Exploring the Chemistry of Natural Dyes

from West Bengal and Tamil Nadu

NAME: ARYADEEP ROY

CLASS: XI
SECTION: J (AFTERNOON)
ID: 10-0246
SCHOOL: SOUTH POINT HIGH SCHOOL
 INTRODUCTION
In West Bengal, the art of dyeing fabrics using natural dyes has been
practiced for centuries. The most famous form of traditional dyeing in
West Bengal is known as "Batik," which involves a resist dyeing
technique using wax to create patterns on the fabric. Other
traditional dyeing techniques in West Bengal include tie-dyeing and
block printing.

Similarly, Tamil Nadu has a rich history of using natural dyes to

colour fabrics. The state is known for its vibrant Kalamkari fabrics,
which are created using natural dyes and hand-painted with intricate
designs. Other traditional dyeing techniques in Tamil Nadu include
block printing, tie-dyeing, and resist dyeing.
 Objective of the Project
To learn more about natural dyes and the chemistry behind them and
their structures, etc.

CHEMISTRY BEHIND NATURAL DYES

Nature expresses itself in a wide spectrum of colours all around us.
The alchemy of colours started from an early time. Indians have been
forerunners in the art of natural dyeing. The advent of synthetic dyes
caused rapid decline in the use of natural dyes, which were
completely replaced by the former within a century. Earlier
understanding of dyeing techniques and their applications was
empirical and was not backed by scientific reasoning. Natural dyeing
had developed essentially as a folk art. However, in recent times the
dyeing technique is interpreted on sound scientific principles, and
the interaction between the dye and the dyed material is well
understood.
Sources of Natural Dyes
There are primarily four sources from which natural dyes are
available.
 Specialised plant and animal sources: Many plants and some
animals have been identified as potentially rich in natural dye
contents, and some of them have been used for natural dyeing for
quite some time. Various parts of plants like roots, stems, barks,
leaves, fruits and seeds may contain colouring matter which can be
exploited. Normally natural dyes are extracted from the roots, stems,
leaves, flowers, fruits of various plants, dried bodies of certain insects
and minerals. Some plants may have more than one colour
depending upon which part of the plant one uses. The shade of the
colour a plant produces will vary according to time of the year the
plant is picked, how it was grown, soil conditions, etc. The minerals in
the water used in a dye bath can also alter the colour. Some natural
dyes contain natural mordants.
By-products (especially lac dye): The lac industry gives lac dye as a
by-product, which is extracted from the effluent. Similarly, from
Cassia tora, used in gum manufacturing, a brown dye is obtained as a
by-product.
Chemical synthesis: This involves synthesis of dyes with molecular
structures identical to those of natural dyes. We have tried to make
such synthesis environmentally less hazardous by using microwave
technology.
Tissue or cell culture by DNA transfer biotechnology: Certain fungi
such as Drechslera and Trichoderma produce anthraquinone
derivatives as secondary metabolites. As anthraquinones are a very
important class of dyes, exploiting the fungi would be advantageous
over their chemical synthesis. If genetic modifications can be
achieved, it is possible to develop fungi that produce substituted
anthraquinones.
 THE CHEMICAL COMPOUNDS IN THE DYES
By Chemical Constitution
Indigoid class:
Two important dyes in this class are indigo blue and Tyrian purple. It
occurs as glucoside indicant in the plant. Another blue dye is woad
having the same chemical class. The chemical structure which
belongs to indigoid class is shown below

Anthraquinone class
Dyes that belong to this class are having anthraquinone structure and
obtained from plant and insect. The red shade is specific to this class.
Madder, lac, kermes and cochineal are some of the examples. The
general chemical structure of this class is shown below

Alpha naphthoquinone
The dyes are having alpha naphthoquinone structure such as 2-
hydroxy 1-4-naphthoquinone. Hina, lawsone and juglone are
examples of this class. The chemical structure of this class is shown

Flavones
The dyes are having yellow shade. The natural dye weld belongs to
this category. Most of the dyes are derivatives of hydroxyl and
methoxy substituted flavones or isoflavones. The chemical structure
of this class of dye is shown.

