Qualitative analysis. Qualitative analysis Determination of tannins in plant materials

Collection output:

METHODS FOR QUANTITATIVE DETERMINATION OF TANNINS IN MEDICINAL PLANT RAW MATERIALS

Mikhailova Elena Vladimirovna

Ph.D. biol. Sciences, assistant at VSMA named after. N.N. Burdenko,

Voronezh

Email: milenok2007@ rambler.ru

Vasilyeva Anna Petrovna

Martynova Daria Mikhailovna

student of VSMA named after. N.N. Burdenko, Voronezh

Email: darjamartynova92@ rambler.ru

Tannins (TS) are a very common group of biologically active substances (BAS) in plants, which have various pharmacological properties, which explains their widespread use in medicine. Therefore, the problem of determining the good quality of medicines and medicinal plant raw materials (MPS) containing this group of biologically active substances is very relevant. One of the main methods for establishing the good quality of MPs is quantitative phytochemical analysis. Currently, there are several methods that allow this type of analysis of medicinal products containing DV, but the literature data are scattered. In connection with the above, it is necessary to systematize methods for quantitative analysis of DVvLRS.

Classical methods for determining the content of DV are gravimetric (weight) and titrimetric methods. The basis of the gravimetric method is the property of DV to be precipitated by gelatin, heavy metal ions, and skin (skin) powder. The first step is to determine the mass of dry residue in the aqueous extract from the drug. In this case, the extract is dried to a constant weight. The next stage is the release of the extract from the DV by treatment with goli powder. In this case, a precipitate forms, which is then removed by filtration, the amount of dry residue is again determined, and the amount of DV is determined based on the difference in the indicated masses of the dry residue.

Titrimetric methods include:

1. Titration with gelatin solution. This method is also based on the property of DV to be precipitated by proteins (gelatin). Aqueous extracts from raw materials are titrated with a 1% gelatin solution. The titer is set based on pure tannin. The equivalence point is established by selecting the smallest volume of titrant that causes complete precipitation of the active substance. This method is highly specific and allows you to establish the content of true DV, but it is quite long in execution, and establishing the equivalence point depends on the human factor.

2. Permanganometric titration. This method is presented in the general pharmacopoeial monograph and is based on the easy oxidation of DV with potassium permanganate in an acidic medium in the presence of indigo sulfonic acid. At the end point of the titration, the color of the solution changes from blue to golden yellow. Despite the cost-effectiveness, speed, and ease of implementation, the method is not accurate enough, which is associated with the difficulty of establishing the equivalence point, as well as with overestimation of measurement results due to the strong oxidizing ability of the titrant.

3. Complexometric titration with Trilon B with preliminary precipitation of DV zinc sulfate. The method is used for the quantitative determination of tannin in the raw materials of tanning sumac and tanning sumac. Xylenol orange is used as an indicator.

Physicochemical methods for the quantitative determination of DV in medicinal plants include the photoelectrocolorimetric, spectrophotometric, amperometric method and the method of potentiometric and coulometric titration.

1. Photoelectrocolorimetric method. It is based on the ability of DV to form colored chemical compounds with iron (III) salts, phosphotungstic acid, Folin-Denis reagent and other substances. One of the reagents is added to the extract from the herbal plant under study, and after a stable color appears, the optical density is measured on a photocolorimeter. The percentage of DV is determined from a calibration graph constructed using a series of tannin solutions of known concentration.

2. Spectrophotometric determination. After obtaining the aqueous extract, part of it is centrifuged for 5 minutes at 3000 rpm. A 2% aqueous solution of ammonium molybdate is added to the centrifugate, then diluted with water and left for 15 minutes. The intensity of the resulting color is measured on a spectrophotometer at a wavelength of 420 nm in a cuvette with a layer thickness of 10 mm. Calculation of tanids is carried out according to a standard model. GSO tannin is used as a standard sample.

3.Chromatographic determination. To identify condensed tannins, alcohol (95% ethyl alcohol) and aqueous extracts are obtained and paper and thin-layer chromatography are performed. GSO catechin is used as a standard sample. Separation is carried out in solvent systems butanol - acetic acid - water (AWA) (40: 12: 28), (4: 1: 2), 5% acetic acid on “Filtrak” paper and “Silufol” plates. Detection of zones of substances on the chromatogram is carried out in UV light, followed by treatment with a 1% solution of ferric ammonium alum or a 1% solution of vanillin, concentrated hydrochloric acid. In the future, it is possible to carry out a quantitative analysis by eluting the DV from the plate with ethyl alcohol and conducting a spectophotometric analysis, taking the absorption spectrum in the range of 250-420 nm.

4.Amperometric method. The essence of the method is to measure the electric current that occurs during the oxidation of –OH groups of natural phenolic antioxidants on the surface of the working electrode at a certain potential. First, a graphical dependence of the signal of the reference sample (quercetin) on its concentration is plotted and, using the resulting calibration, the content of phenols in the samples under study is calculated in units of quercetin concentration.

5. Potentiometric titration. This type of titration of an aqueous extract (in particular, decoctions of oak bark) was carried out with a solution of potassium permanganate (0.02 M), the results were recorded using a pH meter (pH-410). Determination of the titration end point was carried out according to the Gran method using the computer program “GRAN v.0.5”. The potentiometric type of titration gives more accurate results, since in this case the equivalence point is clearly fixed, which eliminates the bias of the results due to the human factor. Potentiometric titration is especially important compared to indicator titration when studying colored solutions, such as aqueous extracts containing DV.

6. Coulometric titration. The method of quantitative determination of the content of DV in medicinal products in terms of tannin by coulometric titration is that the extract from the raw material under study reacts with a coulometric titrant - hypoiodite ions, which are formed during the disproportionation of electrogenerated iodine in an alkaline medium. Electrical generation of hypoiodite ions is carried out from a 0.1 M solution of potassium iodide in a phosphate buffer solution (pH 9.8) on a platinum electrode at a constant current of 5.0 mA.

Thus, for the quantitative determination of DV in medicinal plants, such methods for the quantitative determination of DV in medicinal products are used as titrimetric (including titration with gelatin, potassium permanganate, complexometric titration with Trilon B, potentiometric and coulometric titration), gravimetric, photoelectrocolorimetric, spectrophotometric, amperometric methods.

References:

1. Vasilyeva A.P. Study of the dynamics of the content of tannins in a decoction of oak bark during storage // Youth Innovation Bulletin. - 2012. - T. 1, No. 1. - P. 199-200.
2. State Pharmacopoeia of the USSR, XI edition, vol. 1. - M.: Medicine, 1987. - 336 p.
3. Grinkevich N.I., L.N. Safronich Chemical analysis of medicinal plants. - M., 1983. - 176 p.
4. Ermakov A.I., Arasimovich V.V. Determination of the total content of tannins. Methods of biological research of plants: Proc. Benefit. L.: Agropromizdat. 1987. - 456 p.
5. Islambekov Sh.Yu. Karimdzhanov S.M., Mavlyanov A.K. Vegetable tannins // Chemistry of natural compounds. - 1990. - No. 3. - P. 293-307.
6. Kemertelidze E.P., Yavich P.A., Sarabunovich A.G. Quantitative determination of tannin // Pharmacy. - 1984. No. 4. - P. 34-37.
7. Pat. RF No. 2436084 Method for coulometric determination of the content of tannins in plant raw materials; appl. 04/06/2010, publ. 12/10/2011. [Electronic resource]. Access mode. URL: http://www.freepatent.ru/patents/2436084 (access date: 12/02/2012).
8. Ryabinina E.I. Comparison of chemical-analytical methods for determining tannins and antioxidant activity of plant materials // Analytics and control. - 2011. - T. 15, No. 2. - P. 202-204.
9. Fedoseeva L.M. Study of tannins in underground and aboveground vegetative organs of bergenia, growing in Altai. // Chemistry of plant raw materials. - 2005. No. 3. P. 45-50.

Lecture topic

Lecture No. 11

1. The concept of tannins.

2. Distribution of tannins in the plant world.

3. The role of tannins for plant life.

4. Classification of tannins.

5. Biosynthesis, localization and accumulation of tannins in plants.

6. Features of collection, drying and storage of raw materials containing tannins.

7. Physical and chemical properties of tannins.

8. Assessment of the quality of raw materials containing tannins. Methods of analysis.

9. Raw material base of medicinal plants containing tannins.

10.Ways of using raw materials containing tannins.

11..Medical use of preparations containing tannins.

12.Medicinal plants and raw materials containing tannins

The concept of tannins

Tannins DV(tannids) are complex mixtures of plant high molecular weight polymers of phenolic compounds with a molecular weight from 500 to 3000, having an astringent taste, capable of forming strong bonds with proteins, turning raw animal skins into tanned leather.

The essence of the tanning process is the formation of strong hydrogen bonds between the phenolic hydroxyls of the DV and the hydrogen and nitrogen atoms of the protein molecules - collagen. The result is a strong cross-linked structure - skin that is resistant to heat, moisture, microorganisms, enzymes, i.e. not susceptible to rotting.

Polyphenolic compounds with lower M.w. (less than 500) are only adsorbed on proteins, but are not able to form stable complexes, and are not used as tanning agents. High molecular weight polyphenols (with MW more than 3000) are also not tanning agents, since their molecules are too large and do not penetrate between collagen fibrils.

Thus, the main difference between DV and other polyphenolic compounds is the ability to form strong hydrogen bonds with proteins.

The term “tannin” was first used by the French scientist Seguin in 1796 to refer to substances present in extracts of certain plants that can carry out the tanning process. Another name for DV - “tannids” - comes from the Latinized form of the Celtic name for oak - “tan”, the bark of which has long been used for processing leather.

The first scientific research in the field of DV chemistry dates back to the second half of the 18th century. They were prompted by the practical needs of the leather industry. The first published work was the work of Gleditsch in 1754 “On the use of blueberries as raw materials for the production of tannins.” The first monograph was Dekker's monograph in 1913, which summarized all the accumulated material on tannins. The search, isolation and establishment of the structure of the DV were carried out by domestic scientists L. F. Ilyin, A. L. Kursanov, M. N. Zaprometov, F. M. Flavitsky, G. Povarnin A. I. Oparin and others; foreign scientists G. Procter, K. Freudenberg, E. Fischer, P. Karrer and others.

Distribution of tannins in the plant world

DV are widely distributed in the plant world. They are found mainly in higher plants, most common in representatives of dicotyledons, where they accumulate in maximum quantities. Monocots usually do not contain DV; DV are found in ferns, but in horsetails, mosses, and mosses they are almost absent, or they are found in minimal quantities. The families with the highest content of DV are: sumacaceae - Anacardiaceae (tanning sumac, tanning sumac), Rosaceae - Rosaceae (burnet, cinquefoil erectus), beech - Fagaceae (pedunculate and sessile oak), buckwheat - Polygonaceae (snake knotweed and meat-red, heather - Ericaceae (bearberry, lingonberry), birch - Betulaceae (gray and sticky alder), etc.

The role of tannins for plant life

The biological role for plant life is not fully understood. There are several hypotheses:

1). DV perform a protective function, because when plants are damaged, they form complexes with proteins, which create a protective film that prevents the penetration of phytopathogenic organisms. They have bactericidal and fungicidal properties;

2). DVs participate in redox processes and are oxygen carriers in plants;

3). DV is one of the forms of reserve nutrients. This is indicated by their localization in underground organs and cortex;

4). DV - waste from the life of plant organisms.

Classification of tannins

Since DVs are mixtures of various polyphenols, classification is difficult due to the diversity of their chemical composition.

The classification of G. Povarnin (1911) and K. Freudenberg (1920), based on the chemical nature of DVs and their relationship to hydrolyzing agents, received the greatest recognition. According to this classification, DV are divided into 2 large groups:

1) hydrolyzable DV;

2) condensed DWs.

1. Hydrolyzable additives

Hydrolyzable additives - These are mixtures of esters of phenol carbonic acids with sugars and non-saccharides. In aqueous solutions under the action of acids, alkalis and enzymes, they are capable of hydrolyzing into constituent fragments of phenolic and non-phenolic nature. Hydrolyzable active substances can be divided into 3 groups.

