RU2609176C2 - Monodisperse colloidal aqueous solution of silver ions with antimicrobial and antitoxic action (versions) and method of its production - Google Patents

Abstract

FIELD: nanotechnologies.

SUBSTANCE: invention refers to the area of nanotechnologies and nanochemistry, particularly, to metal citrates, and it may be used in perfumery, food industry, in the medical field and agricultural sector, in biology, and other domains of science, industry, and ecology. The monodisperse colloidal aqueous solution of silver ions contains active metals in the form of citrates, silver ion reducer in aqueous dispersion, and distilled or deionized water. As an active metal, it contains monodisperse colloidal silver ion solution in aqueous dispersion. The reducer is selected from the group of organic acids, to the chemical composition of which the stabilizer of silver ions and hydrophobizator based on organic silicon compounds in aqueous dispersion were additionally included. The production method of monodisperse colloidal aqueous solution of silver ions has the stage of production of polydisperse colloidal mixture of nanostructural particles of silver in aqueous dispersion and direct interaction of obtained solution of nanostructural particles of silver in water with the reducer of silver ions with formation, whereupon, monodisperse colloidal aqueous solution of silver ions (cations) with antimicrobial and antitoxic action against toxic impurities and microbiological contaminations.

EFFECT: inventions allows production of stable monodisperse colloidal aqueous solutions of silver ions (cations) in the presence of citric acid with their specific concentration in aqueous solutions with simultaneous antimicrobial and antitoxic action.

9 cl, 6 dwg, 9 tbl, 5 ex

Description

The invention relates to the field of nanotechnology and nanochemistry, and more specifically to metal citrates, which have both antimicrobial and antitoxic effects, and can be used in perfumery, food industry, medicine, agriculture, biology, and in various other fields of science, industry, and ecology .

Currently, nanostructured metal particles are obtained by physical and chemical methods, including photochemical, radiation-chemical, electrochemical, biochemical methods [Pomogailo AF Polymerimmobilized nanosized and cluster particles. - Advances in Chemistry, 1997, v. 66, No. 8, - p. 750; Revina A.A., Egorova E.M. Radiation-chemical nanostructure technology for the synthesis of stable metal and bimetal clusters. Abstracts of the international conference "Advanced Technologies on the Threshold of the 21st Century", ICAT 98, M., 1998, part II, - P. 411; Pileni M. et al. Nanostructured particles in colloidal systems. - Langmuir, 1997, t. 13, - S. 3266; Sergeev G.B. Nanochemistry: textbook / G.B. Sergeev. - 3rd ed. - M .: KDU, 2009 .-- 336 p .: ill .; Rambidi N.G. Physical and chemical foundations of nanotechnology / N.G. Rambidi, A.V. Berezkin. - M .: FIZMATLIT, 2008 .-- 456 p .; Suzdalev I.P. Nanotechnology: physical chemistry of nanoclusters, nanostructures and nanomaterials / I.P. Suzdalev. - M.: Com. Book, 2006 .-- 597 p.

Particles of a substance in the range of nanometer size 2-100 nm change their chemical, physical and biological properties, the parameters of which are of great practical importance.

Using the characteristic features of substances with particle sizes less than 0.1 nanometers creates additional, completely new opportunities for creating technological methods and tools related to materials science, chemistry, physics, biology, medicine and many other fields of science and technology.

Currently, in connection with the development of the phenomenon of antibiotic resistance of microbes, there is again a growing interest in the development and creation of various kinds of colloidal silver preparations using silver particles in size in the form of colloidal solutions of silver, copper, gold and other active metals or their binary metals compositions, for example, silver and copper ions. [Electron resource / Universal antibacterial disinfectant based on silver and copper: masterbatch SumerSil ^® // - Access mode: http://organic-silver.com/, or organic-silver.com/index/...копия]

Colloidal silver based preparations of this kind are widely used in medicine as antiseptic agents for external use for more than 100 years. Throughout this time, the improvement of compositions and methods for their preparation continues.

Compounds of silver with histidine, tryptophan and arginine are known by the complexation reaction [A.S. Kazachenko, E.V. Legler, O.V. Peryanova et al., Chem.-farm. Zh., 34 (5), 34-35, 2000, E.V. Legler, A.S. Kazachenko, V.I. Kazbanov et al., Chem.-farm. Zh., 35 (9), 35-36, 2001] with a silver content of 40-50%.

These compounds exhibit antimicrobial activity against Staphyllococcus aureus, Candida albigans, Bacillus subtilis and some other bacteria. However, these derivatives have known disadvantages:

- poorly soluble in water (0.1%);

- insoluble in alkalis, acids, organic solvents and soluble only in solutions of ammonia and sodium chloride;

- the presence of amino acids in the composition can cause adverse side effects;

- silver in them is associated with an organic ligand in the form of a complex.

By the interaction of polyacrylic acid with silver nitrate, its silver derivatives (argacryl) were obtained [M.G. Voronkov, A.S. Kogan, L.M. Antonik et al. Antibacterial and hemostatic properties of silver salts of polyacrylic acid. Chem.-farm. Zh., 36, No. 2. 2002. - S. 27-29, RF Patent No. 2220982], containing from 1 to 10% silver. They inhibit the growth of Escherichia coli, Bacillus cereus, Staphyllococcus aureus and some other gram-positive and gram-negative bacteria.

In this case, the silver salts of polyacrylic acid have:

- extremely high molecular weight of 3-10 million;

- high viscosity;

- particle sizes are unknown.

In addition, the presence of non-ionized forms of silver in colloidal solutions, which have lower bactericidal activity compared to ionized forms of silver, leads to a decrease in their biological activity.

To increase the biological activity of the preparations, water-soluble salts, in particular silver nitrate, are used as the ionized form.

The disadvantages of using silver nitrate are associated with low stability due to the formation of silver cations of inactive insoluble compounds with many inorganic and organic compounds.

A known method of obtaining solutions of ionized silver using electrolysis [Kulsky L.A. Silver water. - Kiev: Naukova Dumka. 1983]. When conducting electrolysis, a silver electrode is used as the anode, on which silver is oxidized, followed by the transition of the silver cation to the solution.

However, silver water samples obtained using drinking water as an aqueous medium are unstable and lose their bactericidal activity due to the formation by silver cations of inactive insoluble compounds with chlorides and sulfates.

To increase the stability of aqueous bactericidal compositions obtained by the electrolytic method, the electrolysis is carried out in the presence of inorganic nitrogen [patent RU 2130964, C11D 3/04, publ. 05/27/1999], sulfuric [patent RU 2000109478, C02F 1/50, publ. 02.20. 2002] or phosphoric [patent RU 2197270, A61L 2/238, publ. 01.27.2003] acids, as well as organic food citric or acetic acids [patent RU 2125971, C02F 1/50, publ. 02/10/1999].

The disadvantages of the above methods for producing bactericidal compositions by electrolysis in the presence of inorganic acids and organic food acids are the dependence of the bactericidal activity on the composition of the disinfected medium used, as well as the decrease in the bactericidal activity of the compositions observed at acidic pH values. To increase the bactericidal activity of electrolytic aqueous solutions of ionized silver, obtained in the presence of acid, it is necessary to neutralize it with alkaline reagents.

In [patent RU 2281107, A61K 33/38, A61L 2/16 C02F 1/50, publ. August 10, 2006] described a bactericidal solution based on ionized silver, which is obtained using silver electrodes and an aqueous solution containing an amino acid, mainly glycine, and ammonia in the ratio of components, mass. %: 0.1-5.0 to 0.002-0.055, the rest is water.

The invention relates to silver-based bactericidal compositions obtained by electrolysis, which can be used to disinfect household and medical items, skin, and also to create medicines.

The presence of ammonia increases the pH of the solution and, as a result, the bactericidal composition increases, due to the preparation of a highly concentrated solution of silver ions, which can be significantly diluted to obtain a significant antibacterial effect. The pH of the resulting solution is in the range from 7.9 to 9.2. If necessary, the drug is neutralized to a pH of 6.9-7.1 with dilute acid, for example 2% acetic acid.

A known method of producing nanostructured metal particles by reducing metal ions in an aqueous solution [Butenko A.V. and others. C. Fiz. D. Atoms, Molecules, and Clusters, 1990, v. 17, - p. 283]. In the known method, hydrazine and hydrogen are used as a reducing agent.

The main disadvantage of the known methods is the low stability of nanostructured metal particles obtained with its help, because of which it is necessary to use organic stabilizers, which complicates the structure of the particles and also complicates their practical application. In addition, the production of nanostructured metal particles by this method must be carried out in an inert gas atmosphere or under vacuum, which increases the cost of the final product.

Known bactericidal drugs based on non-ionized metallic silver (collargol and protargol) and silver oxide (protargol) obtained by the chemical method.

To increase the biological activity, these preparations are stabilized by casein hydrolysates (collargol), gelatin hydrolysates (protargol), polyvinylpyrrolidone (poviargol), and the natural polysaccharide arabinogalactan [M.D. Mashkovsky. Medicines T. 2, New wave, M., 2000]. The preparations are stored in a dry powder state and are used in the form of colloidal solutions obtained after dispersion in water. Poviargolum [RF Patent No. 2088234. 1997. BI No. 24. Water-soluble bactericidal composition and method for its preparation. V.V. Kopeikin, E.F. Panarin, Yu.G. Santuryan, Z.A. Pashnikova, E.F. Pass, T.I. Budnikova. State Register of Medicines of Russia, reg. No. 97/167/7] contains in its composition nanoclusters of nullovalent metallic silver with sizes of 2-4 nm. Poly-N-vinylpyrrolidone-2 acts in the claimed method not only as a stabilizer of colloidal silver, but also as a reagent involved in the reduction due to its terminal aldehyde groups.

The drug is easily soluble in water with the formation of a colloidal solution that maintains aggregative stability for from 0.5 to 6.0 months. The drug is approved for serial production and medical use as a bactericidal agent. However, the method of obtaining this tool:

- time-consuming and requires large energy costs, since the production technology involves spray drying, and does not provide for the preparation of monodisperse colloidal aqueous solutions of silver ions with antimicrobial and antitoxic effects;

- has a limitation of the raw material base;

- a synthetic polymer increases the cost of the drug;

- the drug is rapidly excreted by the kidneys (80% in 4 hours).

In addition, these drugs, due to the presence of proteins of variable composition in their composition, have an allergic effect and are not amenable to strict standardization.

The complexes of anionic polysaccharides with silver are known [GB 2392913. Cullen V.M., Addison D., Greenhaigh D., Essler AA complex of an anionic polysaccharide with silver.], Which are salts formed from a silver cation and anionic polysaccharides - alginates hyaluronates, pectins, cellulose derivatives, etc.

Coatings for wounds are also known, containing, among others, colloidal silver or a silver salt as an antiseptic, and alginates, pectins, cellulose derivatives are used from plant polysaccharides [Patent RU 2193896. Gavrilyuk B.K., Gavrilyuk V.B. Coating for wounds. December 10, 2002], as well as coatings including hyaluronan as a polysaccharide component, and silver ions as an antibiotic [US 2002/0068093. Trogolo J.A., Johnston J.B., Pastecki E.A., Pervin E., Stahl A., Hyman M. Bi-laminar, hyaluronan coatings with silver-based anti-microbial properties. 06/06/2002]. All these bactericidal complexes contain silver in ionic form, but recently, the most effective silver-containing ultrafine and colloidal systems that provide higher bactericidal activity have been preferred [Blagitko EM, Burmistrov VA, Kolesnikov AP, Mikhailov Yu .I., Rodionov P.P. Silver in medicine. Novosibirsk: Science Center, 2004, 256 s. ].

Developed in the last 10 years of nanotechnology, it is possible to obtain ultrapure metal carboxylates by the reaction of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles directly with carboxylic acid [Ukrainian Patent Utility Model 39392, IPC C07C 51/41, C07F 5/00, C07F 15 / 00, С07С 53/126 (2008.01), С07С 53/10 (2008.01), A23L 1/00, В82В 3/00, publ. 2009.25.02].