Carotenoids
The natural dyes saffron and annatto belong to this class. The dye
structure of this class has long-chain conjugated double bonds. The
chemical structure of this class is as shown.
Dihydropyrans
The dyes which belong to this category are logwood and sappan
wood. Logwood, a natural dye, produces dark black shade on silk,
wool and cotton.
Anthocyanidins
The natural dye carajurin belongs to this category. The blue and
orange shades are obtained from this class.
Based on colour
Various natural dyes could present all the colours of the visible
spectrum. The natural colour and hue of a dye can be altered by
treating with metal salts. If the dye is of plant origin, the colour may
vary depending on the soil properties, part of the plant, season of
harvesting, cultivation practices, etc.
Red colour: Most red dyes are found in roots or barks of plants or
camouflaged in the bodies of dull grey insects. Unlike the wide
abundance of yellow, the sources of red colour are limited. Cochineal
is an important red dye and it is the brightest of all the available
natural red dyes. Manjith and Kusumbar among the vegetable
sources and lac and Kermiz among the animal sources give red
colours.
Yellow colour: Yellow is the liveliest and perhaps the most abundant
colour in nature. The plants which yield yellow dyes outnumber
those yielding other colours.

Blue colour: Blue is one of the rarest colours in nature. Two of the most
well-known plants to give blue are indigo and woad. The Indigofera
tinctoria is native to India while woad (Isatis tinctoria) is native to
Central Asia and has been widely cultivated through Europe. Both
contain indigotin. But to finish with the plants giving blue, we can also
mention two other sources of blue: wild Guava (Careya Arborea, a tree
species native to India, Afghanistan and Southeast Asia) and Tsuykusa
flowers (Commelina Communis, native to East Asia and the north of
Southeast Asia).

Green colour: Green dyes are also very rare. That’s definitely odd since
the colour coming to mind when talking about nature is green but
that’s natural dyeing chemistry. It’s more common to obtain green
dyes by overdyeing yellow fabric or yarn with indigo or using a modifier
like nettles + copper. Though depending on the time of the year, the
soil, etc, some dyers will get a lovely pale green with only nettles.

Orange colour: Orange dyes can be found in the plants giving red and
yellow dyes. Orange comes from the caronotoid compound. Apart
from madder, you can also get orange with dahlias and annato (Bixa
Orellana).

Brown colour: They mostly belong to the alpha naphthoquinones

compound group. You can get brown easily with walnut husks and
henna.

Chemistry of pH on dyes and design of

hypothetical experiments with probable results
If we introduce a certain dye to color a solution, we are hoping it
does not change color from what’s expected. If the color altered, you
might think something is wrong and your product is bad. Imagine if
you are the manufacturer of Drano® and you pick a dye that is
supposed to color Drano® blue. When you made it, it appeared blue,
but two days later it yellowed. This would be bad because the
blueness of Drano® is a trademark color. A changed shade can affect
consistency, brand awareness, and may cause the customer to think
the product is bad. In this case, the color change occurred because
the dye had alkaline sensitivity, giving you the wrong result. Now
let’s look at a situation where a sock manufacturer wants to dye their
socks red. In this process he needs an acid to fix (or dye) the color to
the sock fabric. He adds his red dye solution to the socks in water,
creating a nice red color. As soon as he adds the acid to finish his
formulation – bingo – the socks turn blue. The dye must have a
sensitivity to acid, causing the reaction to change the color to
blue. Obviously, having blue instead of red socks is not a good thing.
Having awareness of the pH sensitivity can keep you from
inadvertently discoloring your products.

If we introduce a dye in each of the above examples and there is no

color change, then the dyes are stable in those pH systems. Thus,
they would not change color. This is your goal when selecting dyes to
add to existing formulations.