1.1. Gallotannins- esters of gallic, digallic acids and its other polymers with cyclic forms of sugars.

m-digallic acid (depside - D)

The most important sources of gallotannins used in medicine are Turkish galls, formed on the Lusitanian oak and Chinese, formed on the semi-winged sumac, leaves of the tanning sumac and tanning sumac.

Tannin is a heterogeneous mixture of substances of different structures. There are mono-, da-, tri-, tetra-, penta- and polygalloyl ethers.

According to L.F. Ilyin, E. Fischer and K. Freudenberg, Chinese tannin is penta-M-digalloyl-β-D-glucose, i.e. β-D-glucose, the hydroxyl groups of which are esterified with M-digallic acid .

According to P. Carrer, Chinese tannin is a heterogeneous mixture of substances of different structures; the hydroxyl groups of glucose can be esterified with gallic, digallic and trigallic acids.

K. Freudenberg assumed that in Turkish tannin, on average, one of the five hydroxyl groups of glucose is free, the other is esterified with M-digallic acid, and the rest with gallic acid.

DV of this group are contained and predominate in the rhizomes and roots of burnet, rhizomes of serpentine, bergenia, alder fruit, oak bark, and witch hazel leaves.

1.2. Ellagotapnins- esters of ellagic and other acids having a neubiogenetic relationship with cyclic forms of sugars. Contained in the peel of pomegranate fruits, eucalyptus bark, walnut peel, leaves and inflorescences of fireweed (fireweed).

1.3. Non-saccharide esters of phenolcarboxylic acids- esters of gallic acid with quinic, chlorogenic, caffeic, hydroxycinnamic acids and flavans.

Example: Theogalline, found in Chinese tea leaves, is an ester of quinic acid and gallic acid (3-O-galloylquinic acid ).

2. Condensed DV

Condensed DVs do not have an ethereal character; the polymer chain of these compounds is formed through carbon-carbon bonds (-C-C-), which makes them resistant to acids, alkalis and enzymes. When exposed to mineral acids, they do not break down, but increase M.m. with the formation of oxidative condensation products - phlobaphenes or red-brown dyes.

Condensed DV - these are condensation products of catechins (flavan-3-ols), leucoanthocyanidins (flavan-3,4-diols), and less commonly oxystilbenes (phenylethylenes).

The formation of condensed DWs can occur in two ways. According to K. Freudenberg, it is accompanied by rupture of the pyran ring of catechins, and the C2 atom of one molecule is connected by a carbon-carbon bond to the C6 or C8 atom of another molecule.

According to D.E. Hathuey, condensed DVs are formed as a result of enzymatic oxidative condensation of molecules of the “head to tail” type (ring A to ring B) or “tail to tail” (ring B to ring B) at positions 6"-8 ; 6 -2` etc.

Condensed active substances are contained and predominate in viburnum bark, cinquefoil rhizomes, blueberry fruits, bird cherry fruits, St. John's wort herb, and tea leaves.

The composition of DV mixtures also includes simple phenols (resorcinol, pyrocatechol, pyrogallol, phloroglucinol, etc.) and free phenolcarboxylic acids (gallic, ellagic, protocatechuic, etc.).

Most often in plants there is a mixture of hydrolyzable and condensed active substances with a predominance of one or another group, so it is quite difficult to classify them according to the type of active substances. Some types of raw materials have almost the same content of both groups of active substances (for example, serpentine rhizomes).

Biosynthesis, localization and accumulation of tannins in plants

The biosynthesis of hydrolyzable DVs occurs along the shikimate pathway, while condensed DVs are formed via a mixed pathway (shikimate and acetate-malonate). DV are in a dissolved state in the vacuoles of plant cells and are separated from the cytoplasm by a protein-lipid membrane - the tanoplast; during cell aging, they are adsorbed on the cell walls.

They are localized in the cells of the epidermis, parietal cells surrounding the vascular-fibrous bundles (leaf veins), in the parenchyma cells of the medullary rays, bark, wood and phloem.

DVs accumulate mainly in the underground organs of perennial herbaceous plants (the rhizomes of bergenia, serpentine, cinquefoil, rhizomes and roots of burnet), in the root wood of trees and shrubs (oak bark, viburnum), in fruits (cherry fruits, blueberries, alder fruits) , less often in leaves (leaves of scumpia, sumac, tea).

The accumulation of tannins depends on genetic factors, climatic and environmental conditions. In herbaceous plants, as a rule, the minimum amount of DV is observed in the spring during the period of regrowth, then their content increases and reaches a maximum during budding and flowering (for example, cinquefoil rhizomes). By the end of the growing season, the amount of DV gradually decreases. In the burnet, the maximum DV accumulates during the development phase of rosette leaves; during the flowering phase, its content decreases, and in the fall it increases again. The growing season affects not only the quantity, but also the qualitative composition of DV. In the spring, during the period of sap flow, in the bark of trees and shrubs and in the regrowth phase of herbaceous plants, hydrolyzable active substances predominantly accumulate, and in the fall, during the phase of plant death, condensed active substances and the products of their polymerization - phlobaphenes (krasenes).

The most favorable conditions for the accumulation of tannins are temperate climate conditions (forest zone and high alpine zone).

The highest content of DV was observed in plants growing on dense calcareous soils; on loose chernozem and sandy soils their content was lower. Phosphorus-rich soils promote the accumulation of DV; nitrogen-rich soils reduce the content of tannins.

Features of collecting, drying and storing raw materials containing tannins

The procurement of raw materials is carried out during the period of maximum accumulation of additives.

The collected raw materials are air-dried in the shade or in dryers at a temperature of 50-60 degrees. Underground organs and oak bark can be dried in the sun.

Store in dry, well-ventilated areas without direct sunlight according to the general list for 2-6 years.

Physical and chemical properties of tannins

DVs are isolated from plant materials in the form of a mixture of polymers and are amorphous substances of yellow or yellow-brown color, odorless, astringent taste, and very hygroscopic. They dissolve well in water (especially hot water) to form colloidal solutions; they are also soluble in ethyl and methyl alcohol, acetone, ethyl acetate, butanol, and pyridine. Insoluble in chloroform, benzene, diethyl ether and other non-polar solvents, optically active.

Easily oxidizes in air. Capable of forming strong intermolecular bonds with proteins and other polymers (pectin, cellulose, etc.). Under the action of the tanase enzyme and acids, hydrolyzed active substances disintegrate into their component parts, and condensed active substances become larger.

Gelatin, alkaloids, basic lead acetate, potassium dichromate, and cardiac glycosides are precipitated from aqueous solutions.

As substances of phenolic nature, DVs are easily oxidized by potassium permanganate in an acidic environment and other oxidizing agents, forming colored complexes with salts of heavy metals, ferric iron, and bromine water.

Can be easily adsorbed on skin powder, cellulose, fiber, cotton wool.

Assessment of the quality of raw materials containing tannins,

Analysis methods

To obtain the amount of DV, plant materials are extracted with hot water in the ratio 1:30 or 1:10.

Qualitative analysis

Qualitative reactions (precipitation and color) and chromatographic examination are used.

1. A specific reaction is the precipitation reaction with gelatin; use a 1% solution of gelatin in a 10% solution of sodium chloride. A flaky precipitate or turbidity appears, soluble in excess gelatin. A negative reaction with gelatin indicates the absence of DV.

2. Reaction with alkaloid salts, use a 1% solution of quinine hydrochloride. An amorphous precipitate appears due to the formation of hydrogen bonds between the hydroxyl groups of the DV and the nitrogen atoms of the alkaloid.

These reactions give the same effect regardless of the DV group. A number of reactions make it possible to determine the DV group.

Qualitative reactions to DV

The reaction with a 1% alcohol solution of ferroammonium alum - this reaction is pharmacopoeial, is carried out both with a decoction of raw materials (GF-XI - oak bark, serpentine rhizome, alder fruit, blueberry fruits), and to open the DV directly in dry raw materials (GF -XI - oak bark, viburnum bark, bergenia rhizomes).

Quantification

About 100 different methods for the quantitative determination of DV are known, which can be divided into the following main groups.

1. Gravimetric or gravimetric - are based on quantitative precipitation of active substances with gelatin, heavy metal ions or adsorption by skin (skin) powder.

For technical purposes, the standard gravimetric method using solid powder throughout the world is the gravimetric unified method (BEM).

The aqueous extract of DV is divided into two equal parts. One part of the extract is evaporated and dried to constant weight. The other part of the extract is treated with skin powder and filtered. The active substances are adsorbed on the skin powder and remain on the filter. The filtrate and washing waters are evaporated and dried to constant weight. The DV content is calculated by the difference in the mass of dry residues.

The method is inaccurate, because skin powder also adsorbs low molecular weight phenolic compounds, which is quite labor-intensive and expensive.

2. Titrinemetric methods. These include:

A) Gelatin method - based on the ability of DV to form insoluble complexes with proteins. Aqueous extracts from the raw material are titrated with a 1% gelatin solution; at the equivalence point, gelatin-tannate complexes dissolve in excess reagent. The titer is set based on pure tannin. The equivalence point is determined by selecting the smallest volume of titrated solution that causes complete precipitation of the active substance.

The method is the most accurate, because allows you to determine the number of true DV. Disadvantages: length of determination and difficulty in establishing the point of equivalence.

b) Permanganatometric method ( Leventhal's method modified by A.P. Kursanov). This is a pharmacopoeial method, based on the easy oxidation of DV with potassium permanganate in an acidic medium in the presence of an indicator and catalyst indigosulfonic acid, which at the equivalence point turns into isatin, and the color of the solution changes from blue to golden yellow.

Features of the determination that make it possible to titrate only DV macromolecules: titration is carried out in highly dilute solutions (the extract is diluted 20 times) at room temperature in an acidic environment, potassium permanganate is added slowly, drop by drop, with vigorous stirring.

The method is economical, fast, easy to implement, but not accurate enough, because... Potassium permanganate partially oxidizes low molecular weight phenolic compounds.

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Tannins (tannids) - these are complex mixtures of plant high molecular weight polymers of phenolic compounds with a molecular weight from 300 to 5000 (about 500-3000), having an astringent taste, capable of forming strong bonds with proteins, turning raw animal skin into tanned leather.

The essence of the tanning process is the formation of strong hydrogen bonds between the phenolic hydroxyls of tannins and collagen protein molecules. The result is a strong cross-linked structure - skin that is resistant to heat, moisture, microorganisms, enzymes, i.e. not susceptible to rotting.

Polyphenolic compounds with lower molecular weight (less than 300) are only adsorbed on proteins, but are not able to form stable complexes, and are not used as tanning agents. High molecular weight polyphenols (with a molecular weight of more than 5000) are also not tanning agents, since their molecules are too large and do not penetrate between collagen fibrils.

Thus, the main difference between tannins and other polyphenolic compounds is the ability to form strong hydrogen bonds with proteins.

The term “tannin” was first used by the French scientist Seguin in 1796 to refer to substances present in extracts of certain plants that can carry out the tanning process. Another name for tannins, tannins, comes from the Latinized form of the Celtic name for oak, “ tan", the bark of which has long been used for leather processing.

The first scientific research in the field of chemistry of tannins dates back to the second half of the 18th century. They were prompted by the practical needs of the leather industry. The first published work was the work of Gleditsch (1754) “On the use of blueberries as raw materials for the production of tannins.” The first monograph was Dekker's monograph, published in 1913, which summarized all the accumulated material on tannins. The search, isolation and establishment of the structure of tannins were carried out by domestic scientists L.F. Ilyin, A.L. Kursanov, M.N. Zaprometov, F.M. Flavitsky, G. Povarnin, A.I. Oparin and others; foreign scientists G. Procter, K. Freudenberg, E. Fischer, P. Karrer and others.

Distribution in the plant world

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Tannins are widely distributed in living nature. They are found mainly in plants, but are also found in algae, fungi and lichens. Tannins are most common among representatives of dicotyledons, in which they accumulate in maximum quantities. Monocots usually do not contain tannins; ferns contain tannins, but horsetails, mosses, and mosses have practically no tannins, or they are found in minimal quantities.

