WO2011071417A1

WO2011071417A1 - Bactericidal sorbent material and method for producing same

Info

Publication number: WO2011071417A1
Application number: PCT/RU2010/000734
Authority: WO
Inventors: Марат Израильевич ЛЕРНЕР; Елена Алексеевна ГЛАЗКОВА; Сергей Григорьевич ПСАХЬЕ; Наталья Витальевна КИРИЛОВА; Наталья Валентиновна СВАРОВСКАЯ; Ольга Владимировна БАКИНА
Priority date: 2009-12-07
Filing date: 2010-12-06
Publication date: 2011-06-16
Also published as: RU2009145229A; RS1350U; RU2426557C1; BR112012013697A2; DE212010000186U1; RS20120233A1

Abstract

The invention relates to the field of bactericidal sorbent materials for purifying liquids and gases from finely dispersed particles and microbiological pollutants, including for medical use, said sorbent materials having enhanced bactericidal properties while the sorptive properties of the material are maintained. The bactericidal sorbent material comprises at least one base layer made of a non-woven fibrous polymer material with aluminium oxide hydrate particles attached to the fibres thereof, and an inorganic bactericidal component, wherein the inorganic bactericidal component is sorbed on the high-porosity aluminium oxide hydrate particles. A method for producing the material and a method for filtering liquid or gaseous media are also claimed, as well as a medical sorbent for therapeutic and/or hygienic articles, including wound dressings.

Description

SORPTION-BACTERICIDAL MATERIAL AND METHOD FOR PRODUCING IT

FIELD OF TECHNOLOGY

The invention relates to the field of development of sorption-bactericidal materials for the purification of liquids and gases from fine particles and mythobiological contaminants, including for medical purposes. More specifically, the invention relates to the modification of sorption materials, as well as to a manufacturing method and methods for using sorption-bactericidal material.

Nowadays, the need for highly effective sorbents characterized not only by high selectivity, speed and completeness of the extraction of substances from various media, but also by simultaneous bactericidal treatment, for example, for treating drinking water, air, or use as medical sorbents, is becoming more and more urgent. Most of the currently existing bactericidal sorption materials are obtained mainly by modifying organic or inorganic sorbents with silver, less often iodine or other compounds. When filtering various media, microbiological contaminants are sorbed by materials, which are widely used materials with granular and fibrous structures, while the viability of myth-organisms is not only preserved, but their reproduction is in progress. As a result, biofouling of sorbents and the release of microorganisms into the filtrate occur. Prevention of biofouling of sorbents remains an urgent problem, and the development of new sorbents is aimed at solving this problem.

It is known in the art to use powdered activated carbon with a particle size of from 0.1 to 2000 microns. In an integrated method for deep purification and conditioning of water [WO 96/20139 A1, 1996] the treated water is subjected to preliminary filtration,

SUBSTITUTE SHEET (RULE 26) sorption treatment and final microfiltration on filter elements with a pore size of 0.5-10 microns. In this process, numerous sorbents are used in the cleaning process, including a bactericidal sorbent - a silver form of activated carbon.

Also known is a sorption-filtering three-layer fibrous material for gas purification [RU 2188695 C2, 2002], the middle layer of which is made of ultrafine perchlorovinyl fibers containing activated carbon particles treated with silver nitrate, or from activated carbon fibers treated with silver nitrate.