In some cases the color can be completely destroyed if the pH is

either very alkaline (pH of 13) or very acidic (pH of 1). What happens
is that the dye color turns clear shortly after being introduced to
those situations. In other words, the color is destroyed. This is
helpful for water treatment processes, but probably not for dyeing
something like socks or a household cleaner.

The pH is an important factor when considering what dye you want

to use. Ensure you know what the pH is of the solution the dyes will
be dissolved in. Also consider if there is going to be anything added
that might cause a change in pH of the original solution. Choose your
dyes with caution.

Allied photos and diagrams with respect to dyes

and the resist dyeing techniques

Quinoid-based structure
The quinoid-based dye structure can be overviewed as three
chemical structures (a) benzoquinone, (b) naphthoquinone and (c)
anthraquinone. The natural colourant carthamine belongs to
benzoquinone group, and juglone and lawsone are having
naphthoquinone structure. Alizarine dye possesses anthraquinone
structure.
Benzoquinone dyes
In this dye structure the л electron system is small, and the dye
contains another unsaturated group in conjugation to л electron
system. The red colourant carthamine is present in safflower
(Natural Red 26). Safflower (Carthamus tinctorius) is a subtropical
plant and cultivated in India, China, North and South America and
Europe. In dyeing, the water-soluble yellow dye (safflor yellow) is
extracted [18] by cold water, and then red safflorcamin is extracted
by diluted sodium carbonate solution. After the neutralisation of
extracted solution, it can be used in dyeing of wool, silk and cotton.

Naphthoquinone dyes
Lawsone and juglon natural dye belongs to this category. Lawsone is
extracted from hina plant; the leaves also contain flavonoid
colourants lutcolin. It is cultivated in countries like India, Africa and
Australia. Naphthoquinone is present in glycosidic [19, 20] form
named as Hennosid A, B and C. The quantitative analysis of lawsone
can be performed by high-performance liquid chromatography on
reverse-phase C18 column. Chloroform extracted hina leaves were
analysed by high-performance thin layer chromatography
Lawsone
Lawsone form 1:2 complex with Fe(II) and Mn (II) and useful in
dyeing of wool and silk fibre. The better dye uptake is obtained at pH
3.0. Agarwal et al. [21] studied the effect of different mordants and
different mordanting methods to get the different shades. Hina can
be used for dyeing of cotton, polyester, polyamide and cellulose
triacetate as the structure of dye molecules are similar to disperse
dyes [22, 23, 24].
Juglone
Juglone is representative of natural dye with naphthoquinone
structure. The dyestuff is extracted from different part of nut trees.
Juglone is present as a glycoside form in trees and plants. Wool dyed
with juglone are having good resistance with moths and insects.
Mordanting treatment further enhances the fastness properties.
Dyeing of textile materials with aqueous walnut extract yields brown
shade. Wide range of textile fibre, e.g. wool, silk, nylon and
polyester, can be dyed with juglone.
Antharaquinone
It possess biggest group of anthraquinone dyes. Rhubarb (CI Natural
Yellow 23) is extracted from the root of the plant. The extracted dye
contains emodin, chrysophenol, aloe emodin and pyscion (Figure 24).
Rhubarb extract is used in dyeing of wool fibre [25]. It produces
yellow to orange shade after mordanting with alum. The mordanting
treatment improves light fastness of dyed materials.

Figure 24.

Natural dye alizarin, pseudo purpurin and purpurin (Figure 25)

belongs to plant of Rubiaceae family and has an anthraquinone
structure [26]. The dye is obtained from the root of plant.
Figure 25.

Structures of alizarin, pseudo purpurin and purpurin.

Madder (C.I Natural Red 8) natural dye produces red colourant; the
cultivation of madder is done as a source material for red colour in
Europe, Asia and Northern and Southern America. The dyestuff is
extracted from the dried roots of the plant. The roots of the plant
contain 2–3.0% of di- and tri-hydroxyl anthraquinone glucosides.
Carotenoids
Carotenoids are red, yellow and orange pigments present in plants
and animals [17]. It has a polyisoprenoid structure with a series of
centrally located conjugated bonds. The bright colours of many fruits
and vegetables are due to carotenoids. Carotenoids are
polyisoprenoid structure (Figure 26) which contain conjugated
double bonds, which acts as chromophore and responsible for
characteristic absorption spectra. Carotenoids are divided into two
parts:
Hydrocarbon carotenoid
Oxygen containing called xanthophylls
Figure 26.

