Method of producing concentrates of zerovalent metal dispersions with antiseptic properties

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing concentrates of nanodispersions of zerovalent metals such as silver, gold, copper, palladium, platinum and mercury, which have antiseptic properties. Said method involves mixing a solution of a soluble metal salt in a solvent with ammonia to obtain a complex which is then mixed with alkalnolamine to form a solution. The obtained solution is mixed with a solution of a polymer stabiliser to obtain a stabilised metal cation which is then reduced by adding to the solution an organic or inorganic reducing agent to form a stable dispersion of metal nanoparticles. The disclosed method is realised at a defined ratio of components for 10-60 minutes in an air atmosphere at temperature of up to 100°C.

EFFECT: invention is aimed at obtaining metal dispersions with high sedimentation and chemical resistance and high antiseptic power, which are compatible with a physiological NaCl solution; the method also cuts duration of synthesis and considerably simplifies the process, increases efficiency and complete conversion of cationic metal into a zerovalent metal.

38 cl, 3 tbl, 104 ex

 

The invention relates to methods for producing concentrates of nanodisperse (colloidal nanoparticle solutions) nonvalent metals IU0including possessing antiseptic (including biocidal, antimicrobial, antiviral and antifungal properties, and which can be used in various fields of technology, industry, cosmetics, household chemicals, food industry, water treatment as preservatives, various functional additives, antiseptics, as well as in medicine, veterinary medicine, in the pharmaceutical industry for the manufacture of gels, ointments, sprays, impregnations for napkins and the like, which are characterized by high antiseptic (bactericidal, virucidal, and fungicidal) efficacy, toxicity, sedimentation and chemical stability.

Known means, containing in its composition colloidal metals - silver, copper and gold, with bactericidal properties, including Silver, gold, copper - colloid complex / Colloidal Copper Gold & Silver Oligo" company NSP, USA [http://allfarm.ru/copper.html], positioned as anti-inflammatory and antibacterial agent for internal and external use alternative substitute for antibiotics. This silver blocks the multiplication of harmful bacteria, viruses and fungi. Gold and copper increase range of ant is bacterial action. Ingredients: 1 ml of ionized solution contains silver (silver) 0,0107 mg, copper (copper) 0,0225 mg, gold (gold) 0,0007 mg

However, the method of synthesis of this product the company is not described. To well-known disadvantages include the high price of this product, as well as the presence of dispersion, in accordance with the description of the product, ionized (cation) of silver.

In the known preparations of colloidal silver (colloid and protargol)has antiseptic properties, the stabilizer of fine particles of silver are protein polymers, casein and gelatin [Medmaravis. Medicinal product. Vol.2, New wave, M., 2000]. These drugs because of the presence in their structure of proteins volatile compounds have allergic effect and do not lend themselves to strict standards. The presence in their structure of significant quantities of cationic silver gives them a scorching action and incompatibility with saline solution (sodium chloride NaCl, 0.9 wt.%). Their only outlet, the only powders that before you use must be dissolved in aseptic demineralized water.

In addition, adding to the solutions of these drugs in distilled water absorption bands in the electronic spectra, which can be attributed to the plasma resonance of metallic silver nanoparticles in drug colloid and protargol (absorption maxima at 409 and 406 nm, respectively, 1, 2, table 2), disappear (figure 3, 4, table 2), indicating that the disappearance of particles nonvalence metal IU0and the transition nonvalent atoms of silver Ag0in cationic form Ag+(silver chloride AgCl and the like), with a subsequent transition of the silver salts to precipitate out of the volume of the drug.

Known for the preparation of nanoscale silver particles in aqueous solutions - Argovit (VITAR) (TU 9310-13-00008064-00), which is a complex of silver with medical polyvinylpyrrolidone ("Application of preparations of silver in medicine" - a Collection of papers on the materials of scientific-practical conference "New chemical systems and processes in medicine". edit Emmelia, Novosibirsk, 2004, 115 C.). The drug consists of a metallic silver nanoclusters stabilized poly-N-vinyl-pyrrolidone-2, obtained by chemical recovery of water-soluble silver salt, followed by drying to powder.

The resulting silver particles are according to the authors, the size of a few nanometers and as a consequence more active than poviargol, and aggregate stability.

Argovit comes in the form of a stable concentrated solution from which, by dilution with distilled water to prepare a diluted working solutions for the application. Appearance - concentrated Rast is the PR dark brown, diluted solution from brown to yellow color of varying intensity depending on the degree of dilution. According to the authors, diluted solutions sedimentation stable for at least 2 weeks.

However, the drug Argovit and its solutions in water adding saline solution (sodium chloride NaCl, 0.9 wt.%) after a short time fade, and at the bottom of vessel formation occurs in a light grey precipitate. This absorption band with a maximum at 407 nm, attributed to the plasma resonance of metallic silver nanoparticles (figure 5, table 2), lost (6, table 2). Thus revealed as part of Argovit the presence of cationic silver indicates incompatibility of the drug with saline solution (sodium chloride, 0.9 wt.%) and its high chemical activity. Also in this case the content of the dispersion of the metal nanoparticles is significantly reduced, which is manifested as a decrease in the scattering intensity passing through the solution of the laser beam (Tyndall Effect) - beam thinning and its intensity (visibility) drops significantly. In addition, the specific formulations of the compositions and the conditions of its preparation is unknown.

A method of obtaining nanostructured metal particles by metal ion reduction in two-phase system is Birmingham reverse micelles, comprising preparing oratorically dispersion of reducing agent based on the solution of surfactants in nonpolar solvent [EN 2147487, 20.04.2000].

The drawbacks of such dispersions and method of production thereof is that:

- the dimension of the particles in the patent is not defined, either directly or indirectly (including maxima of absorption bands in the electronic spectra, attributed to the plasma resonance of the nanoparticles of metal),

the method of obtaining is quite complex, multistage and costly, especially in the case of aqueous dispersions, so as to obtain a water dispersion of metal nanoparticles required additional surgery for their transfer to the aqueous phase (removal of the organic phase), which complicates and increases the cost of obtaining stable concentrated aqueous dispersions of nanoparticles,

the retrieval process requires a large set of reagents and organic solvents, requires a significant consumption of expensive reductant (which increases the cost of manufacturing metal nanoparticles),

the relatively low concentrations of metallic silver obtained aqueous dispersions (0,00324-0,0324 wt.%),

- the rate of formation of the nanoparticles in a two-phase system is relatively small (vsledstvii necessary diffusion of components through the phase boundary),

in the reactions the authorized system contains an excess of reducing agent and toxic components (including surfactant AOT),

- the presence of dispersion as a dispersion stabilizer a relatively large amount of surfactant in this case, anionic compounds AOT (partially miscible with water and forms a microemulsion) - leads to the optical inhomogeneity of aqueous solutions, as well as to the limited mixing them with different, especially non-aqueous systems,

- in addition, the compatibility of dispersions with different systems, drugs can largely be limited and also anionic nature of the used surfactant (AOT), which may form, for example, cationic compounds including cationic surfactants, insoluble compounds. In addition, many surfactants, including AOT are not authorized for use in food and medical products, which limits their use in these areas.

To obtain silver nanoparticles with improved characteristics known method based on the transfer of a soluble salt of silver in complex with ammonia [EN 2322327, 27.07.2007]. A method of obtaining a preparation of nanostructured metal particles, optionally with additional reducing agents include hydrazine, hydrogen, borohydride sodium, quercetin or stabilizers, for example polymers, by recovery of metal ions using as m is of careactor reverse micelles, comprising preparing oratorically solutions of surfactants in nonpolar solvent, the introduction of a solution of ions of a metal salt, mixing or solubilization ultrasonic treatment, guariroba, recovery of metal ions solvated electrons or reducing radicals generated by ionizing radiation on the prepared aqueous-organic dispersion. The synthesis of nanoparticles when this is carried out in reverse micellar system, the disadvantages described above.

Known use as a method of obtaining spherical particles of silver pre-formed complex of silver with alkanolamine with subsequent treatment of the solution of reducing agent [US 5389122, 14.02.1995].

The method comprises the following steps:

1. The interaction of the aqueous solution of silver salts with alkanolamines (monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine) forming a homogeneous solution of a complex of silver with alkanolamines.

2. The preparation of an aqueous solution of reducing agent is ascorbic acid.

3. Rapid mixing of both solutions at temperatures from 10°C to 100°C, leading to the formation of particles of metallic silver size from 0.77 μm to 20 μm.

4. Separation of particles of silver from a solution.

5. Flushing hour is CI silver.

6. Drying particles of silver.

The disadvantages of this method are the possibility of obtaining particles of metal only large (micron) in size with no sediment stability in a state of dispersion in solvents.

A known method of manufacture of the preparation of nanostructured metal particles by recovery of metal ions in combination with the heterocyclic compound with a chelating properties, which allows chemical industrial method to obtain nano-sized particles of metals using a wide variety of compounds as a source of reagents, allows to reduce the number of operations and to accelerate the process of preparing reaction mixtures, allows you to adjust the mode and conditions of the synthesis of [RU 2312741, 20.12.2007].

This method of synthesis of nanoparticles also has all the drawbacks of the methods of synthesis of metal nanoparticles in reverse micellar solutions of surfactants in nonpolar solvent. The salt concentration in the synthesis is in the range 0.1×10-3-10×10-3M (with molecular mass of silver nitrate 169,8 this corresponds to concentrations 0,0017-to 0.17 wt.%), that is significantly lower than possible in a single-phase system. Specifies that if exceeded, the salt concentration of 0.17 wt.% the output of the nanoparticles of the metal does not change significantly and increases neproizvol the nutrient consumption of metal.

As heterocyclic compounds with chelating properties used natural pigments and synthetic dyes - arylbenzofurans, coumarins, carotenoids, cyanine dyes, the introduction of which, according to the description of a process increases the yield of the nanoparticles. The latter, however, clearly indicates that the method of synthesis of nanoparticles conversion cationic metal deliberate incomplete and the resulting reaction mass contains metals in cationic form. Indeed, these heterocyclic compounds are inherently organic reductants medium strength. In addition, as follows from the description of the invention, in the reaction are formed of silver particles with a maximum absorption band of the plasma resonance in the electronic spectra at 426 nm or more, i.e. large enough.

Known bactericidal solution and method thereof, in which an aqueous solution of silver salts pre-treated with ammonia solution that enables the creation of highly effective microbicides with high biological activity against microorganisms, which keeps for a long time [RU 2341291, 20.12.2008].

Product description given on the website http://www.nanotech.ru/pages/about/ag_part.htm].

According to the site, drugs Agbion" produced by WiseDrive the resultant patent biochemical synthesis method in the form of colloidal solutions of silver nanoparticles, stable in the aqueous phase, in various organic solvents (dodecane, octane), as well as in solutions of mixed type, such as alcohol-water. Outwardly concentrates represent a clear liquid brown, its active component silver nanoparticles ranging in size from 3 to 16 nm, stable molecules of surface-active substances.