However, they also have a number of drawbacks and require serious improvement to obtain monodisperse colloidal aqueous solutions of silver ions with antimicrobial and antitoxic effects.

In this direction, a number of technical solutions are known that can be taken as analogues of the claimed technical solution.

Known palladium (II) acetate, which contains impurities of nitrate ions due to the use of palladium nitrate in its preparation [RF Patent No. 2288214, IPC С07С 53/10 (2006.01), C07F 15/06 (2006.01), publ. 2006.11.27].

Its disadvantage is the low environmental purity of the product due to the presence of nitrate ions.

Known iron compounds for the enrichment of food products obtained by the interaction of sources of ferrous or trivalent iron, phosphate and ammonium [RF patent 2266688, IPC 7 A23L 1/30, A23L 1/304, A23L 2/52, A23C 9/152, publ. 2005.12.27].

The sources of ferrous or ferric iron may be any salt of ferrous or ferric iron, for example, sulfate, chloride, nitrate, acetate. Most importantly, use ferrous or ferrous sulfate. A source of phosphates can be some edible salt of orthophosphates, as well as phosphoric acid, or mixtures thereof. A food source of ammonia, mainly ammonium hydroxide, can serve as a source of ammonia.

The disadvantage is that the obtained iron compounds contain impurities of sulfates, chlorides, nitrates, etc., which can adversely affect the human body and their presence is undesirable in food products.

Known ammonium-iron green citrate obtained from iron sulfate by interaction with ammonium hydroxide [US Patent No. 2644828, cl. С07С 59/265, publ. 1953.07.07]. The precipitate of iron hydroxide that has precipitated is washed with distilled water until no sulfates are present. A citric acid solution is added to the washed iron hydroxide. The mixture is heated for 60-75 minutes and then filtered. The filtrate was concentrated. Ammonium hydroxide is added to pH = 6.05. The solution was concentrated and cooled. Crystallization is completed in 4 days. The green crystals of ammonium citrate are centrifuged, washed with alcohol and dried at 105 ° C. Ammonium-iron green citrate is obtained with an iron content of 14.7%.

The disadvantage is the contamination of the product with sulfates, the presence of which in the finished product limits its use in the food and medical industries.

Ammonium-iron green citrate is known, obtained by the interaction of an iron source - steel chips, oxidized in a solution of nitric and citric acids, with ammonium hydroxide in the presence of water [Novinyuk L.V. Ammonium iron citrates are effective sources of bioavailable iron. G. Food ingredients, raw materials and additives. - 2007. No. 1. - S. 40]. The ratio between solid and liquid phase is 1: 4.5, the product yield is about 92%.

The disadvantage is the contamination of the product with nitrates, since concentrated nitric acid is used.

Famous ammonium-iron citrate is green, which is used as a food additive E381 [Russian Patent N ° 2377929, IPC A23L 1/30 (2006.01), A23L 1/304 (2006.01), publ. 2010.10.01].

The disadvantage is a large amount of impurities (sulfates) - up to 0.3%.

A silver citrate complex is known, which is represented by a formula of the form: K ₂ C ₆ H ₅ O ₇ Ag [Patent US N ° 6,838,095. Ionic silver complex. International Class: A61K 31/19 (20060101); A61K 31/28 (20060101); A61K 47/00 (20060101); A61K 31/185 (20060101). January 4, 2005; http: // www. silver100.com/productinfo.pdf].

A disadvantage of the known silver carboxylate is its low content of base metal (silver) and the presence of a large amount of an alkali metal (potassium) impurity.

An ultrapure aqueous solution of a metal carboxylate of the general formula (RCOO) nMe is known, where Me is a metal, RCOO is a carboxyl anion, n = 1, 2, 3, obtained by reacting a metal, metal oxide or metal hydroxide with a carboxylic acid in an aqueous colloidal solution. The content of chloride, nitrate and sulfate ions does not exceed 0.000001 wt. %, while metal, metal oxide and metal hydroxide are in a colloidal solution in the form of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles obtained by ablation of metal granules in water, and the ratio of the mass of metal carboxylate to the mass of nanoparticles is not less than 1000 [ Patent of Ukraine for utility model N 23550, IPC B22F 9/14 (2007.01), published .. 2007. 25.05. Bull. 7].

The disadvantage of the described product is the low quality of the carboxylate, due to the fact that the pH of the solution is not regulated in it, which can lead to a violation of the stability of the aqueous carboxylate solution and to the appearance of nanoparticles in a solution with a size of more than 2.0 nm, especially in solutions of copper and noble carboxylates metals, which also affects the environmental cleanliness of the final product.

Known ultrapure aqueous solution of a metal carboxylate [patent UA 39397 (U). WO 2011119128 A1, International Classification B82Y 5/00, C07C 59/265, C07C 51/41, C01G 9/00.

Joint classification C01G 1/02, C07C 51/41, B82Y 5/00.

Index according to the European classification C01G 1/02, B82Y 5/00, С07С 51/41. Publ. 03/22/2011].

The basis of this invention is the task of improving the quality of the carboxylate and its environmental friendliness by using metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles to interact with carboxylic acid and obtain a metal carboxylate solution, which have acquired increased chemical activity during their creation as a result of explosive dispersion of metal granules during spark discharges between them in water.

An ultrapure aqueous solution of a metal carboxylate is obtained as follows. Preliminarily obtained by metal ablation, for example, by electropulse ablation, an aqueous colloidal solution in a reactor in which metal granules are placed as described in Ukrainian Patent Utility Model No. 23550, IPC B22F 9/14 (2007.01). Publ. 05/25/2007. Bull. 7. Metal granules are placed in a container for dispersion and evenly placed on the bottom of the tank between the electrodes. Pour water into the container. When passing through a chain of metal granules of pulses of electric current, the energy of the pulses is converted into the sublimation energy of the evaporated metal. At the points of contact of the metal granules, spark discharges arise in which explosive dispersion of the metal occurs. In the discharge channels, the temperature reaches 10 thousand degrees. The surface areas of the metal granules in the zones of spark discharges melt and are explosively destroyed into nanoparticles and vapor. The molten nanoparticles scatter in water, cool in it and create a colloidal solution of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles.

Carboxylic acid is poured into the resulting colloidal solution of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles. Due to the high chemical activity of the obtained nanoparticles, the formation of a metal carboxylate occurs. The high chemical activity of the formed nanoparticles to carboxylic acids made it possible to obtain a high value for the ratio of the mass of metal carboxylate to the mass of nanoparticles.

To speed up the process, the solution is heated and mixed vigorously.

The temperature of the colloidal solution is set at about 70 ° C. This significantly intensified the process of obtaining carboxylates. The process is stopped when the pH of the final product reaches 3.0-5.0.

Due to the high chemical activity of the nanoparticles, the formation of metal carboxylates occurs. Since no other substances were included in the reagents, and nanoparticles almost completely participated in the chemical reaction of the formation of carboxylic acid salts, a product of high environmental purity with a very low content of impurities was formed.

The main disadvantages of an ultrapure aqueous solution of a metal carboxylate are:

- obtaining a polydisperse colloidal aqueous solution of metal carboxylate of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles with nanostructured and ionized forms not established in the invention and the particle size distribution of the mixture of the obtained metals and their interaction in a colloidal solution with each other over time;

- biological effects on the antimicrobial and antitoxic activity of the created ultrapure aqueous solution of metal carboxylate at various concentrations of the content in the aqueous solution of metal carboxylate of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles have not been established;

- the cytotoxicity of an aqueous solution of a metal carboxylate to a biological cell has not been established;

- the concentrations and long-term stability of colloidal aqueous solutions of metal carboxylate have not been established.

Known drug having antimicrobial activity [RF patent No. 2278669, A61K 31/717, A61K 36/15, A61P 31/04, publ. 06/27/2006].

The antimicrobial agent contains silver, a stabilizer and water, with the arabinogalactan polysaccharide being used as a stabilizer. Silver is a nanoscale silver particle with a size of 10-30 nm, stabilized by the natural polysaccharide arabinogalactan.

It is known that natural substances of protective action that increase the stability of hydrophobic colloidal systems include not only lyophilic high molecular weight compounds of peptide nature, but also carbohydrate. Polysaccharides in general have a slightly weaker protective effect than proteins, but they have several advantages, since they do not denature at elevated temperatures, in conditions of increased acidity of the medium and in organic solvents. Earlier studies of systems [Alexandrova GP, Medvedeva S.A., Gishchenko L.A., Dubrovina V.I. Metal derivatives of arabinogalactan, a method of producing metal derivatives of arabinogalactan. RU 2194715. 12/20/2002] show that the arabinogalactan polysaccharide (water-soluble larch hemicellulose) is an effective stabilizer of metal and metal oxide particles, and therefore, can be used to obtain highly dispersed silver preparations.

The fundamental difference between the present invention and the above, including RU 2194715 dated 12/20/2002, is the use of the natural polynaccharide arabinogalactan simultaneously as a reaction dispersion medium and a reducer of silver ions to a zero-valence state.

However, in contrast to the claimed invention, the technical result of the known invention [RF patent No. 2278669] is to obtain stable water-soluble structures containing nanoscale silver particles with a size of 10-30 nm, an increase in the life time of nanostructured particles and the possibility of obtaining a sample in solid powder form.

The use of the natural arabinogalactan polysaccharide simultaneously as a dispersion reaction medium and a silver ion reducer to a zero valence state does not allow the use of stabilizers of these natural substances, including the arabinogalactan polysaccharide, as silver ion stabilizers (cations). In addition, these substances are used to stabilize silver, which is in a zero-valence state, and the size of its nanoparticles is 10-30 nm.

Of the known chemical compositions and methods for producing nanostructured metal particles and the reduction of aqueous solutions of silver ions from them, the closest to the proposed invention by the number of essential features (prototype) are the known chemical composition of citrates of active metals of silver and copper and the technology for the production of disinfectant antibacterial drugs, consisting of: silver citrate (active silver concentration - 250,000 mcg / l), copper citrate (active copper concentration - 250,000 mc g / l), citric acid, deionized water [Electron resource / Universal antibacterial disinfectant based on silver and copper: masterbatch SumerSil ^® // - Access mode: http://organic-silver.com/, or organic-silver. com / index / ... copy].

As indicated in the description of the electronic resource, the known technology for the production of disinfectant antibacterial drugs is implemented in 2 stages:

At the first stage, silver and copper nanoparticles are produced by physical means from metal granules using super-powerful electric pulses and high energies in water, creating the conditions for the implementation of the chain reaction of the explosion of metals (silver and copper) to obtain a solution of highly charged nanoparticles, using the technology above when we describe the well-known ultrapure aqueous solution of a metal carboxylate [patent UA 39397 (U). WO 2011119128 A1. publ. 03/22/2011].

At the second stage, citric acid is poured into the resulting colloidal solution of metal nanoparticles, metal oxide nanoparticles and metal hydroxide nanoparticles. The second stage of the nanotechnological process is based on the direct interaction of the resulting solution of metal nanoparticles in water with citric acid. As indicated in [Electronic resource / Universal antibacterial disinfectant based on silver and copper: SumerSil® superconcentrate // - Access mode: http://organic-silver.com/, or organic-silver.com/index/... copy] charged silver and copper nanoparticles have such high energy that they initiate a direct reaction between metal and citric acid without the use of additional chemicals and toxic catalysts. The result is a highly pure organic solutions of silver and copper with citric acid without chemical impurities and toxic heredity.

The disadvantages of the described known composition and method for producing nanostructured metal particles and the recovery from them of aqueous solutions of silver ions, selected by us as a prototype of the claimed technical solution are all the disadvantages noted above, characterizing the known ultrapure aqueous solution of metal carboxylate [patent UA 39397 (U). WO 2011119128 A1 ,. publ. 03/22/2011] and not allowing to use the given composition and method as a technical solution to obtain the inventive monodisperse colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects.