The families with the highest tannin content are:

• Sumacaceae - Anacardiaceae (tanning sumac, tanning sumac);
• Rosaceae - Rosaceae (burnet, cinquefoil erect);
• beech - Fagaceae (common oak (pedunculate) and sessile oak);
• buckwheat - Polygonaceae (large serpentine and meat-red);
• heatheraceae - Ericaceae (bearberry, lingonberry);
• birch - Betulaceae (gray alder and sticky alder), etc.

Role for plant life

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The biological role for plant life is not fully understood. There are several hypotheses:

1. tannins - waste products of plant organisms;
2. Tannins are a form of storage nutrients. This is indicated by their localization in underground organs and cortex;
3. tannins perform a protective function, because when plants are damaged, they form complexes with proteins, which create a protective film that prevents the penetration of phytopathogenic organisms. They have bactericidal and fungicidal properties;
4. tannins are involved in redox processes and are oxygen carriers in plants.

Biosynthesis, localization and accumulation of tannins in plants

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The biosynthesis of hydrolyzable tannins occurs along the shikimate pathway, while condensed tannins are formed through a mixed pathway (shikimate and acetate-malonate).

Tannins are dissolved in the vacuoles of plant cells; during cell aging, they are adsorbed on the cell walls. They are localized in the cells of the epidermis, parietal cells surrounding vascular bundles (veins of leaves), in the parenchyma cells of the medullary rays, bark, wood and phloem.

Tannins accumulate in large quantities mainly in the underground organs of perennial herbaceous plants (the rhizomes of bergenia, serpentine, cinquefoil, rhizomes and roots of burnet), in the bark and wood of trees and shrubs (oak bark, viburnum), in fruits (cherry fruits, blueberries, alder fruits), less often in leaves (leaves of mackerel, sumac, tea).

The accumulation of tannins depends on genetic factors, climatic and environmental conditions. In herbaceous plants, as a rule, the minimum amount of tannins is observed in the spring during the period of shoot growth, then their content increases and reaches a maximum during budding and flowering (for example, cinquefoil rhizomes). Towards the end of the growing season, the amount of tannins gradually decreases. In the burnet, the maximum amount of tannins accumulates during the development phase of rosette leaves; during the flowering phase, their content decreases, and in the fall it increases again. The growing season affects not only the quantity, but also the qualitative composition of tannins. In the spring, during the period of sap flow, hydrolyzable tannins accumulate predominantly in the bark of trees and shrubs and in the phase of shoot regrowth in herbaceous plants, and in the autumn, during the phase of plant death, condensed tannins and their polymerization products - phlobaphenes (krasenes).

The most favorable conditions for the accumulation of tannins are temperate climate conditions (forest zone and high alpine zone).

The highest content of tannins was observed in plants growing on dense calcareous soils; on loose chernozem and sandy soils their content was lower. Soils rich in phosphorus promote the accumulation of tannins; soils rich in nitrogen reduce the content of tannins.

Preparation, drying and storage of raw materials containing tannins

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The procurement of medicinal plant raw materials containing tannins is carried out according to general rules. However, there are some exceptions to the rules:

• Potentilla rhizomes are harvested in the summer, during flowering, because the content of condensed tannins in them is quite large, and they also take into account the fact that after the plant has flowered and its above-ground part has withered, in the fall, cinquefoil is almost impossible to detect in the grass of marshy areas;
• The rhizomes of the serpentine are dug up immediately after the plant has flowered;
• rhizomes and roots of the burnet should be dug up during the fruiting period, when the dark red inflorescences are easily visible in the grass stand;
• Alder fruits are collected in late autumn or winter, when the leaves are not in the way.

The collected raw materials are dried in dryers at a temperature not exceeding 60 ºС (40-60 ºС). When drying naturally, the raw materials are laid out in a thin layer in the open air or in a closed, ventilated room.

Raw materials can be dried in the sun, because... tannins do not decompose under the influence of ultraviolet rays.

Raw materials containing tannins should be stored according to general rules. Bird cherry and blueberry fruits are stored separately, along with other fruits. Alder fruits are stored together with all types of raw materials, because the fruits are woody and, as experience has shown, are not damaged by barn pests.

Physical and chemical properties

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Tannins are isolated from plant materials in the form of a mixture of polymers and are amorphous substances of yellow or yellow-brown color, odorless, astringent taste, and very hygroscopic. They dissolve well in water (especially hot water) to form colloidal solutions; they are also soluble in ethyl and methyl alcohols, acetone, ethyl acetate, butanol, and pyridine. Insoluble in chloroform, benzene, diethyl ether and other non-polar solvents, optically active.

Easily oxidizes in air. Capable of forming strong intermolecular bonds with proteins and other polymers (pectin, cellulose, etc.). Under the action of enzymes and acids, hydrolyzed tannins break down into their component parts, while condensed tannins polymerize.

Gelatin, alkaloids, lead acetate, potassium dichromate, and cardiotonic glycosides are precipitated from aqueous solutions.

As substances of phenolic nature, tannins are easily oxidized by potassium permanganate in an acidic environment and other oxidizing agents, forming colored complexes with salts of heavy metals, ferric iron, and bromine water.

Capable of being easily adsorbed on skin powder, cellulose, and cotton wool.

Analysis of raw materials containing tannins

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To obtain the amount of tannins, plant materials are extracted with hot water in a ratio of 1:30 or 1:10.

Qualitative analysis

Qualitative reactions (precipitation and color) and chromatographic examination are used.

I. General precipitation reactions– to detect tannins in raw materials:

1. A specific reaction is the precipitation reaction with gelatin; a 1% solution of gelatin in a 10% sodium chloride solution is used. A flaky precipitate or cloudiness appears, which disappears when excess gelatin is added. A negative reaction with gelatin indicates the absence of tannins.
2. Reaction with alkaloid salts, use a 1% solution of quinine chloride. An amorphous precipitate appears due to the formation of hydrogen bonds between the hydroxyl groups of tannins and the nitrogen atoms of the alkaloid.

These reactions produce the same effect regardless of the tannin group. A number of reactions make it possible to determine whether tannins belong to a specific group.

II. Group qualitative reactions for tannins:

№	Reagent	Hydrolyzable tannids	Condensed tannins
1	dilute sulfuric acid	hydrolysis	red-brown phlobafens (krasene)
2	bromine water (5g bromine in 1 liter of water)	———	orange or yellow sediment
3	1% solution of ferric ammonium alum (iron oxide chloride is not used, because its solution is acidic)	black-blue coloration or sediment	black-green color or sediment
4	10% solution of lead acetate (at the same time add 10% solution of acetic acid)	white precipitate, insoluble in acetic acid (the precipitate is filtered and the content of condensed tannins in the filtrate is determined, with a 1% solution of ferroammonium alum - black-green color)	white precipitate, soluble in acetic acid
5	Stiasni test (40% solution of formaldehyde with concentrated hydrochloric acid)	———	brick-red precipitate (the precipitate is filtered and the content of hydrolyzable tannins in the filtrate is determined; in a neutral medium with a 1% solution of ferroammonium alum - black-blue color)
6	1% solution of vanillin in concentrated hydrochloric acid	———	orange-red color (catechins)

The reaction with a 1% alcohol solution of ferric ammonium alum is included in all regulatory documents for medicinal raw materials as a reaction to determine their authenticity. The reaction is recommended by the State Fund XI and is carried out both with a decoction of raw materials (oak bark, serpentine rhizomes, alder fruits, blueberry fruits), and to open tannins directly in dry raw materials (oak bark, viburnum bark, bergenia rhizomes).

Quantification

There are about 100 different methods for the quantitative determination of tannins, which can be divided into the following main groups.

1. Gravimetric, or weight methods- are based on the quantitative precipitation of tannins with gelatin, heavy metal ions or adsorption by skin (leather) powder.

For technical purposes, the gravimetric method using solid powder, the gravimetric unified method (BEM), is standard throughout the world.

The aqueous extract of tannins is divided into two equal parts. One part of the extract is evaporated and dried to constant weight. The other part of the extract is treated with skin powder and filtered. Tannins are adsorbed onto the leather powder and remain on the filter. The filtrate and washing waters are evaporated and dried to constant weight. The content of tannins is calculated by the difference in the mass of dry residues.

The method is inaccurate, because skin powder also adsorbs low molecular weight phenolic compounds, which is quite labor-intensive and expensive.

1. Titrimetric methods. These include:

A) Gelatinous method- based on the ability of tannins to form insoluble complexes with proteins. Aqueous extracts from raw materials are titrated with a 1% gelatin solution; at the equivalence point, gelatin tannate complexes dissolve in excess reagent. The titer is set based on pure tannin. The equivalence point is determined by selecting the smallest volume of titrated solution that causes complete precipitation of tannins.

The method is the most accurate, because allows you to determine the amount of true tannins. Disadvantages: length of determination and difficulty in establishing the point of equivalence.

b) Permanganometric method(Leventhal-Neubauer method modified by A.L. Kursanov). This is a pharmacopoeial method based on the easy oxidation of tannins by potassium permanganate in an acidic medium in the presence of an indicator and catalyst indigosulfonic acid, which at the equivalence point turns into isatin, and the color of the solution changes from blue to golden yellow.

Features of the determination that make it possible to titrate only macromolecules of tannins: titration is carried out in highly diluted solutions (the extract is diluted 20 times) at room temperature in an acidic environment, potassium permanganate is added slowly, drop by drop, with vigorous stirring.

The method is economical, fast, easy to implement, but not accurate enough, because... Potassium permanganate partially oxidizes low molecular weight phenolic compounds.

1. Physico-chemical methods.

A) Photoelectrocolorimetric methods are based on the ability of tannins to form colored compounds with ferric salts, phosphotungstic acid, Folin-Denis reagent, etc.

b) Chromatospectrophotometric And nephelometric methods used in scientific research.

Ways to use raw materials, medical applications, drugs

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In addition to the sources of industrial production of medical tannin, all studied objects are included in order No. 79 of March 18, 1997, allowing the over-the-counter supply of raw materials from pharmacies.

In extemporaneous formulations and at home, raw materials are used in the form of decoctions and as part of preparations.

Herbal preparations are not produced (liquid extracts of bergenia rhizomes and burnet rhizomes and roots are currently excluded from the State Register).

Tannin and the combined preparations “Tanalbine” (a complex of tannin with the protein casein) and “Tansal” (a complex of tanalbin with phenyl salicylate) are obtained from the leaves of tanning sumac, tanning sumac, and Chinese and Turkish galls. The drug “Altan” was obtained from alder fruits.

Raw materials and preparations containing tannins are used both externally and internally

• astringents,
• anti-inflammatory,
• bactericidal and
• hemostatic agents.

Action based on the ability of tannins to bind to proteins to form dense albuminates. Upon contact with the inflamed mucous membrane or wound surface, a thin surface film is formed that protects sensitive nerve endings from irritation. Cell membranes thicken, blood vessels narrow, and the release of exudates decreases, which leads to a decrease in the inflammatory process.

Due to the ability of tannins to form precipitation with alkaloids, cardiotonic glycosides, salts of heavy metals, their used as antidotes in case of poisoning with these substances.

Externally

• for diseases of the oral cavity, pharynx, larynx (stomatitis, gingivitis, pharyngitis, tonsillitis), as well as
• For burns, decoctions of oak bark, bergenia rhizomes, serpentine, cinquefoil, burnet rhizomes and roots, tannin, and “Altan” are used.

Inside

• for gastrointestinal diseases (colitis, enterocolitis, diarrhea, dysentery), tannin preparations (Tanalbine, Tansal), Altan, decoctions of blueberries, bird cherry (especially in children's practice), alder fruits, bergenia rhizomes, and serpentine are used , cinquefoil, rhizomes and roots of burnet.

As hemostatic agents funds

• For uterine, gastric and hemorrhoidal bleeding, decoctions of viburnum bark, burnet rhizomes and roots, cinquefoil rhizomes, and alder fruits are used.

