ACTIVITY 7

Introduction to
Phytochemistry:
Primary and Secondary
Metabolites
Once upon a Time
Winter.
One day, there was a farmer and some cows. He noticed that these cows
were oozing with blood from every orifice. Perplexed, the farmer collected
the blood in a can and brought it to a scientist at a laboratory at the
University of Wisconsin. The laboratory belongs to a chemist named Karl
Paul Link. Curious about the farmer’s problems, he tried to figure out what
was happening. Link found out that the cows were feeding on moldy sweet
clover hays. The chemist wanted to find out what these plants contain to be
able to do such a gruesome thing to a cow. After years of extensive research,
Link and his co-scientists found out what was in the sweet clover (image on
the left). They discovered that it was the deadly molecule coumarin, which
they first named dicoumarol. Dicoumarol is a substance capable of thinning
blood and preventing blood clots from happening. When the cows ate them,
they had an explosive hemorrhage causing blood to come out of every orifice
of the cow’s body.
Who would have thought that this tragic event would be the beginning
of research that would lead to the discovery of a new drug that will save
thousands of lives today?

The discovery of this drug is just one of the hundreds of other

discoveries wherein medicine is derived from plants. But what is with
these plants that make it possible for them to produce such products?
Do the plants even need these plant constituents? These are the
questions we will answer in this lesson.

OBJECTIVES: At the end of this lesson, you should be able to:

1. Describe the characteristics of the primary and secondary metabolites and identify their role for the plant and
their economic and pharmacologic uses.
PHARMACOGNOSY: An Introduction
Plants and their products form the basis of medicines. Several compounds, which are pharmaceutically and medicinally
important, are derived from plant sources. Plant Constituents are the individual chemicals from which plants are
made. These constituents are organic in nature and synthesized in plants by the activity of individual cells. Biosynthesis
is the process by which plant constituents are formed, utilizing simple substances and enzymes.

The medicinal value of a plant depends on the nature of plant constituents present in it, known as the active principle
or active constituent. Active constituents are those chemical substances solely responsible for the therapeutic
activity of the plant. Theories have been proposed as to why these compounds are formed in plants; it is likely that
many of them are produced as part of a chemical defense system to protect the plant. The chemical constituents present
in plants that do not possess any definite therapeutic value are known as inactive constituents.

As the formation of different active and inactive constituents of plants involves various metabolic pathways, the inactive
plant constituents are termed primary plant metabolites. In contrast, active plant constituents are termed
secondary plant metabolites.

Primary plant metabolites are compounds or polymers of simple molecules synthesized by plants. They generally do
not possess therapeutic effects as such but are essential for the life of plants and contain high-energy bonds. I.e.,
carbohydrates, proteins, lipids, and nucleic acids. These are used up for the biosynthesis of secondary metabolites.

Secondary metabolites are complex organic molecules biosynthesized from primary plant metabolites in plant cells.
They are unique to plants or groups of plants and generally possess therapeutic activity. They are neither essential for
plant life nor contain high energy bonds. These are usually stored in vacuoles. These are used as medicine, food, flavors,
colors, dyes, poisons, perfumes, etc.

Part One - Primary Metabolites

I. Carbohydrates
Carbohydrates are the first complex organic compounds formed in plants as a result of photosynthesis. These provide
storage and transport of energy and building blocks of the cell wall. These are the constituents of various metabolites
as glycosides and required precursors for biosynthesis of all other metabolites and the basis of all organic compounds
of the living world.

These carbohydrates are classified into three main categories based on their molecular size:
1. Monosaccharides (True sugars)
2. Oligosaccharides (True sugars)
3. Polysaccharides (Non-sugars)

a. Monosaccharides
Monosaccharides: are characterized by the general formula Cn (H2O) n, the presence of a carbonyl group, and a hydroxyl
group. The number of carbon atoms, most often five or six. These are the simplest sugar molecules and cannot be
hydrolyzed into a simpler form. These are crystalline substances, soluble in water, and practically insoluble in organic
solvents like ether, chloroform, and absolute alcohol. These are optically active and exist in more than one isomeric
form. Further, these are sub-classified based on the number of carbon atoms present.