One of the main directions of modern nanotechnology is the synthesis of nanostructured metal particles, which is based on the reduction of metal ions to atoms, followed by aggregation of atoms and ions with the formation of nanostructured metal particles.

Moreover, among the above methods, the most promising is the biochemical method for producing nanostructured metal particles [Butenko A.V. et al. Zeit. Fiz. D. Atoms, molecules and clusters, 1990, v. 17, - S. 283; Robinson B. et al. Synthesis and Isolation of Microparticles in a Reverse Micelle System: In the collection “Structure and Reactivity in Reverse Micelles”, edited by Pileni M. Tokyo, 1989, p. 198].

The main disadvantages of the above methods for producing nanostructured metal particles are:

- low stability of nanostructured metal particles obtained using many developed methods;

- the complexity of the technological production and practical application of nanostructured metal particles;

- a relatively low rate of formation of nanostructured metal particles, a significant consumption of reducing agent is required, which increases the cost of manufacturing nanostructured metal particles;

- an excess of reducing agent and various reaction products may be present in the reaction system.

Of the known methods for producing nanostructured metal particles, the closest analogues to the claimed invention are:

a) A method for producing nanostructured metal particles by reducing metal ions in a reverse micellar dispersion of a reducing agent based on a solution of a surfactant in a non-polar solvent [RF patent No. 2147487, 7 B22, F 9/24, publ. 2000];

b) A method of obtaining an aqueous dispersion of nanostructured metal particles obtained from their reverse micellar solution [RF patent No. 2202400, 7 B01D 39/00, B01J 20/20, publ. 2003 g].

A method for producing nanostructured metal particles by reducing metal ions in a reverse micelle system involves preparing a reverse micellar dispersion of a reducing agent based on a solution of a surfactant in a non-polar solvent and introducing metal ions into it. Moreover, a substance from the group of flavonoids is used as a reducing agent, sodium bis-2-ethylhexyl sulfosuccinate (RT aerosol) is used as a surfactant, and a substance from the group of saturated hydrocarbons is used as a non-polar solvent.

An aqueous dispersion of nanostructured metal particles is obtained from their reverse micellar solution based on a surfactant in a non-polar solvent, in which the concentration of nanostructured metal particles is selected in the range of 2⋅10 ^-4 -3⋅10 ^-3 g-ion / l, and the concentration of surface -active substance - not more than 1.5%.

c) A bactericidal solution and method for its preparation [patent RU 2341291 A61L 2/16 (2006.01), A01N 65/00 (2006.01), A61K 33/38 (2006.01), A61K 31/79 (2006.01), publ. December 20, 2008].

The known invention relates to the production of dispersions of nanostructured metal particles in water with bactericidal properties used in various fields of medicine, pharmacology, industry and ecology.

This invention is characterized by the fact that a bactericidal aqueous dispersion solution is created consisting of silver nanoparticles, a surfactant and water, with a particle size distribution. The second object is a method for producing this solution by reducing silver ions in a reverse micelle system, including preparing a micellar surfactant solution in a nonpolar solvent from the series: n-hexane, or n-heptane, or n-octane, or n-decane, or cyclohexane, or isooctane, with the addition of a reducing agent. An aqueous solution of silver salt is pre-treated with an ammonia solution. The resulting two-phase system is settled, followed by delamination and separation from the organic layer of the target aqueous solution of silver nanoparticles of a reducing agent from the group of flavonoids, for example quercetin.

The invention provides the creation of a highly effective bactericidal agent with high biological activity against microorganisms, which it retains for a long time.

At the same time, we have established that when implementing the above known methods for producing nanostructured metal particles by reducing metal ions in a reverse micellar dispersion of a reducing agent in volumes of more than 0.1 l, the process of preparing a micellar solution of a reducing agent at room temperature (20-25 ° C) is technologically sufficient time-consuming and requires large energy costs for its dissolution in a non-polar solvent, accompanied by constant mixing of the mixture and takes as Avilo, from 3 to 5 days, which economically leads to large material and energy costs, despite the fact that ultimately leads to the production of nanostructured metal particles with a relatively low concentration in a non-polar solvent (from 2⋅10 ^-4 g-ion / l to 3⋅10 ^-3 g-ion / l).

When implementing the known method for producing an aqueous dispersion of nanostructured metal particles obtained from their reverse micellar solution after separation of the mixture of the aqueous dispersion from a non-polar solvent in a mixture volume of more than 1 l, further purification of the aqueous dispersion of nanostructured metal particles from excess non-polar solvent and surfactant by a known method is a labor-intensive process and takes, as a rule, 3-5 days, which economically leads to large energy and temporary ratam, low productivity output of finished products, and increases the level of fire and explosion hazards of production. Obtaining an aqueous dispersion of nanostructured metal particles by centrifuging a two-phase system of a reverse micellar solution of nanostructured metal particles and water and separating the lower aqueous phase containing nanostructured metal particles is unacceptable in practice for even small (more than 1 L) volumes of obtaining an aqueous solution of nanostructured metal particles.

Among the known methods for producing nanostructured metal particles, the closest to the proposed invention in terms of the number of essential features, (prototype) is the known method for producing nanostructured metal particles [patent RU 2341291 B22F 9/24 (2006.01), C22B 11/00 (2006.01), B82B 1 / 00 (2006.01,) publ. 07/20/2010], devoid of these disadvantages of the known methods for producing nanostructured metal particles, which are the closest analogues to the claimed invention.

The known invention relates to methods for producing nanostructured metal and bimetallic particles with sizes of structural formations of the order of nanometers. The method includes preparing a reverse micellar dispersion of a reducing agent from a group of flavonoids, a surfactant sodium bis-2-ethylhexyl sulfosuccinate, and introducing metal ions into it in the form of an aqueous solution of a metal salt of Ag, and / or Cu, or Fe, or Ni, or Cd with a molar concentration from 3⋅10 ^-4 to 3⋅10 ^-3 M. The dispersion is prepared with stirring, followed by cooling the prepared mixture to a temperature of 20-25 ° C and filtering. Then, metal ions are introduced into it in the form of an aqueous solution of an ammonia metal salt to obtain a reverse micellar solution of nanostructured particles based on a surfactant in a non-polar solvent. Distilled water is added to this solution, mixed, settled and the primary aqueous mixture of nanostructured particles is separated from a non-polar solvent. The separated mixture of nanostructured particles is heated, then cooled and kept until the excess surfactant is completely separated from the aqueous primary mixture to obtain an aqueous dispersion of nanostructured metal or bimetallic particles. The technical result of the invention is to increase the rate of formation and concentration of nanostructured metal and bimetallic particles upon receipt in micellar and aqueous solutions.

Currently, AKVION Closed Joint-Stock Company (Moscow) has organized serial industrial production of nanostructured metal and bimetallic particles when they are obtained in micellar and aqueous solutions according to the technology described in the aforementioned patent RU 2341291, in the form of:

- silver concentrate in organic dispersion for surface protection "Neosilver Concentrate-Organic", TU 2499-005-175720549 (Certificate of Conformity No. ROSS RU AG98.N14190 dated 07.25.14);

- silver concentrate in an aqueous dispersion for surface protection "Neosilver concentrate-Hydro", TU 2499-004-17572054-14 (Certificate of Conformity No. ROSS RU AG98.N14192 dated 07.25.14).

Thus, the analysis of known technical solutions showed the absence of technologies for producing highly purified solutions of silver ions with a given concentration, which have high selective antimicrobial activity and at the same time antitoxic action, and, therefore, the need to develop a modern technology for the production of highly purified monodisperse colloidal aqueous solutions of silver ions (cations) with a given concentration in aqueous solutions with antimicrobial activity and transformation mechanism chemicals with toxic properties (i.e., the mechanism of destruction or degradation of such chemicals), as well as the safety of their use as drugs for various purposes.

To eliminate the above drawbacks in the process of developing a technology for the production of a new generation of colloidal compositions based on monodispersed silver ions (cations), we paid serious attention, first of all, to the focused physicochemical design of nanostructured particles and the strictly controlled recovery of silver ions from them with a given concentration, physical parameters and biological properties.

We found that improving the quality of obtaining colloidal aqueous solutions of silver ions (cations) can be achieved by developing scientifically based phasing technology in the process of recovering from nanostructured silver particles with given parameters of their size distribution and their concentration in aqueous solutions in the presence of a reducing agent and its environmental purity .

First of all, we achieved such results by improving the quality of production of silver nanostructured particles and physicochemical control of the process of reduction of silver cations to obtain highly purified monodisperse colloidal aqueous solutions with specified controlled parameters of the reduced silver cations, their concentration and stability in aqueous solutions.

The problem to which the present invention is directed is to improve the quality of obtaining colloidal aqueous solutions of silver ions (cations) upon their reduction from silver nanostructured particles with predetermined parameters of their size distribution and their concentration in aqueous solutions in the presence of organic food acid and its environmental purity by improving the quality of production of silver nanostructured particles and physicochemical control of the process of recovery of silver cations to obtain mono dispersed colloidal aqueous solutions with predetermined controlled parameters of reduced silver cations and their concentration in aqueous solutions.

The technical result of the present invention is to obtain stable monodisperse colloidal aqueous solutions of silver ions (cations) when they are obtained from nanostructured silver particles in the presence of organic food acid with a given concentration in aqueous solutions having both antimicrobial and antitoxic effects.

The above problem is solved in that a monodisperse colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects, including active metals in the form of citrates, a metal ion reducer in an aqueous dispersion, distilled or deionized water as an active metal, it contains a monodisperse colloidal solution of silver ions in aqueous dispersion, a silver ion reducing agent selected from the group of organic food acids, including citric acid, or ascorbic acid, in the composition additionally, a silver ion stabilizer was introduced in the form of an aqueous solution of a hydroxyl-containing polymer, including polyvinyl alcohol, or chitin, or chitosan, or cellulose, or amylose, or 2-hydroxyethyl methacrylate, or an aqueous solution of an acrylic polymer in the form of an acrylic VD-AK-1113 varnish, or a copolymer in the form of a dispersion of an aqueous acrylic copolymer Novopol-002A or Novopol-002B, or a binary mixture of a hydroxyl-containing polymer and an aqueous solution of an acrylic polymer or copolymer and an aqueous solution of a water-repellent base f organosilicon compounds with a pH of ≤8.0 in the form of siloxanes or silicates in an aqueous dispersion.

