The term ‘tannin’ was first applied by Seguin in 1796 to denote substances

present in plant extracts which were able to combine with protein

of animal hides, prevent their putrefaction and convert them into

leather.

On this basis a tannin is a substance which is detected qualitatively

by a tanning test (the goldbeater’s skin test) and is determined

quantitatively by its adsorption on standard hide powder.

This definition excludes simpler phenolic substances, often present with tannins,

such as gallic acid, catechins and chlorogenic acid, although they may

under certain conditions give precipitates with gelatin and be partly

retained by hide powder.

Such substances of relatively low molecular

weight are called ‘pseudo-tannins’.

Most true tannins have molecular

weights of from about 1000 to 5000. To be effective for tannage

the polyphenol molecule most be neither so large as to be unable to

enter the interstices between the collagen fibrils of the animal skin nor

so small that it is unable to cross-link between the protein molecules

of adjacent fibrils at several points. Many tannins are glycosides.

The

definition of a tannin as given above is an old, essentially practical one

which may be purely fortuitous and, in the light of further research,

could prove misleading from the point of view of plant metabolism and

plant biochemistry. Indeed, modern authors often treat tannins not as a

specific phytochemical group but as examples of polyphenols illustrating

particular aspects of gallic acid and flavan-3-ol phytochemistry.

The characteristic properties of tannins derive from the accumulation

within a moderately sized molecule of a substantial number (1–2 per

100 mol. wt.) of phenolic groups many of which are associated with

o-dihydroxy and o-trihydroxy orientation within a phenyl ring.

The above tannin-protein co-precipitation is important not only in

the leather industry but also in relation to the physiological activity of

herbal medicines, taste of foodstuffs and beverages, and in the nutritional

value of feeds for herbivores. Environmental factors affecting

this process have been studied by H. Kawamoto and F. Nakatsubo

(Phytochemistry, 1997, 46, 479).

Two main groups of tannins are usually recognized; these are the

hydrolysable tannins and the condensed tannins (proanthocyanidins).

Hydrolysable tannins

These may be hydrolysed by acids or enzymes such as tannase. They

are formed from several molecules of phenolic acids such as gallic

and hexahydroxydiphenic acids which are united by ester linkages

to a central glucose molecule. A simple tannin illustrating this point

is one derived from a species of sumac (Rhus), with a possible

structure as shown in Fig. 21.6. Like gallic acid their solutions turn

blue with iron salts. They were formerly known as pyrogallol tannins,

because on dry distillation gallic acid and similar components

are converted into pyrogallol. Two principal types of hydrolysable

tannins are gallitannins and ellagitannins which are, respectively,

composed of gallic acid and hexahydroxy-diphenic acid units.

Ellagic acid (the depside of gallic acid) can arise by lactonization of

hexahydroxydiphenic acid during chemical hydrolysis of the tannin;

thus, the term ellagitannin is a misnomer.

Ellagitannins found in plants of medicinal interest, and for which

structures have been elucidated include geraniin (Herb Robert and

American cranesbill) and tellimagrandins 1 and 2 (Oak bark, Pomegranate

and Meadowsweet); Fig. 21.6.

Modern methods of analysis have made considerable advances in

the study of tannin chemistry of medicinal plants as evidenced by

the work of Okuda on oriental drugs. In 1982 agromoniin, the first

of a new class of oligomeric hydrolysable tannins was isolated from

Agromonia. These tannins are composed of two, three or four monomeric

units. Something less than 20 of these units including geraniin

and tellimagrandins 1 and 2 are known to be involved in the production

of over 150 compounds.

C-glucosidic ellagitannins are common in a number of families

including the Myrtaceae, Hamamelidaceae, Punicaceae and Rosaceae

Examples of drugs containing hydrolysable tannins are:

Gallitannins: rhubarb, cloves, red rose petals, bearberry leaves, Chinese

galls, Turkish galls, hamamelis, chestnut and maple.

