Chemotaxonomy of Medicinal plant

CHEMOTAXONOMY:
Definition:-The approach of taxonomy in which chemical nature of plants are used in
developing classification or in solving taxonomical problems is called chemotaxonomy
,chemosystematics, chemical taxonomy ,chemical plant taxonomy or plant chemo
taxonomy are the common names of chemotaxonomy.
It gives the close relationship between chemical constituents of plants and their
taxonomical status.

Chemotaxonomy establishes relationship between the position of the plant and

exact understanding of biological evaluation and natural relation ship.

Depending upon chemical evidence, plants are classified accurately as alkaloids,
flavonoids, carotenoids, polysaccharides, terpenoids, fatty acids (proteins).

Purpose of chemotaxonomy:-

Chemotaxonomy has been used in all levels of classification. Chemical evidences

have been used in all the groups of the plant kingdom starting from simple
organism like fungi and bacteria up to the most highly advanced and specialized
group of Angiosperms.

The evidence is used in classification of plants into 2 main purposes.
1. To improve the existing system of plants differentiation.
2. To develop the present day knowledge of natural relationship of plants.

o Chemical characters and their use in taxonomy: - Naik divided the chemical
characters into 3 categories.
1. Directly visible characters:-Starch grains, raphides, silica ,gypsum ,etc
2. chemical test characters:-phenolic ,betalins, oil fats, waxes ,alkaloids
3. Proteins
o On the other hand in 1987 some authors divided the natural chemicals plants
products into 2 groups on the basis of molecular weight.

1. Low molecular weight compounds:- That is a molecular weight of 1000 or

less than 1000 called as Micromolecules. Ex:-Amino acids, alkaloids, fatty
acids, terpenoids, flavonoids.
2. High molecular weight compounds:- with a molecular weight of more than
1000 called as Macromoecules. Ex:-proteins, DNA, RNA complex ,
Polysaccharides.

History of Chemotaxonomy:

• The concept of classification of plant based on chemical character is not new. it is

started in 15th &16th centuries by anatomist Newmann, Grew & James petitver.
They recognized similar chemicals or medicinal effects of umbelliferous plants.
(carminative)

By: Anukul
 Chemotaxonomy of Medicinal plant
• Greshoff in 1909, suggested that chemical characters should be included in
natural classification.
• Baker and Smith in 1920, worked on single genus Eucalyptus (176)-collected
morphological and chemical data and finally concluded on the morphological
basis the feather contended leaves having more pinene in their volatile oil.
• Mc Nair in 1935, says that ‘more closely related taxas produce more similar
chemical products’.
• Beale and coworkers in 1940, surveyed 32 species of Tulip for anthocyanin
contents and distribution of group of compounds in genus as a taxonomic
characters.
• Conden et.al. in 1944, develop paper chromatography.
• Bat & smith in 1948, showed that paper chromatography applied to analysis of
plant pigments.

Clasification of Chemotaxonomy: based on the taxonomical and chemical knowledge:

Descriptive taxonomy

Dynamic taxonomy

Serotaxonomy

Descriptive taxonomy deals with the classification of plant and secondary metabolite and
other products like sugar & amino acid. It is also concerned with evolutionary change,
chemical convergence and divergence in the plant.

Dyanamic taxonomy is based on biosynthetic pathway.

Serotaxonomy or semantics is based on pathway of specific proteins and amino acids

sequencing in proteins. It is further classified as;

1. DNA- primary semantics

2. RNA-secondary semantics
3. Proteins-tertiary semantics

Principle of chemotaxonomy

Chemical classification of plants is based on their chemical constitutions; i.e. on

their molecular characteristics.

The same type of metabolites can be the product of two quite different pathways.

Different plants sometimes contain secondary constituents belonging to different

classes of compound but biosynthetically appear to be same.

By: Anukul
 Chemotaxonomy of Medicinal plant

Chemotaxonomic studies include the investigation of the pattern of compound
occurring in the plant and preferentially in all various individual parts of plant
such as the bark , wood, leaves , root, cuticles and seed.

Such integrated investigations are necessary in order to obtain really convincing

evidence for the relationship of plants.

