from the files of JRCLaoingco, R.N., Ph.D.

1
FATS AS LIPIDS
DEFINITION OF LIPIDS:
Lipids are a group of naturally occurring substances consisting of the higher
fatty acids, their naturally occurring compounds and substances found naturally in
chemical association with them. The word "lipids" means greasy or fat like.

PROPERTIES OF LIPIDS
Lipids are characterized as follows:
1. Insolubility in water and soluble in fat solvents such as ether, chloroform, and
benzene.
2. Related to fatty acids, as esters
3. Utilization by living organisms. Lipids must be either ester-like combination of
fatty acids or must be able to form them. They must also perform some useful
function in the body.

CLASSIFICATION OF LIPIDS

I. Simple Lipids - Ester formed on the reaction of fatty acids with various alcohols
a. Fats and oils - are glyceryl esters of higher fatty acids. They are also called
glycerides.
b. Waxes - Fatty acid esters of other- alcohols, not gl ycerol. The al cohol s
are usually higher saturated monohydric alcohols.

II. Compounds Lipids - Esters of fatty acids containing other groups in addi t ion
t o al cohol s and fatty acids.
a. Phospholipids or phosphatides contain phosphoric acid and a nitrogenous
base. Ex. lecithin, cephalin, and sphingomyelin.
b. Glycolipids or cerebrosides - compounds of fatty acids with a carbohydrate,
and also containing nitrogen but no phosphoric acid.
III. Derived Lipids - these are substances derived from group I and II by hydrolysis.
a. Fatty acids of various series
b. Sterols - high molecular weight alcohols of cyclic structure Ex. cholesterol and
ergosterol
c . Fatty aldehydes

IV. Substances associated with l i pids
a. Carotenoids
b. TocopheroIs
c... Vitamin K
d. Steroids



from the files of JRCLaoingco, R.N., Ph.D.

2 A fatty acid consists of a hydrophobic hydrocarbon chain with a terminal carboxyl group.




At physiologic pH, the terminal carboxyl group ionizes. A fatty acid is amphipathic:




*** More than 90% of the fatty acids found in the plasma are in the form of fatty acid esters.











Unesterified fatty acids are transported in the circulation in association with albumin.















Triacylglycerol
Cholesteryl
esters
Phospholipids

from the files of JRCLaoingco, R.N., Ph.D.

3 Fatty acid chains may be saturated or unsaturated.




Mono- vs. Poly- unsaturated fatty acids:






Cis vs. Trans Configuration of Fatty Acids




from the files of JRCLaoingco, R.N., Ph.D.

4
Common names and structures of important fatty acids



Common names and structures of important fatty acids




The carbon to which the carboxyl group is attached is called the alpha carbon


The carbon of the terminal methyl group is called the omega carbon.








from the files of JRCLaoingco, R.N., Ph.D.

5 The carbons in a fatty acid can also be counted beginning at the omega end.









Two fatty acids are dietary essentials in humans.





Precursor of arachidonic acid (substrate for
prostaglandin synthesis)
Linoleic acid
Precursor of other omega-3 fatty acids
(important for growth and development)
Linolenic acid

from the files of JRCLaoingco, R.N., Ph.D.

6 FATS AND OILS AS LIPIDS

Fats are classed as simple lipids. They contain the elements carbon, hydrogen and
oxygen and are found in both plant and animal kingdom. Fats and oils are glycerides. The
liquid glycerides are termed oils: they are liquid at ordinary room temperature. Fats
may exist as (1) simple glycerides or (2) mixed glycerides. Simple qlvcerides are those in
which the fatty acid radicals, saturated or unsaturated, are the same. Ex. tristearin,
tripalmitin. Mixed qlycerides are those wherein the fatty acid radical are not the same (or
different). Ex, stearo-d lolei n

GENERAL FORMULA OF FATS AND OILS
CH
2
- O - CO - R Ex. CH
2
-O-CO-C
17
H
35
CH
2
-O-CO-C
17
H
35

l t l
CH - O - CO - R CH-O-CO-C
17
H
35
CH-O-CO-C
17
H
33

l l l
CH
2
- O - CO - R CH
2
-O-CO-C
17
H
35
CH
2-
O-CO-C
17
H
33

Tristearin or stearin Stearo- diolein
If R are the same, simple glyceride, like tristearin: if R are different, mixed
glyceride, like above example,

PHYSICAL PROPERTIES OF FATS AND OILS

1. Odorless and colorless when pure. If a fat is colored this is usually due to the
presence of some pigments, like carotene and xanthophyl present in human fat and
mi l k fat . If i t has an odor t hi s i s due t o t he presence of a fatty acid such
as butyric acid in rancid butter, which may have been formed by hydrolysis on
exposure to air.