Decoctions are prepared in a ratio of 1:5 or 1:10.

Do not use very concentrated decoctions , since in this case the albuminate film dries out, cracks appear, and a secondary inflammatory process occurs.

Experimentally established antitumor effect tannins an aqueous extract of the pericarp of pomegranate fruits (for lymphosarcoma, sarcoma and other diseases) and the drug “Hanerol”, obtained on the basis of ellagitannins and polysaccharides from the inflorescences of fireweed (fireweed) (for stomach and lung cancer).

Introduction

Despite the fact that tannins became known a long time ago (tannin was first obtained by Dayeux and independently by Seguin in 1797 and was already in a fairly pure state in the hands of Berzelius in 1815) and were studied a lot, by the beginning of the 20th century they were not enough studied, and not only the chemical nature and structure of almost all of them remained unclear, but even the empirical composition of many of them was made differently by different researchers.

This is easily explained, on the one hand, by the fact that, being mostly substances that are not capable of crystallization, they are difficult to obtain in a pure form, and on the other hand, by their low stability and easy changeability.

At present, we can judge with sufficient confidence only the structure of tannin, which is gallic acid anhydride; as for others, it is only apparently possible to assume in them, judging by the decomposition reactions and some others, partly anhydride compounds of polyhydric phenolic acids and phenols, formed either as simple or as esters, partly aromatic ketone acids, which are condensation products of gallic acid derivatives; but some of the tannins should still be considered glucosides. Due to the unknown structure, the impossibility of a natural grouping of tannins is self-evident.

Tannins themselves are classified as a special group of organic compounds that have a certain set of common characteristics, only due to the unknown nature of their structure. It is quite possible that once the latter is clarified, they will be distributed over time into various classes of organic compounds, and then there will no longer be a need for a special general name for them, and the current name “Tannin”, according to Reinitzer’s recent proposal, will probably only have to be retained for those that are actually capable of tanning leather.

Their division according to the coloring produced with iron oxide salts into iron-blue (Eisenblauende) and iron-greening (Eisengrunende) has now been abandoned, because the same tannin can sometimes give a blue and sometimes a green color, depending on which iron salt is taken , and in addition, the coloring can change due to the addition of, for example, a small amount of alkali. The division of tannins into physiological, tanning the skin and at the same time giving pyrocatechol during dry distillation and not giving gallic acid when boiled with weak sulfuric acid, and pathological, less suitable for tanning (although precipitated by a glue solution), giving pyrogallol during dry distillation, and when boiled with weak sulfuric acid - gallic acid, also does not fully correspond to the facts, because, as is currently known, pathological tannins can, although not so successfully, serve for tanning, and in addition, tannin, for example, is mainly a pathological tannin, it is also found, apparently, as a normal product (sumac, algarobilla, myrobolans).

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Summarize and analyze the material on the topic “The use of plants containing tannins in medicine and the national economy”

1. Tannins, general characteristics

Tannins are high molecular weight, genetically related natural phenolic compounds that have tanning properties. They are derivatives of pyrogallol, pyrocatechol, phloroglucinol and have a molecular weight from 1000 to 20,000. Simple phenols do not have a tanning effect, but together with phenolcarboxylic acids they accompany tannins.

Plant raw materials containing tannins have long been used in the national economy for tanning leather, as well as for the production of natural dyes.

1.1 Distribution

In nature, many plants (especially dicotyledons) contain tannins. Among lower plants they are found in lichens, fungi, algae, and among spore plants - in mosses, horsetails, and ferns. Representatives of the pine, willow, buckwheat, heather, beech, and sumac families are rich in tannins. The families Rosaceae, legumes, and myrtaceae include numerous genera and species in which the content of tannins reaches 20-30% or more. Most (up to 50-70%) tannins were found in pathological formations - galls. Tropical plants are richest in tannins. Tannins are found in underground and aboveground parts of plants: they accumulate in cell sap. In leaves, tannins, or tannins, are found in the cells of the epidermis and parenchyma surrounding vascular bundles and veins, in rhizomes and roots - they accumulate in the parenchyma of the bark and medullary rays.

1.2 Factors influencing the accumulation of tannins

The content of tannins in the plant depends on the age and phase of development, place of growth, climatic and soil conditions. The altitude factor has a greater influence on the accumulation of tannins. Plants that grow high above sea level (bergenia, mackerel, sumac) contain more tannins. Lighting is not a decisive factor - increased illumination increases the tannin content in some people, and decreases it in others. Plants growing in damp places contain more tannins than those growing in dry places. Young plants contain more tannins than old ones. In the morning hours (from 7 to 10) the content of tannids reaches a maximum, in the middle of the day it reaches a minimum, and in the evening it increases again. Identifying patterns in the accumulation of tannins in plants is of great practical importance for the proper organization of raw material procurement.

.3 Biological role of tannins

The role of tannins for plants has not been fully elucidated. It is assumed that they are reserve substances (accumulate in the underground parts of many plants) and, having bactericidal and fungicidal properties (phenolic derivatives), prevent wood rotting, that is, they perform a protective function against pathogenic pathogens.

.4 Classification

There are several classifications of tannins. One of them, the oldest, but which has not lost its significance even today, is based on the ability of tannins to decompose when heated.

Table 1. Classification of tannins

According to Freudenberg's (later) classification, tannins are divided into hydrolysable and condensed. Usually the raw materials contain different groups of tannins, but one of them predominates.

· Hydrolysable (gallotannins);

· Partially hydrolyzable (ellagitannins);

· Condensed (catechins).

Hydrolyzable tannides undergo hydrolysis by enzymes (tanase) or acids to release phenolic compounds. They are glycosidic in nature. They contain esters of aromatic hydroxycarboxylic acids (gallic, ellagic, etc.) and a sugar component. With iron oxide salts they form black-blue precipitates. An example of a hydrolysable tannin is tannin. Condensed tannins of non-glycosidic nature. The benzene nuclei are connected to each other through C-C carbon bonds; they are derivatives mainly of catechins and leukoanthocyanidins; with iron salts they give a black-green color.

A component of condensed tannins is the simplest compound of this group - epicachetin.

Oak, bergenia, and cinquefoil contain tannins of a mixed group - condensed and hydrolyzable. Tannins are easily extracted with water and water-alcohol mixtures.

1.5 Physico-chemical properties

Tannins are usually amorphous; many dissolve well in water and alcohol and have an astringent taste. In solution they give a slightly acidic reaction. Only catechins are known in the crystalline state; they are poorly soluble in cold water, better in hot water. Many tannins are optically active. Most tannins are highly hygroscopic. In medicinal mixtures, they cannot be mixed with salts of heavy metals, protein substances and alkaloids, as precipitation will form. Tannins with proteins create a film impermeable to water (tanning). By causing partial coagulation of proteins, they form a protective film on mucous membranes and wound surfaces. When in contact with air (for example, cutting fresh rhizomes), tannins are easily oxidized, turning into phlobaphenes or krasenes, which cause the dark brown color of many barks and other organs and infusions.

Phlobaphenes are insoluble in cold water; they dissolve in hot water, turning decoctions and infusions brown.

Qualitative reactions.

The following reagents are used to detect tannins:

· Gelatin solution - add a gelatin solution drop by drop to 2-3 ml of the test solution; a cloudiness appears, which disappears when adding excess gelatin;

· Bromine water - bromine water is added dropwise to 2-3 ml of the test solution (5 g of bromine in 1 liter of water) until the smell of bromine appears in the solution; If condensed tannins are present, a precipitate will form.

Quantification.

It is carried out by weight and according to the Leventhal method specified in the State Fund of X (by oxidation with potassium permanganate in the presence of indigo carmine or indigo sulfonic acid). Other methods are also used.

Preparation.

Produced during the period of highest content of tannins in plants. After collection, the raw materials must be quickly dried, since oxidation and hydrolysis of tannins occur under the influence of enzymes. It is recommended to dry raw materials at a temperature of 50-60 °C. Store in a dry room in tight packaging, preferably in its entirety, since in the crushed state the raw material undergoes rapid oxidation due to an increase in the surface area of ​​contact with atmospheric oxygen.

Application.

Tannins denature cell proteins to form a protective albuminate film, exerting a bactericidal or bacteriostatic effect on microorganisms. Medicinal raw materials containing tannins exhibit astringent properties, therefore they are used for rinsing, for burns in the form of a powder, orally for gastrointestinal disorders, as well as poisoning with heavy metals and plant poisons.

2. Sources of receipt

In nature, many plants (especially dicotyledons) contain tannins. Among lower plants they are found in lichens, fungi, algae, and among spore plants - in mosses, horsetails, and ferns. Representatives of the pine, willow, buckwheat, heather, beech, and sumac families are rich in tannins.

The families Rosaceae, legumes, and myrtaceae include numerous genera and species in which the content of tannins reaches 20-30% or more. Most of all (up to 50-70%) tannins were found in pathological formations - galls. Tropical plants are richest in tannins.

Oak, cinquefoil, serpentine, burnet, thick-leaved bergenia, leather mackerel, as well as many other plants contain tannins of a mixed group - condensed and hydrolyzed.

Tannins are found in underground and aboveground parts of plants: they accumulate in cell sap. In leaves, tannins, or tannins, are found in the cells of the epidermis and parenchyma surrounding vascular bundles and veins, in rhizomes and roots - they accumulate in the parenchyma of the bark and medullary rays.

Medicinal raw materials containing tannins are used to obtain drugs used as astringents, hemostatic, anti-inflammatory, and antimicrobial agents. Raw materials containing condensed tannins can be used as an antioxidant. In addition, it has been established that hydrolyzable and condensed tannins exhibit high P-vitamin activity, antihypoxic and antisclerotic effects. Condensed tannins exhibit an antitumor effect; they are able to suppress free radical chain reactions, which explains their certain effectiveness in cancer chemotherapy. Moreover, in large doses, tannids exhibit an antitumor effect, in medium doses they have a radiosensitizing effect, and in small doses they have an anti-radiation effect.

In medical practice, infusions and decoctions of plant materials containing tannins are used. Of great value for the treatment of mucous membranes are hydrolyzable tannins, which penetrate into the intercellular spaces and bind enzyme proteins that cause local inflammatory reactions. As a result, a dense film of albuminates is formed and, accordingly, the inflammatory process and pain are reduced.

Tannins can be used as antidotes for poisoning with glycosides, alkaloids and salts of heavy metals.

In world medical practice, some types of galls are widely used to obtain medicinal tannin. Quite often, the so-called ratania root (Radix Ratan-hiae) is used, obtained from the small South American shrub Krameria triandra Ruiz, et Pav. from the Krameria family (Krameria-ceae). Extracts from the root are an astringent.

Quite well known is Catechu, an aqueous extract prepared from the leaves and young twigs of the climbing shrub Uncara gambir (Hunter) Roxb.) from the madder family (Rubiaceae), cultivated in tropical Asia. Catechu, or more commonly gambir-catechu, contains about 7-33% catechins. Another type of catechu (black catechu) is obtained from the wood of Acacia catechu (L. fil.) Willd. Both extracts have an astringent effect.

To a lesser extent, dried pericarps of pomegranate fruits (Punica granatum L.) and the so-called kino (kino) - dried, tannin-rich juice obtained from Pterocarpus marsupium Mart. from the legume family (Fabaceae) are used.

. Examples of medicinal plants containing tannins

3.1 Sheetsumac- Folium Rhus coriariae

Tanning sumac - Rhus coriaria L.

Botanical characteristics. A shrub or small, few-branched tree, 1 to 3 m high. The bark of trees and adult bushes is brownish, loose, fluffy. On annual shoots the bark is brownish, rough and fluffy, on perennial trunks and branches it is dark brown. Leaves are alternate, odd-pinnate, with 4-8 pairs of sessile opposite leaflets, rough fluffy, dark green above, almost gray below, 15-20 cm long, 1.5-3 cm wide, oblong-ovate, with a wide, wedge-shaped base and pointed apex, coarsely bearded-serrate along the edges.