The silver nanoparticles (SNP) are supplied (JSC Concern "NANOINDUSTRY") in two ways:

Concentrate the colloidal solution in an organic solvent "Agbion-1 (TU 2499-002-44471019-2006);

Concentrate the colloidal solution in water - "Agbion-2 (TU 2499-003-44471019-2006).

Shelf life means 2 years, working solutions 14 days.

When diluted with hexane, the product Agbion-1 (TU 2499-002-44471019-2006) detects in the electron spectrum band with maximum absorption at 430 nm that can be attributed to the plasma resonance of the silver particles (Fig.7, table 2). The magnitude of the wavelength of 430 nm clearly indicates relatively large sizes of the silver nanoparticles.

When diluted with water, the product Agbion-2 (TU 2499-003-44471019-2006) detects in the electron spectrum band with a maximum absorption at 410 nm that can be attributed to the plasma resonance of the silver particles (Fig, table 2). Adding to the aqueous solution of the product Agbion-2 saline solution (sodium chloride NaCl, 0.9 wt.%) var is rsia after a short time becomes colourless and at the bottom of vessel formation occurs in a light grey precipitate. This absorption band with a maximum at 410 nm, attributed to the plasma resonance of metallic silver nanoparticles (Fig, table 2), disappears (figure 9, table 2). Thus revealed the incompatibility of the drug, synthesized by the back-micellar technology, with saline solution (sodium chloride, 0.9 wt.%), indicates the presence in the composition of the product Agbion-2 cationic silver, therefore, and its high chemical activity. This is also evidenced by the shelf life of working solutions specified by the manufacturer, only 14 days.

Thus, this method of synthesis of nanoparticles also has all the drawbacks of the methods of synthesis of metal nanoparticles in reverse micellar solutions of surfactants in nonpolar solvent.

The closest analogue of the claimed invention is a method of obtaining water-soluble bactericidal composition containing fine metal silver, stabilized by a protective polymer, by restoring ionic silver in aqueous solutions when heated, followed by drying. Recovery of ionic silver are in the atmosphere of inert gas in the interaction of 0.025-29,73 wt.% the silver nitrate solution with 5.0-38,6 wt.% aqueous solution of ethyl alcohol containing 0,065-of 11.0 wt.% poly-N-wine is pyrrolidone-2, when this reaction is carried out in darkness, heated to 65-75°C (EN 2088234, 27.08.1997).

The disadvantages of the method of obtaining the drug is that the interactions are in the dark and in the atmosphere of inert gas, which complicates the process. However, changing the reaction conditions - changes in the concentration of reducing agent (ethyl alcohol) and the reaction temperature may be accompanied by increased loss of silver due to the reaction of a "silver mirror".

The method of obtaining this means time-consuming and requires much energy, because the production technology involves spray drying the resulting dispersion and storing it in the form of a soluble powder.

The present invention allows to use the advantages of both methods obtain nanodisperse metals (phase - in solutions, and two-phase - in reverse micellar systems), excluding their main weaknesses.

The synthesis of the metal nanoparticles is carried out in a solvent using a covering cations of the metal molecules that hold the metal atoms in the synthesis process and in the resulting dispersion from aggregation and oxidation, due to this reduction in synthesis time and a significant simplification of the process.

A method of obtaining a concentrate of nanodisperse (metal colloidal solution of nanoca the TIC metal) consists in mixing a solution of a soluble metal salt in a solvent with ammonia to produce complex compounds, then mixing the obtained complex compounds with alkanolamines, then mixing the resulting solution with a solution of a polymeric stabilizer with obtaining stable cation metal, recovering the stabilized metal cation is added to the solution of organic or inorganic reducing agent followed by the formation of stable dispersion of nanoparticles of metal. If necessary, allocate stabilized metal nanoparticles from a solution in dry form (in a known way, including Visaginas in herstorical, spray or other drying and the like).

When this unexpectedly discovered that the incorporation in the salt solution of the metal first with ammonia and then alkanolamine in these quantities before the introduction of the polymeric stabilizer and subsequent conduct of reduction reaction leads to the formation of particles recovered (nonvalence M0) metal with high sedimentation and chemical resistance and high antiseptic ability.

The process of chemical recovery of metal cations is thus in a homogeneous single-phase system in solution, in the presence of a polymeric stabilizer dispersions, in particular well-known non-toxic and biocompatible polymer, such as medical low and medium molecular P Is P (or other synthetic or biopolymer, approved for use in medical, pharmaceutical or food-processing purposes), used as an external stabilizer.

The content of components in the reaction mixture according to the invention is in the following intervals (wt.%):

- Soluble salt of the metal (metal) 0,013-2,5,

- Ammonia 0,028-1,67,

- Alkanolamine 0,196 is 5.54,

Polymer stabilizer of 0.4 to 20.0,

Restorer of 0.07-60,

- Solvent to 100 wt.%.

The solvent is used, any suitable solvent, dissolving all of the components of the reaction mixture, including water, ethanol and isopropyl alcohol, glycerin, acetone, dimethylsulfoxide, ethylene glycol, formamide, chloroform, aqueous solutions of organic solvents, etc

As metals can be used in a variety of metals that form stable complexes with ammonia and alkanolamine, including precious metals (silver, gold, palladium, platinum), as well as copper, mercury, zinc, etc.

As a source of cations of the metal used any soluble in the selected synthesis solvent Sol of metal, including the nitrate, acetate, sulfate, chloride of the metal, or hydrochloric acid.

As alkanolamine used a compound containing in its structure at least one hydroxyl and one amino group, divided into about what transto,

for example, methylene groups (at least 2), in particular, the General formula (1):

where R=CH2-or-CH2CH2-or-CH2-CH-CH3;

Y=1-3;

x=3-y;

z=0,1,

including the invention is illustrated by particular examples of such alkanolamines:

the compound of General formula (1):

where R=CH2CH2-;y=1;x=2; z=0;Ethanolamine, EA
R=-CH2CH2-;y=2;x=1; z=0;Diethanolamin, deja
R=-CH2CH2-;y=3;x=0; z=0;Triethanolamine, tea

R=-CH2-CH-CH3,y=2;x=1, z=0,Diisopropanolamine, the DEEP
R=-CH2-;y=3;x=2; z=1;Tris-(oxymethyl)-aminomethane, TRIS

As an external polymeric stabilizer is, in addition to PVP, can also be used and other suitable known as dispersion stabilizers (solubilization, protective colloids) synthetic or natural polymers, such as various polyvinyl alcohols (PVA) and derivatives thereof (including polyvinylbutyral PVB, polyvinylacetal PVS), gelatin VC, cellulose derivatives (methylcellulose MC, hydroxypropylcellulose, carboxymethylcellulose CMC and its sodium salt Na-CMC and the like), glycols or polyethylene oxides (PEG or PEO), polyacrylamide PAA, polymers and copolymers of acrylic acid and their salts (PAK, carbomer), albumin, dextran, plant polysaccharides (including gum), chitosans HTZ, and other polymers, mainly with permission to use them for food, medical, pharmaceutical or cosmetic products.

As a chemical reducing agent can be any suitable known inorganic or organic reducing agents, in particular glycerin, ascorbic acid or sodium ascorbate, sodium citrate, sodium borohydride, hypophosphite sodium salt of divalent zinc and the like, including an inexpensive and non-toxic compounds. For example, hydrazine and its salts because of their high toxicity to obtain dispersions medical or food purposes to apply as will restore the La is not recommended despite their high efficiency.

The process is carried out within a short period of time (from 10 to 60 minutes), in daylight, in an atmosphere of air, at temperatures from room temperature up to 100 degrees Celsius.

Thus, the obtained in this way monophasic dispersions do not contain surfactants, other toxic or allergenic components.

The reaction of the metal mirror during the process in the whole temperature range is missing. In the process of synthesis concentrate nanodisperse and upon subsequent storage also does not occur and the formation of precipitation, i.e. loss of metal during the process virtually absent.

The claimed invention is illustrated by drawings, where figure 1 shows the electronic absorption spectrum of a solution of the colloid; figure 2 - electronic absorption spectrum of a solution of protargol; figure 3 - electronic absorption spectrum of a solution of colloid + saline 0.9%NaCl; figure 4 - electronic absorption spectrum of a solution of protargol + saline 0.9%NaCl; figure 5 is an electronic absorption spectrum of a solution of Argovit in water (1:4); figure 6 - the electronic absorption spectrum of a solution of Argovit (1:4) + saline 0.9% NaCl (solution colorless turbid); 7 - e range absorption dispersion AgBion-1; Fig electronic absorption spectrum of races the thief dispersion AgBion-2; figure 9 - electronic absorption spectrum of a solution AgBion-2 (1:20)+saline 0.9%NaCl; figure 10 is an electronic absorption spectrum of a solution of a dispersion nonvalence silver according to the invention (example 2); figure 11 is an electronic absorption spectrum of a solution of dispersion of nano-silver according to the invention (according to example 2, after a month of storage of dispersion on the light); Fig electronic absorption spectrum of a solution of a dispersion according to example 2 + physiological 0.9%NaCl; Fig electronic absorption spectrum of a solution of a dispersion according to example 2, prepared from the original dispersion, kept within a month the light; Fig, 15 - silver nanoparticles according to example 2, AFM(Multi Mode SPM, Digital Inst, Inc., in tapping-mode using a silicon probe NCH-50, Nanoworld, with a force constant of 42 N/m, resonance frequency of 320 kHz. To the left is a photograph of the nanoparticles, the right - section(profile) of the nanoparticles; Fig electronic absorption spectrum of a solution of dispersion of nano-silver according to the invention (example 2, redispersion of the powder in water); Fig electronic absorption spectrum of a solution of a dispersion of gold nanoparticles; Fig electronic absorption spectrum of a solution of copper nanoparticles; Fig electronic absorption spectrum of a solution of palladium nanoparticles; Fig electronic absorption spectrum of a solution of platinum nanoparticles; Fig - e specification is Tr absorbance of a solution of nanoparticles of mercury; on Fig - transmittance spectrum of a dispersion of nanoparticles of Ag0; Fig - transmittance spectrum of a dispersion of nanoparticles AU0; Fig - transmittance spectrum of a dispersion of nanoparticles of si0; Fig electronic absorption spectrum of a solution Argonika; Fig electronic absorption spectrum of the dispersion of nano-silver (example 51), a diluted solution; Fig electronic absorption spectrum of the dispersion of nano-silver (example 42), a diluted solution; Fig electronic absorption spectrum of the dispersion of nano-silver (example 53), a diluted solution.

Monitoring the depletion of the metal ion in the course of interaction was performed by the method of sampling the reaction mixture using interaction with a 1%solution of sodium chloride NaCl or sodium sulfide Na2S.

The size of the metal particles obtained in accordance with the invention, was evaluated according to the electronic spectroscopy (wavelength of maximum plasma resonance), and according to the atomic force microscope (tunneling microscope).