Structure of β-carotene.

Structural changes by hydrogenation, double bond migration,

isomerization and chain lengthening and shortening resulted in many
carotenoid structure. Carotenoids possess strong UV light resistance,
and β carotene (Figure 26) is a typical structure generally found in
natural colourants.
Pyron dyes
Pyron dyes contain flavonoids and anthocyanins having structure as shown
in Figures 27 and 28. The pyron structure is bound to various sugars by glycosidic
bonds [17]. Flavonoids are classified as flavonols, flavones, anthocyanidins,
isoflavones, flavon-3,4-diols and coumarins. Yellow flavones and flavonols are
used as vegetable dyes. The valuable and very popular flavonoid is yellow
quercetin which possess several bio effect.

Figure 27.

Structure of anthocyanins.
Figure 28.

Structure of quercetin.

Anthocyanins
Anthocyanins are found in fruits and vegetables; some are grape wine, sweet and
sour cherries, red cabbage, hibiscus and different varieties of oranges. There are
more than 500 varieties of anthocyanins that produces red, pink, violet and
orange colours. There are some important anthocyanins which are cyaniding,
delphinidin, pelargonidin, malvidin, peonidin and petunidin. Many plants besides
anthocyanins also contain quercetin and chlorophylls, and the resulted colour is a
mixture of all these.

Dyes from lichens and mushrooms

Violet and purple colours were generally obtained from molluscs and shellfish,
and they were source of dyestuff from ancient to the beginning of the Middle
Ages. Royale purple and Tyrian purple were the name of the colour obtained
originally from molluscs [27]. Lichens and mushrooms are source of natural dyes,
and they produce violet and purple colours. Lichens are found in coastal areas and
were easier to collect. The dyeing methods with lichens are easy; however,
disadvantage associated with lichens is poor light fastness. Therefore, the dyeing
of lichens are limited to cheap quality fabrics. Fungi are also used for dyeing of
textiles. In America and India, red colour is obtained from fungus Echinodontium
tinctorium. In Italy and France, fungi obtained from Polyporales were used to dye
the wool.
The colourants in lichens and fungi are benzoquinone derivatives, especially
terphenylquinone. Some of these species possess compounds such
as Sarcodon, Phellodon, Hydnellum and Thelephora [28, 29]. Orchil and litmus are
the colourants that are responsible for the colour in lichens. The lichens’ colour
are produced through pre-compounds of orchil and litmus by consecutive
enzymatic, hydrolysation, decarboxylation and oxidation [30] reactions,
respectively. Then some pre-compounds are lecanoric acid, atranorin and
gyrophoric acid which take part in the formation of orchil and litmus as shown
in Figure 29.

Figure 29.
Structures of different colourants occurring in fungi and lichens.
In the past, the extraction of colourants from lichens were performed by keeping
the lichens in water with ammonia for several days. The reaction occurred through
enzymatic hydrolysis in which non coloured compounds such as lecanoric acid are
converted into orcinol by hydrolysis and decarboxylation. Orcinol after oxidation
forms purple orceins or litmus. The colour of both litmus and orchil depend on the
pH of the solution [30]. In acidic pH dyestuff forms red cation, and in basic pH, it
forms bluish violet anion. The lichens which belong to species Parmelia, Xanthoria
parietina, Ochrolechia tartarea and Lasallia pustulata are capable to produce
yellowish, brownish and reddish brown colours in dyeing of wool with lichens [31].
The dyeing is done by boiling the wool with lichen solution either premordanted
or without mordanted wool in presence of ammonia.
The mushrooms which belongs to species Sarcodon, Phellodon and Hydlnellum contain
terphenylquinone compounds as a main colourants which produce blue colour in
mushrooms. They are benzoquinone derivatives. The Cortinarius species
mushrooms are richly coloured in brown, red, olive green and violet. They are
anthraquinone derivatives.