Sugar Number of Carbon Atoms Examples

Trioses 3 Glyceraldehydes
Tetroses 4 Threose, erythrose
Pentoses 5 Xylose, arabinose, rhamnose, ribose, ribulose
Hexoses 6 Glucose, Fructose, Galactose
Heptoses 7 Cymarose
These monosaccharides are also classified based on the presence of the carbonyl group:
1. Aldoses- (containing aldehyde group), e.g., glucose, arabinose, and galactose
2. Ketoses- (containing ketone group), e.g., fructose.

B. Oligosaccharides.
Oligosaccharides are formed by the condensation of 2-10 monosaccharide molecules, which involves the in-vivo
formation of the glycosidic linkage. The glycosidic linkage can easily be cleaved by chemical hydrolysis and enzymatic
hydrolysis.

On the basis of type of glycosidic linkage present the disaccharides are of two types:

a. Non reducing disaccharides (linkage involving reducing function of both sugar) e.g. sucrose
b. Reducing disaccharides (linkage involving reducing function of only one sugar) e.g. Lactose, maltose, cellobiose

Examples of Oligosaccharides
SUGAR Source HYDROLYSIS PRODUCTS
Sucrose (Cane Sugar) Sugar cane (Beta vulgaris) Glucose and Fructose
Lactose (Milk Sugar) Milk Glucose and Galactose
Maltose (Malt Sugar) Germination of grains Glucose and glucose
Lactulose Synthetic Disaccharide Galactose and Fructose

C. Polysaccharides (Glycans)
Polysaccharides are high molecular weight polymers of a larger number of monosaccharide molecules. The sugar
molecules are attached to each other by glycosidic linkage. These serve as skeletal material (cellulose) or reserve food
material (starch, glycogen, and inulin). These are non-sugar carbohydrates that do not have a sweet taste. They are
either insoluble in water (cellulose) or form colloidal solutions (starch).

Glycans are further sub-divided in two categories:

a. Homoglycans (homogenous polysaccharides) are formed by the condensation of larger number of same
sugar molecules.
b. Heteroglycans (heterogeneous polysaccharides): formed by the condensation of sugar molecules and non-
sugar moiety.

HOMOGLYCANS

Starch
Starch is the primary reserve energy source and a universal constituent of plants and is derived from glucose. It is
composed of two components, amylose, and amylopectin. Amylose (20 – 30%) is a water-soluble, linear chain molecule
consisting of 250- 300 α-D –glucose having 1-4 linkage. It forms blue color with iodine in the iodine test. Amylopectin
(70-90%) is insoluble in cold-water, branched-chain molecule, composed of about 1000 α-D –glucose with 1-4 and 1-6
linkage. It forms a red to violet color with iodine. Pharmaceutical products like dextrins and cyclo-dextrins are derivatives
of starch.
Cellulose
Cellulose is the universal biological polymer. It is the fibrous substance of cell walls
and is responsible for the structural rigidity of plants in combination with lignin.
Cellulose is a linear polymer of β (1-4) linked D-glucose units. Cotton fibers are the
purest form of cellulose (98%), whereas oxidized cellulose and methylcellulose are
cellulose derivatives used in pharmacy.

Cellulose Fibers in paper

HETEROGLYCANS

Gum
Gums are complex heterogeneous, branched, and uronic acid-containing polysaccharide macromolecules. These are
translucent, amorphous substances, exudates of plants, and produced as the result of trauma. Gums are insoluble in
organic solvents, but most are soluble in water and form colloidal viscous solutions. These are optically active, and gums
in dilute solutions (<1%) are precipitated upon adding ethanol or lead subacetate. Gums on hydrolysis yield sugars
(arabinose, galactose, glucose, mannose, and xylose) with sugar acids (glucuronic acid and galacto-uronic acid).

Mucilage
Mucilages are normal cell constituents of high molecular weight compounds, composed mainly of sulphuric acid esters
of sugar. These neither dissolve in water to form clear colloidal solutions but swells. Mucilages yield sugar (galactose
and arabinose) and sugar acids (uronic acids) on hydrolysis. Seaweed agar and carrageenan contain mucilage composed
of salts of sulfate esters of polysaccharides.

Pectin
Pectins are a group of polymers made-up of partially methylated 1-4 linked α galacturonic acid residue associated with
arabinan and galactan units. These are localized in the middle lamella of the vegetable cell wall, but for industrial
purpose, it is obtained from the inner portion of the rind of citrus fruit or apple. It absorbs water and swells up because
its hydrophilic property forms a stiff jelly. Hence, it is used in pharmaceutical and food technology.