In accordance with these electronic spectroscopy the absorption band attributed to the plasma resonance of metallic silver nanoparticles has a maximum at 386-403 nm (for example, Fig), which is significantly smaller than that of the prototype and its analogues, measured under the same conditions (see Table 2).

Sedimentation and hee the practical stability of the resulting dispersions and their solutions were determined by sedimentation or change the color and transparency of the dispersions or solutions when they have been kept in a tightly closed glass container for a specified time in daylight (excluding direct sunlight). The exposure times were chosen 1 day, 3 days, 7 days, 14 days, 20 days, 30 days. No changes, including spectral characteristics prepared from these solutions the standard concentration (10 mg/kg solution for metal), indicates the stability of the dispersion or solution.

Monitoring the presence (occurrence) of ionic metal during storage solutions was performed by the method of interaction with 0.9%sodium chloride solution NaCl (saline) solution or a 0.1% solution of sodium sulfide, Na2S - no turbidity of the solution and precipitate.

Obtained by this method concentrates nanodisperse can for many applications be used in the form of a liquid solution that is provided by their high sedimentation stability (including at room temperature and exposed to light) and a high concentration on nuevalinea metal. The latter is a significant advantage of the present invention, as it allows to reduce expenses by eliminating the procedure of dissolution in aseptic demineralized water preparations for medical purposes, which is possible only in conditions of a certified pharmaceutical industries. In connection with high resistance to ions usually present in drinking water, such drugs the ATA can be diluted to a working concentration if necessary, even ordinary drinking water.

The liquid solutions can be transferred, if necessary, in powder form by known methods, for example by the method of drying (including spray drying) or by the method of vicadine dispersion (mixing mortar with liquid nerastvorim polymeric stabilizer) with subsequent dosukoi on the air and/or vacuum at room or elevated temperatures. For example, in the case of polymeric stabilizer is PVP, so nerastvorim may be diethyl ether. In this case, the number of components of the final solution of the obtained powder form can be partially or completely removed (namely components, soluble in diethyl ether and mixtures of water and/or volatile), in particular the excess or the whole ammonia, alkanolamine, the products of the oxidation reaction of the reducing agents associated in soluble salts of anionic components of the metal salt (for example, the anions of NO3-, CO32-HCO3-, SO42-, SNCOA-, Cl) and the like, and eventually you can get almost pure two-component system metal nanoparticles - polymer stabilizer, which may be important for some (food, medical) applications.

The stated interval parameters have the following rationale:

The decrease in the concentration of polymer the x stabilizers (PVP and other) less than 0.4% is accompanied by the formation of large particles of metal, the fast formation of a precipitate.

- An increase in the concentration of polymer stabilizers over 20% increases the viscosity of the solution, which reduces the speed of the process and hampers the response.

- Reduction of metal concentration below 0,013% leads to unnecessary cost to the dilution of the concentrate nanodispersions.

The increase of metal concentration over 2.5% leads to accelerated growth of embryos nonvalence metal large metal particles, the deposition of sediment.

The decrease in the concentration of reducing agent is lower than the stated limits leads to a significant slowing of reaction recovery and to the presence in the final product of the traces of the metal ion.

The increase in the concentration of reductant above stated limits affects the hygienic conditions of production and can be accompanied by increased losses reductant.

The decrease in the concentration of alkanolamine below the stated limits is accompanied by the formation of large particles of metal, reducing the sedimentation stability of the dispersion, the fast formation of a precipitate.

The increase in the concentration of alkanolamine over the stated limits reduces the speed of the process makes it difficult to carry out reaction and causes the formation of metallic mirrors.

- Reduction of ammonia concentrations below the stated pradellescabardes the formation of large particles of metal, the decrease in aggregate stability of the dispersion, the fast formation of a precipitate.

The increase in ammonia concentrations above the stated limits reduces the speed of the process makes it difficult to carry out reaction and causes the formation of metallic mirrors. The resulting concentrates dispersion of the metal nanoparticles have a high concentration of metal - to 2.5 wt.%, stable to light and air for a long time (not less than 3 years)are homogeneous transparent colored specific for each metal color nanodispersions (from light yellow to red-brown to silver, from lilac to dark red to gold, red-brown to copper, dark brown to black for palladium, platinum and mercury and so on).

As metal loss during the process is practically absent, the contents of the nanoparticles nonvalence metal (wt.%) the resulting concentrates nanodispersions almost equal to the metal content in the reaction mixture.

When diluted concentrates nanodispersions solvent formed a stable transparent solution:

silver - from light yellow to light red-brown color (wavelength plasmon resonance at the maximum absorption equal 386-403 nm),

gold - pink or purple color (wavelength PLAZMENNOGO the resonance at the maximum absorption equal 521-528 nm),

for palladium, platinum, mercury, zinc - light-brown color (absorption due to the plasma resonance in the near ultraviolet and the visible area of the spectrum, uniformly decreasing with increasing wavelength, without the Express maximum)

which indicates the size of the nanoparticles is in the range from 2 to 20 nm.

Solutions nanodisperse, including diluted, can be stored exposed to light for a long time (not less than 1 year), without changing its color, and without the formation of precipitation.

The lack of same in their composition of cationic metal during the whole period of storage provides solutions drug compatibility, in the case of silver, with saline solution (sodium chloride, 0.9 wt.%) for at least a month (no turbidity of the solutions, the lack of rainfall, including storage on the world).

The obtained dispersion of silver nanoparticles and silver nanoparticles with additions of copper, gold have a higher antimicrobial activity than drugs prototype and analogues, while exhibit antimicrobial activity against pathogenic bacteria Escherichia coli. Salmonella typhimurium, Staphyllococcus aureus. Bacillus subtilis, Candida albigans., sterilizing aqueous solutions (E. coli) at concentrations from 0.1 ppm and above, and also possess virucidal and fungicidal activity, significantly exceeding the known analogues and prototype.

p> Confirmation of this can be data from comparative tests of antimicrobial activity of silver-containing products on different test strains (collargol, protargol, poviargol, argovit)undertaken by the company SRC VB "Vector" [http://vector-vita.narod.ru/Documents/papers/Ag_presentation_2007.pdf]. The highest antibacterial activity against staphylococcus aureus had argovit - 0.5 μg/ml (0.5 ppm) and poviargol - 1 µg/ml (1 ppm), and against E. coli - argovit - 5 µg/ml (5 ppm) and poviargol - 5 µg/ml (5 ppm).

Thus, the bactericidal activity of the resulting product is 5-10 times higher than that of the known products - analogs and prototypes.

Indeed, in the instructions to the drug Poviargol [http://medical-instructions.ru/preparat?id=10209] indicates that poviargol inhibits the growth of most bacteria (Staphylococcus spp., and Streptococcus spp., Pseudomonas aeruginosa and Escherichia coli, Proteus spp., Shigella spp., Salmonella spp. and others) at concentrations up to 100 µg/ml, when the content of the preparation of silver 7.5 to 8 wt.%, corresponds to 7.5-8 ppm.

In comparison with analogues and prototype concentrates of dispersion of the metal nanoparticles have a high concentration of metal, high dispersibility and high aggregate stability of metal particles in aqueous and nonaqueous solutions, reduced toxicity and allergenicity, as well as the reproducibility of the physico-chemical characteristics. The components used is isperia non-toxic and approved for application in medical, pharmaceutical, cosmetic and food products that do not pollute the environment.

Dispersions as additives, well compatible with various systems, including water and alcohol-based, with Dimexidum, glycerin, etc. In the composition of the dispersions, there is virtually no metal cations (as evidenced by the lack of precipitation and cloud solutions) when introduced into the dispersion solutions of sodium chloride or sodium sulfide), as well as ionic surfactants and ionic polymers, which leads to increased compatibility dispersions, including systems and preparations containing ionic components, as well as having an increased or decreased pH. In addition, it provides compatibility dispersion with the majority of known antibiotics that enables the combined use of dispersions of nanoparticles of metal, especially silver, with antibiotics.

The method of obtaining concentrates, dispersions of metal nanoparticles in comparison with analogues and the prototype is simple, fast, good reproducibility, a complete conversion of the metal cations in the metal nanoparticles of silver, no metal loss, low cost and toxicity of the used components. The resulting dispersion can be used in various fields of industry, technology, cosmetics, lifestyle and medicine, is of VETERINARII, food industry, water treatment, as well as the beginning of the current (substance) highly efficient antiseptics, preservatives and other functional additives.

Below are examples of implementation of the invention.

Example 1 (prototype - EN 2088234).

In the dark glass reaction apparatus equipped with a stirrer, addition funnel and a bubbler for blowing an inert gas load 200 g of poly-N-vinylpyrrolidone-2 (PVP) with M 12600, add with stirring a mixture of 1000 ml of water and 300 ml of ethanol (19%solution of ethanol). Received 14% solution of PVP heated for 10 min at 75°C and at this temperature, add with stirring a solution of 27,39 g of silver nitrate (HC) in 500 ml of water (5.2 wt.%). The reaction mixture containing 12% ethanol, 10% PVP and 1.4% silver nitrate, stirred at the same temperature for 60 minutes Aqueous-alcoholic solution is dried in the spray dryer. The yield of the target product 217,2 g (99,9%), silver content 7,94%.

The ratio of PVP:Ag=1:0,086, min bactericidal concentration (St.aur 209)=0,62 mg/ml=0,62 ppm.

Made from powder solution "Poviargol" (made according to this invention) at a concentration of 0.5 wt.% (around 0.04 wt.% silver or 400 mg/kg=400 ppm) is a brown-greenish translucent opalescense liquid, the wavelength is of aximum the diluted absorption solution is 420 nm, that jointly indicates the formation of metallic particles with a size of 60 nm or more.

After 1-2 weeks formed a visible precipitate, i.e. dispersion sedimentation unstable.

Reaction with NaCl - observed sediment after 1 day. After 7 days the dispersion noticeably bleached at the bottom - rich sediment.

In the instructions to the poviargol [http://medical-instructions.ru/preparat?id=10209] indicated that at concentrations up to 100 µg/ml (100 ppm) poviargol inhibits the growth of most bacteria (Staphylococcus spp., Streptococcus spp., Pseudomonas aeruginosa and Escherichia coli, Proteus spp., Shigella spp., Salmonella spp. other). Indicates that the antimicrobial effect of the drug is sharply weakened in solutions of NaCl, so using it in a 0.9% NaCl solution is not recommended. There are contraindications - hypersensitivity side effects - when processing the nasopharynx may increase the amount of discharge of mucus. Way of application and dose: Externally in the form of 1, 3 and 5% solution, which is prepared ex tempore: powder dissolved in distilled water (which corresponds to the concentration of silver 800, 2400, and 4000 ppm). Special instructions: Prepared solutions stored in bottles of dark glass not more than 10 days.

Specific compositions of the reaction mixtures, the synthesis conditions and the concentration of the resulting metallic silver for example 1 is shown in the Table.

Example 2 (invention).

