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