Wherein:

Firstly, a monodisperse colloidal aqueous solution of silver ions, having antimicrobial and antitoxic effects, contains silver ions and a silver ion reductant in an aqueous dispersion in the following ratio of components%, mass:

silver ions 0,00026-0,00185 silver ion reducer 0.05-025 water, the rest up to 100

Secondly, a monodispersed colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects, contains silver ions, a reducing agent of silver ions in an aqueous dispersion, as a stabilizer contains an aqueous solution of a hydroxyl-containing polymer, or an aqueous solution of an acrylic polymer, or a copolymer, or a binary mixture of hydroxyl-containing polymer and an aqueous solution of an acrylic polymer or copolymer and an aqueous solution of a hydrophobizing agent based on organosilicon compounds with a pH of ≤8.0 in the following enii Component% by weight:

silver ions 0,00026-0,00185 silver ion reducer 0.05-0.25 0.1-0.3% (mass) of an aqueous solution of a hydroxyl-containing polymer, or an aqueous solution of acrylic polymers, or copolymers, or a binary mixture of 0.1-0.3% (mass) of hydroxyl-containing polymer and 0.1-0.3% (mass), or an aqueous solution of acrylic polymers, or copolymers with a ratio of 1: 1 mass,% 1.5-2.5 0.1-0.4% (mass) aqueous solution of organosilicon compounds 0.5-1.5 water the rest is up to 100

Thirdly, in a method for producing a monodisperse colloidal aqueous solution of silver ions, comprising the step of producing a colloidal mixture of silver nanostructured particles in an aqueous dispersion and direct interaction of the obtained solution of silver nanostructured particles in water with a silver ion reductant to form a monodisperse colloidal aqueous solution of silver ions, obtaining a monodisperse colloidal aqueous solution of silver ions is carried out in 3 stages, while:

- at the first stage, a reverse micellar solution of silver nanostructured particles is obtained with a concentration of silver nanostructured particles of 0.0399-0.0508% (mass) based on the surfactant sodium bis-2-ethylhexyl sulfosuccinate in a non-polar solvent, by reducing silver ions in a reverse system micelles comprising preparing obratnomitsellyarnoy reducing agent dispersion from the group of flavonoids having a molar concentration of from 6,6⋅10 ^-4 to 3,3⋅10 ^-3 M in a nonpolar solvent from the group of saturated hydrocarbons: n-hexane or n-r ptane, or n-octane, or n-decane, or cyclohexane, or isooctane, a surfactant of sodium bis-2-ethylhexyl sulfosuccinate with a molar concentration of 0.09 to 0.1 M and the introduction of silver ions in it in the form of aqueous a solution of a metal salt of Ag, with a molar concentration of from 3.7 · 10 ^-2 to 5.0 · 10 ^-2 M, while the preparation of a reverse micellar dispersion of a reducing agent of nanostructured silver particles is carried out with stirring of the reducing agent and surfactant in a non-polar solvent at a temperature of 60 -80 ° C with reflux condenser for 0.5-1.0 hours, followed by cooling the prepared mixture to a temperature of 20-25 ° C and filtering, the introduction of silver ions into it is carried out in the form of an aqueous solution of silver ammonia salt;

- at the second stage, the initial concentrate of an aqueous dispersion of silver nanostructured particles with a concentration of silver nanostructured particles of 0.0399-0.0508% (mass), for which purpose the reverse micellar solution of silver nanostructured particles obtained at the first stage based on the surfactant bis-2- Ethylhexyl sodium sulfosuccinate in a non-polar solvent is introduced with distilled or dionized water, stirred, settled and the primary aqueous mixture of silver nanostructured particles is separated from the non-polar solvent, separated by A water-based mixture of nanostructured silver particles with an excess of non-polar solvent and a surfactant in it is heated to a temperature of 50-60 ° C for 1-2 hours until the excess non-polar solvent is completely separated, then cooled to a temperature of 20-25 ° C and kept at this temperature for 24 hours until the excess surfactant is completely separated from the aqueous primary mixture;

- at the third stage, a monodisperse colloidal aqueous solution of silver ions is obtained with the formation of its working solutions, for which a working solution of an aqueous dispersion of silver nanostructured particles is prepared in concentrations of 0.37-2.0% of the mass of the initial concentration of a colloidal aqueous solution of silver nanostructured particles 0.0399 -0.0508% (mass) and heat it to a temperature of 70-80 ° C, then 0.05-0.25% of the mass of silver ion reducer from the group of organic foods are respectively introduced into the corresponding prepared working solution of the aqueous dispersion acid and cooled to 20-25 ° C, after which the resulting binary mixture is stirred for 5-10 minutes until opalescence appears in it, after which the initially cooled reaction mixture is reheated to 70-80 ° C, kept at this temperature for 1-2 hours and re-cooled to 20-25 ° C until the disappearance of opalescence and the formation of silver ions in the aqueous dispersion, while the number of repeated cycles of raising and lowering the temperature of the reaction mixture in a given temperature-time interval depends on the ratio of working concentrations solutions of an aqueous dispersion of nanostructured silver particles and a silver ion reducer in an aqueous dispersion and for a given concentration of mass of silver ions and a silver ion reducer, respectively, is (%) mass:

0,00026-0,00034: 0.05: 1 cycle;

0,00035-0,00046: 0.10: 2 cycles;

0,00069-0,00092: 0.15: 4 cycles;

0.00103-0.00139: 0.20: 6 cycles;

0.00138-0.00185: 0.25: 6 cycles.

Moreover, with the introduction of silver ions, the concentration of an aqueous solution of silver ammonia salt and the concentration of surfactant are selected depending on the degree of hydration, varying from 5.0 to 8.0.

Before settling in the two-phase system, distilled or deionized water in a 1: 1 ratio is added with stirring, the resulting mixture is transferred to a separation column until a binary colloidal mixture of nanostructured silver particles and silver ions in an aqueous dispersion is obtained, which is drained from the bottom of the column into a separate storage ring .

Fourth, to obtain a monodisperse colloidal aqueous solution of silver ions in the stabilizer:

- the resulting colloidal mixture of an aqueous dispersion of silver ions is reheated to 50-60 ° C and 0.1-0.3% aqueous solution of hydroxyl-containing polymer in the amount of 1.5-2.5% of the mass of the aqueous mixture is added to it, then the mixture stirred for 20-30 minutes until the formation of a reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal aqueous solution of silver ions with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% by weight of the aqueous mixture, an additional 0.1-0 is added, 3% solution of acrylic polymer in an amount of 1.5-2.5% by weight of the mass of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal mixture of silver ions in an aqueous dispersion with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% of the mass and 0.1-0.3% solution acrylic polymer in an amount of 1.5-2.5% of the mass by weight of the aqueous mixture, an additional 0, -1.5% of the mass of organosilicon compounds by weight of the aqueous mixture is added, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C.

The minimum and maximum values of the ingredients of chemical substances contained in a monodisperse colloidal aqueous solution of silver ions, expressed as a percentage of their masses, are based primarily on their practical significance of the manifesting properties of the claimed variants of the compositions of the aqueous solution of silver ions and are selected on the basis of established theoretical and experimental studies of the physicochemical state of aggregation of an aqueous solution of silver ions, which does not entail a change in colloidal solution, viscosity and state of aggregation, and also, so that in excess of the chemicals included in the stabilizer (hydroxyl-containing polymer, acrylic polymer or copolymer, water-repellent agent based on organosilicon compounds and variants of their combined use), if necessary, their introduction, not to mask the biological effectiveness of the prepared working solutions of silver ions in aqueous dispersion relative to their antimicrobial activity and physical effectiveness regarding their antitoxic activity.

Thus, in the production of monodisperse colloidal solutions of silver ions (cations) developed by environmentally friendly and economically feasible methods under normal conditions, at the end of the process in a reduced time interval, a highly purified “nuclear” colloidal aqueous solution of stabilized silver ions (cations) with a given controlled concentration without impurities of nanostructured metal particles, nanoparticles of metal oxides and nanoparticles of metal hydroxides, and impurities of chloride, nitrate and sulfate ions.

The absence of the above impurities in the obtained colloidal solution of silver ions provides high controlled stability and environmental safety of colloidal solutions of formed silver ions for a long time, thereby ensuring their high antimicrobial activity and antitoxic effect due to the mechanism of transformation of chemicals with toxic properties.

The developed method for the transformation of the supramolecular structure of silver micelles into a monodisperse colloidal solution of silver ions (cations), which includes a new algorithm for the production process of monodisperse colloidal solutions of silver ions (cations), including targeted and dosed effects on this structure at each stage of the process.

As a result, significant disadvantages inherent in the known compositions and technologies for their preparation were eliminated, which reduce the effectiveness or limit their targeted use as agents that simultaneously have antimicrobial activity and the mechanism of transformation of chemicals with toxic properties, which results in 100% production of ions (cations) ) silver in pure, without impurities, highly purified colloidal aqueous solutions.

When analyzing the known technical solutions, the authors did not find a monodisperse colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects (options) and methods for their preparation with the set of essential features indicated in the proposed technical solution, which proves the conformity of the claimed technical solution to the “novelty” criterion of the invention.

In the studied technical solutions, which are included in the prior art, the authors did not reveal the effect of the transformations prescribed by the proposed technical solution, characterized by significant features distinctive from the prototype, on the achievement of the specified technical result, which proves the conformity of the proposed technical solution to the criteria of the invention “inventive step”.

The method of obtaining monodisperse colloidal aqueous solution (options) is carried out in 3 stages, which include the following operations:

At the first stage, a reverse micellar solution of silver nanostructured particles with a concentration of silver nanostructured particles of 0.0399-0.0508% (mass) based on the surfactant sodium bis-2-ethylhexyl sulfosuccinate in a non-polar solvent is obtained by reducing silver ions in a reverse micelle system including:

- preparation of reverse micellar dispersion of a reducing agent from the group of flavonoids with a molar concentration of from 6.6⋅10 ^-4 to 3.3⋅10 ^-3 M in a non-polar solvent from the group of saturated hydrocarbons and surfactant sodium bis-2-ethylhexyl sulfosuccinate with a molar concentration from 0.09 to 0.1 M;

- introduction into the prepared reverse micellar dispersion of a reducing agent of silver ions in the form of an aqueous solution of a metal salt of Ag, with a molar concentration of from 3.7 · 10 ^-2 to 5.0 · 10 ^-2 M.

In this case, the preparation of a reverse micellar dispersion of a reducing agent of nanostructured silver particles is carried out with stirring of the reducing agent and a surfactant in a non-polar solvent at a temperature of 60-80 ° C with reflux for 0.5-1.0 hours, followed by cooling of the prepared mixture to a temperature of 20- 25 ° C and filtration, the introduction of silver ions into it is carried out in the form of an aqueous solution of silver ammonia salt.

At stage 2, an initial concentrate of an aqueous dispersion of nanostructured silver particles with a concentration of nanostructured silver particles of 0.0399-0.0508% (mass) is obtained, for which:

- distilled or deionized water is added to a reverse micellar solution of silver nanostructured particles of silver nanostructured based on the surfactant sodium bis-2-ethylhexyl sulfosuccinate in a non-polar solvent, mixed, settled, and the primary aqueous mixture of silver nanostructured particles is separated from a non-polar solvent;

- to obtain a concentrate of an aqueous dispersion of nanostructured silver particles, the separated primary aqueous mixture of nanostructured silver particles with an excess of non-polar solvent and surfactant in it is heated to a temperature of 50-60 ° C for 1-2 hours until the excess non-polar solvent is completely separated, then cooled to a temperature of 20-25 ° C and maintained at this temperature for 24 hours until the excess surfactant is completely separated from the aqueous primary mixture.

Moreover, with the introduction of silver ions, the concentration of an aqueous solution of silver ammonia salt and the concentration of surfactant are selected depending on the degree of hydration, varying from 5.0 to 8.0.

Before settling the prepared mixture, distilled or deionized water in a 1: 1 ratio is added to the biphasic system with stirring, the resulting mixture is transferred to a separation column until a binary colloidal mixture of nanostructured silver particles and silver ions in an aqueous dispersion is obtained, which is drained from the bottom of the column into separate drive.

At the 3rd stage, a monodisperse colloidal aqueous solution of silver ions is obtained with the formation of its working solutions, for which:

- prepare a working solution of an aqueous dispersion of nanostructured silver particles in concentrations of 0.25-2.0% by weight of the initial concentration of a colloidal aqueous solution of nanostructured silver particles of 0.0399-0.0508% (mass) and heat it to a temperature of 70-80 ° C ;

- 0.05-0.2% of the mass of the reducing agent of silver ions from the group of organic food acids, for example citric acid, is introduced into the corresponding prepared working solution of an aqueous dispersion in concentrations of 0.25-2.0% of the initial concentration, respectively, and cooled to 20 -25 ° C, after which the resulting binary mixture is stirred for 5-10 minutes until opalescence appears in it;

- the initially cooled reaction mixture is reheated to 70-80 ° C, maintained at this temperature for 1-2 hours and re-cooled to 20-25 ° C until opalescence disappears and silver ions form in the aqueous dispersion.