Ellagitannins: pomegranate rind, pomegranate bark, myrobalans, eucalyptus

leaves, kousso, some Australian kinos, chestnut (Castanea spp.) and oak bark.

Condensed tannins (proanthocyanidins)

Unlike hydrolysable tannins, these are not readily hydrolysed to simpler

molecules and they do not contain a sugar moiety. They are related

to the flavonoid pigments and have polymeric flavan-3-ol structures.

Catechins, which also occur with the tannins and flavan-3,4-diols

(leucoanthocyanidins) are intermediates in the biosynthesis of the

polymeric molecules.

Some drugs (e.g. tea, hamamelis leaves and hamamelis bark) contain

both hydrolysable and condensed tannins.

The following are rich in condensed tannins:

1. Barks: cinnamon, wild cherry, cinchona, willow, acacia (wattle,

mimosa), oak and hamamelis

2. Roots and rhizomes: krameria (rhatany) and male fern

3. Flowers: lime and hawthorn

4. Seeds: cocoa, guarana, kola and areca

5. Fruits: cranberries, grapes (red wines), hawthorn

6. Leaves: hamamelis, hawthorn and tea, especially green tea

7. Extracts and dried juices: catechu, acacia and mangrove cutches,

East Indian kino, butea gum and eucalyptus kino.

‘Complex tannins’

This term has been applied by Okuda to a newly-discovered group

of tannins which are biosynthesized from both a hydrolysable tannin

(mostly a C-glucoside ellagitannin) and a condensed tannin.

The union occurs through a C–C bond between the C-1 of the glucose unit of

the ellagitannin and the C-8 or C-6 of the flavan-3-ol derivative

Pseudotannins

As already mentioned, pseudotannins are compounds of lower molecular weight than true tannins and
they do not respond to the goldbeater’s skin test.

Examples:
1. Gallic acid: rhubarb and most materials which contain gallitannins

2. Catechins: catechu, acacia cutch, many Australian kinos, cocoa,

guarana and many other drugs containing condensed tannins

3. Chlorogenic acid: maté, coffee (particularly unroasted) and nux

vomica (a small quantity only)

4. Ipecacuanhic acid: ipecacuanha

Occurrence of tannins. Tannins are of wide occurrence in plants

and are usually found in greatest quantity in dead or dying cells. They

exert an inhibitory effect on many enzymes due to protein precipitation

and, hence, they may contribute a protective function in barks

and heartwoods. Commercial tannins, as used in the leather industry,

are obtained from quebracho, wattle, chestnut and myrobalans trees.

Pharmaceutical tannin is prepared from oak galls (q.v.) and yields glucose

and gallic acid on hydrolysis; many commercial samples contain

some free gallic acid.

Some plants (clove, cinnamon, etc.) contain tannin in addition to

the principal therapeutic constituents. This may complicate extraction

or produce incompatibilities with other drugs (many alkaloids, for

example,

are precipitated by tannins).

Properties and tests. Tannins are soluble in water, dilute alkalis,

alcohol, glycerol and acetone, but generally only sparingly soluble in

other organic solvents. Solutions precipitate heavy metals, alkaloids,

glycosides and gelatin. With ferric salts, gallitannins and ellagitannins

give blue-black precipitates and condensed tannins brownish-green

ones. If a very dilute ferric chloride solution is gradually added to an

aqueous extract of hamamelis leaves (which contains both types of tannin),

a blue colour is produced which changes to olive-green as more

ferric chloride is added. Other tests are the following.

1. Goldbeater’s skin test. Soak a small piece of goldbeater’s skin

in 2% hydrochloric acid; rinse with distilled water and place in

the solution to be tested for 5 min. Wash with distilled water and

transfer to a 1% solution of ferrous sulphate. A brown or black

colour on the skin denotes the presence of tannins. Goldbeater’s

skin is a membrane prepared from the intestine of the ox and

behaves similarly to an untanned hide (a reference sample of hide

powder, as used in the BP assay of the tannins of Rhatany Root,

may be obtained from the European Pharmacopoeia Secretariat,

Strasbourg).

