Tannins

Group 3: De Castro, Desiree B. Dolleton, Ellisse Anne C. Galang, Jelene Marie R. Gatus, Gracelyn Mae G. Genson, Bernice O. Gumapac, Bea Victoria T.

3-C Pharmacy

Date Submitted: July 20, 2012

Description Tannin is a phenolic compound of sufficiently high molecular weight containing sufficient hydroxyls and other suitable groups (i.e. carboxyls) to form effectively strong complexes with protein and other macromolecules under the particular environmental conditions being studied. Tannins are one of the many types of secondary compounds found in plants.

Characteristics of tannins: oligomeric compounds with multiple structure units with free phenolic groups molecular weight ranging from 500 to >20,000 soluble in water, with exception of some high molecular weight structures ability to bind proteins and form insoluble or soluble tannin-protein complexes

The tannin compounds can be divided into two major groups based on Goldbeaters skin test. A group of tannins showing the positive tanning test may be regarded as true tannins while those, which are partly retained by the hide powder and fail to give the test, are called as pseudotannins. Most of the true tannins are high molecular weight compounds. These compounds are complex polyphenolics, which are produced by polymerization of simple polyphenols. They may form complex glycosides or remains as such which may be observed by their typical hydrolytic reaction with the mineral acids and enzymes. Two major chemical classes of tannins are usually recognized based on this hydrolytic reaction and nature of phenolic nuclei involved in the tannins structure. The first class is referred to as hydrolysable tannins while the other class is termed as condensed tannins.

Hydrolysable tannins HTs are molecules with a polyol (generally D-glucose) as a central core. The hydroxyl groups of these carbohydrates are partially or totally esterified with phenolic groups like gallic acid (-->gallotannins) or ellagic acid (--> ellagitannins). HT are usually present in low amounts in plants. Some authors define two additional classes of hydrolyzable tannins: taragallotannins (gallic acid and quinic acid as the core) and caffetannins (caffeic acid and quinic acid). 1. Gallotannins: The phenolic groups that esterify with the core are sometimes constituted by dimers or higher oligomers of gallic acid (each single monomer is called galloyl) Each HT molecule is usually composed of a core of D-glucose and 6 to 9 galloyl groups In nature, there is abundance of mono and di-galloyl esters of glucose (MW about 900). They are not considered to be tannins. At least 3 hydroxyl groups of the glucose must be esterified to exhibit a sufficiently strong binding capacity to be classified as a tannin. The most famous source of gallotannins is tannic acid obtained from the twig galls of Rhus semialata. It has a penta galloyl-D-glucose core and five more units of galloyl linked to one of the galloyl of the core. 2. Ellagitannins: The phenolic groups consist of hexahydroxydiphenic acid, which spontaneously dehydrates to the lactone form, ellagic acid. Molecular weight range: 2000-5000.

HT properties: hydrolyzed by mild acids or mild bases to yield carbohydrate and phenolic acids Under the same conditions, proanthocyanidins (condensed tannins) do not hydrolyze. HTs are also hydrolyzed by hot water or enzymes (i.e. tannase).

Examples plants containing hydrolysable tannins are Terminalia chebula- contains 20%-40% Gallic acid. it is used a s an astringent and stomachic Teminalia arjuna- contains 20%-40% ellagic acid. Used as a cardio tonic and hypotensive drug Emblica officinalis- contains22%-28% Gallic acid. Used as diuretic and laxative Punica granatum- contains 22% gallotannic acid. It is used as astringent Quercus infectoria- contains 50% to 70% gallotannic acid. It is used as anti dote

Proanthrocyanidins (Condensed Tannins) PAs are more widely distributed than HTs. They are oligomers or polymers of flavonoid units (i.e. flavan-3-ol) linked by carbon-carbon bonds not susceptible to cleavage by hydrolysis. o PAs are more often called condensed tannins due to their condensed chemical structure. However, HTs also undergo condensation reactions. The term, condensed tannins, is therefore potentially confusing. o The term, proanthocyanidins, is derived from the acid catalyzed oxidation reaction that produces red anthocyanidins upon heating PAs in acidic alcohol solutions. o The most common anthocyanidins produced are cyanidin (flavan-3-ol, from procyanidin) and delphinidin (from prodelphinidin). o PAs may contain from 2 to 50 or greater flavonoid units; PA polymers have complex structures because the flavonoid units can differ for some substituents and because of the variable sites for interflavan bonds. o Anthocyanidin pigments are responsible for the wide array of pink, scarlet, red, mauve, violet, and blue colors in flowers, leaves, fruits, fruit juices, and wines. They are also responsible for the astringent taste of fruit and wines. o o PA carbon-carbon bonds are not cleaved by hydrolysis. Depending on their chemical structure and degree of polymerization, PAs may or may not be soluble in aqueous organic solvents. Proanthrocyanidins are related to flavanoids. They are formed by condensing units of catechols. Some examples are: Saraca indica- contains catechols and used as uterine tonic Acacia catechu- contains quercetin and catechin and used as astringents

Pseudotannins are simple phenolic compounds of lower molecular weight. They do not respond to the tanning reaction of Goldbeaters skin test. Gallic acid, Chlorogenic acid or the simple phenolics such as catechin are pseudotannins which are abundantly found in plants, especially in dead tissues and dying cells.