The number of repeated cycles of raising and lowering the temperature of the reaction mixture in a given temperature-time interval depends on the ratio of the concentrations of the working solutions of the aqueous dispersion of nanostructured silver particles of the metal ion reducer from the group of organic food acids in the aqueous dispersion and for the given mass concentrations of silver ions and the metal ion reducer , respectively, is: (%) mass:

0,00026-0,00034: 0.05: 1 cycle;

0,00035-0,00046: 0.10: 2 cycles;

0,00069-0,00092: 0.15: 4 cycles;

0.00103-0.00139: 0.20: 6 cycles;

0.00138-0.00185: 0.25: 6 cycles.

To obtain a monodisperse colloidal aqueous solution of silver ions in a stabilizer:

- the resulting colloidal mixture of an aqueous dispersion of silver ions is reheated to 50-60 ° C and add 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% by weight of the aqueous mixture, then the mixture stirred for 20-30 minutes until the formation of a reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal aqueous solution of silver ions with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% by weight of the aqueous mixture, an additional 0.1-0 is added, 3% solution of acrylic polymer in an amount of 1.5-2.5% of the mass of the weight of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal mixture of silver ions in an aqueous dispersion with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% of the mass and 0.1-0.3% solution acrylic polymer in an amount of 1.5-2.5% by weight of the mass of the aqueous mixture, 0.5-1.5% of the mass of organosilicon compounds and the mass of the aqueous mixture are additionally added, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C.

As an example, to obtain a monodisperse colloidal aqueous solution of silver ions, the following raw materials were used:

- silver nitrate (AgNO ₃ ) according to GOST 1277;

- reference isooctan according to GOST 12433;

- sodium dioctyl sulfosuccinate (C ₂₀ H ₃₇ NaO ₇ S, CAS 577-11-7) (aerosol - RT or AOT);

- quercetin (С ₁₅ Н ₁₀ О ₇₂ ⋅Н ₂ О, pentahydroxyflavone, CAS 6151-25-3);

- water ammonia "OSH" according to GOST 24147;

- citric acid monohydrate food, GOST 908-2004;

- polyvinyl alcohol brand 11/2, 16/1, premium or first grade, GOST 10779-78;

- acrylic varnish VD-AK-1113 according to TU 2310-015-43238048-07;

- water-repellent SOFEXIL 30-04M (50% aqueous emulsion based on oligomethylhydridesiloxane) according to TU 2229-018-42942526-01, amend. 1-4 - distilled water according to GOST 6709-72.

The concentration of the metal salt ranged from 3.7 · 10 ^-2 to 5.0 · 10 ^-2 M The ratio of the molar concentrations of water and surfactant in the reverse micellar dispersion of the metal salt (degree of hydration, W = [H2O] / [AOT] selected in the range of 5 to 8.

The molar concentration of a substance from the group of flavonoids in reverse micellar dispersion of a reducing agent was chosen in the range from 6.6⋅10 ^-4 to 3.3⋅10 ^-3 M.

The following are examples of the invention for the proposed method for producing monodisperse colloidal aqueous solution of silver ions (its variants).

Example 1. Obtaining a concentrate of nanostructured silver particles in a non-polar solvent:

40 g of sodium dioctyl sulfosuccinate are dissolved in 960 ml of isooctane at 20-25 ° C and 300-400 mg of quercetin are added. The resulting mixture was heated in a flask under reflux to 60-70 ° C and stirred for 05-1 hour, after which the heated mixture was cooled to 20-25 ° C and filtered.

9.0 ml of an aqueous solution of silver ammonia salt is added to the micellar solution of quercetin obtained previously. The mixture is stirred at 20-25 ° C for 1-3 minutes to obtain a uniform dark micellar solution of nanostructured silver particles with a concentration of 0.0399% (mass).

Example 2. Obtaining a concentrate of nanostructured silver particles in a non-polar solvent:

Dissolution of sodium dioctyl sulfosuccinate in a non-polar solvent and preparation of a reverse micellar dispersion of a flavonoid at a temperature of 20-25 ° C are carried out analogously to example 1.

Next, the resulting mixture is heated in a flask under reflux to a temperature of 60-80 ° C and stirred for 0.5-1 hour, after which the heated mixture is cooled to 20-25 ° C and filtered.

12.0 ml of an aqueous solution of silver ammonia salt is added to the micellar solution of quercetin obtained previously. The mixture is stirred at 20-25 ° C for 1-3 minutes to obtain a homogeneous dark micellar solution of nanostructured silver particles with a concentration of 0.0508% (mass).

Example 3. Obtaining a concentrate of nanostructured silver particles in an aqueous dispersion:

To 1000 ml of a micellar solution of silver nanostructured particles obtained in Example 1, add 1000-1500 ml of distilled water and mix vigorously at a temperature of 20-25 ° C for 5-10 minutes. Next, the mixed mixture is left to stand for 1-3 hours, until a visualized clear interface between the organic phase of the primary aqueous mixture of silver nanostructured particles and an excess of isooctane and sodium dioctyl sulfosuccinate in it at a temperature of 20-25 ° C, after which the primary aqueous mixture of silver nanostructured particles is separated from isooctane.

The separated primary aqueous mixture of silver nanostructured particles is heated to a temperature of 50 ° -60 ° C for 1 hour until the excess of isooctane is completely removed from the mixture. After that, the heated aqueous mixture of silver nanostructured particles is cooled to a temperature of 20-25 ° C and maintained at this temperature for 24 hours until the finished product is obtained - an aqueous dispersion of silver nanostructured particles with a concentration of 0.0399% (mass).

Example 4. Obtaining a concentrate of nanostructured particles of silver in an aqueous dispersion:

The introduction of distilled water into a micellar solution of nanostructured silver particles, their mixing, settling and separation of the primary aqueous mixture of nanostructured silver particles from isooctane is carried out analogously to example 3.

Next, the separated primary aqueous mixture of silver nanostructured particles is heated to a temperature of 50-60 ° C 60 ° C with stirring for 1 hour until the excess of isooctane is completely removed from the mixture.

The heated primary mixture is cooled with its exposure for 24 hours and the excess of sodium dioctyl sulfosuccinate is separated from the aqueous mixture until the finished product is obtained - an aqueous dispersion of nanostructured metal particles is produced analogously to example 3 until the finished product is obtained - an aqueous dispersion of nanostructured silver particles with a concentration of 0.0508% ( masses).

Example 5. Obtaining monodisperse colloidal aqueous solution of silver ions with the formation of its working solutions (options):

At the first stage, the calculated amount of 0.37-2.0% of the mass of an aqueous solution of silver nanostructured particles (for example, 0.37%, or 0.5%, or 1.0%, or 1.5%, or 2, is prepared in turn. 0% (mass) in distilled water from their initial concentration of 0.0399% (mass), or 0.0508% (mass) of nanostructured silver particles in the aqueous dispersion and heat it to a temperature of 70-80 ° C obtained in example 3 or four.

In the second stage, in the appropriate prepared working solution of the aqueous dispersion in concentrations of 0.37-2.0% of the mass (for example, 0.37%, or 0.5%, or 1.0%, or 1.5%, or 2, 0% mass) from the initial concentration, respectively, 0.05-0.2% of the mass of citric acid (0.05, or 0.1, or 0.15, or 0.2, or 0.25% of the mass) is introduced and cooled to 20-25 ° C, after which the resulting binary mixture for 5-10 min until opalescence appears in it.

At the third stage, to obtain a monodisperse colloidal aqueous solution of silver ions in an aqueous dispersion (variants), the reaction binary mixture of nanostructured silver and citric acid particles in an aqueous dispersion initially cooled to 20-25 ° C is used for each of the prepared options for the percentage of ingredients in the aqueous dispersion reheated to 70-80 ° C, maintained at this temperature for 1-2 hours and re-cooled to 20-25 ° C until opalescence disappears and silver ions form in the aqueous dispersion . The number of repeated cycles of raising and lowering the temperature of the reaction mixture in a given temperature-time interval depends on the ratio of the concentrations of working solutions of an aqueous dispersion of nanostructured silver particles and a metal ion reducing agent from a group of organic food acids, for example, citric acid, in an aqueous dispersion and for given concentrations masses of silver ions and a metal ion reducer, respectively, is: (%) masses:

0,00026-0,00034: 0.05: 1 cycle;

0,00035-0,00046: 0.10: 2 cycles;

0,00069-0,00092: 0.15: 4 cycles;

0.00103-0.00139: 0.20: 6 cycles;

0.00138-0.00185: 0.25: 6 cycles.

In the fourth stage, to obtain a monodisperse colloidal aqueous solution of silver ions in the stabilizer:

- the resulting colloidal mixture of an aqueous dispersion of silver ions is reheated to 50-60 ° C and 0.1-0.3% (for example, 0.1%, or 0.2%, or 0.3% of the mass) of aqueous a solution of a hydroxyl-containing polymer, for example, PVA in an amount of 1.5-2.5% by weight of the weight of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of a reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal aqueous solution of silver ions with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% by weight of the aqueous mixture, an additional 0.1-0 is added, 3% (for example, 0.1%, or 0.2%, or 0.3% mass) of an acrylic polymer solution in an amount of 1.5-2.5% of the mass of the weight of the aqueous mixture, then the mixture is stirred for 20-30 min until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C;

- in the prepared working solution of a monodisperse colloidal mixture of silver ions in an aqueous dispersion with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% of the mass and 0.1-0.3% solution acrylic polymer in an amount of 1.5-2.5% by weight of the weight of the aqueous mixture, an additional 0.5-1.5% by weight of organosilicon compounds, for example, siloxanes or silicates, is added by weight of the aqueous mixture, then the mixture is stirred for 20-30 min until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C.

The formation of silver nanostructured particles and silver ions in the aqueous dispersion was monitored and their stability evaluated spectrophotometrically based on changes in the main characteristics of the optical absorption spectra (for silver nanostructured particles, the positions of the absorption band maximum and the optical density at the absorption band maximum in the region of 400-425 nm, and for stabilized silver ions (cations), the positions of the maximum absorption band and the optical density at the maximum of the absorption band in the region and 465-490 nm.

For the effective application of the developed variants of the inventive monodisperse colloidal aqueous solution of silver ions, in the course of the studies, the physical parameters of the aqueous dispersion of a colloidal aqueous solution of silver ions were studied using:

- control methods for assessing the reliability of the content of silver ions in a monodisperse colloidal aqueous solution during their recovery from silver nanostructured particles in an aqueous dispersion and upon completion of the recovery of silver ions in an aqueous dispersion using a HELIOS ALPHA double-beam UV and visible spectrophotometer (UK ) with microprocessor control system;

- method of atomic emission spectrometry with inductively coupled plasma (AES-ICP), on a plasma device ICAP-6500 Duo (England), ITEVA software.

The presence in the composition of a binary colloidal mixture of nanostructured silver particles and silver ions (cations) recovered from silver nanostructured particles in an aqueous dispersion was determined by spectral analysis methods, respectively, in the 400-425 nm and 465-490 nm region, using a HELIOS ALPNA double-beam spectrophotometer ( United Kingdom) [TU 9185-025-87552538-12 “Colloidal silver concentrate in aqueous dispersion”. - M .: Inbiopharm LLC, 2012. - 16 p .; Pyatnitsky I.I., Sukhan V.V. Analytical chemistry of silver / I.I. Pyatnitsky, V.V. Suhan. - M .: Nauka, 1975 .-- 264 p. ];

- by atomic emission spectrometry with inductively coupled plasma (AES-ICP), on an ICAP-6500 Duo plasma device (England), ITEVA software [Dementeva OV, Filippenko MA, Andreeva TN et al. Nanotechnology 2012. T7 No. 9-10. - S. 54-63; Sedukh E.M., Dementeva O.V., Rudoy V.M., et aii // Book of abstrakts ESAS 2014, March 16-21. Prague, Czech Republic, - P. 231].