2. Gelatin test. Solutions of tannins (about 0.5–1%) precipitate a 1%

solution of gelatin containing 10% sodium choloride. Gallic acid

and other pseudotannins also precipitate gelatin if the solutions are

sufficiently concentrated.

3. Phenazone test. To about 5 ml of an aqueous extract of the drug add

0.5 g of sodium acid phosphate; warm, cool and filter. To the filtrate

add 2% solution of phenazone. All tannins are precipitated, the

precipitate being bulky and often coloured.

4. Test for catechin. Catechins on heating with acids form phloroglucinol

and they can, therefore, be detected by a modification of the

well-known test for lignin. Dip a matchstick in the plant extract,

dry, moisten with concentrated hydrochloric acid and warm near a

flame. The phloroglucinol produced turns the wood pink or red.

5. Test for chlorogenic acid. An extract containing chlorogenic acid

when treated with aqueous ammonia and exposed to air gradually

develops a green colour.

Medicinal and biological properties. Tannin-containing drugs will

precipitate protein and have been used traditionally as stypics and internally

for the protection of inflamed surfaces of mouth and throat. They

act as antidiarrhoeals and have been employed as antidotes in poisoning

by heavy metals, alkaloids and glycosides. In Western medicine their use

declined after World War II when it was found that absorbed tannic acid

can cause severe central necrosis of the liver. Recent studies have concentrated

on the antitumour activity of tannins (M. Ken-ichi et al., Biol.

Pharm. Bull., 1993, 16, 379) and it has been shown that, to exhibit a

strong activity, ellagitannin monomer units having galloyl groups at the

O-2 and O-3 positions on the glucose core(s), as in the tellimagrandins

(Fig. 21.6) are required. Anti-HIV activity has also been demonstrated.

Proanthocyanidins (condensed tannins) are associated with the

beneficial effects of various herbs and infusions produced from them.

The antitumour activity of green and black tea has been extensively

researched in recent years with positive findings. Of the components

of tea, epigallocatechin-3-gallate, specifically, has been shown to prevent

angiogenesis in mice. Cranberry juice has long been used for

reducing bacterial infections of the bladder and these claims have now

been supported by a randomized, double-blind, placebo-controlled

trial carried out on 153 elderly women

Oak Bark

Oak bark is the cut and dried bark from the fresh young branches

of Quercus robur L. (English oak, Common oak), Q. petraea Liebl.

(Sessile or Durmast oak) and Q. pubescens Willd. (Downy oak), family

Fagaceae. The

Principal constituents are phlobatannins, ellagitannins and gallic

acid, a minimum of 3.0% calculated as pyrogallol [C6H3(OH)3 ([Link])]

being specified by the BP/EP.

Oak bark is used medicinally for its astringent properties and

industrially for tanning and dyeing.

Galls and Tannic Acid

Turkish galls (Turkey Galls; Galla) are vegetable growths formed on the

young twigs of the dyer’s oak, Quercus infectoria (Fagaceae), as a result

of the deposition of the eggs of the gall-wasp Adleria gallaetinctoriae.

The dyer’s oak is a small tree or shrub about 2 m high which is found

in Turkey, Syria, Persia, Cyprus and Greece. Abnormal development

of vegetable tissue round the larva is due to an enzyme-containing

secretion, produced by the young insect after it has emerged from the

egg, which by the rapid conversion of starch into sugar stimulates cell

division. As starch disappears from the neighbourhood of the insect,

shrinkage occurs and a central cavity is formed in which the insect

passes through the larval and pupal stages. Finally, if the galls are not

previously collected and dried, the mature insect or imago bores its

way out of the gall and escapes. During these changes the colour of the

gall passes from a bluish-grey through olive-green to almost white.

Galls are collected by the peasants of Turkey and Syria. After drying

they are graded according to colour into three grades, blue, green and

white, which are found on the London market.

