LIPIDS
Lipides, lipins, lipoids
Collective term for fixed oils, fats and waxes
Natural fat-like substances that are insoluble in H2O but soluble in organic/fat/non-
polar solvents like ether, CHCl3, CCl4, CS2, benzene etc
BIOLOGICAL SIGNIFICANCE:
1. Secondary source of energy
2. Insulating material –prevents the escape of heat
3. Important cellular constituents
Occurs both in the cell membrane and mitochondria within the cytoplasm and
acting as a means of transporting fatty acids to the different parts of the body
PROPERTIES OF LIPIDS:
1. Greasy to touch, leaves a permanent oily stain on paper
2. Lighter than water
3. Soluble in organic solvent, insoluble in water
4. When pure, colorless with bland odor and taste
5. Yellow color in fat is due to carotene (provit. A)
6. When heated strongly, undergoes decomposition forming acrid flammable vapors and
when ignited, they burn with a sooty flame. Acridity is due to acrolein (propenal)
PHYSICAL CONSTANTS:
1. Refractive index
2. Melting/solidification point
3. Viscosity
4. Specific gravity
5. Optical rotation
CLASIFICATIONS OF LIPIDS:
I- SIMPLE LIPIDS
Esters of fatty acid and alcohol
1. FATS AND FIXED OILS
Chemically are esters of fatty acids (specifically long chain) with alcohols
Termed as glycerides
Fats are solid in nature (animal fats) at normal temperature – because of the
nature of fatty acids present in the glyceride
Fats have a higher percentage of saturated fatty acid
Fixed oils are liquid vegetable oils at room temperature
Fats have a higher percentage of unsaturated fatty acid
Exemption to the rule:
a. Cocoa butter (Theobroma cacao)
solid
suppository base
plant source
only solid vegetable oil at room temperature
b. Cod Liver Oil
liquid
animal source
only liquid animal fat
3 CLASSIFICATION OF FIXED OILS:
A. Non-drying oils
Have an iodine value of 100 and below
More of oleic acid
Commonly used for food preparation
Eg. coconut oil, peanut oil and olive oil
B. Semi-drying oils
Have an iodine value of 100 – 120
More of oleic and linoleic acid
Commonly used for preparation of dosage forms
Eg. Corn oil, cottonseed oil, wheat, sesame, brazil and soybean oil
C. Drying oils
Have an iodine value of 120 and above
More linoleic and linolenic acid
Primarily important in paint industry
The unsaturated fatty acid of linseed oil (linolenic acid) is able to combine
with air to form oxide or it polymerizes, after which it forms a hard, thick
films upon exposure to air
Eg. linseed oil, sunflower poppyseed oil
GENERAL USES OF FIXED OILS:
1. Emollient
2. Vehicle for other medicaments
3. Manufacture of soaps
4. Manufacture of paints and varnishes
5. Lubricant or lubricating agent
6. Dietary supplement
7. Agents of pharmaceutical necessity
8. Chaulmoogra oil – anti-leprosy
9. Castor oil – laxative or cathartic
10. Sodium morrhuate – anti-sclerosing agent to obliterate varicose veins
2. WAXES
Esters of fatty acid and alcohol (high molecular weight)
USES OF WAXES:
For protection and prevents water loss in plants (waxes are found in the
outer cell walls of epidermal tissues specifically in the fruits and leaves of
plants)
Serve as protection against microorganism (plants)
As water repellants (animals)
Makes feathers of birds pliable and soft (animals)
Pharmaceutically, waxes are used to harden ointments and cosmetic creams
TEST FOR WAXES:
1. Warm a little piece in alcohol, it will dissolve and upon cooling it crystallizes out
2. Warm a small piece in ether, it is soluble
3. Acrolein test
- Heat a small piece with potassium bisulfate