II. Lipids
Lipids are a large and diverse group of naturally occurring organic compounds, esters of fatty acids and alcohols, and
polyols. These are soluble in nonpolar organic solvents (e.g., ether, chloroform, acetone & benzene) and generally
insoluble in water.
Lipids can be further classified as:
a. Simple lipids (esters of fatty acids with alcohols). Examples are triglycerides (fats and oils), and waxes.
b. Compound lipids like phospholipids and glycolipids.

They show great structural variety:

a. Fatty Acids: Lipids on hydrolysis by acids or bases yield the component fatty acid. These long-chain carboxylic acids
are generally referred to by their common names, which in most cases, reflect their sources. Natural fatty acids may
be saturated or unsaturated, and the saturated acids have higher melting points than unsaturated acids of the
corresponding size.
Types of Fatty Acids
Fatty Acid Chemical Formula
Saturated
Lauric Acid CH3(CH2)10CO2H
Myristic acid CH3(CH2)12CO2H
Palmitic acid CH3(CH2)14CO2H
Unsaturated
Oleic acid CH3(CH2)7CH=CH(CH2)7CO2H
Linoleic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2H
Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH (CH2)7CO2H
Two polyunsaturated fatty acids, linoleic and linolenic, are designated “essential” because their absence in the human
diet has been associated with health problems, like scaly skin, stunted growth, and increased dehydration. These acids
are also precursors to prostaglandins, a family of physiologically potent lipids present in minute amounts in most body
tissues.

b. Fats and Oils

Fats and oils are phospholipids of fatty acids with glycerol, commonly known as triglycerides, found in plants and
animals, and compose one of the major food groups of our diet. Triglycerides that are solid or semisolid at room
temperature are classified as fats and found predominantly in animals. The liquid triglycerides are called oils and
originate mainly from plants; triglycerides obtained from fish are also oils. Fats are composed mainly of saturated fatty
acids, while oils are composed of unsaturated fatty acids. Saturated and trans-fatty acid glycerides in the diet have been
associated with atherosclerosis.
Examples of vegetable oils included in different pharmacopeias
a. Almond Oil e. Peanut Oil
b. Castor Oil f. Sunflower Oil
c. Olive Oil g. Evening Primrose Oil
d. Sesame Oil h. Borage Oil

c. Waxes
Waxes are esters of fatty acids with long-chain monohydric alcohols and may contain hydrocarbons. These are widely
distributed in nature like leaves, and fruits of many plants have waxy coatings, which protect them from dehydration.
Examples of some common waxes are Spermaceti wax, Beeswax, and Carnauba wax.

d. Phospholipids
Phospholipids, the main constituents of cell membranes, resemble triglycerides in being ester or amide derivatives of
glycerol or sphingosine with fatty acids and phosphoric acid. The phosphate moiety of the resulting phosphatidic acid is
further esterified with ethanolamine, choline, or serine in the phospholipids themselves. The fatty acid components may
be saturated or unsaturated. The bilayer membrane that separates the interior of a cell from the surrounding fluids is
primarily composed of phospholipids. However, it incorporates many other components, such as cholesterol, that
contribute to its structural integrity. Protein channels that permit the transport of various kinds of chemical species in
and out of the cell are also essential components of cell membranes.

III. Proteins
Proteins are a class of organic compounds vital to every living cell. It is present in the form of skin, hair, callus,
cartilage, muscles, tendons, and ligaments. It protects and provides structure to the body of a multicellular
organism. The enzymes, hormones, and antibodies are made up of proteins, which catalyze and regulate the
physiological activities of plants and human beings. Hemoglobins and various lipoproteins transport oxygen and other
substances within an organism. Proteins may also become toxic like botulinum toxin, venom toxins, ricin, and toxins
produced by microorganisms like tetanus and diphtheria. Proteins and peptides are composed of 15 to 25% nitrogen
and about an equal amount of oxygen. Proteins and peptides can be distinguished by their size; peptides are small
proteins having molecular weights less than 10,000.

Proteins are classified mainly in two groups on the basis of their chemical nature and solubility.
a. Simple proteins: Composed of amino acids and soluble in water, dilute acid solutions, dilute alkali solutions,
dilute salt solutions or in 70% alcohol. E.g. Albumins, globulins, glutelins, protamines and histones.
b. Conjugate proteins: Composed of other structural elements besides amino acids. E.g. chromoproteins,
lipoproteins, metalloproteins and glycoproteins.