Before any important conclusions are drawn about the presence or absence of a
particular compound adequate sampling of a large number of members of the
species at different stages of development and growing in different environment
should be made.

Different stages of Chemotaxonomic investigation:

1. Choice of group, taxonomic survey and sound sampling
2. modification of suitable chemical techniques
3. Analysis of all material
4. interpretation of data and its comparison from all other sources

According to the interest of investigation the relative stages may vary (for
taxonomy, phylogenetic & chemistry)

Sound sampling: an understanding of natural variation within a group and phylogenies

are helpful in good sampling. The collection of plant sample done:

By the help of professional plant collector

From national garden and national herbarium

From professional plant sellers

Personal travel & collection

Modification of suitable chemical techniques:

Depending upon the choice of investigator, what class of material is likely to

exhibit useful variation at the taxonomic level.

Intraspecific chemical variation

Qualitative and quantitative variation between different parts of same plant

Variation due to Seasonal and environmental fluctuation

Analysis of the material: qualitative and quantitative analysis is done by phytochemical

screening, electrophoresis, chromatography, finger print, and spectroscopy. All the
spectra obtained from different technique should be analyses.

By: Anukul
 Chemotaxonomy of Medicinal plant
Interpretation and comparison of data:

All the data obtained from chemistry, phylogenetic and taxonomy is interpreted &
depending upon the evidence the classification of plant should be reconsidered. If only a
minor change occurs in the match of chemical and other variation then the classification
is essentially confirmed.

Three broad categories of compounds are used in Chemotaxonomy:- .

1. Primary metabolites
2. Secondary metabolites,
3. Semantices.

Primary metabolites, are parts of vital metabolic pathways, most of them are of
universal occurrence and is utilized by the plant itself for growth and development.
Example; starch, chlorophyll, aleurone grain, citric acid, aconitic acid, etc.

CARBOHYDRATES IN CHEMOTAXONOMY:

Carbohydrates are universal constituents of living organism and widely distributed in the
plant. Thus, carbohydrate is having little chemotaxonomic significance, but some of the
rare sugars having chemotaxonomic significance. Eg.

• 6-Deoxy hexose;
• 2, 6-Dideoxy hexose;
• Gentiobiose & Gentianose;
• Polyols and polysaccharides,

6-Deoxy hexose: It occurs in the form of methyl ether that is restricted to certain family.
So the presence or absence of such sugars is help in the study of phylogenetic
relationship. Ex. L-thevetose and D-digitalose are used as cardiotonic.

2, 6-Dideoxy hexose: Cardinolides containing D-digitoxose, L-oleandrose, D-cyamarose

sugars are particularly abundant in family apocynaceae and asclepiadaceae (both are
group of unrelated family).

Gentiobiose and gentianose: These are uncommon sugar in amygdalin, characteristic of

family rosaceae and gentianaceae respectively.

Polyols: Among monosaccharide derivatives eg. D-sorbitol, D-mannitol and meso-

xylitol; D-sorbitol occurs naturally in fruits of various rosaceae family. The presence or
absence of these sugar alcohol in rosaceae can be utilized to identify subfamily.

It is reported that sorbitol is present in all species belong to subfamily of rosaceae like
spiraeoidae, pomoidae, prunoidae, and rosoidae, but in species of ulmaria genus belong to

By: Anukul
 Chemotaxonomy of Medicinal plant
rosoidae, sorbitol is absent. So, the absence of this chemotaxonomy marker confirms the
removal of ulmaria from spiraeoidae to rosoidae.

Polysaccharides: It is condensation of large number of monosaccharide molecules.

That is universal in the energy storage forms eg. Starch, dextran, fructan, cellulose, and
inulin. Among these polysaccharides inulin is characteristic of family compositae, while
the fructan is present in family graminae. Thus, polysaccharide is also utilized in
confirming phylogenetic relationship. Eg. Tropical and subtropical species of grasses
accumulate starch in their leaves, while temperate grasses accumulate fructans.

Secondary metabolites present in plant, is used for protection and defence. Eg.
Glycoside, alkaloid, volatile oil, flavonoid and plant phenol.