History. Galls were well known to the ancient writers and Pliny

records the use of their infusion as a test for sulphate of iron in verdigris,

possibly the earliest mention of an attempt to detect adulteration

by chemical means.

Characters. Aleppo galls are globular in shape and from 10 to 25 mm

in diameter. They have a short, basal stalk and numerous rounded projections

on the surface. Galls are hard and heavy, usually sinking in

water. The so-called ‘blue’ variety are actually of a grey or brownishgrey

colour. These, and to a lesser extent the olive-green ‘green’ galls,

are preferred to the ‘white’ variety, in which the tannin is said to have

been partly decomposed. White galls also differ from the other grades

in having a circular tunnel through which the insect has emerged. Galls

without the opening have insect remains in the small central cavity.

Galls have a very astringent taste.

Sections through a gall show a very large outer zone of thin-walled

parenchyma, a ring of sclerenchymatous cells, and a small, inner zone of

rather thick-walled parenchyma surrounding the central cavity. The parenchymatous

tissues contain abundant starch, masses of tannin, rosettes

and prisms of calcium oxalate, and the rounded so-called ‘lignin bodies’,

which give a red colour with phloroglucinol and hydrochloric acid.

Constituents. Galls contain 50–70% of the tannin known as gallotannic

acid (Tannic Acid BP/EP); this is a complex mixture of phenolic

acid glycosides varying greatly in composition. It is prepared

by fermenting the galls and extracting with water-saturated ether.

Galls also contain gallic acid (about 2–4%), ellagic acid, sitosterol,

methyl betulate, methyl oleanolate, starch and calcium oxalate. Two

new compounds, derivatives of ellagic acid and pentahydroxynaphthalene,

isolated from the alcoholic extract of galls have been shown

to have nitricoxide- and superoxide-inhibiting activity (H. Hamid

et al., Pharm. Biol., 2005, 43, 317). Nyctanthic, roburic and syringic

acids have more recently been identified and syringic acid has been

identified as the CNS-active component of the methanolic extract of

galls. (For the isolation of flavonoids of oak galls see M. Ahmed et al.,

Fitoterapia, 1991, 62, 283.)

Tannic acid is a hydrolysable tannin (see above) yielding gallic acid

and glucose and having the minimum complexity of pentadigalloyl

glucose. Solutions of tannic acid tend to decompose on keeping with

formation of gallic acid, a substance which is also found in many commercial

samples of tannic acid. It may be detected by the pink colour

produced on the addition of a 5% solution of potassium cyanide.

Allied drugs. Many different kinds of galls are known. They are

generally produced on plants, but sometimes on animals. In addition

to the large number produced by insects, particularly of the genera

Cynips and Aphis, some are produced by fungi.

Chinese and Japanese galls are of considerable commercial importance.

They are produced by an aphis, Schlectendalia chinensis, on the

petioles of the leaves of Rhus chinensis (Anacardiaceae). These galls,

which the Chinese call ‘wu-pei-tzu’, meaning ‘five knots’, are irregular

in shape and partly covered with a grey, velvety down, the removal

of which discloses a reddish-brown surface. They break easily and

show a large, irregular cavity containing insect remains. They contain

57–77% of tannin and have been valued in China as astringents and

styptics for at least 1250 years.

Crowned Aleppo galls are sometimes found in samples of ordinary

Aleppo galls. They are about the size of a pea, are stalked, and bear

a crown of projections near the apex. The insect producing them is

Cynips polycera.

Hungarian galls are produced by Cynips lignicola on Quercus

robur growing in former Yugoslavia. They are used in tanning. English

oak galls, formed by Adleria kollari on Quercus robur, contain about

15–20% of tannin.

Uses. Galls are used as a source of tannic acid, for tanning and dyeing,

and in the manufacture of inks. Tannic acid is used as an astringent

and styptic.

]Hamamelis Leaf

Hamamelis leaf (witch hazel leaves) consists of the dried leaves of

Hamamelis virginiana L. (Hamamelidaceae), a shrub or small tree

2–5 m high, which is widely distributed in Canada and the USA. It is

official in the BP/EP and is the subject of an ESCOP monograph.