In general, plant proteins contain less content of sulfur-containing amino acids, whereas plant cell wall is rich in
hydroxyproline. Plants do not vary in their protein makeup.

Amino Acids
Hydrolysis of proteins by boiling aqueous acid or base yields an assortment of small molecules identified as α-amino
carboxylic acids. More than twenty such components have been isolated. The amino acids are generally classified into
two categories based on their synthesis in the human body.
1. Essential amino acids: Essential diet components since they are not synthesized by the human body.
2. Non-essential amino acids: Synthesized by the human body.

IV. Nucleic Acids

Nucleic acids are the major components of chromosomes present in the nuclei of
cells. Elemental analysis of nucleic acids revealed the presence of phosphorus, in
addition to the C, H, N & O. Complete hydrolysis of chromosomal nucleic acids
gave inorganic phosphate, 2-deoxyribose, and four different heterocyclic bases;
chromosomal nucleic acids are called deoxyribonucleic acids (DNA). Analogous
nucleic acids in which the sugar component is ribose are termed ribonucleic acids
(RNA). The acidic character of the nucleic acids was attributed to the phosphoric
acid moiety.

The heterocyclic bases present in nucleic acid are of two types:

1. Purines (monocyclic bases): e.g. Adenine and guanine

2. Pyrimidines (bicyclic bases): e.g. Thymine, cytosine and uracil

Part Two - Secondary Metabolites

Alkaloids
Alkaloids are organic compounds of basic nature hence named alkali-like/ alkaloid. They are usually derived from amino
acids. At small doses, they can elicit prominent pharmacologic action. Most alkaloids are alkaline solids like quinine,
emetine, and atropine. Some alkaloids are liquid in form like coniine and nicotine. Generally, alkaloids are colorless, but
some may take colored forms like berberine (yellow) and betain (red). The image on the right shows a condition known
as belladonna eyes. Ladies during the Renaissance used atropine, an alkaloid, to make their eyes look bigger because,
for them, the bigger their eyes, the more beautiful they were.

Chemical Composition: Alkaloids contain C, H, one or more than one N, usually O, and sometimes S. Alkaloids may
have N-atom, which is primary (e.g., mescaline, secondary e.g., ephedrine, tertiary e.g., atropine and quaternary e.g.,
tubocurarine). They are optically active, meaning the L form is pharmacologically more active than the D form.

Physical Characteristics: Alkaloids are bitter. They are available in the salt form; quaternary alkaloids are highly
soluble in water (except for some, e.g., lobeline HCl is soluble in CHCl3, and quinine SO4 is sparingly soluble in water).
Free bases of alkaloids are insoluble in water and soluble in an organic solvent like chloroform and ether (except for
some, e.g., Caffeine and colchicine are soluble in water)

Naming Alkaloids: Alkaloids end with the suffix in -ine and begin with a prefix which is usually based on the plant’s
genus, species, common name, discoverer (Pelleerine and Ajmalacine), and physiological activity

Distribution: Like many secondary metabolites, plants apparently synthesize alkaloids for defensive purposes. Nicotine
and derivatives are among the earliest known and most potent insecticides. Significant sources of alkaloids are
angiosperms and distributed unevenly in families. The plant families with the highest alkaloid levels are the
Papaveraceae, Berberidaceae, Fabaceae, Boraginaceae, Apocynaceae, Asclepiadaceae, Liliaceae, Gnetaceae,
Ranunculaceae, Rubiaceae, Solanaceae, and Rutaceae.

Alkaloids are distributed in different parts of plants like in the seed (nux-vomica, colchicum), fruits (black pepper,
opium), leaves (datura, belladonna, hyoscyamus, vinca, tobacco), barks (cinchona, cinnamon), roots and rhizomes
(rauwolfia, ipecac, aconite), and also in the whole plant (ephedra, lobelia).
Note: Some animals also contain alkaloids like butterflies (contain pyrrolizidine alkaloids) because they feed upon the
plants containing these alkaloids. Salamanders, amphibians, and arthropods also contain small amounts of alkaloids.
Insects, marine organisms, and lower plants have also been reported to contain small amounts of alkaloids like ergot
alkaloids from the fungus.

Classification of alkaloids based on origin:

(a) True Alkaloids: These are basic, derivatives of amino acids having nitrogen in a heterocyclic ring and occur in
plants as salts of organic acids.
(b) Proto/amino-alkaloids: These are simple biological amines, basic in nature, derivatives of amino acids, and do
not have heterocyclic nitrogen atoms in the ring system (but in the side chain)
(c) Pseudo alkaloids: These are weakly basic nitrogenous compounds, and are not derived from amino acids but have
heterocyclic nitrogen atoms.