2. All fats have a greasy feeling and produce a grease spot when tested on paper.

3. Fats are usually insoluble in water but soluble in such organic solvents as ether, benzene,
chloroform, carbon tetrachloride and hot alcohol.
4. Fats are lighter than water, hence they float on water.

5. Solid and liquid forms depend on the amount of unsaturated glycerides in the fat and the
room temperature.

6. Fats can be emulsified or kept suspended in tiny particles in a mixture by means of such
colloidal substances like soap, dextrins, proteins, and gum arabic. These emulsifying
agents reduce surface tension of the liquid and prevent the fat particles from coagulating.

from the files of JRCLaoingco, R.N., Ph.D.

7 FATTY ACIDS IN FATS

The fatty acids present in fats and oils usually contain even number of carbon atoms,
and can either be saturated or unsaturated. If the R of the RCOOH conforms to the general
formula C
n
H2
n-1
, then the fatty acid is saturated; if less hydrogen than the saturated acid, then
it is unsaturated.

Examples of saturated fatty acids: butyric acid C
3
H
7
COOH, palmitic acid C
15
H
31
COOH,
and stearic acid, C
17
H
33
COOH, Examples of unsaturated fatty acids are: Oleic acid C
17
H
33
COOH
Linoleic acid C
17
H
31
COOH; Linolenic acid C
17
H
29
COOH, Arachidonic acid C
17
H
31
COOH.

Oleic acid has a double bond; linoleic acid has two double bonds, linolenic acid has three
double bonds, and arachidonic acid, four double bonds, hence they are unsaturated acids. Of these
the three essential fatty acids from the standpoint of nutrition are 1inoleic, 1inolenic and
arachidonic acids. They are nutritionally essential in that they are not synthesized by the body or
not rapidly enough to meet its needs so that they must be furnished in some form in the diet.

Glycerides formed from unsaturated fatty acids are also unsaturated. These unsaturated
glycerides together with glycerides from simple saturated fatty acids, like butyric, are in the form of
liquid at ordinary room temperature; while saturated long-chain glycerides, such as palmitin (lard)
and stearin are solids at the same temperature. Since both animal and vegetable fats consist of
mixtures of simple and mixed glycerides, the consistency of fat depends on the proportion of
unsaturated glycerides. When the proportion of unsaturated glyceride is high, the fat is in liquid
form at ordinary temperatures, has a low melting point and is usually called an oi1. When the
percentage of unsaturated glycerides or simple, saturated glycerides is not so high, the fat is in a
solid state and has a higher melting point.


CHEMICAL PROPERTIES OF FATS

1. Hydrolysis - when fats are hydrolyzed in the body or outside, glycerol and fatty acids are
formed. Ex. In the hydrolysis of stearin, glycerol and stearic cid are formed:

CH
2
-O-CO-C
17
H35 CH
2
~OH
l l
CH-O-CO-C
17
H
35 +
3 H
2
O ------------> 2 CHOH + 3 C
17
H
35
COOH
l l stearic acid
CH
2
-O-CO-C
17
H
35
CH
2
OH
Glycerol

Hydrolysis of fats may take place by the action of fat-splittinq enzymes called lipases
or are brought about by the action of certain bacteria, or by long continued exposure to air and
hear, by the action of varying amounts of heat, by steam under pressure, by acids and alkalies.
Hence butter must be refrigerated to prevent formation of objectionable butyric acid.

2. Saponification - the alkaline hydrolysis of fats or oils is called saponification. If fat or oil
is hydrolyzed by means of a strong alkaline, such as NaOH or KOH,
soap and glycerol are formed.


from the files of JRCLaoingco, R.N., Ph.D.

8
3. Oxidation - since fats contain the elements carbon, hydrogen and oxygen, carbon dioxide
and water are formed on complete oxidation of fats in the tissues, as well as
outside the body.

4. Rancidity of Fats - rancidity or deterioration of fats consists usually of two processes:
(1) Hydrolysis, with the formation of objectionable fatty acids, and
(2.) Oxidation at the double bonds, of the unsaturated glycerides. In
hydrolytic rancidity, lipases in the fats in the presence of
moisture and warm temperature hydrolyze the fat into glycerol
and fatty acid. Only short chain fatty acids like butyric acid
formed from butter have an objectionable odor and taste; fatty
acids of high molecular weight, like stearic acid are odorless,
Oxidative rancidity is due to oxidation taking place at the double
bonds with the formation of peroxides which in turn hydrolyze to
form objectionable aldehydes. The addition of small amounts of
antioxidants or reducing compounds, such as hydroquinones, to
lards and hydrogenated oils has been effective in retarding
oxidative rancidity. To prevent the fat in baked goods and potato
chips from becoming rancid the products are sealed and then
placed in light-proof containers.