Macroscopical characters. The leaves are shortly petiolate, 7–15 cm

long, and broadly oval to ovate in shape; base asymmetrically cordate,

apex acute. The lamina is dark brownish-green to green in colour and

very papery in texture. The venation is pinnate and the margin crenate

or sinuate-dentate. The veins are very conspicuous on the lower

surface; they leave the mid-rib at an acute angle and run straight to the

margin, where they terminate in a marginal crenation. Odour, slight;

taste, astringent and bitter.

The BP/EP drug is required to contain not more than 7% of stems

and not more than 2% of other foreign matter.

Microscopical characters. The drug has very distinctive microscopical

characters. These include characteristic stomata present on the lower

surface only; very large lignified idioblasts, crystal cells accompanying

the pericyclic fibres, tannin-containing cells and, especially in young

leaves, stellate hairs. The calcium oxalate is in monoclinic prisms

10–35 μm long. The stellate hairs (Fig. 42.1H) consist of 4–12 cells

united at the base. Each cell is thick-walled and up to 500 μm long.

Constituents. Hamamelis contains gallitannins, ellagitannins, free

gallic acid, proanthocyanidins, bitter principles and traces of volatile

oil. With ferric chloride solution the gallitannins and the free gallic

acid give a blue colour and the ellagitannins, green

Allied drugs. Hamamelis bark occurs in curved or channelled

pieces which seldom exceed 10 cm long or 2 cm wide. The bark

is silvery grey and smooth, or dark grey and scaly. The inner surface

is pinkish and often bears fragments of whitish wood. Sections

show a cortex containing prismatic crystals of calcium oxalate, a

complete ring of sclerenchymatous cells, and groups of phloem

fibres. The bark contains a mixture of hamamelitannin and condensed

tannin; the former has recently been demonstrated to be a

potent oxygen scavenger (H. Masaki et al., Phytochemistry, 1994,

37, 337). Three separate hamamelitannins, α-, β- and γ-, are now

known. The most important, β-hamamelitannin, is formed from two

gallic acid molecules and one molecule of the sugar hamamelose.

Newer galloylhamameloses and proanthocyanidins have now been

identified (C. Haberland and H. Kolodziej, Planta Medica, 1994,

60, 464; C. Hartisch and J. Kolodziej, Phytochemistry, 1996, 42,

191). For the fractionation of those polymeric proanthocyanidins

having similar structures but different molecular weights, see A.

Dauer et al., Planta Med., 2003, 69, 89.

Uses. Hamamelis owes its astringent and haemostatic properties to

the tannins. Hamamelitannin and the galloylated proanthocyanidins

isolated from H. virginiana are reported to be potent inhibitors of

5-lipo-oxygenase, supporting the anti-inflammatory action of the drug

(C. Hartisch et al., Planta Medica, 1997, 63, 106). The above compounds

are presumably not present in Hamamelis Water or Distilled

Witch Hazel, which is, however, widely used as an application to

sprains, bruises and superficial wounds and as an ingredient of eye

lotions. It contains safrole and other volatile components.

Tormentil

There are over 300 spp. of Potentilla family Rosaceae of which

several, including P. anserina, (silverweed), P. reptans (creeping

cinquefoil) and P. erecta (common tormentil), find medicinal

use. Tormentil BP/EP consists of the whole or cut dried rhizome,

freed from roots of P. erecta (L.) Raeusch. (P. tormentilla Stokes).

This perennial plant is widely spread throughout central and northern

Europe, favouring the acidic soils of marshes, meadows, open

woods and hills. Commercial supplies come from East European

countries.

Plants are up to 30 cm tall with several loosely pilosed stems bearing

leaves consisting of three- to five-toothed finely haired leaflets. Yellow

flowers in loose terminal cymes have long pedicels and, unusually for

the genus, four petals.