Glycosides
In nature, glycosides are formed by the interaction of nucleotide glycosides like uridine
phosphate glucose with alcohol, phenol, steroid, triterpenoid, and flavonoids and joined
by glycosidic linkage. These are non-reducing (do not reduce Fehling solution) organic
substances, which on hydrolysis yield one or more sugar molecules and non-sugar
molecules. The sugar molecule is known as glycone, and the non-sugar molecule is
termed as the aglycone part. Glycosides can be defined as the condensation product of
the hydroxyl group of aglycone and the hemiacetal hydroxyl group of sugar. The aglycone
may be any compound containing at least one hydroxyl group.
Physical Characteristics
Glycosides are colorless (except for some, e.g., flavonoids are yellow-colored whereas anthracene glycosides are red to
orange). They are crystalline or amorphous solid substances and are generally poisonous. Glycosides are also soluble
in water and alcohol but insoluble in ether and chloroform. Similar to alkaloids, glycosides are also optically active,
usually levorotatory

Classification of Glycosides: Glycosides are generally classified in two ways:

A. On the basis of glycosidic linkage

1. O - glycosides: Sugar molecule is combined with phenol or OH group of aglycone.
2. N – glycosides: Sugar molecule is combined with N of the –NH (amino group) of aglycone.
3. S – glycosides: Sugar molecule is combined with the S or SH (thiol group) of aglycone.
4. C – glycosides: Sugar molecule is directly attached to the C – atom of aglycone.

B. On the basis of the chemical nature of aglycone and pharmacological activity

1. Anthraquinone glycosides: These are derivatives of anthraquinones,

and possess purgative properties. Anthraquinone derivatives are often
orange-red colored compounds, soluble in hot water and alcohols. Aloe
barbadensis, the image on the left, contains anthraquinone glycosides.

Senna, an ingredient of Senokot® also contains anthraquinone

glycosides and is primarily used as a laxative.

2. Cardiac glycosides: Cardiac glycosides are steroidal aglycone with a 5-membered lactone ring and act on cardiac
muscles. These are also known as cardiotonic glycosides, and cardiac activity is dependent on both the aglycone and a
sugar molecule. Activity resides in the aglycone, but the sugar renders the compounds more soluble, which increases
the power of fixation of the glycoside to the heart muscles. These are divided into two sub-groups:
a. Cardenolides: Cardenolides have a 5-membered lactone ring at the C-17 position. (eg. Digoxin, Digitoxin)
 b. Bufadienolides: Bufadienolides have a 6-membered lactone ring at the C-17 position of steroidal rings. (eg.
Scillarenin A)

3. Saponin glycosides: These form honeycomb-like foam when

shaken with water and causes hemolysis of blood. Saponins are
complex organic compounds distributed in higher plants and are
toxic to cold-blooded animals and lower organisms like earthworms
and fishes. These are soluble in alcohol but insoluble in ether and
light petroleum; on hydrolysis, it gives aglycone known as
sapogenin (generally steroids) and sugars.

Froth/Foam Test

Depending on the aglycone moiety, saponins are of two types:

 Steroidal saponin (tetracyclic triterpenoids) contain
cyclopenteno-perhydro-phenanthrene ring (eg. Diosgenin)
 Pentacyclic triterpene saponin are polymers of isoprenes
and mainly derivatives of β-amyrine. (eg. Glycyrrhetinic
acid)

4. Cyanophoric or Cyanogenic Glycosides: The glycosides that on hydrolysis yield hydrocyanic acid (HCN),
benzaldehyde, and sugars. The therapeutic activity of cyanogenic glycosides is due to the presence of hydrocyanic acid,
and these are the characteristics of the family Rosaceae. (eg. Amygdalin, Prunasin)

WARNING!

Before eating any dish containing cassava, make sure that it is properly cooked at an appropriate amount of time.
Also, do not consume much. Cassava contains Cyanogenic glycosides which release cyanide inside the body and
cause poisoning.

5. Isothiocyanate glycoside: These are sulfur-containing compounds abundant in the family Brassicaceae, also
known as glucosinolates, and on hydrolysis yields isothiocyanate (-NCS) group. These glycosides are generally
irritants and hence used externally as a counter-irritant. (eg. Sinigrin, sinalbin, and gluconapin).