- (+) result – no production of acrid irritating odor
EXAMPLES:
A. Beeswax – chiefly made up of myricyl palmitate
B. Spermaceti – made up of cetyl palmitate
C. Cholesteryl esters
Schuller – Christian Disease – abnormal high concentration of cholesteryl ester deposits
in the liver, brain, kidneys, nerves and other tissues of the body
II- COMPOUND LIPIDS
Esters of fatty acid, alcohol and another compound
A. PHOSPHOLIPIDS
– “Phosphatides”
- Phosphorized fats
1. LECITHIN OR PHOSPHATIDYL CHOLINE
Composition:
glycerol
2 fatty acids
H3PO4
N – base: Choline = HO – CH2 – CH2 – N – (CH3)3
OH
General Formula:
USES:
A. PHYSIOLOGICAL
Good emulsifying agent
Mobilize cholesterol
Aid in the transport and absorption of fatty acids
B. INDUSTRIAL
Provide a creamy consistency to oleomargarine
Prevent corrosion of storage tanks due to lead in gasoline
2. CEPHALIN OR PHOSPHATIDYL ETHANOLAMINE
Thromboplastic substance which initiates blood coagulation
COMPOSITION:
glycerol
2 fatty acids
H3PO4
N – base: Ethanolamine = HO – CH2 – CH2 – NH2
General Formula:
3. SPHINGOMYELIN
Contains amino alcohol, sphingosine
Pathology: Sphingomyelin lipidosis / Niemann –Pick Disease
- Due to the inability to degrade sphingomyelins as a result of a deficiency
in the enzyme sphingomyelinase
B. GLYCOLIPIDS
1. GLUCOCEREBROSIDES
CHO –glucose
Pathology: Gaucher’s Disease / Glucocerebrosidosis
- Due to inability to degrade glucocerebrosides as a result of a deficiency in
the enzyme glucocerebrosidase
GALACTOCEREBROSIDES
CHO – galactose
Pathology: Krabbes Disease / Galactocerebrosidosis
- Due to the inability to degrade galactocerebrosides as a result of a
deficiency in the enzyme galactocerebrosidase
2. GANGLIOSIDES
Pathology: Tay Sach”s Disease
- Due to the inability to degrade gangliosides as a result of a deficiency in
the enzyme gangliosidase
Symptoms:
- Severe psychomotor deterioration
- Blindness
- Mental retardation
- Death
3. SULFOLIPIDS
4. GALACTOSYL DIGLYCERIDES
III- DERIVED LIPID
Product of simple and compound lipid upon hydrolysis
A. FATTY ACIDS:
1. Saturated Fatty Acids (CnH2nO2)
No. of NAME CHEMICAL FORMULA SOURCE
Carbon
a. Straight Chain
4 Butyric C4H8O2 Butter
6 Caproic C6H12O2 Butter, coconut, nut
and palm oil
8 Caprylic C8H16O2 Butter, coconut, nut
and palm oil
10 Capric C10H20O2 Butter, coconut, nut
and palm oil
12 Lauric C12H24O2 Laurel, coconut oil
14 Myristic C14H28O2 Nutmeg, coconut oil
and animal fats
16 Palmitic C16H32O2 Plant (palm) and
animal fats
18 Stearic C18H36O2 Plant (Tallow) and
animal fats
20 Arachidic C20H40O2 Peanut butter, lard
22 Behenic Beneoil
24 Lignoceric C24H48O2 Peanut oil , glycol
and phospholipid
26 Cerotic C26H52O2 Beeswax, wool fats
b. Branched Chain
19 Tuberculostearic acid C19H38O2 Human T.B. bacilli
Palmitic acid makes up about 15 to 50% of total fatty acids in fats
Myristic and stearic acids are also frequent
Tuberculo stearic acid occur in the lipids of human tubercle bacilli
PROPERTIES OF SATURATED FATTY ACIDS:
Low molecular weight
Liquid at ordinary room temperature (ten or less carbon atoms)
Low melting point and are volatile
The rest are solids, with high melting point and are non-volatile
2. Unsaturated Fatty Acids (CnH2n = O2)
No. of NAME No. of CHEMICAL SOURCE
Carbon db FORMULA
18 Oleic acid series 1
CnH2n_O2
4 Crotonic acid C6H6O2 Croton oil
14 Myristoleic acid C14H26O2 Butter, fish liver oil, sperm
16 Palmitoleic acid C16H30O2 oil
18 Oleic acid C18H34O2 Butter, fish oils, hen fat
20 Gadoleic acid C20H28O2 Plant and animal fats, olive
24 Nervonic acid C24H46O2 oil