The flowers are unisexual, small, greenish-white, inconspicuous, collected in large conical apical and smaller axillary inflorescences in male and female panicles. Male panicles are spreading, 25 cm long, female panicles are denser, 15 cm long. Sepals are round-ovate, green, petals are ovate-elongated, whitish. The fruits are small, spherical or kidney-shaped single-seeded red drupes.

It blooms in June-July, with secondary flowering sometimes observed in autumn. The first fruits ripen in July, their mass ripening occurs in September-October.

Spreading. It grows in the lower and middle mountain zones up to an altitude of 1000 m above sea level in the Crimea and the Caucasus and up to an altitude of 1800 m in the Pamir-Alai. Usually it does not form continuous thickets. It grows on dry slopes with southern exposure, which indicates its high drought resistance.

Habitat. It grows on open, dry, rocky, mostly limestone slopes and cliffs, in sparse forests and on the edges of the lower and middle mountain zones. Cultivated in shelter forest plantations. Heat-loving, but quite cold-resistant, tolerates temperatures down to -20 ° C.

Preparation. When harvesting sumac leaves, branches should not be allowed to break off; only intact leaves should be collected, i.e., a complex blade consisting of 3-10 individual leaves, tearing it off entirely from the bush. Leaves are collected during the summer (June-August)

Drying. Leaves are dried in attics with good ventilation, under awnings or in dryers at a temperature of 40-45 ° C. Raw materials should be carefully protected from dampness to avoid darkening and loss of presentation. Wetting the raw material is unacceptable because this will wash out the tannin, which determines its value. When harvesting, young leafy shoots are sometimes cut off entirely. In this case, after drying, the shoots need to be threshed on a clean threshing floor (preferably on a tarpaulin) and the stems removed. Since tannin is found mainly in the leaf parenchyma, the quality of the raw material is improved by winnowing and cleaning not only from the stems, but also from the leaf petioles. Procurement of raw materials in thickets is carried out no more than once every 2 years.

External signs. The raw material consists of dried whole leaves or leaves that have broken down into separate leaves. The color of the dried leaves should be dark green on top, gray underneath, and the taste should be astringent. According to GOST 4565-79, the moisture content in raw materials should not exceed 12%; total ash no more than 6.5%; ash, insoluble in 10% hydrochloric acid, no more than 1.2%; tannin content not less than 10%; particles passing through a sieve with holes with a diameter of 2.8 mm, no more than 5%; leaves that have lost their normal color, no more than 2%; stem parts of sumac no more than 4%; organic impurity no more than 1%; mineral - no more than 1%.

Chemical composition. Sumac leaves contain up to 25-33% tannins, of which 15% is tannin. In addition, they contain free gallic acid, essential oil, gallic acid tetrasaccharide and methyl ester, ascorbic acid, myricitrin and other flavonoids (including flavone glycosides). The composition of sumac tannin is dominated by a component in which out of 6 galloyl residues, 2 are digalloyl and 2 are monogalloyl.

Storage. The shelf life of raw materials is 2 years.

Pharmacological properties. Tannins obtained from sumac leaves have astringent, anti-inflammatory and antiseptic effects.

Medicines. Preparations "Tanalbine", "Tansal".

Application. In medicine, tannins are used externally - for burns, weeping ulcers, purulent wounds, chronic eczema, for rinsing during inflammatory processes of the mouth: internally - for bleeding of the gastrointestinal tract, diarrhea, enteritis, colitis, for gastric lavage in case of poisoning with alkaloids and salts of heavy metals .

A tincture of fresh leaves is used in homeopathy for diarrhea, rheumatism, gout, paralysis, exhaustion, and diseases of the biliary tract. Crushed fresh leaves are applied to burns, weeping ulcers, purulent wounds and parts of the body affected by eczema.

.2 Leaf of Cotini - Folia Cotini coggygriae

Cotinus coggygria Scop.

Sem. Sumacaceae - Anacardiaceae

Other names: skumpia koggigria, zheltinnik, common skumpia

Botanical characteristics. A large deciduous shrub (sometimes in the form of a small tree) up to 5 m high, with a dense spherical or umbrella-shaped crown. The trunks are branched, with grayish-brown bark; The stems of the current year's shoots are green or reddish, with milky juice. Leaves are alternate, ovate, elliptical or almost round, up to 8 cm long and up to 4 cm wide, with petioles, leaf blades are entire, with sharply protruding veins, dark green above, grayish-green below, first turning yellow in autumn, then intensely reddening , becoming purple, sometimes with a purple tint. The flowers are small, inconspicuous, collected in multi-flowered spreading panicles. Most of the flowers in the inflorescence are underdeveloped, their stalks, covered with long protruding hairs, become greatly elongated after flowering, as a result of which the panicles become very large (up to 30 cm long) and fluffy, which gives the shrub an elegant appearance (the hairs on the stalks are of different colors in different individuals : white, reddish, greenish, which further increases the decorativeness of the mackerel). Normally developed flowers with a five-leaf green calyx remaining with the fruit, a five-petal greenish-white corolla with a diameter of about 3 mm, 5 short stamens and a pistil with a superior ovary and three styles. Their pedicels after flowering also become greatly elongated, but are almost completely devoid of pubescence. In addition to inflorescences with bisexual flowers, panicles with male flowers and separately with female flowers develop. The fruits are small ovoid or kidney-shaped drupes up to 5 mm long, with drying pulp, turning black when ripe, located on long stalks. It blooms in May-July, the fruits ripen in August-September.

Spreading. Mackerel tannerum is widespread as a wild, feral and cultivated plant in different regions of Eurasia. Large thickets of it are found in the Caucasus, including on the northern macroslope within Russia: in Dagestan, Stavropol and Krasnodar territories, etc.

Habitat. Thickets are located along treeless, sunny slopes from the foothills to an altitude of approximately 1000 m above sea level. As a rule, such thickets occupy habitats inconvenient for agriculture: rocky and gravelly, often quite steep slopes, limestone outcrops. Single bushes of mackerel settle along rock cracks. Groups of bushes form part of the undergrowth of sparse mountain oak forests and pine forests and grow when the tree stand is cleared. Mackerel is widely used in green construction, field protection and roadside afforestation in the south of European Russia, especially in the Rostov region, Kuban, Lower Volga region, and North Caucasus republics. It easily runs wild and forms clumps that renew well without maintenance.

Preparation. It is produced during the period of the highest content of tannins in plants - the leaves are collected during flowering and fruiting.

Security measures. Drying is done outdoors

External signs. The leaves are round or oval in shape, on long petioles, dark green, bluish below, entire, fragile, whole or broken into pieces, with pinnate venation. On the underside of the leaf, the veins protrude strongly. The length of whole leaves is from 3 to 12 cm, width from 2 to 6 cm. The petioles and main veins are light green or more often with a brownish-purple tint. The smell is aromatic, the taste is astringent.

Humidity no more than 12%, flavonoids no less than 1%, tannin no less than 15%. The raw materials should not contain blackened or reddened leaves (indicates late collection).

Chemical composition. The leaves contain up to 25% gallotannin, free gallic acid, flavonoids myricitrin and fustin, essential oil (up to 0.2%, the main component is myrcene), camphene (up to 9%), linalool and a-terpineol. The stems contain the flavonoid fisetin.

Storage. In a dry place, protected from light. Packed in bags. Shelf life of raw materials - 2 years

Pharmacological properties. Tannin has astringent, anti-inflammatory and antiseptic properties. Flavonoids have a choleretic effect. Medicines. “Tanin”, “Tanalbine”, Novikov liquid, “Tansal” and “Flacumin” tablets, “Neoanuzol” suppositories.

Application. Tannin (Tanninum, Acidum tannicum), or gallotannic acid, is a light yellow or brownish-yellow amorphous powder with a weak peculiar odor and an astringent taste. Easily soluble in water and alcohol. Aqueous solutions form precipitates with alkaloids, solutions of protein and gelatin, and salts of heavy metals. Used as an astringent and local anti-inflammatory agent for inflammatory processes in the oral cavity, nose, pharynx, larynx in the form of rinses (1-2% aqueous or glycerin solution) and lubrication (5-10%) for burns, ulcers, cracks, bedsores ( 3-5-10% ointments and solutions). Tannin is not taken internally (as an antidiarrheal agent), since it primarily interacts with the proteins of the gastric mucosa; when taken orally in large doses, it causes loss of appetite and indigestion. Tannin should not be given as enemas; with cracks in the rectum, blood clots may form. Due to the fact that tannin forms insoluble compounds with salts of alkaloids and heavy metals, it is often used for oral poisoning with these substances; It is recommended to wash the stomach with a 0.5% aqueous solution of tannin.

Tanalbin (Tannalbinum) is a product of the interaction of tannins with protein (casein), it is an amorphous dark brown powder, practically insoluble in water and alcohol. Used as an astringent for acute and chronic intestinal diseases (diarrhea). Tanalbin and other astringents should be used for infectious intestinal diseases (including those of dysentery origin) only as adjuncts in addition to specific treatment methods. Adults are prescribed 0.3-0.5-1 g per dose 3-4 times a day, children - 0.1-0.5 g, depending on age. Often combined with bismuth, benzonaphthol, phenyl salicylate.

Tablets "Tansal" (Tabulettae "Tansalum") contain tanalbin 0.3 g and phenyl salicylate 0.3 g. Used as an astringent and disinfectant for inflammatory bowel diseases (colitis, enteritis) 1 tablet 3-4 times a day.

Flacuminum is a sum of flavonol aglycones obtained from mackerel leaves. Greenish-yellow fine-crystalline powder with a weak specific odor and slightly bitter taste. Practically insoluble in water, slightly insoluble in alcohol. It has a choleretic effect, having mainly an antispasmodic effect on the bile ducts and promoting the release of bile from the gallbladder. Used as a choleretic agent, especially for biliary dyskinesia. Take flakumin orally 0.02 - 0.04 g (1-2 tablets) 2-3 times a day before meals. The course of treatment is 3-4 weeks.

3.3 Rhizomes and roots of burnet - Rhizomata et Radices Sanguisorbae

Burnet - Sanguisorba officinalis L.

Sem. Rosaceae - Rosaceae

Other names: redhead, bebrenets, hernia grass, orchard grass, button grass, twig grass, owl grass, black grass, cones

Botanical characteristics. A perennial herbaceous plant up to 1 m high. The stem is erect, bare, branched upward. The basal leaves are long-petiolate, odd-pinnate, with small stipules (from 7 to 15 leaflets), oblong-ovate in shape, with a sharply serrated edge, bluish-green at the bottom, collected in a rosette. Stem leaves are sparse, sessile, glabrous, dark green above, bluish-green below. The flowers are purple, collected in dense short oval-shaped inflorescences-heads, sessile on long peduncles. The fruit is a nut. Blooms in June-August.

Spreading. It grows in large quantities in Siberia, the Far East and Kazakhstan; it is rare in the European part of the country. Grows in the Caucasus and Crimea.

Habitat. In dry and flooded meadows, in bushes, at the edge of forests, clearings and clearings.

Preparation. The underground organs are dug out towards the end of flowering or after haymaking, when the above-ground mass has time to grow a little and the plant can be easily recognized. They clear the soil, cut off small thin and old rotten parts, place them in baskets and wash them with water. Thick rhizomes are cut lengthwise and dried in the sun.

Security measures. If the plant is dug up in the fruiting phase, then in place of the dug up rhizomes with roots, seeds are poured into the hole for renewal and covered with earth. The frequency of procurement is 5 years.

Drying. In dryers with artificial heating or in the sun, under a canopy.

External signs. According to Global Fund XI, the raw material consists of whole rhizomes with roots extending from them; Individual large roots are allowed. Rhizomes are up to 12 cm long, 2 cm in diameter, cylindrical in shape, woody; the roots are smooth, less often longitudinally wrinkled, up to 20 cm long. The outside of the rhizomes and roots are dark brown, almost black, yellowish at the break. Odorless, astringent taste. An aqueous decoction of rhizomes and roots with a solution of ferroammonium alum forms an intense black-blue color. The quality of raw materials is reduced by rhizomes that have turned brown at the fracture, crushed parts, other parts of the plant, and organic and mineral impurities.