6. Bitter glycosides: These are complex organic compounds containing lactone ring, soluble in water, and very bitter
in taste even in much diluted solutions. These increase the secretions of GIT by reflex action and are used as
stomachic, febrifuge, and bitter tonic. (eg. gentiopicrin and quassin)

7. Coumarin glycosides: These are aromatic compounds containing a benzo-α-pyrone ring system. These are
generally used externally in skin disorders and suntan preparations because they have the property of absorbing UV
radiation from sunlight. (eg. esculin and psoralen)

8. Flavone glycosides: These are complex organic compounds containing a phenyl-benzo-χ-pyrone ring system.
Flavones are present in plants in a free state or glycosidal state (O-glycoside or C-glycoside) with different derivatives
like flavane, flavonol, flavonone, isoflavone, and chalcones. (eg. Rutin, quercitrin, diosmin, and hesperidin)
Terpenoids(C5H8)n
Terpenoids are hydrocarbons of plant origin and refer to the oxygenated, hydrogenated, and dehydrogenated derivatives
of hydrocarbons. Terpenoids are also the building blocks of isoprene units, joined together in a head-to-tail fashion.

Physical Characteristics
Terpenoids are generally colorless compounds and are lighter than water. Their boiling point is between the range of
150-180 °C. Terpenoids are optically active liquids (few terpenoids are solid) and are insoluble in water but soluble in
organic solvents.

The term terpene originates from the mixture of isomeric hydrocarbons (C 10H16) in turpentine oil. Now, terpenes are
only limited to a class of terpenoid compounds called monoterpene hydrocarbon (C5H8)2.

The pleasant-smelling parts of the plants like flowers, leaves, stems, bark, wood, and fruits are due to some volatile
oils known as essential oils. The chief constituents of essential oils are terpenoids having atoms up to C15. Terpenoids
are located in the cytoplasm of plant cells. Essential oils are sometimes present in special glandular cells on the leaf
surface, whereas carotenoids are mainly associated with chloroplast in leaves and chromoplast in petals. Di- and
triterpenoids are primarily found in gums and resins. Some triterpenoids are also present in the animal kingdom.

Classifications of Terpenoids
Terpenoids Examples
Monoterpenoids
a. Acyclic Geraniol and Linalool
b. Monocyclic Limonene and Menthol
c. Bicycle Camphor
d. Irregular Loganin
Sesquiterpenes
a. Acyclic Farnesol
b. Monocyclic Abscisic Acid
c. Bicycle Cadinene
d. Irregular Santonin
Diterpenoids
a. Acyclic Phytol The image showcases a pricey animal vomit, the ambergris.
b. Bicyclic Agathic acid The vomit comes from the sperm whale and is used as an
c. Tricycle Abietic Acid ingredient in perfumes. It is extremely rare. The ambergris
d. Gibberllins Gibberellic Acid contains a terpene called ambroxan and ambrinol.
Triterpenoids
a. Triterpenes Squalene
b. Steroids
c. Saponins
d. Cardiac Glycoside
e. Steroidal Glycosides

Other types of Terpenoids

Tetraterpenoids (carotenoids)
These are lipid-soluble pigments widely distributed in all plants, including bacteria. Carotenoids are either in simple
unsaturated hydrocarbon form or their oxygenated derivatives known as xanthophylls. Crocin obtained from Crocus
sativus is the only water-soluble carotenoid present in plants.
a. Hydrocarbons: Carotenes and Lycopene
b. Xanthophylls: Zeaxanthin, Capsanthin, and Lutein
Volatile Oil/ Ethereal Oil /Essential Oil
Volatile oils are odorous, volatile principles of plant and animal sources. They produce their characteristic odor when
these oils evaporate when exposed to air, hence known as volatile or ethereal oils. Volatile oils represent the essence
of active constituents of the plant, hence also known as essential oils.

Chemical Characteristics
Chemically derived from terpenes (mainly mono and sesquiterpene) and their oxygenated derivatives

Physical Characteristics
They are soluble in alcohol and other organic solvents, practically insoluble in water, and lighter than water (Clove oil is
heavier). They possess characteristic odor and have a high refraction index. Most of them are optically active. Volatile
oils are colorless liquids, but when exposed to air and direct sunlight, these become darker due to oxidation. Unlike
fixed oils, volatile oils do not leave permanent grease spots on filter paper. They are not saponified with alkalis.