Tannins
Tannins are polymeric polyphenols with typical aromatic ring structure with
hydroxyl constituents and have relatively high molecular weight. In plants two
different groups of tannins are found, (a) hydrolysable tannins and (b)
proanthocyanidins (condensed tannin) [32, 33]. Tannins are present in plant cell
and are concentrated in epidermal tissues. Tannins are found in wood, leaves,
buds, stems, florals and roots [34]. The hydrolysable tannins are concentrated in
the roots of several plants. The plants are the source of different variety of
tannins. The three major tannins (hydrolysable tannins) are grouped as
gallotannins [35] or ellagitannins and which are gallic acid or ellagic acids. The
most widespread gallotannins are pentagalloyl glucose. Ellagitannins are esters of
hexahydroxydiphenic acids. Gallic acid and hexahydroxydiphenic acid occur
together in some hydrolysable tannins [36].
Condensed tannins are polymers of 15-carbon polyhydroxyflavan-3-ol monomer
units such as (−) epicatechin or (+) catechin. The complex chemical nature of
tannins makes the biosynthesis and polymerisation a difficult task; however, there
are some established pathways for bio synthesis. The precursor for biosynthesis of
hydrolysable tannins is shikimic acid. The direct aromatization of 3-
dehydroshikimic acid produces gallic acid, which upon esterification forms polyol.
The bio synthesis of condensed tannins occurs through two different ways (a) by
phenylpropanoid and (b) by polyketide. The polyketide pathway takes malonyl
moieties for aromatic ring formation in flavonoid biosynthesis. The
phenylpropanoid pathway takes aromatic amino acid, L-phenylalanine, which is
non-oxidatively deaminated to E-cinnamate by phenylalanine ammonia-lyase.
Resist dyeing
Resist dyeing (resist-dyeing) is a traditional method of dyeing textiles with patterns.
Methods are used to "resist" or prevent the dye from reaching all the cloth,
thereby creating a pattern and ground. The most common forms use wax, some
type of paste made from starch or mud,[1] or a mechanical resist that manipulates
the cloth such as tying or stitching. Another form of resist involves using a
chemical agent in a specific type of dye that will repel another type of
dye printed over the top. The best-known varieties today include tie-dye, batik,
and ikat.

Basic methods
Wax or paste
In wax or paste resists, melted wax or some form of paste is applied to cloth
before being dipped in dye. Wherever the resist medium has seeped through the
fabric, the dye will not penetrate. Sometimes several colors are used, with a series
of steps including dyeing, drying, and the repeated application of the resist. The
resist may also be applied to another piece of cloth to make a stencil, which is
then placed over the cloth, and dye applied to the assembly; this is known
as resist printing.[2]

Stencils
In stencilled resists, a stencil is placed over the fabric where it is to be shielded
from ink, similar to how screen prints are made.

Mechanical
Mechanical resist dyeing ties, stitched or clamps the cloth using clothespegs or
wooden blocks to shield areas of the fabric from the dye.

Chemical
Chemical resist dyeing is a modern textile printing method, commonly achieved
using two different classes of fiber reactive dyes, one of which must be of the vinyl
sulfone type. A chemical-resisting agent is combined with dye Type A, and printed
using the screenprint method and allowed to dry. A second dye, Type B, is then
printed overtop. The resist agent in Type A chemically prevents Type B from
reacting with the fabric, resulting in a crisp pattern/ground relationship.[3]

CONCLUSION
It was a fun project to do. It has improved my knowledge about dyes, their
structures and their origin.

BIBLIOGRAPHY
• INDIAN ACADEMY OF SCIENCES
• WIKIPEDIA
• INTECH OPEN
• THE FOX AND THE KNIGHT