 O

CH2OH
HOCH
CH2OH

RCOOH
+

1,2,3-Propanetriol
(Glycerol, glycerin)

R'COOH
R''COOH
Fatty acids

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 most common fatty acids.

Carbon Atoms: Common
Double Bonds Name
Saturated Fatty A cids

Higher
mp

12:0
14:0
16:0
18:0
20:0

Melting Point
(C)

Lauric acid
Myristic acid
Palmitic acid
Stearic acid
Arachidic acid

44
58
63
70
77

Unsaturated Fatty A cids

Lower
mp

16:1
18:1
18:2
18:3
20:4

Palmitoleic acid
1
Oleic acid
16
Linoleic acid
-5
Linolenic acid
-11
Arachidonic acid -49

26-5

Triglycerides

Physical properties depend on the fatty acid

components.
Melting point increases as the number of carbons in
its hydrocarbon chains increases and as the number
of double bonds decreases.
Oils: Triglycerides rich in unsaturated fatty acids are
generally liquid at room.
Fats: Triglycerides rich in saturated fatty acids are
generally semisolids or solids at room temperature.

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.
palmitate (16:0)
O
oleate (18:1)
O CH2OC(CH2) 14CH3
stearate (18:0)
CH3(CH2)7 CH=CH(CH2 )7COCH O
CH2OC(CH2) 16CH3

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 and Detergents

Natural soaps are prepared by boiling lard or

other animal fat with NaOH, in a reaction called
saponification (Latin, sapo, soap).
O
CH2 OCR

O
RCOCH

O
CH2 OCR

+ 3NaOH

A triglyceride
(a triester of glycerol)

saponification
CH2 OH
CHOH

CH2 OH
1,2,3-Propanetriol
(Glycerol; Glycerin)

O
+
3RCO Na
Sodium soaps

COO Na

26-9

Soaps and Detergents

Soaps clean by acting as emulsifying agents:

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

Soaps and Detergents

A soap micelle: nonpolar (hydrophobic) hydrocarbon
chains cluster in the inside and polar (hydrophilic)
carboxylate groups lie on the surface.

26-11

Soaps and Detergents

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 fats, the nonpolar parts of the soap micelles
dissolve these nonpolar dirt molecules and they are
carried away in the polar wash water.

26-12

Soaps and Detergents

Soaps form water-insoluble salts when used in

water containing Ca(II), Mg(II), and Fe(III) ions
(hard water).
water
-

+ +

2CH3 ( CH2 ) 1 4 COO Na

2+

Ca

A sodium soap
(soluble in water as micelles)
-

2+

[CH3 (CH2 ) 1 4 COO ] 2 Ca

Calcium salt of a fatty acid
(insoluble in water)

2Na

26-13

Synthetic Detergents

The design criteria for a good detergent are:

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
1. H2 SO4

CH3 (CH2 ) 1 0 CH2

Dodecylbenzene

2. NaOH

CH3 (CH2 ) 1 0 CH2

SO3 Na

Sodium 4-dodecylbenzenesulfonate
(an anionic detergent)

Also added to detergent preparations are:

foam stabilizers.
bleaches.
optical brighteners.
26-15

Prostaglandins

Prostaglandins: A family of compounds that have

the 20-carbon skeleton of prostanoic acid.
9

3
4

1
2

COOH

10
11 12

13

14

15

16

17

18

19

20

Prostanoic acid

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

11 12

14

COOH

15

Arachidonic acid

26-17

Prostaglandins, examples
Among the prostaglandins synthesized biochemically
from arachidonic acid are:
O

PGE2

COOH
HO
HO

PGF2

11

15

HO H
9

COOH
HO

11

15

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.
extra methyl group
at carbon-15

HO
9

COOH
HO

11

15

HO CH3
(15S)-15-Methyl-PGF2

26-19

Prostaglandins
The PGE1 analog, misoprostol, is used to prevent the
ulceration associated with the use of aspirin.
O

COOH

PGE 1
15

HO

16

HO H

O
COOCH3

Misoprostol

HO
HO

CH3

15 16

26-20

Eicosanoids

The prostaglandins are members of an even

larger family of compounds called eicosanoids,
eicosanoids
all of which contain 20 carbons and are derived
from polyunsaturated fatty acids.
1

HOOC
9

COOH

O
11

12

13

14

15

OH

Thromboxane A2
(a potent vasoconstrictor)

20

O
H 9

6
7
8

11

14

20

15

13

OH
OH
Prostacyclin
(a platelet aggregation inhibitor)

26-21

Eicosanoids

Leukotrienes are found primarily in white blood

cells.
One function is constriction of smooth muscles,
especially those of the lungs.
11

20

HO
6

COOH

14

L-cysteine
Leukotriene C4 (LTC 4)
(a smooth muscle constrictor)

COOH
N
H

HN
O

COOH
NH2

glycine
L-glutamic acid

26-22

Steroids

Steroids: A group of plant and animal lipids that

have this tetracyclic ring structure.
C
A

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

26-24

Cholesterol

H3 C
H3 C

H
H

HO

26-25

Androgens

Androgens - male sex hormones.

H3 C
H3 C

H
H

OH
H

Testosterone

H3 C
H3 C

H
H

HO

Androsterone

26-26

Synthetic Anabolic Steroids

A way to increase the testosterone concentration is to
use a prohormone, which the body converts to
testosterone; for example andro.
H3 CHO CH3
H3 C

H3 C
H3 C

Nandrolone decanoate

Methenolone

O
OC(CH2 )8 CH3

CH3

H
H

OH

CH3

Methandrostenolone
H3 C

H3 C

H
H

H3 C

4-Androstene-3,17-dione
(andro)

26-27

Available on the internet, dangerous

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 - female sex hormones.

CH3

H3 C
H3 C

H
H

H3 C

HO

Testosterone

H3 C
H3 C

H
H

HO

Estrone

OH
H

H
H

Progesterone

H3 C

H3 C

H
H

C=O
H

Androsterone

26-29

Synthetic Estrogens

Progesterone-like analogs are used in oral

contraceptives.
"Nor" refers to the absence
of a methyl group here.
The methyl group is present
in ethindrone

HO
C CH
H3 C

H
H

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
H3 C

O
H3 C

C=O
OH

H
H

O
Cortisone

CH2 OH
H3 C

HO
H3 C

C=O
OH

H
H

O
Cortisol

26-31

Mineralocorticoid Hormones
Synthesized in the adrenal cortex.
Regulate blood pressure and volume by stimulating
the kidneys to absorb Na+, Cl-, and HCO3-.
CH OH
OH 2
C=O
CH

O
H3 C

H
H

Aldosterone

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

COOH

H
H
HO
H

H
OH

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)
cholesterol

sex hormones (e.g., testosterone and estrone)

mineralocorticoid hormones (e.g., aldosterone)
glucocorticoid hormones (e.g., cortisone)

26-34

Vitamin E
OH

Four isoprene units, joined

head-to-tail, beginning here
and ending at the aromatic ring

O
Vitamin E (-Tocopherol)

26-35

Phospholipids

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 esters of
phosphatidic acid (glycerol 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).

26-36

Phosphatidic acids, an example

A phosphatidic acid

Further esterification with a low-molecular weight

alcohol gives a phospholipid.
26-37

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:
fluid Signifies that the protein components of
membranes float in the bilayer and can move freely
along the plane of the membrane.
mosaic:
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 fat-soluble vitamins include A, D, E, and K.

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

Vitamin A and the Chemistry of Vision

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 E is a group of compounds of similar

structure, the most active of which is tocopherol.

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