In p is a promotional vessel - 3-necked flask equipped with stirrer, make distilled water in the amount of 65 g, a solution of poly-N-vinylpyrrolidone-2 (medical) with a concentration of 10 wt.% in the amount of 0.6 g and stirred (360 revolutions of the stirrer per minute) for 10 minutes at room temperature. Get the solution "A".

In a glass to make 50 ml distilled water in an amount of 23 g, then a portion of the sulphate of silver 0,0188 g mix (360 revolutions of the stirrer per minute) to dissolve. Then add 1% solution of ammonia in the amount of 1.45 g, and then a portion of triethanolamine in the number being 0.036, the Solution is stirred for 10 minutes (360 revolutions of the stirrer in a minute) and get the solution "B".

In a glass 20 ml make distilled water in the amount of 9.9 g, then a portion of sodium borohydride in the number 0,023 g mix (240 revolutions of the stirrer per minute) to dissolve. The solution is stirred for 3-5 minutes and get the solution.

In the reaction vessel, 3-necked flask containing a solution "And"make under stirring (360 revolutions of the stirrer in a minute) solution B was stirred 10 minutes and then with vigorous stirring (1200-1500 rpm stirrer in a minute) add the solution and stirred for 5 minutes. Then the speed of the agitator is reduced to 360 rpm and stirred for 2 hours.

Get 100 grams of clear red-brown solution with a concentration on metal silver 0,013% 130 mg/kg or 130 ppm). Upon dilution of the solution the color of the solution is light yellow. The maximum wavelength of absorbance at 403 nm (figure 10, table 2).

The dispersion is stable - does not give a precipitate was not observed haze, opalescence, and the color of the diluted solution does not change for more than 4 weeks, as well as the maximum wavelength of absorption of the same dilute solution (same 403 nm, 11, table 2), indicating a high stability of the dispersion in diluted form.

Within 1 hour after the reaction in the glass is molded about 1 g of a dispersion, is added 5 g of distilled water and added 5 g of NaCl solution with a concentration of 1 wt.% or pharmacy saline solution (0.9% NaCl). The turbidity of the dispersion is not observed, the sediment is also not formed, the electronic spectrum of a dilute solution of this dispersion (Fig, table 2) practically does not differ from the spectrum, see figure 11, which shows the compatibility of the diluted dispersion with saline solution.

After 4 weeks of storage at light received from the source of dispersion is again prepared aqueous solution. Electronic spectrum of a solution similar to the spectrum of the original solution (Fig). After 7, 14, 21 and 30 days sediment and turbidity of this diluted solution is not observed, the color of the solution also does not change, which indicates the stability of the obtained di is Persia in the original (undiluted) form.

Thus, the synthesized according to the invention the dispersion of metallic silver forms a stable colloidal solution with the size of the piece of silver is not more than 10-15 nm (as indicated by the maximum value of the wavelength electronic absorption spectrum of 403 nm, figure 10, 11, and measurement data of the atomic force microscope, Fig, 15), is stable over time, not less than 4 weeks (actually at least 2 years, stability tests are ongoing), and during all this time in the composition of the solution there are no detectable amounts of silver in cationic form.

Next, 10 g of the obtained liquid (containing, besides water, 0,692 g components) under stirring trickle in for 1 minute enter diethyl ether in an amount of 10 ml, stirred for 10 minutes and add about 10 ml of diethyl ether. This forms a flocculent precipitate, painted in dark brown color, and the solution above the sediment becomes colorless, which means that all the silver nanoparticles with PVP passed into the sediment. Next, the precipitate is separated, washed 2 times with 10 ml of diethyl ether and dried at 80°C and then at 120°C in a ventilated drying Cabinet to constant weight and condition at room temperature during the day. Get 0,61 g of light brown powder. Thus, the main part of the components of the stable the EAP nanodispersions silver was removed (soluble in diethyl ether, it mixes with water, and volatile at 120°C). After that, the powder of the drug easily redispersible in water or other suitable solvents practically without changing its properties, including almost without changes in the band maximum plasma resonance of metallic silver nanoparticles (Fig, table 2).

Specific compositions of the reaction mixtures, the synthesis conditions and the concentration of the resulting metallic silver and properties of the obtained dispersions of example 2 are shown in Table 1.

In the SE of epidemiology and Microbiology them. Nofamily RAMS conducted Microbiological study of the bacteriostatic action of the sample thus obtained dispersion to conditionally pathogenic microorganisms (In accordance with the guidelines of TORMENT 4.2. 801-99).

In the paper, we used the following strains of microorganisms:

.li (ATSS);

Candida albicans (ATCC 10231);

Staphylococcus aureus (ATCC 6538);

Pseudomonas aeruginosa (ATCC 15442);

Crop and quantitative monitoring was carried out on the following nutrient medium:

Endo - for cultivation and quantitative accounting of E.coli;

Staph-agar for cultivation and quantitative records of S. aureus;

BIGGY agar for cultivation and quantitative accounting of Candida albicans;

Cetrimid agar for cultivation and quantitative accounting of Pseudomonas Aeruginosae;

Other environments Becton, Dickinson and Company (USA).

For measuring the population density (turbidity) of bacterial suspension was used scale McFarland company BioMerieux (France) to prepare a dilution culture from 10 3up to 106CFU/ml

All consumable materials: Petri dishes, Pasteur and volumetric pipettes, spatulas, and others, were disposable manufactured by Danies (Italy).

For research biocidal properties were used to sample the dispersion according to Example 2, the original content of the active component (metal recovered silver) CAg0)=130 ppm (0,013% Ag0).

The working dilutions of the original sample of colloidal silver and the quantification of the test microorganisms in the process of experiments was performed ten-fold serial dilutions with seeding in the appropriate medium after culturing in an incubator at 37°C for 18-22 hours.

The quantification of Candida albicans after 24 to 48 hours at a temperature of cultivation 22-25°C in the medium BIGGY agar.

Deferred consideration of the number of test strains was performed on the 5th day.

Data load microbiological tests showed that when the concentration of nanoparticles of metallic silver C(Ag0) in the range of 0.05-0.1 ppm sample variance silver had a bactericidal effect against Staphylococcus aureus; pronounced bacteriostatic effect against E. coli, Candida albicans, Pseudomonas aeruginosa, Bacillus subtilis, taken at a concentration of 106CFU/g of microorganisms. At higher concentrations of metallic silver nanoparticles Ag0and test strains from which echino bactericidal activity of the studied sample of colloidal metallic silver.

Research virucidal ability of drugs was carried out on a standard strain of hepatitis b, by the method of enzyme-linked immunosorbent assay (Institute of Virology RAMS, aged 1 hour. The method for determining the activity of the virus after treatment with discrestion based on the reaction of the coloring after the annexation of the enzyme peroxidase to the complex antigen-antibody, which is formed by the interaction of the virus and monoclonal antibodies, are added to the standard number to each sample. The result is read on a spectrophotometer at a wavelength of 492 nm.

It is shown that the activity of nanodispersions silver is 85-93% at a concentration of silver of 0.01%, which is higher than the activity of the silver nitrate solution of the same concentration (76.7 per cent) and higher activity of 1% (silver content of 0.075%) of the drug poviargol (37%), measured under the same conditions.

Also marked 100% virucidal activity nanodispersions metallic copper, however, at higher concentrations of 0.5% (1 hour).

Thus, in comparison with analogues and prototype obtained by this method, the dispersion of metallic silver has compared to the prototype higher stability, especially in the form of a dilute solution, does not form precipitation with sodium chloride solution, i.e. compatible with a physiological solution, and about lady higher antiseptic activity, than the prototype:

- bactericidal and bacteriostatic activity of 0.05-0.1 ppm, against 0,62-1 ppm for the prototype;

- virucidal activity 85-93%, versus 37% (at higher concentrations).

The size of silver particles obtained by this method, is also smaller than the particle size obtained by the prototype, as evidenced by the shorter wavelength of maximum absorption of the plasmon resonance 386-403 nm 420 nm against the prototype.

Examples 3-54 (invention).

Synthesis of dispersions in examples 3-54 was performed as in example 2 except that as the salt of silver used, in addition to sulfate silver SS, and also the silver nitrate NA acetate silver AU, silver carbonate COP, except PVP used other polymers, in addition to the tea - other alkanolamine, in addition to sodium borohydride - other reducing agents at various concentrations.

Specific compositions of the reaction mixtures, the synthesis conditions, the concentration of the resulting metallic silver and properties of the resulting dispersions for examples 3-54 shown in Table 1.

Examples 55-61 (invention).

Synthesis of dispersions in examples 55-61 was performed as in example 2, except that instead of silver salts used the salts of gold, copper, palladium, platinum, mercury, at various concentrations.

Specific compositions of the reaction mixtures, the synthesis conditions, the concentration of the resulting metal nanoparticles and the properties of the obtained dispersions for examples 55-61 are shown in Table 2. Electronic spectra of the obtained dispersions of the nanoparticles is shown in Fig-21.

Examples 62-69 (invention).

Synthesis of dispersions in examples 62-69 was performed as in example 2, except that the main components were used beyond their concentration.

Specific compositions of the reaction mixtures, the synthesis conditions and properties of the resulting dispersions for examples 62-69 are shown in Table 1.

Examples 70-74 (invention).

Synthesis of dispersions in examples 70-74 was performed as in example 2, except that the composition of the reaction mixture was absent ammonia and ethanolamine.

Specific compositions of the reaction mixtures, the synthesis conditions and properties of the resulting dispersions for examples 70-74 are shown in Table 1.

In the examples 3-74 as a solubilizer (polymer protective colloid used, except for PVP, also different grades of polyvinyl alcohol PVA (grade PVA BF-03, PVA BP-05, PVA Unutika, PVA 11/2, PVA 16/1), polyethylene glycol (PEG 1500, PEG 600, PEG 400), xanthan gum (QC), gum Arabic (GA), a mixture of PVP and gum Arabic (PVP+HA), methylcellulose (mark MC-100), oksipropilmetiltselljuloza (grade Methocel E5), chitosan HTZ, polyvinyl butyral, polyacrylic acid PAK, as well as other suitable synthetic or biopolymers.

In the examples 3-74 as a reducing agent, in addition to sodium borohydride BG working when the room is Noah temperature, also used sodium ascorbate, an, operating at room temperature, and sodium citrate TSN, hypophosphite sodium GN, a mixture of sodium citrate and sodium borohydride CN+BG, glycerin GL, and the reaction was conducted at 100°C (water bath) for 1-1,5 hours, in one neck of the flask were established in the reflux condenser, and the second was closed by a sealing plug.

In the examples 2-74 ammonia was used in the form of aqueous solutions with concentrations of 1, 10 and 28 wt.%.