Glycosides in chemotaxonomy:
Glycosides are compounds in which one or more sugars are combined with non-sugar
components by glycosidic linkage or by hemiacetal linkage involving oxygen (O-
glycoside).

Depending upon the linkage the glycoside may be classified as:

• O-glycoside; eg. Rhein.

• C-glycoside; eg. Aloin, cascaroside.
• N-glycoside; eg. Adenosine.
• S-glycoside; eg. Sinigrine.

Distribution of O-glycosides is widespread, so it is having little chemotaxonomic

value.

The nature of sugar moiety and its position of attachment to aglycone maybe
characteristics of cardiac glycosides. Eg. L-thevetose, D-digitalose, D-
cymarose,L-oleandrose (cardiotonic)

C-glycosides, which possess a direct carbon linkage between sugar and non-sugar
are rare in nature. They are found in some plants containing anthraquinone
derivatives eg. Aloin in aloe-liliaceae; cascaroside in cascara-rhamnaceae.

About 25 C-glycosides of flavonoid group are known more are flavone and few
iso-flavone and flavanone, these are plant phenol, but studied in C-glycosides.

S-glycosides are examplified by those produce isothiocyanate on hydrolysis.
These compounds are characteristic of the family cruciferae, moringaceae,
capparaceae. So these family having phylogenetic relationship.

By: Anukul
 Chemotaxonomy of Medicinal plant
Cyanogenetic glycoside in chemotaxonomy:

Plant species having ability to produce hydrogen cyanide by enzymatic hydrolysis

are common in family Rosaceae, Passifloraceae, Leguminosae, Gramineae.

Different amino acid like phenyl alanine, tyrosine, valine, leucine, and isoleucine
are precursor for the biosynthesis of cyanogenetic glycosides, but they are
restricted to particular family. Example: Leucine-Leguminosae and sapindaceae.

On the basis of amino acid precursors some conclusion may be derived, at family
level cyanogenetic glycoside amygdaline synthesized from phenyl alanine,
restricted rosaceae, but same compound synthesized from amino acid valine or
isoleucine is restricted to Leguminosae. The accumulation of cyanogenetic
glycoside is also significant in confirming the position of certain family.

Thioglucoside in chemotaxonomy:

These are responsible for the characteristic flavors of various plants or family
brassicaceae and few related family like, Capparidaceae, Tropaeolaceae and
Resedaceae.

On the basis of alkyl component of glucosinolate compound, brassica species can
be differentiated eg. Brassica juncea (mustard) from Indian subcontinent contain
3-butenyl glucosinate and allyl glucosinate while those from Asiatic country
contain only allyl compound. So ancestry of Indian species is doubtful, because
that is hybrid of B. nigra (allyl glucosinate) and B. compestris (3-butenyl
glucosinate).

ALKALOID IN CHEMOTAXONOMY

Alkaloids are compounds, containing heterocyclic nitrogen, basic character and

complex molecular structure. Such compounds are restricted to plant kingdom.

o True alkaloids have a nitrogen-containing nucleus derived from biogenetic

amine.

o Proto alkaloids – derived from amino acids, but lack a heterocyclic ring.
Natural protoalkaloids are usually simple amines e.g. ephedrine ,
mescaline.Some times they may be precursor of true alkaloids.

o Pseudo alkaloids biologically unrelated to amino acids.Most of them

derived from- terpenes, sterols , nicotinic acid or purines.

By: Anukul
 Chemotaxonomy of Medicinal plant

Occurrence and Distribution:

Higher plants particularly in the dicotyledons, abundance in the Angiosperms

families Apocynaceae, Papaveraceae, Ranculaceae, Rubiaceae, Rutaceae,
Solanaceae, but less frequent in lower plants and fungi.

In plants, alkaloids, due to their basic nature, generally exist as a salt of organic
acid like, oxalic acid, citric acid, malic acid,, tartaric acid, tannic acid etc.

Some alkaloids like narceine and nicotine are occurring free in nature.

A few alkaloids occur as glycoside of sugars like glucose, rhamnose, and
galactose. E.g. alkaloids of solanum and veratrum groups as amides (Piperine), as
esters (Atropine, Cocaine) of organic acid.

