Lipids

Lipids (fixed oils, fats, and waxes) are esters of long-

chain fatty acids and alcohols, or of closely related

derivatives.

The chief difference between these substances is the

type of alcohol;
in fixed oils and fats, glycerol combines with the fatty acids;
in waxes, the alcohol has a higher molecular weight, e.g.,

cetyl alcohol[CH3(CH2)15OH].

Fats and oils are made from two kinds of

molecules: glycerol (a type of alcohol

with a hydroxyl group on each of its
three carbons) and three fatty acids
joined by dehydration synthesis. Since
there are three fatty acids attached,

these are known as triglycerides.

triglyceride
O
H2C

where

HC

O
C
O

R'

H2C

R''

R, R', and R" are long alkyl chains; the three fatty

acids RCOOH, R'COOH and R"COOH can be all different, all

the same, or only two the same.

(CH2)6COOH

Structure of Fatty Acids

The

tail of a fatty acid is a long

hydrocarbon chain, making it

hydrophobic.
The

head of the molecule is a

carboxyl group which is hydrophilic.

Fatty acids are the main component of

soap, where their tails are soluble in oily
dirt and their heads are soluble in water
to emulsify and wash away the oily dirt.
However, when the head end is
attached to glycerol to form a fat, that
whole molecule is hydrophobic.
H3C

Linoleic acid

The

terms saturated, mono-unsaturated, and polyunsaturated refer to the number of hydrogens attached to the
hydrocarbon tails of the fatty acids as compared to the
number of double bonds between carbon atoms in the tail.

 Fats, which are mostly from animal sources, have all

single bonds between the carbons in their fatty acid tails,
thus all the carbons are also bonded to the maximum
number of hydrogens possible.

Since the fatty acids in these triglycerides contain the

maximum possible amount of hydrogens, these would be

called saturated

fats.

The hydrocarbon chains in these fatty acids are, thus,

fairly straight and can pack closely together, making
these fats

solid at room temperature.

 Oils, mostly from plant sources, have some double

bonds between some of the carbons in the hydrocarbon
tail, causing bends or kinks in the shape of the
molecules.

Because some of the carbons share double bonds,

theyre not bonded to as many hydrogens as they could if
they werent double bonded to each other. Therefore
these oils are called unsaturated fats.
Because of the kinks in the hydrocarbon tails,
unsaturated fats (or oils) cant pack as closely together,
making them liquid

at room temperature.

In unsaturated fatty acids, there are two ways the pieces of the
hydrocarbon tail can be arranged around a C=C double bond
(cis and trans).
In cis bonds, the two pieces of the carbon chain on either side
of the double bond are either both up or both down, such
that both are on the same side of the molecule.
In trans bonds, the two pieces of the molecule are on opposite
sides of the double bond, that is, one up and one down
across from each other.

 Naturally-occurring

unsaturated

vegetable oils have almost all cis

bonds, but using oil for frying

causes some of the cis bonds to

convert to trans bonds.

If oil is used only once like when you fry

an egg, only a few of the bonds do this
so its not too bad. However, if oil is
constantly reused, like in fast food
French fry machines, more and more of
the cis bonds are changed to trans until
significant numbers of fatty acids with
trans bonds build up. The reason for this
concern, is that fatty acids with trans
bonds are carcinogenic, or cancercausing.

Although most vegetable oils are liquid

at ordinary temperatures and most

animal fats are solid, there are notable
exceptions, such as cocoa butter, which
is a solid vegetable oil, and cod liver oil,
which is a liquid animal fat.

Production of fixed oils and fats

Fixed oils and fats of vegetable origin are

obtained by:

1.

Extraction by expression
Fixed oils are obtained by expression in hydraulic
presses. If the expression is carried out in the cold,
the oil is known as a "virgin oil" or a "cold-pressed
oil." In contrast, if the expression is carried out in
heat, the oil is known as a "hot-pressed oil."

2.

Extraction by solvents
Sometimes organic solvents are used for the
extraction of oils.

Animal fats are separated from other

tissues by rendering with steam, with or

without pressure. The heat melts the fat,
which rises to the top and may be
separated by decantation.