Brain, phospholipids, fish liver
oil
Glycolipids
18 Linoleic acid series 2 C18H32O2 Linseed oil, lard, cotton seed
CnH2n_4O2 oil
Linoleic acid
18 Linolenic acid series 3
CnH2n_6O2
Linolenic acid C18H30O2 Linseed oil, fish liver oil
Arachidonic acid series 4
CnH2n_8O2
18 Stearidonic acid C18H28O2 Cod liver oil
20 Arachidonic acid C20H32O2 Lecithin, cephalin, butter,
liver fats
Clupadonic acid series 5
CnH2n_10O2
22 Clupadonic acid C22H34O2 Brain and liver phospholipid
Oleic acid is the most abundant fatty acid found in nature
It forms about 50% of the total fatty acid in many fats and is seldom less than 10%
It is found in all existing fats and phospholipid
Linolenic acid is the chief constituent of linseed oil, which is the main drying oil of paint
industry
PROPERTIES OF UNSATURATED FATTY ACIDS:
Unsaturated fatty acids are unstable and reactive due to the presence of the double
bonds in their molecules (the reactivity increases with the increase of the double bonds)
Insoluble in ordinary solvents
Liquid at room temperature and are non volatile
3. HYDROXY AND CYCLIC ACID:
No. of NAME CHEMICAL FORMULA SOURCE
Carbon
1. Hydroxy acids:
a. Saturated :
18 Dihydroxystearic acid C17H33(OH)2 COOH Castor oil
24 Cerebronic acid C23H46(OH)COOH Brain glycolipids
32 Lanoceric acid C31H61(OH)2COOH Wool fat
b. Unsaturated (one
double bond):
18 Ricinoleic acid C17H32(OH)COOH Castor oil
24 Oxynervonic acid C23H44(OH)COOH Glycolipids
2. Cyclic acids
16 Hydnocarpic acid C16H28O2 Chaulmoogra oil
18 Chaulmoogric acid C18H32O2 Chaulmoogra oil
26 Phthioic acid C26H52O2 Human Tubercle
bacilli
Chaulmoogra oil has attracted the attention of medical practitioners because
the ethyl esters and sodium salts of hydnocarpic and chaulmoogric acid are used
in the treatment of leprosy
Phthioic acid - is a saturated cyclic acid and is liquid at ordinary temperature.
- It has been shown to produce proliferation of epitheloid and giant cells
and is probably the agent responsible for the manifestations of
tuberculosis
B. ALCOHOLS - low molecular weight specifically glycerol
Glycerol
Sphingosine
Sterol
Common Structure:
Cyclopentanoperhydrophenanthrene
EXAMPLES:
1. CHOLESTEROL – animal sterol
2. ERGOSTEROL – plant sterol; more unsaturated
3. HORMONES
A. Progesterone – female hormone
B. Testosterone – male hormone
4. VITAMIN D
A. Vitamin D3 – irradiated 7-dehydrocholesterol
B.Vitamin D2 – irradiated ergosterol
COMMON ABNORMALITY:
ARTERIOSCLEROSIS
Hardening of the arteries
Thickening of or hardening of the vessel walls due to the presence of calcium or lime
This kind of hardening is usually proceeded by ATHEROSCLEROSIS, a kind of
degeneration or softening of the inner lining of the vessel walls
CHEMICAL PROPERTIES:
1. Acrolein test
Heating with potassium bisulfate
(+) result – acrid irritating odor
2. Test with osmic acid
(+) result – black coloration
3. Reaction with alkanet pigment
(+) result – red color
4. Reaction with an alkali
KOH
NaOH
Saponification
- reaction of glycerides and alkali
- alkali catalyzed hydrolysis of fats and fixed oils
- production of soap
2 TYPES OF SOAP:
A. SOFT SOAP (bath soap)
made by reacting KOH as the alkali + triolein
chemical name – potassium oleate
Equation:
B. HARD SOAP
made by reacting NaOH as the alkali + tristearin
chemical name – sodium stearate
Equation:
5. Test for unsaturation (Halogenation)
Addition of halogen (X2) to –C=C
Reagent: Hubl’s reagent – I in KI
A. Iodine T.S.
Done by adding the iodine to the unsaturated fatty acid
(+) result – decolorization of dark brown color of Iodine T.S.