In the examples 2-74 as examples of alkanolamines by the formula 1 used:

- Monoethanolamine IEA

- Diethanolamin deja

- Triethanolamine, tea

- Diisopropanolamine of the DEEP

- Tris-(oxymethyl)-aminomethane, TRIS,

The substance used, the brand, qualification, GOST

1. Salts of metals:

Sulphate of silver. Silver sulfate, Ag2SO4, HC THE 6-09-3703-74 or THE 2625-046-00205067-2004 (SS)

Silver nitrate, Silver nitrate, AgNO3, HC GOST 1277-75; (NS)

The silver acetate, Silver acetate, Ag(OAc), analytical grade, THE 6-09-02-213-2001. (AU)

Silver (I) carbonate, Ag2CO3. clean THE 6-09-3743-74 (SK)

Soloconsolidation acid water H[AuCl4]·nH2O (n=3-4, the gold content 49%), clean, THE 2612-025-00205067-2003 (AuXBK)

Palladium (II) chloride (PdCl2clean, TU 2625-048-00205067-2003 or THE 2625-011-57979587-04

Platinochloride acid 6-water (H2PtCl6*6H 2O clean THE 2612-034-00205067-2003 or THE 2612-018-57979587-04 (PtXBK)

Copper (II) acetate, si(CH3Soo)2*H2Oh, analytical grade, GOST 5852-79

Copper (II) sulfate 5-water, CuSO4*5H2O, analytical grade, GOST 4165-78. (MS)

Mercury (I) nitrate 2-water, h, Hg2(NO3)2*2H2O, GOST 4521-78.

2. Polymers:

Polyvinylpyrrolidone medical weight 35000±5000, FS 42-2238-98, PVP-35, the low-molecular Polyvinylpyrrolidone medical Mm, FS-1194-98, PVP-12.

The low-molecular polyvinylpyrrolidone medical 8000±2000 for the manufacture of the drug Gemodez-N, (Polyvidone* (Polyvidone*), Polyvinylpyrrolidonum), FS 42-3678-98, PVP-8,

or PVP imported food additive E, E.

Polyvinyl alcohol PVA 11/2 FS 42-2299-85, highest grade, GOST 10779-78.

Polyvinyl alcohol PVA 16/1 FS 42-2299-85, highest grade, GOST 10779-78.

Polyvinyl alcohol import brand PVA BP-05, Clariant GMBH DE.

Polyvinyl alcohol import brand PVA BF-03, Clariant GMBH DE.

Polyvinyl alcohol import brand PVA Uvitika POVAL, Clariant GMBH DE.

Polyethylene glycol PEG 1500, THE 6-00205601.083-2000, or import - LIPOXOL 1500 Med (SASOL Germany GmbH).

The polyethylene glycol is PEG 400, THE 6-00205601.083-2000, or import - LIPOXOL 400 Med (SASOL Germany GmbH), or Lutrol E 400 (PEG-8), BASF.

The polyethylene glycol is PEG 600, import - LUTROL E 600, BASF (PEG-12).

Xanthan gum (KK), CAS. Nr. 11138-66-2, food additive E, gum xanthan gum, PRC.

Gum Arabic (GA), gum Arabic AGRIGUM SPRAY R, R/E, G/MH, MGH, R-HP, import.

The methylcellulose MC edible water-soluble (mark MC-100), THE 2231-107-05742755-96.

Oksipropilmetiltselljuloza (grade Methocel E-5 premium), import.

Carboxymethylcellulose, sodium salt (Na-CMC), polycell CMC - 7 H (mark 85/300), THE 2231-017-32957739-02.

Polyvinyl butyral PVB, Mowital B60H and Mowital B30H, Clariant GMBH DE.

Polyacrylic acid (PAC), import, ALDRICH, PAA Poly(acrylic acid), PAA, Mw=1800 or PAA Mn=130000.

Chitosan (HTZ), CJSC "Bioprogress, Russia, or Qingdao Scitech Co., Ltd., China.

Food gelatin P-11, GOST-11293-89.

3. Reducing agents:

Sodium borohydride BG, TU 1-92-162-90, import, CAS No. 16940-66-2.

Sodium ascorbate, NA, Sodium salt of ascorbic acid, dietary Supplement E.

Sodium citrate TSN, sodium citrate trehzameshchenny, 5,5-water (E 331), Na3C6H5O7*5,5H2O, h, GOST 22280-76.

Hypophosphite sodium GN, Sodium, posterolaterally 1-water, NaH2PO2*H2O, analytical grade, GOST 200-76.

Glycerin GL reactive reagent-grade GOST 6259-75, glycerin FS 42-2202-99.

4. Supplements:

Ammonia water FS 79-1096-1 GOST 42-1299-79.

Ammonia water, 10% OSC 17-4, GOST 3760-79.

Monoethanolamine IEA, CHP, THE 2632-094-44493179-04, THE 2632-016-11291058-96.

Diethanolamin deja, CHP, THE 6-09-2652-91, or import, Diethanolamine, 99%, D83303-1L.

Triethanolamine, tea, HC, THE 6-09-2448.

Diisopropanolamine, DEEP, import, ALDRICH, Bis(2-hydroxypropyl)amine, ≥98.0%, 14960-250G.

Tris(hydroxymethyl)aminomethan (TRIS)4H11 NO3, OFS, GER, Dia, or Tris (hydroxymethyl)aminomethane for biochemistry, 99+% (FAS. 0.5 kg).

5. Solvents:

Distilled water GOST 6709-72, or demineralized.

Ethyl alcohol, reagent-grade, GOST 18300-72.

Isopropyl alcohol, reagent-grade, THE 2632-015-11291058-95, THE 6-09-402-87.

Dimethyl sulfoxide, Dimexidum (DMSO), P 75.244.9.

6. Excipients:

Sodium chloride NaCl, solution for infusions of 0.9%, n PN 001119/01.

Sodium sulphide /sodium sulfur/ Na2S (bag of 25 kg) China, GOST, GB/T 10500-2000.

Acetic acid, reagent-grade, ice GOST 61-75.

As can be seen from these Tables 1-2, the dispersion of metals obtained in accordance with the invention, its characteristics are significantly better than the dispersion in accordance with the prototype and analogs, and the proposed method of synthesis easier and more efficient.

The tests showed that the formed red-brown dispersion of nano-silver (in diluted form light yellow), are stable for at least 12 months when stored in the light. The maximum absorption band of the plasma resonance of the obtained dispersions of silver is in the area 386-403 nm, i.e. formed of spherical particles with sizes of a few nm (transmittance Spectrum yellow dispersion Ag0maximum wavelength PLA is monogo resonance 402 nm, Fig), which is less than the corresponding solutions of nanodisperse prototype and analogues (table 2).

In the case of gold are formed purple or purple-lilac dispersion with a maximum absorption band of the plasma resonance in the field 521-528 nm (transmittance Spectrum "purple" dispersion AI0, Fig).

In the case of copper - red-brown (transmittance spectrum "brown" dispersion, Fig), dark green and mixed color variance depending on the ratio of the particles and/or shells of the nanoparticles of the composition of Cu2O (with a maximum absorption band of the plasma resonance in the field of 450-480, Fig) and actually nanoparticles nonvalence si0(with the maximum of the absorption band of the plasma resonance in the field of 520-580 nm, Fig).

Since the maximum of the absorption band plasmon resonance of the obtained dispersions of silver is in the area 386-403 nm of gold in the area 515-540 nm, i.e. formed of a spherical particle with size 3-7-15 nm, which was confirmed by atomic force microscope AFM (Fig, 15).

On Fig shows the electronic spectra of another analog of the present invention, the drug Argonika.

On Fig - 28 shows the electronic spectra of dilute solutions of nanodisperse nonvalence silver, synthesized using as various external protective colloids (polymers), and the property named is: polyacrylic acid PAK in aqueous solution (Fig), polyvinyl alcohol PVA in aqueous solution (peg) and polyvinyl butyral in ethanol solution (Fig).

The use of other non-PVP protective colloids, especially in an alcohol solution of PVB, as can be seen from these figures, gives the maximum plasma absorption of silver nanoparticles at shorter wavelengths - 390, 397, and 386 nm, respectively.

Shorter-wavelength values of the maximum wavelength for an alcohol solution of PVB, as well as for aqueous solutions of PVA and PAK, compared to PVP, can be a consequence, taking into account theory of Mi Drude, stronger electron-donating ability of these polymers, increasing the surface electronic charge on the nanoparticles of silver.

Indeed, according to theory of Mi Drude (Mie.Drude), described in the article [BEGEROW. Nanoparticles of metals in aqueous solutions: electronic, optical and catalytic properties. Grew up with. chem. W. (J. ROS. chem. of the society to them. Mendeleev), 2001, .XLV, No. 3, p.20-30], the position of the maximum absorption band of surface plasmons in the metal is determined by the equation

λ2max=(2πc)2m(ε0+2n)/4πNee2,

where C is the speed of light, m is the effective mass of the electron;eis the electron charge; ε0- permittivity metal; n is the refractive index of the medium; Ne- the density of free electrons in the metal. IDNO, the increase of Neshould lead to a shift of the absorption band plasmons in metal blue, i.e. in the UV region, and the reduction of Ne- in the red.

Table 2 shows the maxima of the absorption bands of the plasmon resonance of metal nanoparticles obtained in accordance with the invention, prototype and analogues.

Table 2
The maxima of the absorption bands of the plasma resonance of the nanoparticles nonvalent metals obtained in accordance with the invention, prototype and analogs measured in identical conditions. The spectrophotometer SF-56, quartz cuvette 1 cm
Nanoparticles, dispersions (slurries)Wavelength, nm
Nanodisperse silver according to the invention (Example 2), diluted403

Nanodisperse silver according to the invention (Example 2), diluted in a month403
Nanodisperse silver according to the invention (Example 2), diluted powder401
Nanodisperse the silver according to the invention (Example 2), diluted + physiological solution (0.9% NaCl)398
Nanodisperse silver according to the invention (Example 48), diluted400
Nanodisperse silver according to the invention (Example 42), diluted397
Nanodisperse silver according to the invention (Example 51), diluted390
Nanodisperse silver according to the invention (Example 53), diluted386
Poviargol diluted dispersion413
Poviargol diluted dispersion, in a week413-gone
Poviargol diluted dispersion + physiological solution (0.9% NaCl)413-gone
Protargol diluted dispersion406
Protargol diluted dispersion + physiological solution (0.9% NaCl)406-gone
Collaros diluted dispersion409
It is laral diluted dispersion + physiological solution (0.9% NaCl) 409-gone
Argovit source407
Argovit diluted 4 times in a week421
Argovit source+physiological solution (0.9% NaCl)407-gone
Argonika421
Ag-Bion-1 diluted with hexane dispersion430
Ag-Bion-2 diluted dispersion410
Ag-Bion 2 + physiological solution (0.9% NaCl)410-gone
Nanodisperse gold according to the invention (Example 55), diluted528
Nanodisperse gold according to the invention (Example 56), diluted521
Nanodisperse platinum according to the invention (Example 57), diluted230
Nanodisperse palladium according to the invention (Example 58), diluted240
Nanodisperse mercury according to the invention (P is emer 59), diluted240, shoulder 300
Nanodisperse copper according to the invention (Example 60), diluted475
Nanodisperse copper according to the invention (Example 61), diluted560

As follows from Table 2, the metal nanoparticles nonvalence silver received in accordance with the invention, have a maximum absorption due to plasmon resonance at shorter wavelengths than that of the prototype and its analogues, in accordance with mie theory Drude, indicates their smaller size, and according to the article ["the Synthesis and properties of silver nanoparticles: achievements and prospects". Wascritical and other, UH, 77 (3) 2008, s-269] wavelength 415 nm corresponds to the size of silver nanoparticles 10-25 nm.