5. Hydrogenation of Oils - Hydrogenation is the adding on of hydrogen atoms to unsaturated
glycerides, changing the fat or oil from a liquid to a solid state in
the presence of a catalyst. When hydrogen gas is bubbled through a
liquid fat or oil in the presence of finely divided nickel as a catalyst,
two atoms of hydrogen are added on each double bond of the
unsaturated glyceride.
Ex. Oleic acid may be converted to stearic acid by hydrogenation. Olein
may be converted to stearin:

CH
2
-O-CO-C
17
H
33
CH
2
-O-CO-C
17
H
35

l l
CH-O-CO-C
17
H
33
+ 3H
2
------> CH-O-CO-C
17
H
35

l l
CH
2
-O-CO-C
17
H
33
CH
2
-O-CO~C
17
H
35

olein stearin

Hydrogenated oils are used as shortenings or as butter-substitutes. In the
making of margarines skin milk, inoculated with flavor-producing bacteria, is
added to melted mixtures of hydrogenated vegetable fats. This mixture is
churned and allowed to ripen. Then salt is added, it is worked the same as
butter, and is fortified with carotene to make it like butter in Vitamin A content.

6. Test for Glycerol (and of Fats): Acrolein Test: Potassium bisulfate
As fats are strongly heated they are first hydrolyzed to form glycerol and fatty
acids. On continued heating, alone or with solid potassium bisulfate, KHS04,



from the files of JRCLaoingco, R.N., Ph.D.

9
as a catalyst, the glycerol is dehydrated forming acrolein or acrylic aldehyde,
a compound with an acrid odor (or odor of burned copra):

CH
2
OH CH2
l heated l
CHOH --------------> CH + 2 H
2
O
l KHSO
4
l


CH
2
OH CHQ
acrolein


PHYSIOLOGICAL FUNCTIONS OF FATS IN THE BODY
1. Fuel - Fats are the highest energy-giving foods. One gram of fat furnishes 9,500
calories of heat.
2. Reserved supply of fuel - Fat, in the form of adipose tissue, is distributed under the
skin and around the abdominal organs as a reserve fuel supply. This reserve remains
inert until it is needed, as illness and starvation.
3. Protector of nerve endings and delicate organs.
4. Insulation - Fat protects the animal from cold because it is poor conductor of heat
and limits the heat lost by the internal tissues through the skin.
5. Supplies the essential fatty acids in the body.
6. Constituent of protoplasm.

OTHER LIPIDS
Waxes: Classed as simple lipids, along with fats and oils are waxes. They are the
esters of fatty acids wit h monohybri d al cohol s of hi gh mol ecul ar
weights, containing 16 carbon atoms.
Common waxes in nature are:
1. Lanolin or wool was is a very important wax in the medical and cosmetic
fields being used as a basis for many ointments and creams. Since it forms as
emulsion with water it can carry water-soluble substances in its lotions.
2. Spermaceti wax, obtained from the sperm whale, is used in making cosmetics
and some pharmaceutical products, and is also used as a lubricant in oiling
watches.
3. Carnauba wax, obtained from the leaves of the carnauba palm finds extensive
use in polishes for automobiles, floors and furnitures.
4. Bees wax often used in raising the melting point of ointments and other
cosmetics.




from the files of JRCLaoingco, R.N., Ph.D.

10
STEROLS (DERIVED LIPIDS)

Sterols are high molecular weight, solid alcohols of a cycl i c st ruct ure. They are
hydroxyl deri vat i ves of cyclopentanoperhydro-phenanthrene or steroids. They are
found in a free state or as esters in animals and plants.

Cholesterol, C
27
H
45
OH, the most important sterol, is abundant in brain and nerve
tissue, but is also present in all living cells, existing free or as an ester. It is a constituent of
gallstones. It is also found deposited in the walls of the arteries in arteriosclerosis and in
the kidneys, in nephritis. It is also found in butter fish oil, and liver oils, and wheat oil as
an unsaponifiable factor (incapable of being saponified or changed into soap by an alkali).
Functions of Cholesterol:
1. It plays a role in the transportation of fat to the tissues and in the metabolism of
fats.
2. It aids in the synthesis of bi l e salts.
3. It may also be the parent substance of the sex and adrenal cortical hormones,
which are solid steroids.
Test for Cholesterol
1. Salkowski's Test - A solution of cholesterol in chloroform with conc. suIfuric
acid wi l l give a cherry-red color.
2. Liebermann-Burchard Test - The sterol is treated with chloroform, acetic
anhydride, and conc. sulfuric acid. An emeraId green color will be produced.

Ergosterol and Calciferol:
Another important sterol is ergosterol, the precursor of its isomer, calciferol or
Vitamin D
2
. It is found widely distributed in both plant and animal cells, usually in
association with cholesterol. On irradiation, ergosterol is changed i nt o i t s i somer,
cal ci ferol , or Vi t ami n D
2
. However, over exposure to ultraviolet rays produces a
toxic isomer called toxisterol.