On microscopy, very small cork cells, conducting elements (bast, wood, vessels) in radial triangular sections, small drusen, starch grains (on a cross section).

Chemical composition. All parts of the plant contain tannins (according to the PS no less than 14%) with a predominance of hydrolyzable substances of the pyrogall group (tannins). At the same time, the rhizomes of Burnet officinalis contain 12-13%, roots - up to 17%, and calli (influxes) - up to 23% of tannins. In addition, free gallic and ellagic acids, starch, triterpene saponins (up to 4%) - sanguisorbin, loss - containing arabinose as a sugar residue were found in the roots. The leaves contain up to 0.9% ascorbic acid.

Storage. In a dry place, protected from light. Shelf life: 5 years.

Medicines. Rhizomes and roots, decoction.

Application. The raw material has long been used in Chinese and Tibetan medicine for bleeding and diarrhea. Widely used in folk medicine of Siberia. For an introduction to scientific medicine, it was proposed by the Irkutsk Faculty of Pharmacy and the Tomsk Medical Institute. It is used as an astringent for gastrointestinal diseases (enterocolitis, diarrhea of ​​various etiologies), as a hemostatic for internal bleeding (hemorrhoids, dysentery, in gynecology - uterine bleeding), for gargling, in the treatment of stomatitis and gingivitis. Widely used in veterinary medicine.

A decoction of burnet 15:200 is also used. To prepare the decoction, pour a tablespoon of raw material into 200 ml of boiled water at room temperature and boil in a water bath for 30 minutes, filter without cooling. Take a tablespoon 5-6 times a day before meals.

In folk medicine, burnet is widely used for hemoptysis in tuberculosis (“consumptive”) patients, for heavy menstruation, and as an external treatment for wound healing.

3.4 Rhizomes of the serpentine (crayfish necks) - Rhizomata bistortae

Snake knotweed - Polygonum bistorta L.

Meat-red knotweed - Polygonum carneum S. Koch

Sem. buckwheat - Polygonaceae

Other names: serpentine, crayfish, bistorta, knotweed, uneven grass, turtledove, crustaceans, snake root, crooked potion, wild buckwheat

Botanical characteristics. A perennial herbaceous plant up to 50-80 cm high with a straight, arched, unbranched hollow stem. The stem leaves are small, narrow, few in number, emerging from brownish sockets. The basal leaves are on long petioles, oblong-lanceolate, large, sometimes with a heart-shaped base. The flowers are small, pinkish, fragrant, collected in a dense oblong spike-shaped inflorescence. The fruit is a triangular dark brown shiny achene in the form of a nut. It blooms in May-June, the fruits ripen in July.

Spreading. Snake knotweed grows almost everywhere, with the exception of the Caucasus and Central Asia.

Habitat. In wet and dry meadows, clearings, near rivers, ditches, ponds, in forest clearings. It often forms thickets that are convenient for harvesting.

Preparation. Rhizomes are harvested after flowering or in early spring (they are difficult to find after mowing). Cut off the stems and small thin roots. Wash in water, cut off the rotten parts of the rhizomes, and dry a little in air.

Security measures. The most useful rhizomes are those aged 15-30 years, so only the most developed plants are harvested. The frequency of procurement in the same place is 5 years. When digging underground parts, several well-developed plants are left at the collection site for restoration.

Drying. The final drying of raw materials is carried out in heated dryers at a temperature of 50-60 ° C or in attics under an iron roof. A defect in the raw material is considered to be rhizomes that have turned black at the fracture. When dried slowly, the rhizomes turn brown inside.

External signs. The rhizome is hard, has a serpentine shape, which gave rise to calling it a serpentine; on the upper side with transverse folds, on the lower side - with traces of cut roots, on the outside - dark brown, at the break - brownish-pink; length 5-10 cm, thickness 1-2 cm. The taste is strongly astringent, bitter. There is no smell. The quality of raw materials is reduced by rhizomes that have darkened at the fracture, the presence of roots, and organic and mineral impurities. An aqueous decoction of rhizomes with ferric ammonium alum gives a black-blue color (tannins of the pyrogall group). On a transverse section or fracture of the rhizome under a magnifying glass, vascular bundles are visible, arranged in an intermittent ring, medullary rays pass between them, the core is inside, and a layer of brown plug is outside.

Chemical composition. The rhizomes contain tannins (15-25%), free polyphenols (gallic acid and catechin), oxyanthraquinones, starch (up to 26%), calcium oxalate. The herb contains ascorbic acid and flavonoids (hyperoside, rutin, avicularin).

According to GF XI, a tannin content of at least 15% is required.

Pharmacological properties. Snake knotweed preparations have astringent properties and also have a resorptive sedative effect. Astringent properties when taken orally appear slowly as the active substances are broken down under the influence of digestive juices. Snake knotweed preparations are low-toxic and do not produce side effects.

When applied externally, they have an astringent, anti-inflammatory and hemostatic effect. Based on the active ingredients of snakeweed and other plants, a complex drug has been developed for the treatment of experimentally induced allergic enterocolitis.

Medicines. Rhizomes, decoction, collection.

Application. The rhizome of the serpentine plant was known to the medicine of various nations. Even in the Chinese Encyclopedia of Medicinal Substances, published in the 11th century BC, the medicinal properties of this plant were mentioned. Ancient Indo-Tibetan medical literature also indicates the medicinal use of the plant. In European medicine, serpentine became known in the 15th century, and in the 16th century it was widely used by doctors of that time as a good astringent in the form of a decoction or tincture orally for various diseases: stomach ulcers, gastric and pulmonary bleeding, uterine bleeding, acute and chronic dyspepsia, dysentery , hemorrhoids, rectal fissures, urethritis, colpitis, gingivitis, inflammatory diseases of the ENT organs.

For the same indications, snakeweed is still used today as an astringent and hemostatic agent. It is used for acute and chronic intestinal diseases accompanied by diarrhea.

The coil is used as a domestic substitute for imported ratania. NTD allows for use red knotweed, which grows widely in the Caucasus. It differs from the snakeweed in its larger rhizome and the red (rather than pink) color of the flowers.

In dental practice, a decoction of snake knotweed is used to gargle or lubricate the gums for stomatitis, gingivitis, chronic tonsillitis and other inflammatory diseases of the oral cavity.

Decoction of snake knotweed (Decoctum Bistortae fluidum). Rhizomes (10 g) are crushed to particles no larger than 3 mm, placed in an enamel bowl, poured with 200 ml of water at room temperature (taking into account boiling losses), cover with a lid and heated in a boiling water bath with frequent stirring for 30 minutes. . Strain immediately after removing from the water bath. Take 1 tablespoon 3-4 times a day before meals.

For dyspepsia, a mixture of cinquefoil and knotweed rhizomes in equal parts is also used: prepare a decoction of 1 tablespoon of the mixture per 200 ml of water. Drink 200 ml of decoction during the day in 3-4 doses.

A decoction (per 200 ml of water) is prepared from 10 g of a mixture including the rhizomes of snakeweed (1 part) and the rhizomes of burnet (1 part). Take a decoction of 1/3-1/4 cup 3-4 times a day for diarrhea.

3.5 Rhizomes of cinquefoil - Rhizomata tormentillae

Potentilla erecta (L.), Hatpe (syn. Potentilla tormentilla Schrank)

Sem. Rosaceae - Rosaceae

Other names: wild galangal, Dubrovka, Uzik, ovary root, navel, Drevlyanka, braid, navel grass

Botanical characteristics. A perennial herbaceous plant up to 15-40 cm high. The stems are thin, erect, forked at the top. Leaves are trifoliate with two large stipules, alternate: basal - petiolate, upper - sessile; stems and leaves are covered with hairs. The flowers are solitary yellow, with orange-red spots at the base, axillary, on long pedicels with regular perianth. The calyx is double, with a subcup. The corolla consists of 4 separate petals, unlike other cinquefoils (diagnostic sign). Ovary superior. The flowers are solitary. The fruit is an ovoid, slightly wrinkled achene of dark olive or brown color. The fruit consists of 5-12 achenes. Blooms from May to August. The fruits ripen in August-September.

Spreading. The entire forest zone of the European part of the country, Western Siberia, the Caucasus.

Habitat. In damp and dry places, between bushes, in meadows, in young plantings, in pastures, sometimes in swampy places, thinned coniferous and coniferous-small-leaved forests.

Preparation. The rhizomes are collected in the fall. They dig it up with a shovel, free it from lumps of earth, cut off thin roots and branches of the stems, place it in baskets and wash it. The workpieces are laid out on site to dry from external moisture and dried, and then delivered to the place of final drying.

Security measures. When harvesting, it is necessary to leave several flowering plants per 1 m for propagation by seeds. After digging it grows back slowly. There are similar plants.

Drying. In artificial dryers at temperatures up to 60 ° C or in rooms with good ventilation. The raw materials need to be stirred periodically.

Table 1. Distinctive features of different types of cinquefoil

Diagnostic signs	Potentilla erecta (L.)	Silver cinquefoil - Pargentea L.	Bloodrootgoose- Potentilla anserina L.
Underground organs	Rhizomes unevenly thickened, cylindrical or tuberous	Tap root, covered in upper part with remains of leaves	Tap root
Pubescence with hairs		Thick, white tomentose on the stems and on the underside of the leaves	Dense, silky-silver on the underside of the leaf
	Sessile, trifoliate, with 2 stipules, forming a “foot” on the stem	Petiolate, odd-pinnate with 5-7 lobes	Petiolate, unparpinnate with 15-23 lobes. The leaves are finger-toothed, the teeth are curved, the leaves are smaller towards the base, white-silky.

External signs. The rhizome is straight or curved, cylindrical or tuberous, often shapeless, hard and heavy, with numerous pitted marks from cut roots. Length up to 7 cm (average 3-4 cm), thickness 1-2 cm. The color is dark brown on the outside, red or red-brown at the break, the break is even or slightly fibrous. The smell is weak. The taste is very astringent. The quality is reduced by rhizomes darkened at the break, admixture of roots and aerial parts, organic and mineral impurities.

On microscopy, conductive elements in the form of intermittent radial stripes and concentric belts, sieve tubes, cambium, vessels, fibers. There are large calcium oxalate druses and small starch grains.

Qualitative reactions. An aqueous solution of rhizomes (1:10) forms a black-green color (condensed tannins) with a solution of ferric ammonium alum.

Chemical composition. Potentilla rhizomes contain 15-30% tannins with a predominance of condensed tannins, as well as triterpene saponins (tormentoside) and quinic acid. In addition, both the rhizomes and the aerial part of the plant contain flavonoids, ellagic acid, phlobaphenes, waxes, resins, and starch. Ascorbic acid was found in the above-ground part of the plant (especially a lot of it during the period of full flowering of the plant). The highest content of tannins in the rhizomes was found during the flowering period, and in the aboveground part - during the period of full flowering. After flowering ends, the amount of biologically active substances (especially tannins) decreases.

Storage. In a dry place, protected from light, in bales or boxes. Shelf life: 3 years.

Pharmacological properties. The main substances that determine the pharmacological activity of cinquefoil are condensed tannins, triterpene saponins and flavonoids. The rhizomes of the plant have an astringent, bactericidal, anti-inflammatory and hemostatic effect. The local anti-inflammatory effect is associated with tannins that can create a biological film that protects tissues from chemical, bacterial and mechanical influences that accompany inflammation. At the same time, capillary permeability decreases and blood vessels narrow. These features of action are well manifested on inflamed, reddened mucous membranes with pharyngitis, stomatitis, gingivitis, as well as gastritis and enteritis. The general anti-inflammatory effect is associated with the effect of flavonoids.

Medicines. Rhizomes, decoction, briquettes, collections.

Application. Potentilla decoctions are prescribed orally for enteritis, enterocolitis, dyspepsia, dysentery, ulcerative colitis with bleeding from the intestines, gastritis, gastric and duodenal ulcers, as a choleretic agent for cholecystitis, cholecystocholangitis, acute and chronic hepatitis, cirrhosis of the liver, including in the edematous-ascitic stage.