FATS VS WAXES
Fats may be saponified by either aqueous
or alcoholic alkali, but waxes are only
saponified by alcoholic alkali.

This is used to determine if fats were

added to adulterate waxes.

Biosynthesis of lipids

The biosynthesis of saturated and

unsaturated fatty acids is from combinations

of acetate units (acetate pathway).

Applications of fixed oils and fats

1.

Soap manufacture

2.

Suppositories, tablet coating

3.

Dietary supplements

4.

Emulsifying agents

5.

Manufacture of paints, varnishes and lubricants

6.

Therapeutic uses (castor oil).

Examples
Castor oil
Olive oil
Peanut oil
Soybean oil
Sesame oil
Almond oil
Cottonseed oil
Corn oil
Safflower oil
Cocoa butter

PLANTS CONTAING FIXED OILS

i.

ii.
iii.
iv.

Olive oil
Cod-liver oil
Castor oil
Theobroma oil

OLIVE OIL
DEFINITION: Olive oil is the oil
expressed from the ripe fruits
of Olea europea (Oleaceae
Family). The latifolia variety
bears larger fruit, but the
longifolia variety yields the
best oil.
COMMON NAMES: Salad oil,
sweet oil

GEOGRAPHICAL SOURCES:
Mediterranean, California,
Spain, France, Greece &
Tunisia.

OLIVE OIL
COLLECTION & PREPARATION
The methods used for
preparations vary
according to the local
conditions. In modern
factories hydraulic presses
are widely used but in
more remote districts the
procedure is the same as it
had been for hundreds of
years.
1st oil expressed: Virgin oil
Subsequent extractions:
marc is solvent extracted
lower quality oil.
Superior grades of oil: Extravirgin, Virgin, Pure, or
Refined.

OLIVE OIL: CHARACTERISTICS

Olive oil: Pale yellow
liquid, sometimes
with a green tint.
Oil has a slight odour &
bland taste.

OLIVE OIL: CONSTANTS

If the fruits used to produce
the oil have been
allowed to ferment, the
acid value will be higher
than is officially
permitted.
Oil should comply with the
tests for absence of
arachis, cotton-seed,
sesame & tea-seed oil
(C. sasanqua).

OLIVE OIL: CONSTITUENTS

Oils from different sources differ slightly in
their constituents (composition). This
may result due to the different varieties
of olive used, or to climate differences.
2 types of oil are distinguished
i.
That produced in Italy, Spain, Asia &
CA
(contains more olein & less linolein)
ii. Produced in Tunisia

Type I Type II
BP Limits
_______________________
%
%
%
_________________________________________
Oleic Acid

78-86

65-70

56-85

Linoleic Acid

0-7

10-15

3.5-20

Palmitic Acid

9-12

15

7.5-20

Stearic Acid

9-12

15

0.5-5.0

OLIVE OIL: USES & ACTIONS

Used in the
preparations of
soaps, plasters etc.
Salad oil
May protect against
colonic cancer (due
to its action on
prostaglandins).

COD-LIVER OIL
DEFINITION: Medicinal cod-liver
oil is a fixed oil prepared from
the fresh liver of the cod,
Gadus callarias, & other Gadus
spp. (Gadidae Family), under
conditions which make it
palatable & containing a certain
amount of Vitamins.
GEOGRAPHICAL SOURCES:
Norway & Iceland

NOTE: Fish-liver oils should not

be confused with fish-body oils.

COD-LIVER OIL: HISTORY

Cod-liver used to be
exported from Norway to
Europe during the Middle
Ages, although for nonmedicinal purposes.
The original method of
preparation was the
rotting process, in
which the livers where
allowed to rot in barrels.
The oil rising to the
surface was skimmed off.
The more modern process
of steaming was
introduced in 1850.

COLLECTION & EXTRACTION

Cod-livers (contain
50% oil), are
removed
immediately after
the fish are caught &
transferred to
steamers & stored at
low temperature.
Process normally takes
place in Norway or
Iceland.