Criteria for using Alkaloids in taxonomy:

Definition of alkaloids

Definition of alkaloid plants

The type of alkaloids that can be distinguished

Homologous and analogous characters

Definition:

Alkaloids are more or less toxic substances having physiological action. They are
basic in nature, contain heterocyclic nitrogen, and are synthesized in plants from
amino acid and or their intermediate derivatives. They are of limited distribution
in plant kingdom.”

But such definition excludes a number of nitrogen containing plant constituents,
which are normally thought as alkaloids. E.g. Biological amines like Ephedrine
,Hardenine,Betain ,Cholin, Muscarine. All such alkaloids are separately referred
as protoalkaloids or biological amines or amino alkaloids.

But when protoalkaloids and true alkaloids occur in same genus or family, both
are usually classified as alkaloids. Ex. – Hardenine, Mescaline in cactaceae
family.

Another group of nitrogen compounds that fall outside our definition of alkaloids
are mono, sesqui,di-terpenes, steroids, nicotinic acid, purines. These can also
be classified according to precursor on which they are based and collectively
called as pseudo alkaloids.E.g . Conessine, Caffeine.

By: Anukul
 Chemotaxonomy of Medicinal plant
Definition of alkaloid plants:

There is no sharp dividing line between alkaloids containing plants and alkaloids
free plants.

From practical point of view, we can define lower limit as 0.01% of dry weight.
Another characteristic of true alkaloid is that it always contains more than one
alkaloid.

E.g. Ricinine is only alkaloid in Ricinus communis and Genitianine only alkaloid
in Gentianaceae, that’s why these two bases have been kept outside the class of
true alkaloids.

Type of alkaloids that can be distinguished: –

It has been found that amino acids phenylalanine, ornithine, tryptophan, lysine,
histidine, Anthranilic acid are primary precursors of alkaloids in plants.

Each of this amino acid can be regarded as starting point for synthesis of one or
more types of alkaloids.

Therefore we may put the alkaloids into families corresponding to six amino acids
mentioned above.

There are also numbers of alkaloids which can be regarded as hybrids.

E.g.

Phenylalanine family –Hardenine, Ephedrine, Anahaline group, Papaverine

group, Morphine group.

Tryptophan family - Ajamaline, Yohimbine, vinblastine etc.

Ornithine family - Hygrine, Atropine, Ecgonine etc .

Lysine family - Coniine, Anabasine etc.

Homologous and analogous chemical characters:

Two similar substances or even same substance may be isolated from two
different plants and are taxonomically important if the compounds are derived
from exactly same metabolically process.

But same compounds or similar compounds are produced by different metabolic
pathways in different plants.

By: Anukul
 Chemotaxonomy of Medicinal plant

E.g. Anabasine in Nicotiana genus (Solanaceae family) is formed from one

molecule of lysine on the other hand in Leguminosae family two molecules of
lysine are involved. Thus it seems that Anabasine of Solanaceae is not equivalent
(homologous) to that in Leguminosae.

Similarly quinine has been isolated from several unrelated genera.

The quinoline alkaloids of cinchona bark are obviously quite different

structurally from yohimbine alkaloids from yohimbe bark but they are closely
related biosynthetically and this points to a close relation between the plants in
which they occur.

Generally ornithine and lysine families of alkaloids are closely related.

Therefore, they should be treated as one unit from chemotaxonomic point of view.

Some alkaloids are restricted to only very certain plants

e.g.

Morphine is restricted to P. somniferum

Coniine is restricted to Umbeliferous sp.

Strychnine is restricted to strychnos species

Accumulation of Isoquinoline alkaloids in families Fumariaceae and

Papaveraceae, indicate that there is close relationship between two families. Both
families accumulate Isoquinoline alkaloids, and always contain Protopine.

There are instances where alkaloid biosynthesis can be helpful to chemotaxomist

for arranging the species within genus according to their alkaloid content.

Evidences from basic moiety:

 Pyridine and Piperidine

The parent base pyridine occurs in some plants as

Lobeline obtained from Lobelia inflata family Lobeliaceae.