In a review article devoted to the optical properties of nanoparticles of a number of metals [BEGEROW. Nanoparticles of metals in aqueous solutions: electronic, optical and catalytic properties. Grew up with. chem. W. (J. ROS. chem. of the society to them. Mendeleev), 2001, .XLV, No. 3, p.20-30], shows the band maxima plasmon resonance of the nanoparticles of palladium (230 nm), platinum (215 nm), silver (380-410 nm), gold (510-540 nm), copper (565 nm), mercury (300 nm), and by radiation-chemical reduction of Pd ions II and Pt II observed images is of spherical particles with an average size of 2.4 nm, and by chemical reduction with hydrogen reaches the size of approximately 8 nm. The spectra are a band with a maximum at 215 nm for platinum and the band at 230 nm for palladium, which gradually decrease in the long-wavelength region.

Comparison of literature data with our data demonstrates that the electronic spectra and the wavelength of maximum absorption of the plasmon resonance of the synthesized nanoparticles of silver, gold, copper, practically coincide with the literature data for aqueous solutions, and platinum and palladium is a bit more (10-15 nm)than the literature data, which is a confirmation of exactly synthesis of nanosized nonvalent metal particles of these metals.

The wavelength of maximum absorption of the plasmon resonance of the nanoparticles mercury according to literature data equal to 300 nm, at the same time, we synthesized according to the invention, the nanoparticles of mercury observed band with a maximum at 240 nm and a shoulder at 300 nm. Perhaps this is in accordance with mie theory Drude indicates the presence in the composition of the dispersion of a significant number of nanoparticles or clustered particles of mercury are smaller than they were from the authors.

Thus, the inventive method of synthesis of nanoparticles nonvalent metals allows to synthesize nanoparticles in the form of nanodisperse with dimensions sootvetstvujushchijemu science, and less than synthesis technology prototype and analogues.

However, the proposed method is distinguished by the simplicity, performance, full conversion of the cationic metal mulvanerty, high stability of the dispersions, including compatibility with physiological NaCl solution (0.9%), the absence in the composition of the dispersion of toxic or harmful to health and environment components.

This, in turn, allows us to produce on the basis of the data received by way of nanodisperse a wide range of products, characterized by the absence of toxicity, high stability and enhanced antimicrobial efficacy.

Region and examples obtained according to the invention of nanodisperse nonvalent metals include, including the following classes of products:

Household chemicals

- Disinfectant silver, silver with the addition of copper and/or zinc. Application: disinfection of surfaces by the method of spraying or wiping in industries, offices and homes (including furniture, gas and electric stoves, pens, tables, cutting boards, office equipment), and institutions of social security, housing, services (consumer markets, public facilities, hotels, hostels, swimming pools, baths, saunas, parikmaherskiy the x, beauty salons, places of a mass congestion of people and so on), at the enterprises of the food trade and public catering institutions.

- Disinfectant silver, silver with the addition of copper and/or zinc - antimicrobial spray for treatment of the common areas.

- Disinfectant silver, silver with the addition of copper and/or zinc - spray-deodorant for shoes. Application: treatment of shoes, socks, socks, insoles, deodorant for feet. Prevents odors, freshens and protects against bacterial, viral and fungal diseases.

- Disinfectant silver, silver with the addition of copper and/or zinc is an important wipes (wipes impregnated with a solution of nanodispersions with the addition of functional additives). Application: wet cleaning and disinfection, treatment of hands, etc.

- Anti-microbial Laundry detergent. Application: add when washing, disinfection and making linen biocidal properties.

- Antimicrobia additive for detergents and cleaning agents.

- Antimicrobial gel based on silver, silver with the addition of copper and/or zinc. Application: treatment of hands, feet, body. Prevents odors, freshens and protects against bacterial, viral and fungal diseases.

- Antimicrobial gel based on gold. Application processing of the joints. Filter materials

- Fillers - filter media and filter elements for water, food industry, ventilation and air conditioning systems, including the food industry, air filters, air-conditioning system.

Packaging industry, the production of pottery

- Packaging materials for food products, prolonging shelf life.

- Disposable, reusable dishware with bactericidal properties of the surface.

- Food containers.

- Food trays of cold rooms and display cases.

Products for agriculture

- Antimicrobial agent against mastitis, foot rot.

Medical product

- Antimicrobial gels, ointments, sprays, plasters, wipes, bandages, dressings, sanitation, prostheses, tools, etc.

Food products

- Preservatives

- Dyes

Cosmetic products

- Antimicrobial additives and preservatives for shampoos, creams, pastes, gels, foams, lipstick, mascara, powders, masks, rinses, etc.

- UV-absorbing additives for protective creams (nanodispersions silver) with high protective ability.

Pharmaceuticals

- Gels, ointments, sprays, foams for the treatment of wounds of various types.

Other products

Tablets, solutions, gels disinfects and water and drinks

- Wet wipes for personal hygiene

- Catalysts (nanodispersions of platinum, palladium, silver, gold, incl. printed on the media - activated carbon, metal oxides, silica gels and the like).

- Electrically conductive inks and pastes.

Table 3 gives some specific examples of using the obtained nanodisperse nonvalent metals, their composition and properties.

The formulations based on nano-nonvalent metals, their use

Table 3
# exampleCompositionThe type and purposeProperties, mode of administration, the working concentration, %, mg/kg (ppm)
75- Nanodispersed mulvanerty palladium
The activated carbon or aluminum oxide or silica gel
CatalystPd0=0,3-1,5%
Granules of activated carbon or aluminum oxide or silica gel, treated with a dispersion of nanoparticles of palladium.
76- Nanodispersed nonvalence silver
- Matrix
DyeHell0 =5-500 mg/kg
The products are painted in light-jetty or yellow, and if necessary, in the range

wavelengths 360-420 nm can be achieved values of optical density D to 6-20 units and more.
- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Solvent
Disinfecting compositionAg0=1-10 mg/kg
Cu0=10-100 mg/kg Solution spray
77Nanodispersed nonvalence silver
The solvent (water)
Disinfectant and preservativeAg0=0.05-0.15 mg/kg
For water and drinks
78Nanodispersed nonvalence silver
The solvent (water)
Preservative for food productsAg0=0,15-0,25 mg/kg
Salt and salted fish, berries, fruits, etc.
79Nanodispersed nullvalue is the things silver
- Nanodispersed mulvanerty copper
- Functional additives
The solvent (water)
Preservative for cosmetics.Ag0=0.5 to 15 mg/kg
Cu0=1-10 mg/kg
Cream, shampoo, gel, spray
80Nanodispersed nonvalence silver
- Functional additives
Gel-based
Gel for the treatment of wounds, burnsAg0=20-100 mg/kg
Gel for the treatment of wounds, burns, including infected
81Nanodispersed nonvalence silver
- Functional additives
Ointment base
Ointment for treating wounds and burnsAg0=50-300 mg/kg
Ointment for treating wounds and burns, including infected
82Nanodispersed nonvalence gold
- Functional additives
Gel-based
Gel for the treatmentAI0=20-200 mg/kg
Gel for the treatment of diseases of the joints
83- Nanodispersed nonvalence silver
- Nanodispersed nonvalence gold
- Nanodispersed mulvanerty m is d '
- Functional additives
- Solvent
The solution, powder food SupplementAg0=0,1-10 mg/kg
Cu0=1-10 mg/kg
Zn=1-20 mg/kg
The solution, powder SUPPLEMENTS, food Supplement and drinks
84- Nanodispersed nonvalence silver
- Functional additives
- Solvent
The solution for treatment of fillersAg0=0,1-10 mg/kg
Cu0=10-100 mg/kg
Fillers for toilets animals (domestic, laboratory, kennels, zoos)
85- Nanodispersed nonvalenceSorptionAg0=0,1-10 mg/kg

silver
- Nanodispersed mulvanerty copper
- Functional additives
Carrier (alumina, silica gel, activated carbon, etc.)
material with bactericidal, virucidal and fungicidal propertiesC0=10-100 mg/kg
Used in medical and consumer products.
86- Nanosized zero is lentsoe silver
- Functional additives
Cream Foundation
Cream
Gel
For veterinary use
Ag0=10-50 mg/kg
Cream and gel for milking cattle, processing the udder before and after milking
87- Nanodispersed nonvalence silver
Antibiotic
- Functional additives
Tablet
Solution
Ag0=100-500 mg/kg
Combined drug antituberculosis action, the combined use of silver nanoparticles and antibiotics increases the efficiency of the drugs and allows, if necessary, to reduce the burden of antibiotic.
88- Nanodispersed nonvalence silver
- Functional additives
Cream Foundation
Cream, gel for handsAg0=100-500 mg/kg
Cream, gel, hand, moisturizing, protective, antiseptic effect
89- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Basis
Paper, fabric with biocidal propertiesAg0=5-50 mg/kg
C0=10-100 mg/who g
Paper, fabric with biocidal properties. Clothing, packaging.
90- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Solvent
Solution. Means for cleaning and disinfecting contact lensesAg0=10-50 mg/kg
Cu0=10-100 mg/kg
Solution.
Means for cleaning and disinfecting contact lenses
91- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Solvent
SolutionAg0=0,05-0,25 mg/kg
Cu0=0.5-1 mg/kg
Means for disinfection of circulating water of swimming pools. Ensures the absence in the pool water coliforms, coliphages, Staphylococcus aureus, Escherichia coli, intestinal agents, etc.
92- Nanodispersed nonvalence silver
- Functional additives
- Solvent
Impregnation napkinAg0=10-30 mg/kg
Napkin paper or fabric with antimicrobial and moisturizing properties,hygienic, deodorizing. Base (fabric, paper, non-woven material)
93- Nanodispersed nonvalence silverThe solution tabletAg0=10-20 mg/kg solution
The solution tablet

- Functional additives
- Basis
For the treatment and prevention of diseases of the gastrointestinal tract
94- Nanodispersed nonvalence silver
- Functional additives
- Solvent
A mouthwashAg0=10-20 mg/kg
The way to care for your mouth.
Eliminates bad breath, promotes treatment of gingivitis and other diseases of the oral cavity.
95- Nanodispersed nonvalence silver
- Functional additives
- Topical or gel-based
Gel, ointment savetofileAg0=50-500 mg/kg
Gel, ointment for protection against ultraviolet radiation in the wavelength range 360-420 nm can be achieved C is achene optical density D to 6-20 units and more.
96- Nanodispersed nonvalence silver
- Functional additives
- Pigments nanodispersed
- Basis
Films, coatings SitophilusAg0=200-5000 mg/kg
The filters, protective masks, goggles for eye protection against ultraviolet and laser radiation in the range 200-1100 nm.
97- Nanodispersed nonvalence silver
- Functional additives
- Gel-based
Gel for bodyAg0=3-10 mg/kg
Gel for ultrasound with antibacterial and antiviral effect, reduces or eliminates the probability of transfer of pathogens.
98- Nanodispersed nonvalence silver
- Functional additives
- Solvent
Spray liquidAg0=10-20 mg/kg
The remedy for the prevention and treatment of rhinitis, intranasal tool, a tool for prevention and treatment of ENT diseases.
Drops, spray, liquid for rinsing
99- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Basis
DeodorantAg0=10-50 mg/kg
Cu0=10-100 mg/kg
Deodorant for the body.
Gel, spray, roll-on deodorant, wipes.
100- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Based ointment
Ointment for the treatment and prevention of animal diseasesAg0=10-50 mg/kg
Cu0=10-1000 mg/kg
Ointment for the treatment of dermatitis, ulcers, putrid diseases of the hoof, microbacteria, bruises, infected skin wounds and limbs.
The treatment procedure is repeated no later than 1-2 days. The treatment time is reduced to 5-7 days
101- Nanodispersed nonvalence silver
- Functional additives
- Gel-based
Gel for the treatment of mastitisAg0=50-200 mg/kg
Gel for the treatment of mastitis.
The gel is injected by syringe into the diseased udder in the amount of 5-10 grams.

102- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper Functional additives
The basis of the MAZ is th
Foot creamAg0=50-200 mg/kg
C0=10-100 mg/kg
Foot cream for the treatment of calluses and cracks on the feet, healing cracks on legs, damaged tissue, diaper rash and rubs, protection against bacteria and fungi. The cream is applied on the skin every evening.
103- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
- Based ointment
Gel footAg0=50-200 mg/kg
C0=10-100 mg/kg
Foot gel deodorant.
The cream is applied on the skin every morning and evening. Designed for anti-odor, reduces sweating.
104- Nanodispersed nonvalence silver
- Nanodispersed mulvanerty copper
- Functional additives
The base cream
Nourishing hand cream.Ag0=20-50 mg/kg
C0=5-10 mg/kg
Nourishing hand cream. Apply every day. Removing redness, irritation, softening of the skin.

1. A method of obtaining a concentrate of nanodispersions of silver, gold, copper, palladium, platinum, and mercury, characterized in that the process p is avodat for 10-60 min in daylight in an atmosphere of air and at temperatures up to 100°C, when this mix a solution of a soluble metal salt in a solvent with ammonia to produce complex compound, and then mixing the obtained compound with alkanolamines before the formation of the solution, then mixing the resulting solution with a solution of a polymeric stabilizer with obtaining stable cation metal, then restore stable the cation of the metal by adding to the solution of organic or inorganic reducing agent followed by the formation of a stable dispersion of nanoparticles nonvalence metal in the following ratio, wt.%:

Soluble salt of the metal (metal)0,013-2,5
Ammonia0,028-1,67
Alkanolamine0,196 is 5.54
Polymer stabilizerof 0.4 to 20.0
The restorer0,07-60
Solventthe rest,

and as alkanolamine use connection total
formula:
(HO-R)y(C)z-N(H)x,
where R is-CH2-or-CH2CH2-or-CH2-SSN 3;
y=1-3;
x=3-y;
z=0,1.

2. The method according to claim 1, characterized in that it additionally produce metal nanoparticles from the mixture in dry form.

3. The method according to claim 1, characterized in that the solvent used water, or ethyl and/or isopropyl alcohol, or glycerin, or acetone, or dimethyl sulfoxide or ethylene glycol, or formamide, or chloroform, or aqueous solutions of organic solvents.

4. The method according to claim 1, characterized in that as a soluble metal salt use nitrate, or acetate, or sulfate, or a metal chloride, or hydrochloric acid.

5. The method according to claim 1, characterized in that as alkanolamine use ethanolamine, or diethanolamine, or triethanolamine, or diisopropanolamine, or Tris-(oxymethyl)-aminomethan.

6. The method according to claim 1, characterized in that, as a polymer stabilizer medical use of low and medium molecular polyvinylpyrrolidone or polyvinyl alcohols and their derivatives, or gelatin or cellulose derivatives, or glycols or polyethylene oxides, or polyacrylamides or polymers and copolymers of acrylic acid and their salts, or albumin or dextran, or vegetable polysaccharides, or chitosans.

7. The method according to claim 6, characterized in that as a derivative of polyvinyl spirtovodochnaya polyvinylbutyral or polyvinylacetal.

8. The method according to claim 6, characterized in that as the cellulose derivatives used methylcellulose, or hydroxypropylcellulose, or carboxymethylcellulose, or sodium carboxymethyl cellulose.

9. The method according to claim 6, characterized in that as a polymer of acrylic acid using polyacrylic acid or carbomer.

10. The method according to claim 6, characterized in that as plant polysaccharides used gum.

11. The method according to claim 1, characterized in that in use as a reducing agent glycerin, or ascorbic acid or sodium ascorbate, or sodium citrate, or sodium borohydride, or hypophosphite sodium, or salt of divalent zinc.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: invention refers to catalytic cracking method of heavy oil stock with high content of resins and asphaltenes in presence of nanodimensional nickel powder with average particle size of 10-20 nm, which has been taken in quantity of 0.5-1.0 wt % for original stock, at temperature of 430-450°C and pressure of 0.5-1.0 MPa in tight autoclave in inert gas environment.

EFFECT: high output of distillate fractions without coke formation.

7 ex, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to biochemistry. Disclosed is a peroxidase enzymatic activity stabiliser. The stabiliser is in form of cobalt ferrospinel nanoparticles, components of which vary in the interval Co0.7±0.05Fe2.3±0.05O4-Co1±0.05Fe2±0.05O4, which are suspended in a sodium phosphate buffer solution with concentration of 0.01-10 mg/ml.

EFFECT: maintenance of 40-42% enzymatic activity of peroxidase for 105-255 days with given magnetisation intensity of cobalt ferrospinel particles.

2 tbl

FIELD: nanotechnologies.

SUBSTANCE: invention relates to ordered photochromic ferromagnet arrays of nanowires on the basis of (tris)oxalates of transition meals and cations of spirocyclic row and may be used as light-sensitive magnetic nanomedia with supercapacious magnetooptic memory. The assigned task is solved by compounds in the form of derivative (tris)oxalates of transition metals and cations of spirocyclic row with general formula PCMe1Me2(C2O4)3, where M1, M2 - 3d metals, PC - photochromic cations having photomagnet properties. Ordered arrays of nanowires of photochromic ferromagnets are produced by incorporation of above compounds into pores of the membrane from anodixed aluminium oxide (AOA), density of which makes 1011-1013 cm-2, and pore size is 20-200 nm. Ordered arrays of nanowires of photochromic ferromagnets are used as light-sensitive magnetic media for production of materials with supercapacious magnetooptic memory of up to 1013 bit/cm2.

EFFECT: development of ordered arrays of nanostructures, in which elementary cells are nanowires of photochromic material with magnetic ordering.

3 cl, 6 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to olefin hydroxidation catalysts. Proposed catalytic composition for production of olefin oxide by olefin hydroxidation comprises gold nanoparticles deposited on particles of nanoporous titanosilicate carrier. Note here that said catalyst is obtained by method including deposition of cluster complex gold-ligand on nanoporous titanosilicate carrier at minus 100°C to 300°C to produce catalyst precursor, and heating at not over 50-800°C and/or chemical treatment of catalyst precursor for 15 min to 5 h to form catalyst. Invention covers also the method of producing olefin oxide comprising bringing olefin with, at least, three carbon atoms in contact with oxygen in the presence of hydrogen and catalyst with above described composition. Note here that said contact is realized at 160°C and lower that 300°C and pressure varying from atmospheric pressure to 3549 kPa (500 psi). It covers also catalyst precursor composition including cluster complex ligand-gold deposited on particles of nanoporous titanosilicate carrier.

EFFECT: high catalytic activity, longer life and higher efficiency.

16 cl, 15 tbl, 19 dwg, 24 ex

FIELD: medicine.

SUBSTANCE: there are offered nanocomposites showing antiviral activity and used for intracellular viral genome inactivation. Said nanocomposites consists of titanium dioxide nanoparticles whereon polyamine oligonucleotide derivatives (PA-oligo) are immobilised. Polyamines contain 3 to 1000 aminogroups in a molecule, and preferentially represent polylysine, polyethyleneimine and spermine. The titanium dioxide nanoparticles can be presented both in amorphous, and in crystalline state (anatase, brookite). Said nanocomposites can penetrate into cells by common endocytosis without electroporation and other methods disturbing cell membranes. Besides, what is offered is a method for making titanium dioxide nanocomposites whereon conjugated oligonucleotides and linker are immobilised. The method provides making conjugated oligonucleotides and polyamines with yield 90-100%.

EFFECT: invention considerably simplifies a process for making the nanocomposites and maintained high immobilisation density of conjugated oligonucleotides on the titanium dioxide nanoparticles with higher strength of the surface binding.

12 cl, 5 dwg, 2 tbl, 32 ex

FIELD: medicine.

SUBSTANCE: invention refers to medicine. What is described is a method for deposition of a bioactive nano and microstructured calcium phosphate coating on a titanium and alloy implants involving anodic oxidation of titanium and alloys with the process performed in phosphoric acid of the concentration of 5-25% and sulphuric acid of the concentration of 5-10% additionally containing CaO powder to achieve a supersaturated condition and 5-10% hydroxylapatite suspension of the dispersion less than 70 mcm in this supersaturated solution supplied by direct or pulse current 80-250 V in a spark discharge environment at pulse repetition frequency 0.3-15.0 Hz for 10-40 min at constant stirring and temperature 20-35°C and additionally placed in a special medium possessing osteogenic and antimicrobial activity for 30-60 minutes at temperature 20-37°C. The coatings are used for the purpose of providing better fixation of introduced implants if standard techniques fail to ensure stable coupling with bone tissue and the presence of an infectious process.

EFFECT: development of the effective method for coating deposition.

1 tbl, 3 dwg, 2 ex

FIELD: physics.

SUBSTANCE: method of forming an ordered array of nanosized spheroids on a substrate involves transfer of a film substance deposited on the surface of a transparent donor plate onto an acceptor substrate via pulsed laser exposure of the film through the plate, wherein a sacrificial interlayer which evaporates upon exposure, is deposited between said film and plate.

EFFECT: high resolution of forming a pattern, possibility of making microstructures with minimum dimensions, much smaller than the wavelength of radiation which initiates the technological process.

5 cl, 3 dwg

FIELD: physics.