PREPARATION
Main processes involved in the preparation
of cod-liver oil include
i.
Refining
ii. Drying
iii. Winterization
iv. Deodourization
v. Standardization of the vitamin content

REFINING OF THE CRUDE OIL

The quality & flavour of codliver oil are improved by
refining the oil under air-free
conditions to avoid
oxidation.
Method: Crude oil is rapidly
heated to 77 C. A reagent
is then added to remove
impurities. This also causes
further dissolution of the
small amount of liver tissue
present. The oil & water are
removed without contact
with air. This process is
then repeated another 2
times.

DRYING
Drying is carried out in
a vacuum drying
tower which
continuously
evaporates any
small amount of
residual water.
Result: a clear bright,
highly refined oil.

WINTERIZATION
All medicinal &
veterinary oils are
cooled to 0 C,
which causes the
stearin to separate.
The solid is removed
by filtration and a
polyunsaturated
product is left.

DEODORIZATION
Final deodorization is
achieved by
steaming under
vacuum. This
removes aldehydic
& ketonic impurities.
It also protects the oil
from oxidation.

STANDARDIZATION
The medicinal oil is
standardized for
vitamin content by
blending.
BP standards: 1 g oil
should contain at
least
- 600 IU vitamin A
- 60 IU vitamin D

STORAGE OF COD-LIVER OIL

Cod-liver oil should be
stored in well-fitted
airtight containers.
It should be protected
from light & stored in
a cool, dry place.

COD-LIVER OIL: CHARACTERS

Medicinal cod-liver oil is
very pale yellow liquid
with only a slightly fishy
odour & taste.
The acid value: should not
exceed 1.2 but it varies
with age.
Iodine Value: high (150180).
Unsaponifiable matter: low
(1.5%) unlike halibutliver oil.

COD-LIVER OIL: CONSTITUENTS

The oil consists of glycerides of
unsaturated (85%) and saturated (15%)
acids.
[Polyunsaturated acids play an important
role in human health]
Saturated fatty acids: myristic acid,
palmitic acid & traces of stearic acid.

ACTIONS & USES

The medicinal properties of codliver oil are mainly due to the
Vitamins A & D.
It is widely used in
underdeveloped countries for
the prevention & treatment of
rickets.
Europe & USA: Traditionally
used as a vitamin supplement.
Recent research: relief of
rheumatic pains & joint &
muscle stiffness.
Reduces blood cholesterol.
Protects against CVD

COD-LIVER OIL:
ALLIED DRUGS
Halibut-liver oil: the fixed oil
obtained from the livers of
the Halibut, Hippoglossus
vulgaris (Pleurnectideae).
It is a pale yellow liquid
containing large amounts
of vitamin A & D.
Unsaponifiable matter is not
less than 7%.
Uses: similar to cod-liver oil
(smaller doses).
Many other fish-liver oils
resemble cod-liver oil, &
shark-liver oil, Oleum
Selachoidei, is included in
the Indian Pharmacopoeia.

CASTOR OIL
DEFINITION: Castor
oil is a fixed oil
obtained from the
seeds of Ricinus
communis
(Euphorbiaceae).
GEOGRAPHICAL
SOURCES: Native
to India. Produced
in Brazil, India,
China, Russia &
Thailand.

CASTOR SEEDS:
BOTANICAL CHARACTERISTICS
Seeds show considerable
difference in colour &
size. They are oval,
slightly compressed
Colour: uniform grey,
brown or black, mottled
with brown or black.
If grown in good conditions,
they have very little
odour & the taste is
slightly acrid.
If the testa are broken,
rancidity will develop.

CASTOR OIL: PREPARATION

90% of the worlds castor oil is prepared in India &
Brazil. Small amounts of raw seeds are now
exported.
Method of preparation: Seeds are removed from
the testa. Kernels are cold-pressed with a
hydraulic press. Oil is then refined by steaming,
filtration & bleaching.

Cold-expression yields 33% of medicinal oil.