According to the developed methods, the presence and concentration of nanostructured silver particles and silver ions in the studied concentrations of nanostructured silver particles in the aqueous dispersion (0.37-2.0%, masses from the initial concentration of silver nanostructured particles 0.0508% mass) was determined by the optical density at the maximum absorption bands for the studied following options, in accordance with the description in the description of example 5:

- option 1: 0.37% aqueous solution of silver nanostructured particles and silver ions of the initial concentration of silver nanostructured particles of 0.0508% (mass);

- option 2: 0.5% aqueous solution of nanostructured silver particles and silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 3: 1.0% aqueous solution of nanostructured silver particles and silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 4: 1.5% aqueous solution of nanostructured silver particles and silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 5: 2.0% aqueous solution of nanostructured silver particles and ions of the initial concentration of nanostructured silver particles of 0.0508% (mass).

The total silver content in ionic form as part of a monodisperse colloidal aqueous solution of silver ions using inductively coupled plasma atomic emission spectrometry (ICP-AES) on an ICAP-6500 Duo plasma instrument (England), ITEVA software, was determined for the subjects the following options, in accordance with the above step described in example 5.

- option 1: 0.37% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass);

- option 2: 0.5% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass);

- option 3: 1.0% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass);

- option 4: 1.5% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass);

- option 5: 2.0% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass).

The results of the qualitative and quantitative control of the presence of silver nanostructured particles and silver ions (cations) in the studied aqueous solutions and their concentration for the corresponding solution variants using the UV and visible HELIOS ALPHA dual-beam spectrophotometer (Great Britain) are shown in FIG. 1-6 and are shown in tables 1-3, where:

FIG. 1 - The dependence of light absorption of 0.37% (mass) of an aqueous solution of silver nanostructured particles in the wavelength band in the region of 400-425 nm on the initial concentration of 0.0508% (mass) (option 1):

1 - spectral characteristic of a 0.37% aqueous solution of nanostructured silver particles (prototype) in the wavelength band in the region of 400-425 nm;

2 is a spectral characteristic of the remaining part of silver nanostructured particles in their 0.37% aqueous solution after one recovery cycle of silver ions in a 0.05% citric acid solution for 1-2 hours without temperature heating in the wavelength band in the region 400-425 nm;

3 - spectral characteristic of a 0.37% aqueous solution of silver nanostructured particles after one recovery cycle of silver ions in a 0.05% citric acid solution for 1-2 hours with temperature heating from 70 to 80 ° C in the wavelength band in the region 400-425 nm;

FIG. 2 - Dependence of light absorption by 0.5% (mass) of an aqueous solution of silver nanostructured particles on the initial concentration of 0.0508% (mass) in the wavelength band in the region of 400-425 nm (option 2):

1 - spectral characteristic of a 0.5% aqueous solution of nanostructured silver particles (prototype) in the wavelength band in the region of 400-425 nm;

2 - spectral characteristic of the remaining part of silver nanostructured particles in their 0.5% aqueous solution after two cycles of reduction of silver ions in a 0.1% citric acid solution for 2-4 hours with temperature heating from 70 to 80 ° C but without reducing the temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

3 - spectral characteristic of a 0.5% aqueous solution of silver nanostructured particles after two cycles of reduction of silver ions in a 0.1% solution of citric acid for 2-4 hours with temperature heating from 70 to 80 ° C and with a decrease in temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

FIG. 3 - The dependence of light absorption of 1.0% (mass) of an aqueous solution of silver nanostructured particles in the wavelength band in the region of 400-425 nm on the initial concentration of 0.0508% (mass) (option 3):

1 - spectral characteristic of a 1.0% aqueous solution of nanostructured silver particles (prototype) in the wavelength band in the region of 400-425 nm;

2 - spectral characteristic of the remaining part of silver nanostructured particles in their 1.0% aqueous solution after four cycles of reduction of silver ions in a 0.15% citric acid solution for 4-8 hours with temperature heating from 70 to 80 ° C but without reducing the temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

3 - spectral characteristic of a 1.0% aqueous solution of silver nanostructured particles after four cycles of reduction of silver ions in a 0.15% solution of citric acid for 2-4 hours with temperature heating from 70 to 80 ° C and with a decrease in temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

FIG. 4 - Dependence of light absorption by 1.5% (mass) of an aqueous solution of silver nanostructured particles on the initial concentration of 0.0508% (mass) (option 4) in the wavelength band in the region of 400-425 nm:

1 - spectral characteristic of a 1.5% aqueous solution of nanostructured silver particles (prototype) in the wavelength band in the region of 400-425 nm;

2 - spectral characteristic of the remaining part of silver nanostructured particles in their 1.5% aqueous solution after six cycles of reduction of silver ions in a 0.2% citric acid solution for 6-12 hours with temperature heating from 70 to 80 ° C but without reducing the temperature heating between cycles to a temperature of 20-25 ° C in a strip in the wavelength band in the region of 400-425 nm;

3 - spectral characteristic of a 1.5% aqueous solution of silver nanostructured particles after six cycles of reduction of silver ions in a 0.2% solution of citric acid for 6-12 hours with temperature heating from 70 to 80 ° C and with a decrease in temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

FIG. 5 - The dependence of light absorption of 2.0% (mass) of an aqueous solution of silver nanostructured particles on the initial concentration of 0.0508% (mass) (option 5) in the wavelength band in the region of 400-425 nm:

1 - spectral characteristic of a 2.0% aqueous solution of nanostructured silver particles (prototype) in the wavelength band in the region of 400-425 nm;

2 - spectral characteristic of the remaining part of silver nanostructured particles in their 2.0% aqueous solution after six cycles of reduction of silver ions in a 0.25% citric acid solution for 6-12 hours with temperature heating from 70 to 80 ° C but without reducing the temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

3 - spectral characteristic of a 1.5% aqueous solution of silver nanostructured particles after six cycles of reduction of silver ions in a 0.25% solution of citric acid for 6-12 hours with temperature heating from 70 to 80 ° C and with a decrease in temperature heating between cycles to a temperature of 20-25 ° C in the wavelength band in the region of 400-425 nm;

FIG. 6 - Dependence of light absorption of 0.37-2.0% aqueous solution of silver ions on the initial concentration of silver nanostructured particles of 0.0508% (mass) in the wavelength band in the region of 465-490 nm:

1 - spectral characteristic of a 0.37% aqueous solution of silver ions in the wavelength band in the region of 465-490 nm;

2 - spectral characteristic of a 0.5% aqueous solution of silver ions in the wavelength band in the region of 465-490 nm;

3 - spectral characteristic of a 1.0% aqueous solution of silver ions in the wavelength band in the region of 465-490 nm;

4 - spectral characteristic of a 1.5% aqueous solution of silver ions in the wavelength band in the region of 465-490 nm;

5 - spectral characteristic of a 2.0% aqueous solution of silver ions in the wavelength band in the region of 465-490 nm.

As a result of a study of the total silver content in ionic and metallic form in a monodisperse colloidal aqueous solution of silver ions using inductively coupled plasma atomic emission spectrometry (ICP-AES), using an ICAP-6500 Duo plasma device (England), software ITEVA, it was found that:

- in the prepared according to option 1: 0.37% monodisperse colloidal aqueous solution of silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass), the total amount of silver is 1.75 mg / l;

- in the prepared according to option 2: 0.5% monodisperse colloidal aqueous solution of silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass), the total amount of silver is 2.96 mg / l;

- in the prepared according to option 3: 1.0% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass), the total amount of silver is 5.64 mg / l;

- in the prepared according to option 4: 1.5% monodisperse colloidal aqueous solution of silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass), the total amount of silver is 8.52 mg / l;

- in the prepared according to option 5: 2.0% monodisperse colloidal aqueous solution of silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass), the total amount of silver is 10, 1 mg / l, which does not contradict the results of a qualitative control of the presence of ions silver in similar versions by monitoring the assessment of the reliability of the content of silver ions in a monodisperse colloidal aqueous solution using a two-beam UV and visible spectrophotometer HELIOS ALPHA (Great Britain) with m the microprocessor control system and confirms the reliability of their production using the claimed variants of the method for producing a monodisperse colloidal aqueous solution of silver ions.

Thus, as a result of studies on the development and creation of a monodisperse colloidal aqueous solution of silver ions (options) with antimicrobial and antitoxic effects, we obtained documentary evidence describing the control process at the nanoscale (spectral characteristics, etc.) of nanotechnological processes (formed in water a solution of a binary mixture of nanostructured silver particles and silver ions in the process of reduction of silver ions in an aqueous dispersion) into the technological process e their production.

To confirm the biological effectiveness of the inventive monodisperse colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects, and the method for its preparation, we conducted laboratory tests of samples of aqueous solutions of silver ions at an in vitro level with the determination of their antimicrobial and antitoxic activity in comparison with the known prototype nanostructured particles silver in aqueous dispersion.

The antimicrobial activity of a monodisperse colloidal aqueous solution of silver ions was studied for 5 concentrations of silver nanostructured particles in an aqueous dispersion of a composition with a concentration of 0.37%, 0.5% 1.0%, 1.5% 2.0% of the initial concentration of nanostructured particles silver 0.0508% (mass) by agar diffusion method (wells) in accordance with GP XII (Diffusion method in agar OFS 42-0068-07) and the Microbiology Workshop edited by A.I. Netrusova. - M.: Publishing Center "Academy", 2005. - 606 p.

The method is based on the ability of antibiotic substances to diffuse into agarized media and form zones in which test organisms do not grow. The size of the zone of lack of growth indicates the degree of activity of this antibiotic substance in relation to the test organism.

Antimicrobial activity of the studied samples of the drugs was tested on Test cultures:

- gram-positive - Micrococcus flavus and spore Bacillus mycoides;

- gram-negative - Escherichia coli 113/3;

- microscopic fungi - Aspergillus niger and Penicillium chrysogenum (collection of the Department of Microbiology, Moscow State University named after MV Lomonosov).

Bacteria were grown on MPA, micromycetes were grown on Saburo medium of the following composition (g / l): 40.0; peptone - 10.0; agar - 20.0; chloramphenicol - 2.5%.

As a control, we used samples of nanostructured silver particles in an aqueous dispersion, made in accordance with Example 4 in the description of the invention (prototype) with a concentration of silver nanostructured particles from 0.37% to 2.0% of their initial concentration of 0.0508% ( masses):

- sample No. 1, C = 0.37%;

- sample No. 2, C = 0.50%;

- sample No. 3, C = 1.0%;

- sample No. 4, C = 1.5%;

- sample No. 5, C = 2.0%.

As experimental samples of silver ions in one dispersion were tested, made in accordance with Example No. 5 given in the description of the invention with a concentration of silver nanostructured particles from 0.37% to 2.0% of their initial concentration of 0.0508% (mass):

- sample No. 1, C = 0.37%;

- sample No. 2, C = 0.50%;

- sample No. 3, C = 1.0%;

- sample No. 4, C = 1.5%;

- sample No. 5, C = 2.0%.

The manufacture of holes in agar was performed as follows.

Test cultures preliminarily grown on shoals in agar media were washed from the shoals with saline to obtain a bacterial suspension with 1 × 10 ⁹ cells (OD = 0.9 light filter No. 6, cell 10) or according to the industry standard turbidity sample (TCO turbidity) developed by the State Research Institute for Standardization and Control of Medical Biological Products named after L.A. Tarasevich, Moscow.

The suspension was added to MPA (for bacterial cultures) or Saburo medium (for micromycetes) and poured into 20 ml Petri dishes.

Wells with a diameter of 7 mm were made using a sterile metal drill (pretreated with 70% alcohol and sealed in a burner flame) in a frozen agar medium with a test culture.