Occurrence
Volatile oils are secreted in special structures like duct cells, schizogenous or lysogenous glands, trichomes, and vittae.
Volatile oils are commonly found in families like:
Lamiaceae: Peppermint Zingiberaceae: Cardamom, Ginger
Apiaceae: Coriander, Fennel, Caraway, Cumin Myrtaceae: Clove, Eucalyptus
Lauraceae: Cinnamon Poaceae: Lemon grass
Asteraceae: Marigold

Resins
Resins are poorly defined chemically but are more related to each other in their physical properties and appearance.
Resins are amorphous mixtures of essential oils, oxygenated products of terpenes, and carboxylic acids. They are
obtained as exudates from plants and considered the end product of metabolism.

Physical Characteristics
Resins are generally solid or semi-solid amorphous products of complex chemical nature and usually insoluble in water
but soluble in an organic solvent like alcohol, volatile oils, fixed oils, benzene, and ether. Resins are also complex
mixtures of several compounds; isoprene (C 5H8) units are the fundamental building blocks of all true resins. These are
non-crystallizable translucent masses that soften and melt on heating and burn with smoky flames on ignition. Resins
are denser than water and contain a large number of carbon atoms

Occurrence
Resins occur in different secretory structures like resin cells (Ginger), Schizo or Schizolysogenous ducts or cavities (Pinus
sp.), and glandular hairs (Cannabis). Resin sources include gymnosperms (present in the family Pinaceae (Pinus sp.)
known as Colophony and Tar- mainly composed of hydrocarbons) and angiosperms which may include the following
families:

 Cucurbitaceae: Colocynth
 Fabaceae: Tolu Balsam Myrrh is used in
 Dipterocarpaceae: Gurjan Balsam mummification during
 Burseraceae: Myrrh the embalming
 Apiaceae: Asafoetida process
 Zingiberaceae: Ginger and Turmeric
 Cannabinaceae: Cannabis
 Convovulaceae: Jalap

Classification of resins:
1. On the basis of their formation
a. Physiological resins- formed as a normal product of metabolism w/o making injury to the plants and mainly
present in specialized cells like Schizogenous glands: Copaiba; Secretion cells: Ginger; Oil glands: Clove; Oil ducts:
Apiaceae fruits
b. Pathological Resins- formed due to a wound, injury, or abnormal circumstances on the plant and produce a
number of resin ducts. (Benzoin, Colophony, Balsams, Aloe resin)
2. On the basis of chemical nature
A. Resin acids: HMW acids, AKA resinolic acids. In combination with alkali, these
form their metallic salts known as resonates. Resin acids are generally found in a
free state or in combination with resin alcohols as esters. (Colophony)

B. Resin alcohols: HMW compounds, also known as resinols, occur either in free
form or as esters in combination with balsamic acids or resin acids. These are tetra
or pentacyclic alcohols and usually derivatives of amyrines. (Storax)
Asafoetida is one of the most
foul-smelling resin C. Resin phenols (Resinotannols): HMW compounds with a phenolic group, occur
either in free form or as esters. Resinotannols are soluble in aqueous alkali solution
due to the formation of phenoxide. These are insoluble in water and soluble in alcohol and ether. These give color
reactions with FeCl3. (Peru balsam, Tolu balsam, and Benzoin)

D. Ester Resins: These are esters of resin alcohol or resinotannols with resin acids or balsamic acids. On treatment with
alkali, these are mostly converted to free acids. (Benzoin and Storax)

E. Resenes: These are complex neutral, chemically inert HMW hydrocarbons generally found in a free state; neither
show any characteristic property nor effected by moisture and light. Resenes are soluble in chloroform and benzene but
insoluble in water. (Asafoetida).

3. On the basis of occurrence with other secondary metabolites

1. Oleoresins: homogenous mixtures of resins and volatile oils; depending on the

amount of volatile oil, these may exist as a liquid, solid or semisolid. (Copaiba,
Canada balsam, Capsicum, Ginger, and Turpentine)

2. Gum resin: Naturally occurring mixtures of resin with gum. (Gamboage)

3. Oleogum resins: Naturally occurring combinations of volatile oil, gum, and

resin. (Myrrh, Asafoetida)

Resins are produced in response 4. Glycoresins: Resins in combination with sugars as glycosides. These can be
to injury or an infection hydrolyzed with acids to get glycone and aglycone parts. (Jalap and Podophyllum)

5. Balsams: Naturally occurring resinous mixtures containing cinnamic acid, benzoic acids, and/or their esters. (Benzoin,
Balsam of tolu, Balasam of Peru, Storax).