The rhizomes are dark brown on the outer corky layer and white

on the inside when freshly broken, but turning red on exposure to the

air. The chopped dried drug consists of hard pieces of rhizome with

the remains of roots attached. Depressed pale scars from the stems

are visible and some remains of stems in the form of fine, branching

strands, less than 1 mm in diameter, may also be attached to the rhizome.

The fracture is granular, odour faint but not unpleasant and the

taste strongly astringent.

Characteristic features of the powder include brown cork cells, parenchymatous

tissue containing tannin, sclerenchymatous tissues, vascular

elements, starch in conglomerates or as single grains up to about

20 μm in length, and abundant cluster crystals of calcium oxalate up to

about 50 μm in diameter.

Constituents. The rhizome contains a mixture of both hydrolysable

and condensed tannins (proanthocyanidins). Among the former is agrimoniin,

a dimeric ellagitannin found also in Agrimonia and Alchemilla,

and belonging to the same biosynthetic group, ellagic acid and catechol

gallates. Other components are flavan-3-ols, the pseudosaponin

tormentoside, quinovic acid and various phenylpropanes together with

a trace of volatile oil.

Standards. BP/EP requirements are a minimum of 7.0% tannins

calculated as pyrogallol for the dried rhizome. A maximum of 3% for

roots, stems and rhizomes with a black fracture. Other foreign matter

limited to 2%. Compliance with a TLC test for identity using catechin

as a reference substance.

Uses. As an astringent; internally as an antidiarrhoeic and externally

for gargles and inflamed mucous membranes.

Hawthorn

The leaves, flowers and false fruits are all medicinally useful, the

leaves and flowers being used principally for the preparation of infusions,

etc. with the fruits employed in the manufacture of prepared

medicaments. The dried false fruits of Crataegus monogyna and

C. laevigata, family Rosaceae, together with their hybrids are official

in the EP, BP and BHP; similarly the leaf and flower, for which there

is also an ESCOP monograph.

The thorny, deciduous trees are native to Europe and have a long

medical and ethnobotanical history. Commercial supplies of the dried

fruits, required to contain not less than 1.0% procyanidins, originate

from Eastern Europe.

Characters. Characteristic of a number of genera of the family

Rosaceae, so-called hawthorn berries are false fruits (pomes, and

not in the strict botanical sense berries) in which the carpels become

adherent to the hollow, fleshy receptacle and the sepals, petals and

stamens become situated at the upper end of the fruit. The carpels

become stony so that the pome comes rather to resemble a drupe

(Ch. 41). The false fruits of C. monogyna with one carpel contain a

single stony true fruit whereas those of C. laevigata with two or three

carpels contain two or three fruits.

The dried reddish-brown to dark red fruits have a slight odour and

mucilaginous, slightly acid taste; with C. monogyna they are up to

10 mm in length and slightly larger for C. laevigata. At the upper

end of the false fruit are the remains of the five reflexed sepals which

surround a shallow depression from the base of which arise stiff

Constituents. The fruits contain 1–3% oligomeric procyanidins, the

structures of which appear to be only partially ascertained together

with flavonoids, principally hyperoside about 1%. The leaves in

contrast

contain less hyperoside and more vitexin rhamnoside.

Allied species. Adulteration of the readily available product is rare;

other species of Crataegus may be detected by their having more than

three seeds. C. pinnatifida fruits are used in Chinese medicine.

Uses. Hawthorn is widely used as a mild cardiac tonic particularly

for patients of advancing age. It does not have the toxic effects of

Digitalis and can usefully be employed before recourse is made to the

digitalis cardioactive glycosides.

Agrimony

Agrimony BP/EP, BHP family Rosaceae consists of the dried flowering

tops of Agrimonia eupatoria L

The BP drug is required to contain a minimum of 2.0% tannins,

expressed as pyrogallol when assayed by the official ‘determination

of tannins in herbal drugs’. The TLC test of identification exploits

the flavonoid content (rutin and isoquercitroside as test substances).