Decoctions are used for hypermenorrhea and uterine bleeding of various origins as a hemostatic agent orally; For colpitis, vaginitis, and cervical erosions, the decoction is used for douching.

Cinquefoil is used for rinsing for inflammatory diseases of the oral cavity (stomatitis, gingivitis), bleeding gums, sore throat and chronic tonsillitis. In the form of an application, a decoction of cinquefoil is used for hemorrhoids, burns, eczema, neurodermatitis, cracks in the skin and mucous membranes, and sweating of the feet.

To prepare the decoction, pour 1 tablespoon of cinquefoil rhizomes into a glass of water at room temperature, bring to a boil, boil in a water bath for 10-15 minutes, cool, filter, take 1 tablespoon 3-4 times a day for 1-1.5 hours before meals for diseases of the stomach and intestines.

Potentilla rhizomes are sold in the form of briquettes. Two briquettes are poured with 200 ml of boiling water, boiled in a water bath for 30 minutes, and filtered. Use in the same way as a decoction.

3.6 Viburnum bark - Cortex Viburni

Viburnum viburnum - Viburnum opulus L.

Sem. Honeysuckle - Caprifoliaceae

Other names: snowballs

Botanical characteristics. Branched shrub 2-4 m high. The bark is grayish-brown. The leaves are opposite, round, three to five lobed, coarsely toothed along the edge, petiolate. Umbrella-shaped inflorescences on the tops of young branches. The marginal flowers in the inflorescence are white, sterile, their corolla is five-lobed, up to 2.5 cm in diameter, the rest are bell-shaped, yellowish, bisexual, fragrant, about 0.5 cm in diameter. The fruit is a drupe, oval, juicy, red, up to 1 cm in diameter , with a flat bone. It blooms from May to July, bears fruit in August-September.

Spreading. Everywhere, more often in the middle zone of the European part of the country and Siberia.

Habitat. Among bushes, in open forests, along river valleys and terraces.

Preparation. The bark is collected in the spring at the beginning of spring development and active sap flow with the permission of the forestry department. Cut the side branches with knives, remove the groove-shaped pieces up to 2 mm thick. Fresh raw materials are examined and pieces of bark with wood residues are discarded.

Security measures. Harvesting bark from the main trunk is prohibited. The plant grows slowly; re-harvesting of raw materials is allowed only after 10 years. Viburnum resources are gradually decreasing due to the development and drainage of river floodplains, large harvests of bark and fruits, and active and constant fragmentation of fruiting branches. It is recommended to widely develop the culture of viburnum in natural conditions, using inaccessible and waste lands and household plots.

Drying. Outdoors. The bark is laid out in a layer of 3-5 cm and mixed periodically. The end of drying is determined by the fragility of the bark. The yield of dry raw materials is 38-40%.

External signs. According to State Fund XI and GOST, the bark is in the form of tubular or grooved pieces. The outer surface is wrinkled or smooth with lenticels. Thickness up to 2 mm, length 10-25 cm. Inside the color is brownish-yellow with red spots. The smell is peculiar, weak. The taste is bitter-astringent. The quality of raw materials is reduced by the admixture of bark with remains of wood and branches, parts shorter than 10 cm or pieces darkened inside, as well as the bark of other plants and minerals. The authenticity of the raw material is confirmed by microscopy and qualitative reactions to tannins with the formation of a black-green color from iron (III) salts. Under a microscope, the characteristic cork cells, parenchyma cells with numerous drusen and starch, yellowish, and in some places very large stony cells are clearly visible.

Chemical composition. The previously called glycoside “viburnin” turned out to be a complex of nine iridoids, which contain from 3 to 6%. Viburnum bark contains tannins, as well as up to 6.5% yellow-red resin, the saponifiable part of which includes organic acids (formic, acetic, isovaleric, capric, caprylic, butyric, linoleic, crotinic, palmitic, oleanolic and ursolic) , the unsaponifiable contains phytosterol, phytosterol. In addition, viburnum bark contains about 20 mg% of choline-like substances, up to 7% triterpene saponins, vitamin K1 (28-31 mcg/g), ascorbic acid (70-80 mg%), carotene (21 mg%). Tannins, up to 32% invert sugar, isovaleric and acetic acids, and ascorbic acid were found in the fruits. The seeds contain up to 21% fatty oil.

Glycosides (1.12-1.38%), organic acids (3.48-3.6%), tannins (3.44-3.52%), as well as saponins, phenolic compounds, mucilages were found in the leaves.

Storage. In a dry place, loosely packed or pressed into bales and bales. Shelf life up to 4 years.

Pharmacological properties. In the experiment, liquid extract and decoction of viburnum bark, administered intravenously, according to thromboelastogram and other studies, accelerate the process of blood clotting, shorten the duration of bleeding, reduce the amount of blood loss, and increase the platelet content in peripheral blood. The amount of active ingredients of viburnum, in addition, inhibits fibrinolysis by blocking plasminogen and partial inactivation of fibrinolysin. When studying preparations from the leaves and flowers of viburnum, hemostatic activity was found, similar to that of bark preparations.

Viburnum bark preparations increase the tone of the uterine muscles and have a vasoconstrictor effect. This action is associated with the glycoside viburnin. An animal study conducted in the laboratory of pharmacology of the VILR showed that viburnum fruits increase heart contractions and increase diuresis. Infusions of viburnum flowers (5 and 10%) have a pronounced antimicrobial effect against sarcina, lemon yellow staphylococcus, and pseudoanthrax bacillus. Infusions of viburnum leaves (5 and 10%) are active against Proteus and lemon yellow Staphylococcus. Viburnum berries have a weak antimicrobial effect. The tannins of viburnum bark, when introduced into the stomach, denature the proteins covering the mucous membranes and form a protective film that protects the stomach from irritation and reduces the inflammatory reaction. In experiments, a decoction of viburnum bark has an antitoxic effect and an anticonvulsant effect.

Herbal preparations from viburnum flowers also have an anticonvulsant effect. The fruits and bark of viburnum, containing valeric and isovaleric acids, have a sedative, calming effect on the nervous system, and have antispasmodic properties. In veterinary medicine, viburnum bark, fruits and flowers are used to treat foot and mouth disease in cattle. The experiments also revealed the hypocholesterolemic effect of extracts from viburnum bark administered with food, caused by phytosterols, as well as diuretic and cardiotonic effects.

Pharmacological properties. Viburnum bark, cut in packs of 100 g, decoction and liquid extract of the bark.

Pharmacological properties. Viburnum bark preparations are used as a hemostatic agent in the postpartum period, for uterine bleeding due to gynecological diseases, for painful and heavy menstruation, for nasal and pulmonary bleeding, for pulmonary tuberculosis, for rinsing the mouth, for sore throat, chronic tonsillitis, stomatitis and periodontal disease. . Decoctions of viburnum bark are used for eczema and diathesis. For hemorrhoids, viburnum bark extract is used in suppositories, and a decoction of viburnum bark is used for washing, sitz baths, and applications to inflamed and bleeding hemorrhoids.

Viburnum berries are used as a sedative and hypotensive agent for hypertension, menopausal neuroses, asthenic conditions, as a general tonic, stimulating the heart, and as an antitussive for whooping cough. Viburnum berries serve as a source of vitamins. Berries are used to stimulate gastric secretion when it is insufficient; as a mild laxative and disinfectant for colitis and atonic constipation.

The medical industry produces liquid viburnum extract (Extractum Viburni fluidum). It is prepared from coarse powder of viburnum bark in 50% alcohol in a ratio of raw material to extractor of 1:10. Prescribed orally, 20-40 drops 2-3 times a day, taken before meals.

3.7 Rhizomes of bergenia - Rhizomata Bergeniae

Bergenia crassifolia - Bergenia crassifolia

Sem. Saxifragaceae - Saxifragaceae

Botanical characteristics. Perennial herbaceous plant up to 50 cm high. Rhizome 3.5 cm thick, branched, creeping with root lobes. The stem is leafless, ending in a paniculate-corymbose inflorescence. The flowers are regular, five-membered, lilac-pink, corolla petals with a marigold. The leaves are in a basal rosette, juicy, “cabbage-like,” entire, glabrous, leathery, shiny, round, blunt-toothed, about 30 cm in diameter. By autumn the leaves turn red and overwinter. The fruit is an elliptical capsule with small seeds. It blooms in May-July, the seeds ripen in July-August.

Spreading. Siberia (Altai, Sayan Mountains, Baikal region, Transbaikalia). Plant of limited range. As an ornamental plant it is used for landscaping populated areas. It grows in the mountain forest belt at an altitude of 300 to 2600 m above sea level on stony, rocky soils. It forms dense thickets, sometimes covering hundreds of hectares. The plant was introduced into industrial culture and develops slowly.

Habitat. The rhizome is located almost at the surface of the earth. Harvested during the summer growing season. Dig or tear out of the soil, clear of soil and roots, cut into pieces of various lengths

Preparation. To ensure seed propagation, 10-15% of the most developed individuals are left untouched in the zardel. Repeated harvesting should be carried out in the same place after 10 years.

Security measures. First, the rhizome is dried. Dry slowly in dryers. Rapid heat drying reduces the amount of tannins. The raw material dries within 3 weeks. The yield of dry raw materials is 30-35%.

External signs. Pieces of rhizomes are cylindrical in shape, about 3 cm in diameter. Dark brown on the outside, light brown in the fracture with dark dots of conducting bundles in an intermittent ring around the fleshy core. The smell is not characteristic. The taste is astringent. Pieces of a different color, affected by rot, impurities, and roots reduce the quality of raw materials.

Chemical composition. Rhizomes contain up to 28% tannins of the pyrogallol group, polyphenols, isocoumarin bergenin, starch. According to SP XI, tannins should be at least 20%. The leaves contain tannins up to 20%, free polyphenols - gallic acid up to 22%, hydroquinone, arbutin. Tannin content ranges from 8 to 10%. The isocoumarin derivative bergenin, ascorbic acid, starch and sugars were found in the rhizomes.

Storage. In a dry place, in a well-packed container. Shelf life: 4 years.

Pharmacological properties. Bergenia preparations have hemostatic, astringent, anti-inflammatory and antimicrobial properties.

Medicines. Decoction.

Application. Bergenia as a hemostatic agent was found in multi-compound prescriptions of Tibetan medicine.

A decoction of bergenia rhizomes is used in gynecological practice for heavy menstruation due to inflammatory processes of the uterine appendages, for hemorrhagic metropathy, uterine fibroids, and for bleeding after termination of pregnancy. Locally - for the treatment of cervical erosion and colpitis in the form of douching and vaginal baths.

Bergenia preparations are also used for colitis of non-dysenteric etiology; with their dysentery. prescribed in combination with antibiotics and sulfonamides.

In dental practice, bergenia is used as an anti-inflammatory, astringent and hemostatic agent for stomatitis, gingivitis, periodontal disease, for lubricating gums and rinsing.

To prepare the infusion, pour 2 teaspoons of crushed raw materials into 200 ml of hot boiled water, leave for 30 minutes and rinse your mouth with the warm infusion.

As an astringent, anti-inflammatory and hemostatic agent, bergenia decoction is used for gastrointestinal diseases.

A decoction of bergenia (Decoctum Bergeniae) is prepared as follows: 10 g (1 tablespoon) of bergenia rhizomes is poured into 200 ml (1 cup) of boiling water, placed in a boiling water bath and heated for 30 minutes, cooled, filtered, and boiled water is added to the original volume. Take 1-2 tablespoons before meals 2-3 times a day.

The leaves are especially promising as a raw material containing arbutin.

Conclusion

So, tannins are usually called high-molecular, genetically interconnected phenolic compounds, derivatives of pyrocatechol, pyrogallol and phloroglucinol.

Tannins are nitrogen-free, non-poisonous, usually amorphous compounds, many of them are highly soluble in water and alcohol and have a strongly astringent taste. In medicinal mixtures, they cannot be mixed with salts of heavy metals, protein substances and alkaloids, as precipitation will form. With proteins, tannins create a film impermeable to water (tanning). By causing partial coagulation of proteins, they form a protective film on mucous membranes and wound surfaces. When in contact with air, tannins are oxidized and converted into phlobaphenes (or reds), which cause the dark brown color of bark and other tissues. They are insoluble in cold water and color decoctions and infusions brown.