Further amounts of lower quality oil may be
obtained by other methods

CASTOR OIL:
CHARACTERISTICS
Medicinal castor oil is a
colourless or pale yellow
liquid, with a slight odour
& faintly acrid taste.
Acid value: increases with
age. If initially high
indicates the use of
damaged sees or
careless extraction or
storage.
Viscosity: Extremely high

CASTOR OIL: CONSTITUENTS

Castor seeds contain 46-53 % fixed oil.
These fixed oils consist of the glycosides of
- Ricinoleic
- Isoricinoleic
- Steric
- Dihydroxystearic acids
The cake, after expression, contains extremely
poisonous toxins (ricins) unfit for cattle feed.
In the body they produce and anti-toxin (antiricin).
Ricin D is a sugar protein with a strong lethal
toxicity.

CASTOR OIL: USES & ACTIONS

Once widely used as a
domestic purgative.
Now more restricted to hospital
use for administration after
food poisoning & as a
preliminary to intestinal
examination.
Because of the ricin, the seeds
have a much more violent
action than the oil and is not
used as a purgative in the
West.
Non-pharmaceutical uses of oil:
Turkey Red Oil, soaps,
paints, varnishes &
lubricants.

CASTOR OIL: ALLIED DRUGS

Croton seeds obtained from Croton
triglium (Euphorbiaceae) a
small tree producing similar
capsules to those of castor. The
seeds resemble castor in size and
shape but have a dull, cinnamonbrown colour.

Oil contains 50% fixed oil. Contains

croton resin & crotin: a mixture of
crotin-globulin & crotin-albumin
comparable to ricin. Also contains
diterpenes, capric, lauric & palmitic
acids. These are anti-inflammatory
& vesicant.
Esters: potential anti-HIV activity.
Should be used with caution. Not
used medicinally in the West.
Internally violent cathartic.

CASTOR OIL: ALLIED HERBS

Physic nuts or Purging nuts seeds of
Jatropho curcas (Euphorbiaceae).
Contain 40% fixed oil & contain a
substance similar to ricin called
curcin. Both the seeds & the oil are
powerful purgatives.
Abrus sees (prayer beads) are the
seeds of Abrus precatorius
(Leguminosae). Contain a toxic
glycoprotein (abrin) resembling ricin.
Also contain indole-alkaloids. Used
in folk medicine in Asia, Africa & S.
America to treat many ailments, to
procure abortion & to hasten labour.
In India they are also used as an oral
contraceptive. (weigh 1 carat =
200mg traditional weights).

ALMOND OIL
DEFINITION: Almond oil is
the fixed oil obtained by
expression from the
seeds of Prunus
amygdalus (Roseceae)
var. dulcis (sweet
almond) or var. amara
(bitter almond).
GEOGRAPHICAL
SOURCES:
Mediterranean countries:
North Africa, France,
Spain, Italy)

SWEET & BITTER ALMONDS

Young fruit have a soft, felt-like pericarp, the inner
part of which gradually becomes
sclerenchymatous as the fruit ripens to form a
pitted endocarp (shell), also consisting of
sclerenchymatous cells. This is sometimes
ground and used to adulterate powdered herbs.

The testa of the seed is removed by soaking it in

warm water (known as blanching).
Bitter almonds are sometimes found in samples of
sweet almonds, especially in those from N. Africa.
Their presence may be detected the sodium
picrate test for cyanogenic glycosides.

ALMOND OIL: CONSTITUENTS

Both varieties contain
40-55 % fixed oil, 20%
protein, mucilage &
emulsin.
Bitter almonds contain
2.5-4% cyanogenic
glycoside, amygdalin.
Olein
Glycosides of linoleic &
other acids

ALMOND OIL: PRODUCTION &

CHARACTERS
Almond oils is produced by
grinding the seeds &
expressing them in a
canvas bag between
slightly heated iron
plates.
They are sometimes ground
before expression (no
added advantage). The
oil is then clarified by
filtration.
Oil is pale yellow liquid with
a slight odour & bland,
nutty taste.

ALMOND ESSENTIAL /
VOLATILE OIL
Essential oil is obtained
from the cake left after
expressing bitter
almonds. This is
macerated with water
for some time to allow
for the hydrolysis of
amygdalin. The
benzaldehyde and
hydrocyanic acid are
separated by steam
distillation.

ALMOND OIL: ACTIONS & USES

Almond oil is used in the
preparation of many
ablution articles.
When taken internally, it
has a mild laxative
action.
Volatile almond oil is used
as a flavouring agent.