Methodology for determining the spectrum of action of samples of silver ions in an aqueous dispersion

900 μl of each of the test samples was added to test culture agar wells prepared according to the method described above. To study the spectrum of antimicrobial action, 2 series of samples (prototype and experimental) were used in 5 concentrations each and in replicates of at least 3. As control, sterile distilled water (volume 900 μl), also inoculated into the well, was used. After daily incubation at temperatures optimal for crop growth (37 ° C for bacteria Micrococcus flavus and Bacillus mycoides, 42 ° C for E. coli, and for Aspergillus niger and Penicillium chrysogenum fungi - 28 ° C) and for the next 6 days conducted measurements of the sizes of diameters of inhibition of growth of test cultures relative to the wells with the studied samples.

The antimicrobial effect of the test samples was compared with the activity of antibiotic preparations. Indicator paper discs saturated with antibiotics were used. For gram-positive bacteria (Micrococcus flavus and Bacillus mycoides), disks with ristomycin (25 μg), an antibiotic belonging to the group of polycyclic glycopeptides, whose action is to suppress the synthesis of nucleic acids, were used. Ristomycin is widely used to treat infections caused by gram-positive bacteria. For gram-negative (Escherichia coli 113/3) discs were used with chloramphenicol (30 μg), which belongs to the family of aromatic antibiotics. Levomycetin (chloramphenicol) inhibits protein synthesis, has a wide spectrum of bactericidal action, but does not inhibit the growth and development of micromycetes. This antibiotic is widely used in medical practice. For micromycetes (Aspergillus niger and Penicillium chrysogenum), disks with nystatin (15 μg) belonging to the family of polyene antibiotics that have a fungicidal effect were used.

According to the test results, the growth inhibition values of Penicillium chrysogenum, Bacillus mycoides, Escherichia coli 113/3, Aspergillus niger and Penicillium chrysogenum on an agarized medium with the studied samples (1-5) of silver ions in an aqueous dispersion (experiment series 3) and nanostructured aqueous solution composition were established silver particles and ions (experiment series 1, prototype) for 1-6 days, depending on the concentration in the samples of nanostructured silver particles equal to 0.37-2.0% of their initial concentration of 0.0508% (mass) in comparison with the prototype and antibiotic control Ristomycin, Chloramphenicol and Nystatin.

The test results are presented in tables 4-8.

As a result of testing the developed variants of silver ions in an aqueous dispersion and the known composition of unstabilized nanostructured silver particles and silver ions in an aqueous dispersion (prototype) according to the above methodology for determining the spectrum of the studied variants with a concentration from 0.37% to 2.0% of their initial concentrations equal to 0.0508% (mass) by agar diffusion (wells), it was found that almost all of the tested 5 concentrations of the inventive monodisperse colloidal aqueous solution of silver ions in their antibacterial The serial and fungicidal activity significantly exceed the antibacterial and fungicidal activity of the prototype and the activity of all control values of the studied antibiotics over the entire 6 days of observation.

It should be noted that the advantage of the activity of the inventive monodisperse colloidal aqueous solution of silver ions (experiment series 3) over the activity of the prototype (experiment series 1) and known antibiotics is objectively confirmed by the inhibition values of test cultures on an agar medium from the 1st to the 6th day observations inclusive.

So, it was found that in the first 3 days all concentrations (from 0.37% to 2.0%) of the inventive monodisperse colloidal aqueous solution of silver ions inhibit the growth of all the studied test organisms at the level of inhibition of the known antibiotics used. Starting from 4 days to the end of the test (6 days), all 5 test samples in terms of the activity of inhibiting test cultures do not reduce the level of effectiveness of the concentrations of drugs established in the first 3 days, while the applied prototype composition is significantly inferior in its the activity of the claimed monodisperse colloidal aqueous solution of silver ions, and the used antibiotics Nystatin for inhibiting Penicillium chrysogenum, Levomycetin for inhibiting E. coli 113/3 and Ristomycin for inhibiting Micrococcus flavus completely lost antimicrobial activity, as a result of which secondary growth of test cultures occurs on control Petri dishes with these options.

Thus, the experimentally established facts of the antibacterial and fungicidal activity of samples of a monodisperse colloidal aqueous solution of silver ions (1-5), studied under laboratory conditions on test cultures in an agar medium, unconditionally confirm the technical result of the advantages of the inventive monodisperse colloidal aqueous solution of silver ions having an antimicrobial the action and method of its preparation before the known composition of unstabilized nanostructured particles of silver and silver ions and in an aqueous dispersion selected as a prototype.

Test results of the antitoxic effect of monodisperse colloidal aqueous solution of silver ions

The effectiveness of the antitoxic effect (catalytic properties) of a monodisperse colloidal aqueous solution of silver ions was studied in the process of modeling air purification of volatile carbohydrates (test air pollutants: acetone and carbon dioxide vapors) dissolved in air in an isolated sealed box according to the developed method using a special laboratory control and measurement instrument complex [patent for the invention of the Russian Federation No. 2400286 of March 13, 2009, publ. 09/27/2010 Bull. Number 27. Filtering material for purification of liquid and gaseous substances and the method of its production] when filtering air pollutants with a porous carrier (cartridge) of an air filter with an active catalyst preliminarily deposited on its surface in the form of a monodisperse colloidal aqueous solution of silver ions with a given concentration.

Modification of the filter material with silver ions in practice is carried out using the proposed method.

In the experimental development of options for filter material used:

- as a porous base - a synthetic non-woven hydrophobic roll material [GOST R 51251-99, CENEN 779-1993; CENEN 1822-1998] brand FM - 3X, h = 15 mm, cleaning class G3, fiber type polyester;

- as an active catalyst:

- option 1. 2% aqueous solution of a binary colloidal mixture of nanostructured silver particles and silver ions from the initial concentration of nanostructured silver particles of 0.0508% (mass) obtained in example 1 (prototype);

- option 2. 0.37% aqueous solution of a monodisperse colloidal aqueous solution of silver ions obtained in example 2, from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 3. 2% aqueous solution of monodisperse colloidal aqueous solution of silver ions obtained in example 2, from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 4. 2% aqueous solution of monodisperse colloidal aqueous solution of silver ions obtained in example 3, from the initial concentration of nanostructured silver particles of 0.0508% (mass);

- option 5. 2% aqueous solution of monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass), stabilized with 0.2% aqueous solutions of PVA grade 11/2, 16/1, premium or first grade, GOST 10779-78 in an amount of 2.0% by weight of the binary mixture obtained in example 4.

Modification of the filter material with nanostructured silver particles and silver ions was carried out according to the claimed invention.

Variants of examples of a specific implementation of the method of obtaining filter material:

Example 1 (prototype). Prepare 1 l of an aqueous solution of silver nanoparticles with a concentration of 2% aqueous solution of a binary colloidal mixture of nanostructured silver particles and silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass). To apply a binary mixture of silver nanostructured particles of silver ions (catalyst) onto a porous media of filtering material, a plate made of synthetic nonwoven fabric of the FM - 3X grade, cleaning class G3, h = 15 mm, size 330 × 330 mm at a temperature of 20-25 ° C is placed into the prepared aqueous solution and incubated at this temperature for 1 hour. Next, the plate is dried at 40-50 ° C for 3-4 hours. Option 1 of the cartridge with the catalyst deposited on its surface is ready for use.

Example 2. In accordance with the description of the application example 5, 1 liter of 0.37% monodisperse colloidal aqueous solution of silver ions is prepared from the initial concentration of silver nanostructured particles of 0.0508% (mass).

In each prepared solution, one plate of FM-3X brand non-woven material is placed, cleaning class G3, h = 15 mm, size 330 × 330 mm, and the porous base of the material is impregnated for 5-10 minutes at a temperature of plus 20-25 ° C, then dried at a temperature of plus 60-70 ° C for 3-4 hours to establish their constant weight. Options 2, 3 cartridges with a catalyst deposited on their surface are ready for use.

Example 3. In accordance with the description in the application example 5, 1 l of a 2% monodisperse colloidal aqueous solution of silver ions is prepared from the initial concentration of silver nanostructured particles of 0.0508% (mass). A plate of non-woven material of the FM-3X brand, cleaning class G3, h = 15 mm, size 330 × 330 mm, is placed in the prepared solution and the porous base of the material is impregnated for 5-10 minutes at a temperature of plus 20-25 ° C, then dried at temperature plus 60-70 ° C for 3-4 hours until their constant weight is established. Options 4 of the cartridge with a catalyst deposited on its surface are ready for use.

Example 4. In accordance with the description of the application example 5, prepare 1 l of a 2% monodisperse colloidal aqueous solution of silver ions from the initial concentration of silver nanostructured particles of 0.0508% (mass), stabilized with 0.2% aqueous solutions of PVA grade 11/2, 16/1, premium or first grade, GOST 10779-78 in an amount of 2.0% by weight of the binary mixture. Further technological operations are carried out analogously to example 2 or 3.

The filtration efficiency or the filtering ability of the manufactured versions of the filtering material for air purification from test air pollutants was carried out by the example of air purification from a mixture of OHS acetone and carbon dioxide in a special laboratory-measuring complex.

The complex consists of the following parts:

- sealed box with a volume of 200 l, made of stainless steel;

- a computer that records and displays sensor signals in real time.

In the box there is an electric heater for evaporating a liquid test substance.

In the side wall of the box there are fittings for introducing gaseous test contaminants into the box and connecting an external gas sensor.

To measure the concentration of volatile carbohydrates during the tests, stationary gas analyzers of the IGS-98 series, manufactured by FSUE NPP DELTA, are used. The gas sensors required for testing are connected to the data recording system of the control and measuring complex.

To record the concentration of carbon dioxide, an external optical infrared gas sensor IGS-016-00 was used, which has a built-in microprocessor for recirculating air from the box. The measurement range of the relative concentration of carbon dioxide is 0-1%. Sensor accuracy ± 0.1%.

To record the concentration of acetone vapor, a gas thermocatalytic hydrocarbon sensor was used.

Previously, the thermocatalytic hydrocarbon sensor was calibrated in a test box using VHF acetone vapor (mV / mg). Sensor accuracy ± 10%.

All gas analyzers are certified in the Russian Federation and passed state verification.

Outside the box, there is a power supply and signal processing unit for gas sensors and an electronic unit for signal processing and communication with a computer.

As an experimental sample of an air purifier, we used a modified commercially available case with a fan from the Aero Barrier photocatalytic air purifier, model AP270FC.

In the modified Aero Barrier air cleaner housing, sequentially manufactured versions of the filter material (see examples 1-4) were installed as an air cartridge to be tested. An air cleaner with an installed cartridge option was placed in the box.

The air purifier was turned on, the operation mode of its fan was set AIR MEDIA (0 ~ 150 m ³ / h), after which the box was closed. All other equipment turned on.

After a while (~ 10 min.), A binary mixture of test contaminants was injected into the box through an air nozzle: carbon dioxide and OHS acetone.

During the experiment, the destruction of pollutants occurs under normal atmospheric conditions when blowing the gas mixture through a nanocatalytic porous membrane (cartridge) with an air filter fan.

Within ~ 1.5 ... 3.5 hours, the sensor readings are recorded and automatically recorded in the computer memory from the beginning of the inclusion of the filter for dropping the concentration of test contaminant in the box, in time. Registration and recording of sensor readings is performed for a specified time with a measurement accuracy of 1 s. In this case, a decrease in the concentration level of the test pollutant is recorded during the deep destruction of the pollutant into the simplest components of the molecule: (C, H ₂ , O ₂ ).

The rate of destruction of volatile hydrocarbons is represented by a change in the relative concentration in time:% / hour, and is converted into absolute values, mg / hour.

Thus, when testing manufactured versions of the filtering material for air purification, the operating efficiency of each version of the manufactured cartridge for the destruction of test pollutants over time was obtained.

The results of evaluating the effectiveness of air purification by an air purifier from test pollutants, in particular a mixture of carbon dioxide and VOC acetone vapors, with test cartridges made using catalysts based on the inventive monodisperse colloidal aqueous solution of silver ions and nanostructured silver particles (prototype) are shown in table 9.