There are many plants in nature that contain tannins. There are especially many of them in dicotyledonous plants. Of the lower plants, they are found in lichens, fungi, and algae. A significant amount of tanids is contained in spore plants (mosses, horsetails, ferns), as well as representatives of the families pine - Pinaceae, willow - Salicaceae, buckwheat - Polygonaceae, heather - Ericaceae, beech - Fagaceae, sumac - Anacardiaceae. In representatives of some families, for example Rosaceae, Fabaceae, Myrtaceae, the tannid content reaches 20-30% or more. The largest number of them was found in pathological formations - galls (up to 50-70%).

Tannins are contained in both underground and above-ground parts of plants. Tropical plants are richest in tannins. The content of tannins in plants depends on their age and phase of development, place of growth, climatic and soil conditions. Plants found high above sea level contain more tannins (bergenia, mackerel, sumac).

Plants growing in damp places accumulate more tannins than plants in dry habitats. There are more tanning substances in young organs than in old ones. In the morning hours (from 7 to 10) their content reaches a maximum, decreases during the day, and increases again in the evening. Identifying patterns in the accumulation of tannins in plants is of great practical importance for the proper organization of raw material procurement.

There are several classifications of tannins. According to Freudenberg's (later) classification, tannins are divided into hydrolysable and condensed. An example of hydrolyzable substances is tannin.

Medicinal raw materials containing tannins have astringent and bactericidal properties and are used as rinses, for burns as a powder, orally for gastrointestinal diseases, as well as for poisoning with heavy metals and plant poisons. This raw material is also widely used in the leather industry for tanning leather.

Raw materials of plants containing tannins are harvested during the period of greatest content of these substances. After collection, the raw materials must be dried quickly, since tannins decompose under the influence of enzymes. It is recommended to dry the raw materials at a temperature of 50-60 °C. Raw materials are stored in tight packaging, in a dry place, preferably in their entire form. In the crushed state, the raw material undergoes rapid oxidation, as the surface of its contact with atmospheric oxygen increases.

The raw material base meets the needs of the medical industry and pharmacy chain.

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Isolation from MP . Tannins are a mixture of various polyphenols that have a complex structure and are very labile, so the isolation and analysis of individual components of tannins is very difficult. To obtain the amount of tannins, medicinal plants are extracted with hot water, cooled, and then the extract is processed sequentially:

Petroleum ether (cleaning from chlorophyll, terpenoids, lipids);

Diethyl ether, extracting catechins, hydroxycinnamic acids and other phenols

Ethyl acetate, into which leukoanthocyanidins, hydroxycinnamic acid esters, etc. pass. The remaining aqueous extract with tannins and other phenolic compounds and fractions 2 and 3 (diethyl ether and ethyl acetate) is separated into individual components using various types of chromatography. Use:

a) adsorption chromatography on cellulose columns,

b) partition chromatography on silica gel columns;

c) ion exchange chromatography;

d) gel filtration on Sephadex columns, etc.

Identification of individual tannins is based on comparison Rf in chromatographic methods (on paper, in a thin layer of sorbent), spectral studies, qualitative reactions and the study of decomposition products (for hydrolyzed tannins).

Quantitative determination of tannins . can be divided into gravimetric, titrimetric and physico-chemical.

Gravimetric methods are based on the quantitative precipitation of tannins with heavy metal salts, gelatin or adsorption with solid powder. Weight Unified Method (BEM) widely used in the leather industry. The method is based on the ability of tannins to form strong compounds with skin collagen. To do this, the resulting aqueous extract from the drug is divided into two equal parts. One part is evaporated, dried and weighed. The second part is treated with skin (skin) powder and filtered. The filtrate is evaporated, dried and weighed. Based on the difference between the dry residues of parts 1 and 2 (i.e., control and experiment), the content of tannins in the solution is determined.

Titrimetric method, included in GF-XI, referred to as the Leventhal-Neubauer method, is based on the oxidation of phenolic OH groups with potassium permanganate (KMnO 4) in the presence of indigo sulfonic acid, which is a regulator and indicator of the reaction. After complete oxidation of tannins, indigo sulfonic acid begins to oxidize to isatin, as a result of which the color of the solution changes from blue to golden yellow. Another titrimetric method for the determination of tannins, the method of tannin precipitation with zinc sulfate followed by complexometric titration with Trilon B in the presence of xylene orange, is used to determine tannin in the leaves of tannin sumac and tannine mackerel.

Physico-chemical methods for determining tannins:

1) colorimetric– DV give colored compounds with phos-molyb or phos-tungsten-mi in the presence of Na 2 CO 3 or with the Folin-Denis reagent (for phenols).

2) chromato-spectrophotometric And nephelometric methods that are used mainly in scientific research.

Distribution in the plant world, conditions of formation and role of plants. A low content of tannins was noted in cereals. In dicotyledons, some families - for example, Rosaceae, buckwheat, leguminous, willow, sumac, beech, heather - contain many genera and species, where the tannin content reaches 20-30% or more. The highest content of tannins was found in pathological formations - galls (up to 60-80%). Woody forms are richer in tannins than herbaceous ones. Tannins are unevenly distributed throughout plant organs and tissues. They accumulate mainly in the bark and wood of trees and shrubs, as well as in the underground parts of herbaceous perennials; green parts of plants are much poorer in tannins.

Tannins accumulate in vacuoles, and during cell aging they are adsorbed on cell walls. Most often, plants contain a mixture of hydrolyzed and condensed tannins with a predominance of compounds of one or another group.

As plants age, the amount of tannins in them decreases. Plants growing in the sun accumulate more tannins than those growing in the shade. Tropical plants produce significantly more tannins than temperate plants.

Bio-medical action and use of tannins . Tannins and medicinal products containing them are used mainly as astringents, anti-inflammatory and hemostatic agents.

A. Predominantly hydrolyzable:

Rhizomata Bistortae – Serpentine rhizomes.

Snake knotweed (snake root, coil) (Polygonumbistorta) – sem. Buckwheat, Polygonaceae

Chemical composition of medicinal products: 15-25% tannins, mainly hydrolyzable, gallic, ellagic, ascorbic, phenolcarboxylic and organic acids, flavonoids (quercetin)

The main action of the drug: astringent, antiseptic.

Nature of application. Infusion and decoction are used as an astringent, hemostatic, anti-inflammatory for minor bleeding in the gastrointestinal tract, acute and chronic inflammation of the stomach, food poisoning, dermatoses, burns, inflammation of the oral cavity, vagina, hemorrhoids.

Folia Cotinus coggygriae – Skumpia leather leaves.

Mackerel leather (Cotinus coggygria) – sem. Sumacaceae, Anacardiaceae- branchy shrub

Chemical composition of medicinal products. 0.2% essential oil (predominantly myrcene), ~25% tannin, flavonoids.

The main action of the drug: astringent, disinfectant.

Nature of application. used for the industrial production of tannin and its preparations, as well as the drug Flacumin, which is the sum of flavonol aglycones from mackerel leaves and has a choleretic effect.

FoliaRhuscoriariae – Sumac leaves.

Tanning sumac (Rhuscoriariae) – sem. Sumacaceae, Anacardiaceae– bush

Chemical composition of medicinal products. tannins (25%, tannin predominates), flavonoids (2.5% - derivatives of quercetin, myricetin, kaempferol), gallic and ellagic acids.

The main action of the drug: astringent, disinfectant.

Nature of application. are used for the industrial production of tannin and its preparations, used in the treatment of inflammatory processes in the oral-nasal cavity by rinsing with a 2% aqueous or aqueous-glycerin solution, ulcers, wounds and burns by lubricating with 3-10% solutions and ointments.

Rhizomata Bergeniaecrassifoliae – rhizomes of Badana thickifolia.

Bergenia thickleaf (Bergeniacrassifolia) – sem. Saxifragaceae, Saxifragaceae- perennial herbaceous plant

Chemical composition of medicinal products: tannins (~27%, of which tannin – 8-10%), gallic acid, arbutin (up to 22%), free hydroquinone (2-4%), coumarins, resins, vitamin C, sugar,

Nature of application. Infusion and decoction of the roots and rhizomes of bergenia are used in gynecology, dentistry to stop bleeding and as an anti-inflammatory, antiseptic, for the treatment of gastritis and ulcers of the stomach and duodenum, in folk medicine - for the treatment of pulmonary tuberculosis.

Rhizomataetradices Sanguisorbae –rhizomes and roots of burnet.

Burnet (officinalis) (Sangusorba officinalis) – sem. Rosaceae, Rosaceae- perennial herbaceous plant

Chemical composition of LR: tannins, mainly hydrolyzable (12-20%), ellagic, gallic acids, flavonoids, anthocyanins, catechins, saponins.

The main action of the drug: astringent, hemostatic.

Nature of application. The rhizomes and roots of burnet are used in the form of a decoction and liquid extract as an astringent for gastrointestinal diseases, enterocolitis, and diarrhea; as a hemostatic for uterine and hemorrhoidal bleeding, hemoptysis.

FructusAlni – infructescence (cones) of Alder.

FoliaAlniincanae – gray alder leaves.

Folia Alniglutinosa– black alder leaves.

Black alder(sticky) (Alnusglutinosa), O. gray (Alnusincana) – sem. Birch, Betulaceae– trees or large shrubs.

Chemical composition of medicinal products: alder fruits contain tannins, gallic acid (up to 4%), flavonoids. In the leaves o. gray and o. black contains flavonoids.

The main action of the drug: astringent, disinfectant, anti-inflammatory.

Nature of application. The decoction and infusion are used orally for acute and chronic enteritis, colitis, dysentery; externally – for gargling, mouthwash.

B. Mainly condensed:

CorticesQuerqus–oak bark

Common oak(Querqusrobur) – sem. Beech, Fagaceae– powerful tree

Chemical composition of medicinal products: tannins (10-20%, hydrolyzed and condensed), gallic, ellagic acids, flavonoids

The main action of the drug: astringent, antibacterial.

Nature of application. in the form of a decoction and infusion as an external astringent and anti-inflammatory agent for the treatment of stomatitis, gingivitis, inflammation of the oral cavity, female genital organs, skin burns, sweating.

Rhizomata Tormentillae – rhizomes of Potentilla erecta.

Cinquefoil erecta– Potentillaerecta– sem. Rosaceae, Rosaceae- perennial herbaceous plant

Chemical composition of medicinal products. tannins (15-30%: condensed tannins predominate), anthocyanins, catechins.

The main action of the drug

Nature of application. The decoction and infusion are used internally as an astringent and anti-inflammatory agent for inflammatory conditions of the mouth and larynx, gastrointestinal disorders, and externally for eczema.

Fructus Vaccinium mirtilli – blueberry fruits

Cormi Vaccinii mytilli – blueberry shoots.

Blueberry (Vaccinium myrtillus L.) –Heather, Ericaceae- small shrub

Chemical composition of medicinal products. tannins (18-20%), including condensed (5-12%), flavonoids (hyperin, rutin), anthocyanins.

The main action of the drug: astringent, anti-inflammatory.

Nature of application. more often in the form of infusion, decoction, jelly in connection with fermentation and putrefactive processes in the intestines, colitis. Blueberries have been shown to improve blood supply to the eyes, stabilize the structure of the retina, and improve night vision.

FructusPadi –bird cherry fruits.

Bird cherry (Padusavium), part asian (P. asiatica) – sem. Rosaceae, Rosaceae– tree up to 10 m tall

Chemical composition of medicinal products: tannins (15%: mainly condensed), phenolcarbonic and organic acids, vitamin C, sugars, terpenoid glycosides

The main action of the drug: astringent, disinfectant.

Nature of application. The decoction and infusion are used as an astringent and gastrointestinal disinfectant: for dysentery and diarrhea. Bird cherry fruits are a component of gastric preparations.