Vitamins, triterpenes, volatile oil have also been reported as components

of the drug.
Among other herbal uses, agrimony is employed as a mild astringent,

internally and externally, against inflammation of the throat and

for gastroenteritis.

Alchemilla

Other constituents are flavonoids,

quercetin 3-O-β-d-glucoside having been isolated as the major

flavonoid in leaves of French origin.

Alchemilla acts as an astringent against bleeding and diarrhoea

and has a long tradition of use for gynaecological conditions such as

menorrhagia.

Rhatany

Rhatany of the BP and EP (Krameria) is the dried root of Krameria triandra

(Krameriaceae, a small family related to the Leguminosae), a small

shrub with decumbent branches about 1 m long. The drug is collected in

Bolivia and Peru and is known in commerce as Peruvian rhatany

A phlobaphene (krameria-red), starch and calcium oxalate

are also present. Stahl and Ittel (1981) reported the isolation of two

benzofuran derivatives, ratanhiaphenols I and II, from the root

The drug is used as an astringent and the significant antimicrobial

activity of the extract gives rational support for its use in mouth and

throat infections.

The pomegranate fruit is one of the oldest known to man and has featured

in mythology, and as a food and medicine from ancient civilizations

of the Middle East to its present wide cultivation in India and

surrounding countries, Turkey, southern Europe and California.

Pomegranate rind consists of the dried pericarp of the fruit of

Punica granatum (Punicaceae). It occurs in thin, curved pieces about

1.5 mm thick, some of which bear the remains of the woody calyx or a

scar left by the stalk. The outer surface is brownish-yellow or reddish.

The inner surface bears impressions left by the seeds. Pomegranate

rind, used in India as a herbal remedy for non-specific diarrhoea, is

very astringent and contains about 28% of tannin (ellagitannins) and

colouring matters. It should be distinguished from the root bark, which

contains alkaloids.

For a discussion of the biochemistry, health effects, commercialization,

plant growth and improvement of the pomegranate fruit, see

N. P. Seeram et al. (eds), R. Hardman (series ed.) 2006 Medicinal and

aromatic plants – industrial profiles, Vol 43. Pomegranate. CRC Press,

Taylor and Francis Group. Boca Raton, FL., 244 pp.

Aspidosperma barks

The bark of Aspidosperma quebracho-blanco (Apocynaceae),

which is used as a tanning material, was formerly official in several

pharmacopoeias.

Myrobalans

Myrobalans are the dried fruits of Terminalia chebula (Combretaceae),

a tree common in India. The immature fruits are black, ovoid and about

1–3 cm long. They contain about 20–40% of tannin, β-sitosterol,

anthraquinones and a fixed oil containing principally esters of palmitic,

oleic and linoleic acids. The tannin and anthraquinone constituents

make the drug both astringent and cathartic in action. Microbiological

tests support the Indian use of an aqueous extract of the fruit as an anticaries

agent (A. G. Jagtap and S. G. Karkera, J. Ethnopharmacology,

1999, 68, 299).

Catechu

Gambir or pale catechu of the BP 1989; BP (Veterinary), 2007 is a

dried, aqueous extract prepared from the leaves and young twigs of

a climbing shrub, Uncaria gambir (Rubiaceae). It must be carefully

distinguished from black catechu or cutch. The plant is a native of

Malaya and it is largely cultivated for the production of the drug in

Indonesia and Malaya for marketing through Singapore.

History. The catechu described by Barbosa (1514) was black catechu

or cutch, and the first account of gambir appears to be that of

a Dutch trader in 1780. In addition to the cube gambir used in pharmacy,

large blocks of the extract are imported for use in dyeing and

tanning. Other forms are used in the East for chewing with betel

leaf.

Preparation. The preparation of catechu in Johore differs only

slightly from the procedure adopted in Indonesia. It consists of

extracting the leaves and young twigs with boiling water, evaporating

the extract to a pasty consistency and dividing it into cubes, which are

then sun-dried. Fuller details of the preparation are given in the 10th

edition.