ARACHIS OIL
DEFINITION: Arachis oil
is obtained by
expression from the
seeds of Arachis
hypogaea
(Leguminosae).
COMMON NAMES:
Earth-nut, ground nut,
peanut.
GEOGRAPHICL
SOURCES: Tropical
Africa, India, Brazil, S.
USA & Australia.

PREPARATION
During ripening, the fruits bury themselves in the sandy soil
in which the plants grow. Each fruit contains1-3 redbrown seeds.
Fruits shelled by machine.
Kernels contain 40-50% fixed oil.
Because of the high oil content of the seeds, when
crushed, it is difficult to express. Therefore, after
boiling, part of the oil is removed in a low pressure
expeller and the remaining cake is solvent extracted.
The 2 oil fractions are then mixed together before
undergoing purification.
The pressed cake makes excellent cattle feed.
The ground pericarp is used as an adulterant for powdered
herbs.

ARACHIS OIL: CONSTITUENTS

Glycosides of
- Oleic
- Linoleic
- Palmitic
- Arachidic
- Stearic
- Lignoceric
- And other acids

ARACHIS OIL: ACTIONS & USES

Similar properties to olive oil.
It is an ingredient of
camphorated oil.
Mainly used in the production
of margarine & cooking
fats.
Hydrogenated oil is also
official.
Arachis oil is the most likely
oil to be used to adulterate
other types of oil.

LINSEED & LINSEED OIL

DEFINITION: Linseed is
the dried ripe seed of
Linum usitassimum
(Linaceae).

COMMON NAMES:
Linseed, flaxseed
GEOGRAPHICAL
SOURCES: S. America,
India, USA, Canada,
England.

LINSEED: CONSTITUENTS
30-40 % fixed oils
Mucilage
Protein
Small amounts of cyanogenetic
glycosides: Linamarin & Lotaustralin
Flavonoids
Lignan potential cancer preventative

LINSEED OIL
DEFINITION: Extraction of
linseed oil is done by hot
expression of linseed
meal. The cake is
adjusted to leave in
sufficient oil to make it
suitable for cattle feed.
Linseed oil is a yellowbrown drying oil with a
characteristic odour &
bland taste.

LINSEED OIL: CONSTANTS

On exposure to air it
gradually thickens &
forms a hard
varnish.

Iodine value: high (at

least 175) has
high amounts of
unsaturated acid
glycosides.

LINSEED OIL: CONSTITUENTS

Linolenic acid
Linoleic acid
Oleic acid

Myristic
Stearic
Palmitic acids

USES & ACTIONS

Crushed linseed is used as a poultice
and whole seeds are used to make
demulcent preparations.
Oil is used as a liniment.
Research: anti-bacterial properties in
topical applications effective
against Staphylococcus aureus
strains resistant to anti-biotics.
Linseed cake is a valuable cattle feed.

For use in paints, linseed oil is boiled

with driers such as Mangenese
resinate (by forming metallic salts,
the oil is dried more rapidly not
safe for medicinal use)

OIL OF THEOBROMA
DEFINTION: Theobroma
oil is obtained from the
ground kernels of
Theobroma cacao
(Sterculiaceae) by hot
expression. The oil is
filtered and allowed to
set into moulds.
COMMON NAMES: Cocoa
butter

GEOGRAPHICAL
SOURCES: Holland

THEOBROMA OIL:
CONSTITUENTS
Glycerides of
- Stearic
- Palmitic
- Arachidic
- Oleic
- And other acids
It is the most expensive of all the fixed oils,
and is commonly adulterated with waxes,
stearin, animal or vegetable tallows.

THEOBROMA OIL:
CONSTANTS & USES
Boiling point: 31-34
C.
This makes it ideal for
the use in the
preparation of
suppositories.

Waxes
Like fats, waxes are esters of fatty acids. The
alcohol, however, is not glycerol but usually a
long-chain, high-molecular weight alcohol.
In plants, waxes are generally found covering
the external parts, like the epidermis of leaves
and fruits, where their main function is to
prevent the loss of water.
Wax is also produced by insects, e.g. the
honeycombs of bees and wasps.