Use

a. Pharmacologic Used as an antiseptic on skin and mucus membrane Used in healing of inflammation, burns Used as uterine tonics They are anti-diarrheal, styptic, and anti-infective agents They also act beneficially in gastritis, and bowel disorders Treatment for varicose ulcers Used in the inflammation of gums Antidote for heavy metal poisoning Antiviral activities for treatment of viral diseases including AIDS. Used in the treatment of HFE hereditary hemochromatosis, a hereditary disease characterized by excessive absorption of dietary iron, resulting in a pathological increase in total body iron stores.

Prolonged use of tannins may act as potential carcinogenic agent. Habitual chewing of betel nut and having black tea may affect the oral mucosa as an irritant and can cause cancer.

b. Traditional The word tannin is very old and reflects a traditional technology. "Tanning" (waterproofing and preserving) was the word used to describe the process of transforming animal hides into leather by using plant extracts from different plant parts of different plant species. c. Industrial Tannin has several industrial uses as preservatives. In dry wood and leather, tannin averts rotting, changing of shape and decay by bacteria and fungi. It also repels insects and herbivores and protects the plants. Bacteria and fungi cannot grow on plants or wood containing tannin by restricting the flow of extra-cellular microbial enzymes. As a result of this, microorganisms are not allowed to develop colonies in plants containing tannin or timber and leather treated with the substance. Most significantly, tannins destroy the microbes metabolism process by depriving them of iron and other metal ions through restriction of oxidative phosphorylation. Tannin is a component in a type of industrial particleboard adhesive developed jointly by the Tanzania Industrial Research and Development Organization and Forintek Labs Canada. Pinus radiata tannins has been investigated for the production of wood adhesives. Condensed tannins, i.e. quebracho tannin, and Hydrolyzable tannins, i.e., chestnut tannin, appear to be able to substitute a high proportion of synthetic phenol in phenol-formaldehyde resins for wood particleboard. Tannins can also be used for production of anti-corrosive primer, sold under the brand name-Nox Primer for treatment of rusted steel surfaces prior to painting, rust converter to transform oxidized steel into a smooth sealed surface and rust inhibitor. Tannins are used as mordant in dyeing, manufacture of ink, sizing paper and silk, and for printing fabrics. It is used along with gelatin and albumin for the manufacture of imitation horn and tortoise shell. It is also used for clarifying beer or wine, in photography or as a coagulant in rubber manufacture. Tannins are used for the manufacture of gallic acid and pyrogallol, and sometimes as a reagent in analytical chemistry. The use of resins made of tannins has been investigated to remove mercury and methylmercury from

solution. Immobilized tannins have been tested to recover uranium from seawater.

Example of Plants Tannins are widely distributed in the plant kingdom. They are common both in Gymnosperms and Angiosperms. Within Angiosperms, tannins are more common in Dicotyledons than in Monocotyledons. Examples of families of Dicotyledons rich in tannins are: Leguminosae : Acacia sp. (wattle); Sesbania sp.;Lotus sp. (trefoil); Onobrychis sp. (sainfoin); Anacardiaceae: Scinopsis balansae (quebracho) Combretaceae: myrobalan Rhizophoraceae : mangrove Myrtaceae: Eucalyptus sp., Mirtus sp. (Myrtle) Polinaceae: canaigre.

Other

important

tannin

containing

plants

are Quercus sp.

(oak), Acer sp.

(maple), Betula sp.

(birch),Salix

caprea (willow), Pinus sp. (Pine), Sorghum sp. Tannins are located mainly in the vacuoles or surface wax of the plants. In these sites they do not interfere with plant metabolism. Only after cell breakdown and death can they act and have metabolic effects. Sample Extraction Tannins are extracted with an aqueous organic solvent. 70% acetone and 30% water is a more effective extractant than alcoholic solvents. o Acetone inhibits tannin-protein interaction. This is a limitation in protein precipitation assays.

In many plants, there is a large fraction (sometimes >50%) of the tannins that cannot be extracted (insoluble tannins). o This unextractable fraction cannot be ignored because of its nutritional effects.

Sample purification and isolation Tannins need to be purified from low molecular weight phenolics and pigments that are present in crude plants extracts. Purification is essential for the preparation of suitable standards. Purification of large quantities of tannins can be done by taking advantage of their absorption by Sephadex LH20. An alternative and faster isolation method has been developed by Giner-Chavez, 1996.

Test for tannins Shows color reaction with ferrous chloride. Turns blue or green. With ammonia and potassium ferric cyanide it gives deep red color.

References: http://www.ansci.cornell.edu/plants/toxicagents/tannin.html#def Retrieved July 17, 2012 http://www.bukisa.com/articles/336504_tannins-classification-testing-and-uses Retrieved July 18, 2012 http://www.herbs2000.com/h_menu/tannins.htm Retrieved July 18, 2012 http://nsdl.niscair.res.in/bitstream/123456789/591/1/revised+Tannins+containing+Drugs.pdf Retrieved July 18, 2012 http://en.wikipedia.org/wiki/Tannin Retrieved July 17, 2012