The more drops of iodine T.S. added the more unsaturated the fixed oil
B. Bromine T.S.
(+) result – reddish brown color
6. Hydrolysis (acidic)
Fats are readily hydrolyzed by acids, enzymes or superheated steam with
the liberation of fatty acids and glycerol
Breaking-up of ester linkages in fats/oils in the presence of an acid and
enzymes (esterase, lipase)
Rancidity
- Hydrolysis of fats and fixed oils
- Fats/fixed oil → glycerol + fatty acid
- Rancid Fat or Oil – disagreeable odor, not good for human
consumption
2 TYPES of RANCIDITY:
1. HYDROLYTIC RANCIDITY
- Induces the hydrolysis of fats/oils due to moist air
- Products: volatile fatty acids
TWO WAYS OF PREVENTING HYDROLYTIC RANCIDITY:
Storage of fat/ oil in tightly sealed containers
Refrigeration
2. OXIDATION RANCIDITY
- Systems of multiple bonds
- Products: aldehyde, ketones
- As a result of exposure to atmosphere or heat
ANTIOXIDANTS:
A. Naturally occurring: Vitamin C & E
B. Synthetically Prepared: Butylated Hydroxyanisole (BHA)
: Butylated Toluene (BHT)
7. Hydrogenation
The liquid oil produces semi-solid fats that are extensively used as
cooking oil and shortening
Polymerization of linolenic fatty acid
Used in the conversion of vegetable oil to fat
Used in the manufacture of margarine
Fixed oils are may be hydrogenated by passing hydrogen in the presence
of nickel or palladium through the oil heated to 160°C to 200°C
8. Sulfonation/Sulfation
Obtained by reacting sulfuric acid with the oil, keeping the temperature
down by chilling. The oil is then washed and neutralized. If the oil
contains an olefinic linkage , the acid molecules add into the double bond
CHEMICAL CONSTANTS: Identification of Fats and Fixed Oil
1. Saponification number
The number of milligrams of alkali required to neutralize the fatty acids
and saponify the esters contained in one gram of fat or the substance
Significance:
- Means of detecting the presence of adulterants
- Means of detecting fresh fixed oils
- Means of detecting palmitic and stearic glycerides
2. Acid number
The number of milligrams of KOH required to neutralize the free fatty
acid in 1 gram of fat or the substance which indicates the amount of free
fatty acids present in the oil
The higher the acid value the more rancid the fixed oil is
Significance:
- Used to determine the efficiency/freshness of fixed oil or fat
3. Polenske Number
The number of milliliters of 0.1N KOH required to neutralize the insoluble
fatty acids (those which are not volatile with steam distillation) from 5
gram of fat
4. Reichert-Meissl Number
This is the amount of 0.1N alkali required to neutralize the volatile fatty
acids distilled from 5 grams of fat.
Saponification number refers to all fatty acid molecules capable of being
saponified by an alkali, while Reichert-Meissl number refers only to
volatile fatty acids
Obtained by saponification, acidification and distillation
Butter is the only fat which gives a high Reichert Meissl number
5. Acetyl number
This represents the number of milligrams of KOH necessary to neutralize
the acetic acid liberated from the hydrolysis of one gram of acetylated fat
Significance:
- This measures the number of hydroxyl groups present in the fat
Procedure:
- First fat is acetylated by treating with acetic anhydride and is
subsequently saponified with KOH.
- The fatty acid are liberated by H2SO4
- The acetic acid is separated from the insoluble fatty acid and is
titrated with standard alkali solution
6. Iodine number
The number of grams of iodine absorbed under prescribed conditions by
1oog of fat or the substance
Significance:
- Indicates the degree of unsaturation (the higher the iodine value,
the more unsaturated the fixed oil is
- Serves as a means of classifying fixed oils
DIFFERENCES BETWEEN FIXED OILS AND VOLATILE OILS:
DIFFERENCES FIXED OIL/FAT VOLATILE OIL
Can be distilled no yes
Glyceryl ester of fatty acid Glyceryl spot Varies in composition
Can be saponified with yes no
alkalies
Greasy spot Leaves spot No spot
Odor bland Characteristic odor
Specific gravity lighter Some are lighter
Some are heavier
Rancidity yes terenbentinate
MCP