Pharmaceutical application of resins: Generally, resins are local irritants and hence act as local cathartics (Jalap), as
anti-cancer (Podophyllum), in bronchial asthma (Cannabis) also used externally as a mild antiseptic in the form of
tinctures (Benzoin) ointment and plasters (Turpentine and Colophony). Resins are also used in the preparation of
emulsion and sustained release formulations.

Tannins
Tannins are a mixture of complex organic, non-nitrogenous substances derivatives of polyhydroxy benzoic acid
(polyphenols)with the ability to precipitate proteins (astringent). Tannins have a high molecular weight (500 to > 20000)
and are non-crystallizable. They are soluble in water (forming colloidal solution), dilute alkali, alcohol, glycerol, and
acetone while sparingly soluble in ethyl acetate, chloroform, and other organic solvents. Aqueous solutions of tannins
are acidic due to the presence of free phenolic and carboxylic groups. They precipitate heavy metals, alkaloids,
glycosides, and gelatin (proteins) from solutions. Tannins combined with proteins by cross-links making raw animal skin
to leather and on application to the living surface it renders proteins resistant to proteolytic enzymes (astringent
property), which forms the basis of therapeutic application of tannins; which is due to the formation of hydrophobic
bonds between collagen fibers that imparts resistance to water, heat, and abrasion.
Tannins are widely distributed in the plant kingdom; localized in specific plant parts such as leaves, fruits, barks, or
stems; often found in immature fruits and disappear during ripening. These are mainly present in cell saps and vacuoles
in higher plants in solution form. The hydrolyzable tannins are characteristic of dicot plants, while condensed tannins
are found in all plants, including pteridophytes and Gymnosperms.

Tannins are mainly classified into two categories on the basis of their chemical nature and biogenetic origin.

1. Hydrolysable tannins: These are esters of sugars and phenolic acid molecules (gallic acid and ellagic acid),
hydrolyzed by mineral acids, alkalis, and tannase enzymes, yielding gallic acid or hexahydroxydiphenic acid with
sugar (mainly glucose). Hydrolyzable tannins on dry distillation yield pyrogallol, and reaction with FeCl3 produce a
bluish-black precipitate. These are further subdivided into gallotannins and ellagitannins based on their product of
hydrolysis.
a. Gallotannins: These are the simplest ones, also known as galloylglucose. (Nutgall, Rhubarb, Clove, and
Chest nut)
b. Ellagitannins: This is composed of phenolic acids as a dimer of gallic acid and attached to a glucose molecule.
(Oak)

2. Condensed tannins: These are also called flavolans, proanthocyanidins, nonhydrolyzable tannins, catechol
tannins, and phlobatannins. Condensed tannins are resistant to hydrolysis and do not contain sugar molecule. On
treatment with acids or enzymes, condensed tannins are converted to a red water-insoluble compound called
phlobaphene, which imparts typical brownish color to many plant materials, mainly bark. On treatment with ferric
chloride give brownish green color, with dilute HCl yields phloroglucinol that gives a red color with matchstick on
reaction with lignin, with vanillin HCl gives red color and precipitated with bromine water. (Green tea, Cinnamon
bark, Cinchona bark, Wild cherry bark, Oak, Coca, Catechu)

3. Complex tannins: These are formed by the combination of hydrolyzable and condensed tannins.

4. Pseudo tannins: These are also known as prototannins or tannin precursors; high molecular weight compounds
do not respond to protein precipitation tests. (Gallic acid)

Pharmaceutical applications of tannins: The basis of its use therapeutically depends on its astringent property. Tannins
are used in GIT problems, burns, the leather industry, and for the formation of inks. It precipitates proteins and is
traditionally used as a styptic agent and internally for the protection of the surface of the mouth and throat. These also
act as anti-diarrheal agents and antidotes in the poisoning caused by heavy metals, alkaloids, and glycosides. The use
of tannins is reduced nowadays because tannic acid causes necrosis of the liver. Recently it has been demonstrated that
tannins are useful as an anticancer and anti-HIV agent.

Phytochemical screening refers to extracting, screening, and identifying medicinally active substances
found in plants.