SUBSTANCE: copper ions are implanted into quartz glass with radiation dose of 5·1015-2·1017 cm-2 and ion energy of 35-45 keV. The luminophor is then thermally treated in an air atmosphere at temperature 750-900°C for 1-2 hours, followed by treatment with ultraviolet radiation in the 240-260 nm wavelength range. The ultraviolet radiation source used can be an ultra-high pressure mercury lamp, a deuterium low-pressure lamp or a KrF excimer laser. Curve 1 shows the luminescence spectrum of a luminophor treated with a KrF excimer lamp, while curve 2 shows the luminescence spectrum of a luminophor treated with a low-pressure deuterium lamp and curve 3 shows the luminescence spectrum of a thermally treated luminophor without treatment with ultraviolet radiation.

EFFECT: high luminescence intensity and possibility of controlling the luminescence spectrum.

1 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention can be used to produce materials used particularly for packaging film with barrier properties, cable sheath and other polymer articles in machine building. The exfoliated nanocomposite polymer/clay is obtained by mixing a matrix polymer and nanofiller - clay, modified with a quaternary ammonium salt. The process is carried out with shear grinding at temperature higher than the melting point of the matrix polymer until achieving nanofiller concentration of 51-70 wt %. The matrix polymer is then added to the obtained mixture until achieving nanofiller concentration of 0.1-30 wt %.

EFFECT: invention increases clay exfoliation efficiency, mechanical properties of the nanocomposite and reduces power consumption when producing said nanocomposite.

2 tbl, 12 dwg, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to hardening of cutting tool. Cutting tool is subjected to plastic deformation to produce nanocrystalline structure on its surface. Said plastic deformation is carried out at intensive deforming attack by pulses of ultrasound frequency of 20-25 kHz produced by cylindrical penetrators that moves axially along normal line to machined surface with impact power of 0.3-0.9 kgf and local heating of contact point to 300-500°C.

EFFECT: higher hardness, deeper nanocrystalline structure of surface layer.

FIELD: metallurgy.

SUBSTANCE: the invention relates to powder metallurgy, in particular, to metal powder products. It can be used in production of ceramic metal materials for interrupting contacts based on silver and used in low-voltage equipment. The intermediate thermally unstable composition components Ag2O and Na2SnO3 are produced during the single-stage deposition from the solution containing AgNO3, Na2SnO3 and NaOH. The deposit containing SnO2 is extracted from the resulting mixute, and the mixture is dried and thermally processed.

EFFECT: production of material with equal distribution of finely dispersed oxide phase over the whole volume.

3 dwg, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of nano-sized powders of iron-group metals used in data record-and-store systems and magnetic sensors intended for medicine, biology etc. Proposed method comprises preparing solution of salts of iron sulfate heptahydrate and cobalt chloride hexahydrate, its heating and depositing by metal alkali in the form of iron and cobalt hydroxides in continuous mixing. Note here that, in mixing, 20-25 g of solid sodium hydroxide alkali is added in solution to deposit iron and cobalt hydroxides. Then, 20-40 ml of solution of 65 wt % of hydrazine hydrate is added and allowed for 5-20 minutes.

EFFECT: nano-sized powder with no oxide-hydroxide compounds and diamagnetic impurities.

3 cl, 1 tbl, 3 dwg, 17 ex

Method of reduction // 2431546

FIELD: process engineering.

SUBSTANCE: invention relates to metallurgy, namely, to producing barrier metal powders. Mix containing precursor of barrier metal and nonreacting liquid diluter is fused in first reactor. Said mix is placed in at least second reactor to add reducing agent therein. Reduction of barrier metal precursor to barrier metal is conducted at temperature and in interval that allow initiating reduction reaction. Produced powder features particle shape factor f defined from REM-images in the range of 0.65≤f≤1.00.

EFFECT: powder with uniform grain size with dense size distribution containing less than 20 ppm of magnesium admixture.

38 cl, 1 dwg, 2 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention refers to manufacturing method of nanoparticles of metallic silver with diameter of 1 to 100 nm and average diameter of 20 to 40 nm, which are characterised with monodispersion, stability during more than 12 months, in wide range of concentrations. Method involves preparation of water solution of silver salt, which contains 0.01 to 20 wt % of soluble silver salt; preparation of water solution of reducing agent, which contains 0.01 to 20 wt % of the compound of group of tannins; mixing of the above water solutions in order to perform the reaction between them, separation of mother solution from silver nanoparticles obtained in the above reaction. At that, the above reaction is performed by mixing those solutions and pH control in the value range of 10.5 to 11.5. Obtained particles can be repeatedly dispersed in various media, such as water, alkydal and phenol resins, cellulose nitrate, polyurethane resin, vinyl and acrylic compounds, alcohols and in many organic materials and polymers, such as high-density and low-density polyethylenes, nylon, acrylonitrile-butadiene-styrene resin and/or their mixtures.

EFFECT: obtaining nanoparticles of metallic silver, which are characterised with monodispersion, stability during more than 12 months in wide value range of concentrations.

20 cl, 5 dwg

FIELD: metallurgy.

SUBSTANCE: method for obtaining nanostructure metal particles involves sorption of metal ions on cationite, desorption of metal ions with water and reduction of desorbed metal ions. At that, ion desorption is performed from cationite containing up to 35% of ions from total exchange capacity (TEC) of cationite. Desorption and reduction is performed by washing off the cationite with water to solution of the substance of the group of flavonoids. During sorption there used are ions of such meals as Ag, Cu, Ni, Fe, Cd. Desorption of metal ions is performed to solution of flavonoids with concentration in the range of 2·10-5 - 30·10-5 M to concentration of metal ions in the range of 2·10-4 - 5·10-3 M.

EFFECT: obtaining nanoparticles at total exchange capacity of cationites, enlarging the range of obtained nanoparticles of metals in "cationite-water solution of ions" system.

3 cl, 1 ex

FIELD: metallurgy.

SUBSTANCE: procedure for production of nano-structured agglomerate of metal cobalt consists in interaction of solutions of cobalt salt of general formula CoX2, where X2 are chlorides, nitrates and/or sulphides with reagents and in reduction at higher temperature. A stabilising agent is introduced into solution before reaction of solutions of cobalt salts with reagents. As a stabilising agent there is used sodium-potassium tartrate. Simultaneously introduced alkali in form of NaOH or KOH are used as reagents at interaction and reduction, while as a reducing agent there is used hydrazine hydrate.

EFFECT: production of new nano structured fractal agglomerates of metal cobalt by simple method under soft process conditions; production of target product of high purity.

7 cl, 4 dwg, 5 ex

FIELD: metallurgy.

SUBSTANCE: procedure for production of nano dispersed copper powder by reduction consists in mixing copper salt with solution of glucose, in dissolving salt at heating, in introduction of sodium hydroxide, in conditioning under isothermal mode and in successive extraction of metal copper in form of nano dispersed powder. Also, sulphate of copper is used as copper salt. Copper sulphate is mixed with solution of glucose at mole ratio of glucose to copper equal to (1.0-2.5):1.0. Dissolving is carried out at 50-60°C. Sodium hydroxide is introduced upon complete copper sulphate dissolving and solution heating to temperature 70°C. It is carried out gradually at several stages for maintaining pH equal to 6-11 in process of reduction reaction, preferably, to 8-9, first to formation of oxide of univalent copper, and further to metal copper.

EFFECT: simplified, with reduced prime cost process of production of nano dimension particles of copper due to reduced number of process operations of synthesis.

2 cl, 3 dwg, 1 tbl, 16 ex

FIELD: process engineering.

SUBSTANCE: invention relates to hydrometallurgy of nonferrous metals, particularly, to production of bismuth powder modified by metal catalyst, thermoelectric materials, light alloys and medicinal preparations. Proposed method comprises reducing modifying metal and removing impurities formed in reduction. Note here that reduction is performed by processing bismuth powder by solution of appropriate modifying metal at solution pH=0.3-3.0. Impurity, bismuth main salt, is carried in reduction on adding ethylene diamine tetraacetic acid or sodium ethylenediaminetetraacetate to salt solution at solution pH=0.6-3.0 and molar ratio of ethylenediaminetetraacetate-ions to bismuth equal to 1.0-1.5. Impurity is removed on flushing obtained product by ethylene diamine tetraacetic acid or sodium ethylenediaminetetraacetate solution at pH=0.6-7 and molar ratio of ethylenediaminetetraacetate-ions to bismuth equal to 1.0-1.5.

EFFECT: simplified process, higher product purity.

3 cl, 1 tbl, 7 ex

FIELD: metallurgy.

SUBSTANCE: nano particles of gold are used in perfume, cosmetic and jewel industries, also for treatment and diagnostics of diseases. The procedure for production of nano particles of gold consists in reduction of precursors of gold contained in solution using an extract of tea leaves as reducer. Solution containing precursors of gold is made of iron ore stock by ion flotation of iron ore stock. Further, produced concentrate is dissolved in aqua Regis and ions of gold are flotation extracted with surface-active substances into extract. Upon flotation extraction they are concentrated.

EFFECT: expanded set of precursors and nano particles of gold produced from them, namely, production of nano particles of hybrids of nano particles of gold out of iron ore stock.

1 ex

FIELD: metallurgy.

SUBSTANCE: in compliance with proposed method, solution of metal complex salt is obtained by interaction between of the mix crystallohydrated metal salt solution and complexing agent taken in stoichiometric relationship. Powder is settled from produced solution by introducing reducing agent therein. The latter represents powder of zinc or aluminium in amount of 100-200 kg/t of crystallohydrated salt to produce suspension. Note here that solution is heated to 70-80°C and conditioned on mixing for 2-3 hours. Suspension is filtered, rinsed and dried.

EFFECT: reduced power consumption, simple equipment and high purity.

3 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to microcapsules used in agrochemical compositions as part of any type of composition used to in agriculture, as well for microencapsulation of pharmaceutical and medical compounds, flame-retardants, phase transition materials, thermosetting materials, ink and catalysts. The microcapsules contain a material with water solubility of less than 750 mg/l at 20°C. The wall of the microcapsules is formed via interphase polymerisation of materials which form the wall: (a) aliphatic isocyanate(s), and (b) aromatic isocyanate(s), and (c) compound(s) of formula (I), acetylene carbamide derivatives

,

where R1, R3, R5, R7 independently denote methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butylene, tert-butyl; R2, R4, R6, R8 independently denote hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; R9, R10 denote hydrogen or hydroxymethyl; including oligomeric forms of compounds (I), where the number of moles of compounds (I) ranges from 2 to 10; and the microcapsules have average diameter from 0.3 to 25 mcm when using a conventional laser diffraction analyser to measure particle size with preliminary conventional dissolution in water while stirring. The invention also describes a method of producing an agrochemical composition of a typical encapsulated suspension, containing said microcapsules, and versions of using said microcapsules.

EFFECT: obtaining microcapsules with possibility of controlling the speed of release of the microencapsulated material, and improvement of the toxicological profile of the microcapsules and compositions containing said microcapsules.

12 cl, 12 ex, 13 dwg

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