As a result of laboratory tests of the manufactured filter material options for air purification, the following was established.

During the operation of the air purifier for all variants of the filter material obtained in accordance with the inventive method for their preparation, during a given time of air filtration, there is a significant decrease in the concentration of carbon dioxide test pollutants and VOC acetone vapors from the concentration originally created in the box, while increasing the level the destruction of carbon dioxide on cartridges with the inventive catalyst in comparison with the destruction of carbon dioxide on a cartridge with a known catalyst from nanostructured silver particles.

During the work of experimental samples of the air purifier, there is a significant decrease in the concentration of hydrocarbons in acetone from the concentration originally created in the chamber with a destruction rate of 8.2-18.5 mg / h, and there is also a significant destruction of carbon dioxide at speeds of 290-330 mg / h, ~ initial concentrations of 0.25% CO ₂ (all variants tested filter material its geometrical dimensions of 330 × 330 mm) that exceeds the level of purification, for example the existing fleet of air cleaners fotokataliti eskogo type of acetone, and is unique for carbon dioxide:

MIDEA, model KJ180-T, made in China;

DAIKIN, model MC704VM, made in Japan;

BORK, model APRJH1515SI, made in Germany;

VITEK, model VT-1775, production Austria;

NHW, model 968, made in China.

Moreover, the destruction of each pollutant occurs according to a scheme identical to the destruction of a mono pollutant, that is, the efficiency of the filter material depends little on the amount of pollutants in the air without the influence of the destruction of one substance on another.

The tests showed the high efficiency of the catalytic properties of a monodisperse colloidal aqueous solution of silver ions stabilized on the porous support of the air filter cartridge of the claimed method.

Thus, on the basis of our own research results and comparing them with the known results of the antimicrobial and antitoxic activity of known compositions based on nanostructured silver particles and silver ions in aqueous dispersions, we can conclude that today among the developed innovative nano formulations the most promising for protection against modern infectious environmental and human pollutants and to prevent the development of its diseases are p zrabotanny authors secure monodisperse colloidal aqueous solution of silver ions having antibacterial and antitoxic effect. In terms of chemical composition, the developed form of the composition is a monodisperse aqueous homogeneous colloidal liquid of silver ions, containing a solution of silver ions (cations) in an aqueous dispersion, a reducing agent, if necessary a stabilizer, distilled or deionized water.

Possessing both catalytic and disinfecting (bactericidal, fungicidal and virucidal) actions, the use of the developed monodisperse colloidal solution of silver ions in an aqueous dispersion creates a real barrier to prevent contamination of the surfaces of objects and the surrounding air from toxic impurities and microbiological pollution, thereby protecting the human body from pathogenic chemically and biologically hazardous contaminants.

As follows from the above examples, the present invention allows to obtain environmentally friendly stable monodisperse colloidal aqueous solutions of silver ions having antimicrobial and antitoxic effects with a given concentration of silver ions in an aqueous dispersion, having both antimicrobial and antitoxic effects.

Thus, the invention ensures the achievement of a technical result.

The present invention can be used to obtain monodisperse colloidal aqueous solutions of silver ions with antimicrobial and antitoxic effects both without and in the presence of polymer stabilizers with antimicrobial and antitoxic effects, which can serve as effective catalysts, as antimicrobial and antitoxic agents in the manufacture of filter devices for the comprehensive purification of drinking water and air, as well as for the production of various forms of medical preparations production of composite and metal-polymer materials to create technological methods and tools related to materials science, chemistry, physics, biology, mechanics, and many other fields of science and technology.

Claims (16)

1. Monodispersed colloidal aqueous solution of silver ions with antimicrobial and antitoxic effects, including active metals in the form of citrates, a metal ion reducing agent in an aqueous dispersion, distilled or deionized water, characterized in that it contains a monodispersed colloidal solution of silver ions in water dispersion, a reducing agent of silver ions is selected from the group of organic food acids, including citric acid or ascorbic acid, which will complement A silver ion stabilizer was introduced as an aqueous solution of a hydroxyl-containing polymer, including either polyvinyl alcohol, or chitin, or chitosan, or cellulose, or amylose, or 2-hydroxyethyl methacrylate, or an aqueous solution of an acrylic polymer, or a copolymer, or a binary mixture of a hydroxyl-containing polymer and an aqueous a solution of an acrylic polymer or copolymer and an aqueous solution of a hydrophobizing agent based on organosilicon compounds with a pH of ≤8.0 in the form of siloxanes or silicates in an aqueous dispersion. 2. Monodisperse colloidal aqueous solution of silver ions having the antimicrobial and antitoxic effect according to claim 1, characterized in that it contains silver ions and a silver ion reductant in an aqueous dispersion in the following ratio of components, wt. silver ions 0,00026-0,00185 silver ion reducer 0.05-025 water the rest is up to 100 3. A monodisperse colloidal aqueous solution of silver ions having the antimicrobial and antitoxic effect according to claim 1, characterized in that it contains silver ions, a reducing agent of silver ions in an aqueous dispersion, contains an aqueous solution of a hydroxyl-containing polymer, or an aqueous solution of an acrylic polymer, or copolymer, or a binary mixture of a hydroxyl-containing polymer and an aqueous solution of an acrylic polymer or a copolymer and an aqueous solution of a water-repellent agent based on organosilicon compounds with pH≤8.0 and the following ratio of components%, mass .: silver ions 0,00026-0,00185 silver ion reducer 0.05-0.25 0.1-0.3% (mass.) An aqueous solution of hydroxyl-containing polymer, or an aqueous solution of acrylic polymers, or copolymers, or a binary mixture of 0.1-0.3% (mass.) hydroxyl-containing polymer and 0.1-0.3% (mass.), or an aqueous solution of acrylic polymers, or copolymers with a ratio of 1: 1 mass.,% 1.5-2.5 0.1-0.4% (mass.) Aqueous solution of organosilicon compounds 0.5-1.5 water the rest is up to 100 4. A method of producing a monodisperse colloidal aqueous solution of silver ions, comprising the step of producing a polydisperse colloidal mixture of nanostructured silver particles in an aqueous dispersion and direct interaction of the obtained solution of nanostructured silver particles in water with a silver ion reductant to form a monodisperse colloidal aqueous solution of silver ions, characterized in that obtaining a monodisperse colloidal aqueous solution of silver ions is carried out in 3 stages, while in the first stage receive reverse micellar solution of silver nanostructured particles with a concentration of silver nanostructured particles of 0.0399-0.0508% (mass) based on the surfactant sodium bis-2-ethylhexyl sulfosuccinate in a non-polar solvent, by reducing silver ions in a reverse micelle system, including preparation reverse micellar dispersion of a reducing agent from the group of flavonoids with a molar concentration of 6.6⋅10 ^-4 to 3.3⋅10 ^-3 M in a non-polar solvent from the group of saturated hydrocarbons: n-hexane, or n-heptane, or n-octane, or n - decane, or cyclohexane, or isooctane, a surfactant of sodium bis-2-ethylhexyl sulfosuccinate with a molar concentration of 0.09 to 0.1 M and the introduction of silver ions in it in the form of an aqueous solution of Ag metal salt, with a molar concentration of 3 , 7⋅10 ^-2 to 5.0⋅10 ^-2 M, while the preparation of a reverse micellar dispersion of a reducing agent of nanostructured silver particles is carried out with stirring of a reducing agent and a surfactant in a non-polar solvent at a temperature of 60-80 ° C under reflux for 0 5-1.0 hours followed by by cooling the prepared mixture to a temperature of 20-25 ° C and filtering, the introduction of silver ions into it is carried out in the form of an aqueous solution of silver ammonia salt, at the second stage, an initial concentrate of an aqueous dispersion of silver nanostructured particles with a concentration of silver nanostructured particles is obtained, 0.0399-0, 0508% (mass.), For which distilliro is introduced into a non-micellar solution of silver nanostructured particles based on the surfactant bis-2-ethylhexyl sulfosuccinate sodium obtained in the first stage in a non-polar solvent bath or dionized water, mix, sediment and separate the primary aqueous mixture of silver nanostructured particles from a non-polar solvent, the separated primary aqueous mixture of silver nanostructured particles with an excess of non-polar solvent and surfactant in it is heated to a temperature of 50-60 ° C for 1 -2 hours until complete separation of the excess of non-polar solvent, then cooled to a temperature of 20-25 ° C and maintained at this temperature for 24 hours until complete separation of the excess surface-active of substances from the aqueous initial mixture, the third step is prepared monodisperse colloidal aqueous solution of silver ions to form its working solutions then prepared for the working solution an aqueous dispersion of silver particle nanostructure in concentrations of 0,37-2,0 wt%. from the initial concentration of a colloidal aqueous solution of nanostructured silver particles 0.0399-0.0508% (mass.) and heated to a temperature of 70-80 ° C, then 0.05-0.25%, respectively, is introduced into the corresponding prepared working solution of the aqueous dispersion mass a reducing agent of silver ions from the group of organic food acids and is cooled to 20-25 ° C, after which the resulting binary mixture is stirred for 5-10 min until opalescence appears in it, after which the initially cooled reaction mixture is reheated to 70-80 ° C, kept at this temperature for 1-2 hours and re-cooled to 20-25 ° C until the disappearance of opalescence and the formation of silver ions in the aqueous dispersion, while the number of repeated cycles of rise and decrease in temperature of the reaction mixture at a given temperature-time the specified interval depends on the ratio of the concentrations of the working solutions of the aqueous dispersion of silver nanostructured particles and the silver ion reductant in the aqueous dispersion and for the given mass concentrations of silver ions and silver ion reductant, respectively (%) mass .: 0,00026-0,00034: 0.05: 1 cycle; 0,00035-0,00046: 0.10: 2 cycles; 0,00069-0,00092: 0.15: 4 cycles; 0.00103-0.00139: 0.20: 6 cycles; 0.00138-0.00185: 0.25: 6 cycles. 5. The method according to p. 4, characterized in that when the introduction of silver ions, the concentration of an aqueous solution of silver ammonia salt and the concentration of surfactant is selected depending on the degree of hydration, varying from 5.0 to 8.0. 6. The method according to p. 4, characterized in that before settling in the two-phase system, distilled or deionized water is added with stirring in a 1: 1 ratio, the resulting mixture is transferred to a separation column to obtain a layer of a binary colloidal mixture of nanostructured silver particles and silver ions in aqueous dispersion, which is poured from the bottom of the column into a separate drive. 7. The method according to p. 4, characterized in that to obtain a monodisperse colloidal aqueous solution of silver ions in the stabilizer, the resulting colloidal mixture of an aqueous dispersion of silver ions is reheated to 50-60 ° C and 0.1-0.3% aqueous a solution of hydroxyl-containing polymer in an amount of 1.5-2.5% of the mass. by weight of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C. 8. The method according to p. 4, characterized in that in the prepared working solution of a monodisperse colloidal aqueous solution of silver ions with a content of 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% of the mass. from the mass of the aqueous mixture add an additional 0.1-0.3% solution of acrylic polymer in an amount of 1.5-2.5% of the mass. by weight of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of the reaction dispersion medium and cooled to a temperature of 20-25 ° C. 9. The method according to p. 4, characterized in that in the prepared working solution of a monodisperse colloidal mixture of silver ions in an aqueous dispersion containing 0.1-0.3% aqueous solution of hydroxyl-containing polymer in an amount of 1.5-2.5% mass and 0.1-0.3% solution of acrylic polymer in an amount of 1.5-2.5% of the mass. from the mass of the aqueous mixture additionally add 0.5-1.5% of the mass. organosilicon compounds by weight of the aqueous mixture, then the mixture is stirred for 20-30 minutes until the formation of a reaction dispersion medium and cooled to a temperature of 20-25 ° C.

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