Many different forms of catechu are used in the East, and the drug

for the Eastern market frequently has 20–50% of fine rice husks added

as the liquid coagulates in the tubs. Such catechu is, of course,

unofficial, and contains starch.

Macroscopical characters. Catechu occurs in cubes, which are

very friable and may be broken up in transit or, if incompletely dried,

may be more or less agglutinated. Of the samples available, those

from Indonesia measure 17–22 mm and have a reddish-brown surface,

often stamped with a maker’s mark, while those from Johore measure
24–29 mm and have a blackish exterior and the faces of the cube are

depressed. Internally, both varieties are cinnamon-brown and porous.

Odourless; taste, very astringent and at first somewhat bitter, afterwards

sweetish.

Microscopical characters. When mounted in water, catechu shows

minute, acicular crystals of catechin, many of which are branched and

interlacing. They dissolve on warming and a considerable amount of

vegetable debris is left. The leaves, particularly the stipules, bear simple,

unicellular hairs up to about 350 mm long, with smooth, moderately

thick, lignified walls. The twigs have lignified pericyclic fibres,

wood fibres, and spiral, annular and pitted vessels. Minute starch

grains are commonly present, particularly in the Indonesian drug, but

the amount should be strictly limited. Rice husks have been observed

in some samples.

Chemical tests

1. For gambir-fluorescin. Extract a little of the powdered drug with

alcohol and filter. To the filtrate add solution of sodium hydroxide.

After shaking, add a few millilitres of light petroleum, shake again

and allow to stand. The petroleum spirit layer shows a strong green

fluorescence.

2. For catechin. This is a modification of the usual test for lignin.

Phloroglucinol is formed from catechin and with hydrochloric acid

turns a matchstick red.

Constituents. Gambir contains about 7.33% of catechins, 22–50%

of catechutannic acid, catechu red, quercitin and gambir-fluorescin.

BP (Vet.) 2007 standards include a loss on drying of not more than

15.0% and a water-insoluble matter of not more than 33.0% with

reference

to the dried material.

Catechin forms white, acicular crystals which are soluble in hot water

and alcohol and give a green colour with ferric salts. Catechutannic

acid is an amorphous phlobatannin which appears to be formed from

catechin by loss of the elements of water. It readily yields the phlobaphene

catechu-red. If the drug is carefully prepared, it will contain a

high proportion of catechin and correspondingly smaller amounts of

catechutannic acid and catechu-red.

Allied drug. Cutch or black catechu is an extract prepared from

the heartwood of Acacia catechu (Leguminosae). Cutch occurs in

black, somewhat porous masses. The taste resembles that of gambir.

Microscopical examination of the water-soluble residue shows wood

fibres and large vessels and sometimes fragments derived from the

leaves on which the drug is spread.

Cutch contains 2–12% of catechins, 25–33% of phlobatannin, 20–30%

of gummy matter, quercitrin, quercitin, moisture, etc. It yields 2–3% of

ash. The catechin (acacatechin) is not identical with that in gambir.

Uses. Catechu is used in medicine as an astringent.

Kinos

The name ‘kino’ has been applied to a number of dried juices, rich in

phlobatannins and formerly used for their astringent properties. They

include Malabar kino from Pterocarpus marsupium (Leguminosae),

butea gum or Bengal kino from Butea frondosa (B. monosperma)

(Leguminosae) and eucalyptus kino or red gum from Eucalyptus

rostrata (Myrtaceae).

Croton lechleri

The bark of this and related euphorbiaceous trees yield, when slashed,

a blood-red sap commonly known in South American folk medicine as

Sangre de Grado, Sangre de Drace, or dragon’s blood (not to be confused

with the dragon’s blood obtained from species of Daemonorops palms,

q.v.). It is used locally for its anti-infective, antitumour and woundhealing

properties. Cai et al. (Phytochemistry, 1991, 30, 2033; 1993,

32, 755) have shown proanthocyanidins to be the principal constituents

(c. 90%) which vary from monomers to heptamers.