Nicotine obtained from Nicotiana tobaccum family Solanaceae

Anabasine obtained from Nicotiana gluaca family chenopodiaceae.

Anabasine occurs in tobacco, where it is formed from lysine and nicotinic
acid. In the legume and chenopod species where Anabasine also occurs, it
can be synthesized from two molecules of lysine.

 Isoquinoline Alkaloids
Isoquinoline alkaloids are obtained from following plants.

E.g. Papaverine is obtained from P. somniferum family
Papaveraceae

By: Anukul
 Chemotaxonomy of Medicinal plant

Berberine is obtained from Hydrastis canadensis family
Berberidaceae

The amino acid phenylalanine and tyrosine act as precursor for
isoquinoline nucleus.

Hydrastine which is found in Berberidaceae and
Rannunculaceae.

 Tropane alkaloids

Among the best-known members of the group are the solanaceae alkaloids,
which are very characteristic of the solanaceae. Atropine and Hyoscyamine
serve as example.

In erythroxylum, cocaine alkaloids are found which are same in nucleus but
do not occur in the solanacae.

Ornithine is the precursor

 Indole Alkaloids
Indole alkaloids are found in following plants.

Physostigmine obtained from Physostigma venonsum family
Leguminosae.

Yohimbine obtained from Rauwolfia serpentina family
Apocyanaceae.

Vinblastine obtained from Catharanthus roseus family
Apocyanaeae.

Indole alkaloids origination from Phenylalanine as in
Erythria alkaloids (Leguminosae) such as Erysopine.

In most cases e.g. Tryptamine (Loganiaceae), yohimbine
(Apocyanaceae) and strychnine (Loganiaceae) the parent
compound is tryptophan.

Plant Phenol in chemotaxonomy:

Most commonly occurred phenolic compound is mono or Dihydroxy derivatives

of benzoic and cinnamic acid. Phenolic compounds having restricted occurrence
may have chemotaxonomic value eg; Trihydroxy derivatives of benzoic acid and
cinnamic acid.

Eg: Ellagic acid is absent in fern, gymnosperm and monocotyledon, but it is

infrequently found in dicotyledon family. It is useful chemotaxonomic marker in
subfamily rosoidae (tribe-kerrieae)-rosaceae.

4-hydroxy benzoic acid and 4-hydroxy phenyl acetic acid have been reported in
eight genera of family saxifragaceae, but in case of Astilbe genus, 4-hydroxy
phenyl acetic acid is replaced by 2-hydroxy phenyl acetic acid.

By: Anukul
 Chemotaxonomy of Medicinal plant

Coumarin derivatives are common volatile constituent responsible for odour in
many plants. The hydroxylated derivative are having restricted distribution can
be utilized as chemotaxonomic marker eg. Umbelliferone occurs widely in
Umbelliferae while in Compositae it is characteristic of genus Hieracium
(hawkweed).

Flavonoids are largest group of phenolic compounds. They are mostly found in
the vacuole of higher plant and absent in lower plant.

Different classes of flavanoids:

• Flavones
• Flavanone
• Isoflavanone
• Isoflavonoids
• Anthocyanidin
• Chalcone

All flavonoids have common biosynthetic origin and therefore it posses the same
basic structural element, e.g. 2-phenylchromone skeleton. They may be present in
many classes depending on degree of oxidation of pyran ring which may be open
and cyclize into furan ring, e.g. 2-phenyl benzo pyrilium: anthocyanin & 2-phenyl
chromone: flavone, flavanol, isoflavone.

Flavone & flavanols and their glycosides are universally distributed but some of
the substitution patterns are restricted to certain family, having chemotaxonomic
importance.
• E.g. 6-o-substituted flavonoids in family: Laminaceae,Rutaceae,
Asteraceae.
• 5-deoxy flavone in family: Fabaceae
• 2-o-substitueted flavonols in family: Laminaceae, Solanaceae.

Anthocyanidins, water soluble pigments responsible for red, pink, purple,

blue,violet colours to flower and fruit.these pigments occurs as glycoside
anthocynidins and their aglycones anthocyanidins. These are rare in gymnosperm
but mostly occurs in angiosperm. Except in Caryophyllales.

By: Anukul