USES OF WAX
1.

Wax is used in pharmacy to make soft

ointments harder and to prepare lip salves.

2.

The technical uses of waxes are substantial,

e.g. in shoe polishes and car waxes.

Waxes fixed oils and fats

Wax has a melting point above
approximately 45 C (113 F) (which
differentiates waxes from fats and oils).
Fats and oils my be saponified by
means of either aqueous or alcoholic
alkali but waxes are only saponified by
alcoholic alkali. (this fact is used for the

detection of fats when added as adulterants to

waxes).

Examples

Jojoba wax (Simmondsia chinensis)

Carnauba wax (Copernicia cerifera)

Wool fat

Beeswax (Apis mellifera)

WOOL FAT
DEFINITION: Wool fat
(anhydrous lanolin)
is a purified fat-like
substance prepared
from the wool of the
sheep, Ovis aries
(Bovidae).

WOOL FAT: PREPARATION

Raw wool contains
considerable quantities
of wool grease or crude
lanolin, the potassium
salts of fatty acids &
earthy matter.
Raw lanolin is separated by
cracking with sulphuric
acid & purified to be fit
for medicinal use.
Purification may be done
by centrifuging with
water & by bleaching.

WOOL FAT: CHARACTERS

Wool fat is a pale yellow, tenacious
substance with a faint but
characteristic odour.
It is insoluble in water.
Melting point: 36-42C
Soluble: in ether & chloroform.
Like other waxes, it is not readily
saponified by aqueous alkali, but
with a alcoholic solution of alkali.
Saponification value: 90 105.
Iodine value: 18 32.
Acid value: not more than 1

WOOL FAT: CONSTITUENTS

25 % water
Cholesterol & isocholesterol (main active
constituents).
Unsaturated alcohols
Fatty acids
(- lanoceric
- lanopalmitic
- & carnaubic fatty acids)

WOOL FAT: USES

Wool fat is used as an
emollient base for
creams & ointments.

BEESWAX
DEFINITION: Beeswax is
obtained by melting and
purifying the honeycomb of
Apis mellifica and other
bees.

GEOGRAPHICAL
SOURCES: West Indies,
California, Chile, Africa,
Madagascar & India.
Separate monographs exist
for yellow and white
beeswax.

BEESWAX: PREPARATION
Wax is secreted by worker
bees in cells on the
ventral surface of the last
4 segments of their
abdomen. The wax
passes out through
pores in the chitinous
plates of the sternum &
is used, particularly by
the young workers, to
form the comb.

PREPARTION OF
YELLOW BEESWAX
Yellow beeswax is prepared,
after removal of the
honey, by melting the
comb under water. This
causes solid impurities to
sink to the bottom while
any residual honey is
dissolved). This is then
strained and the wax is
allowed to solidify in
suitable moulds.

PREPARATION OF WHITE
BEESWAX
White beeswax is prepared from
yellow beeswax which is treated
with charcoal, potassium
permangante, chromic acid, or
chlorine, by the slow bleaching
action of light, air & moisture. In
this method the melted wax is
allowed to fall on a revolving
cylinder which is kept moist.
This then slowly becomes
bleached. This is then repeated
at least one more time. The wax
is finally cast into circular cakes.

BEESWAX: CHARACTERS
Beeswax is a yellowbrown or yellow-white
solid.
It breaks with a granular
fracture & has a
characteristic odour.
It is insoluble in water &
slightly soluble in cold
alcohol, but dissolves
in chloroform and also
in warm fixed & volatile
oils.

BEESWAX: CONSTITUENTS
Beeswax is a true wax:
Consists of 80% myricin
(myricyl palmitate)
Contains a little myricyl stearate.
Free cerotic acid
Aromatic substances

BEESWAX: ADULTERANTS
Japan wax: not a true
wax, but a fat (may
be saponified by
means of boiling
aqueous sodium
hydroxide waxes
are unaffected by
aqueous alkali).
Japan wax is prepared
from the fruits of
Rhus
(Anacardiaceae).

BEESWAX: USES
Beeswax is used for
the preparation of
plasters, ointments
and polishes.