All of the above materials were obtained by treating the carrier material with metal salts, for example, a silver salt solution. The bactericidal additive is on the surface of these materials either in the form of isolated ions or in the form of complex compounds. These materials, mentioned above, do not provide the necessary level of cleaning efficiency from colloidal particles and viruses, the size of which is within 30 nm. To the disadvantages is added that the bactericidal properties of the materials used are determined by the ions of the bactericidal components that pass into the cleaned medium during the filtration process, thus polluting it. In addition, to ensure the duration of the preservation of bactericidal properties for these materials, it is necessary to impregnate carriers with concentrated solutions of metal salts, while it is known that at certain elevated concentrations of bactericidal metal ions they are toxic. Water containing silver ions has a toxicological effect on the human body, since silver belongs to highly hazardous substances according to the degree of harmful effects on higher organisms according to GOST 12.1.007-76. According to sanitary standards, the maximum concentration limit for silver in drinking water is 0.05 mg / l. In addition, all known methods for producing modified sorbents are associated with prolonged chemical surface treatment of the matrix with a bactericidal additive. Therefore, these bactericidal materials cannot be used for the purification of highly pure liquids, as well as for the purification of pharmaceuticals, drinking water and other liquids consumed by humans. Known [US2008026041 A1, 2008] is a filter material in which, for the antimicrobial effect, nanofibres of aluminum oxide are impregnated with ionic silver. The disadvantages of using ionic silver are noted above.

Recently, interest in the special conditions of materials, the so-called metallic nanoaggregates, has intensified. Aggregates are colloidal particles of metals of nanostructured sizes and have special, unexpected properties, different both from the properties of isolated atoms and from bulk metal. Increased reactivity is associated with a more developed surface area and a more active surface of nanostructured particles. Stable nanostructured particles, for example, silver, have a high bactericidal activity and are of interest for creating effective bactericidal filter elements on their basis for cleaning various media, ensuring effective cleaning not only of various impurities, but also of pathogens.

In medical practice and veterinary medicine, the antimicrobial action of metals such as Ag, Au, Pt, Pd, Cu, and Zn is widely known [H.E, Morton. Pseudomonas in Disinfection, Sterilization and Preservation, ed. SS Block, Lea and Febider 1977 and N. Grier Silver and Its Compounds in Disinfection, Sterilization and Preservation, ed. SS Block, Lea and Febiger, 1977]. Although these compounds are effective as soluble salts, they do not provide long-term protection because they are lost due to leaching or complexation of free silver ions. To solve this problem, these compounds must be renewed at short intervals. Repeated the use is not always practicable, especially in cases where permanent or implanted medical devices are used.

A dressing kit is known [RU 71068 U1, 2008], in which the layer in contact with the skin has an additional layer containing metal particles of silver nanoparticles from 80 to 99.7%, iron from 0.1 to 20%, aluminum from 0, 1 to 20%, copper from 0.1 to 20% and a wound cover [RU 2314834 C1, 2008] based on woven and non-woven materials of natural or synthetic origin, containing metal particles having biological activity to the pathogenic flora, while as particles metal it contains silver nanoparticles from 80 to 99.7%, iron from 0.1 to 20%, aluminum from 0.1 to 20%, copper from 0.1 to 20%. Metal nanoparticles are deposited in a vacuum chamber using magnetron sputtering. The dressing kit is expensive and is obtained by sophisticated technology.

The closest in technical essence and the achieved result to the claimed material, the method of its manufacture and the filtering method is an embodiment of a filter material for a gaseous medium [WO 2009031944 A2, 2009], which contains as a basis at least one layer of non-woven polymer fibrous material on the fibers of which are fixed particles of aluminum oxide hydrate. The material further comprises an antimicrobial additive represented by silver nitrate. The disadvantages of this material include the use, primarily, of ionic silver, since silver in ionic form is less active than silver in the form of colloidal silver as a bactericidal component. Also described is a method of obtaining a filter material for a gaseous medium in which particles of an aluminum-based material are applied in the form of an aqueous or aqueous-alcoholic suspension, and then hydrolysis of the particles of an aluminum-based material is carried out. Additionally, antimicrobial substances are introduced into the aqueous or aqueous-alcoholic suspension before applying it to the base. To the main The disadvantage of the prototype material production method can be attributed to the fact that the ion sizes of silver nitrate used do not allow sorption on aluminum oxide hydrate particles and are retained by them, and therefore they pass into the cleaned medium during the filtration process, thus polluting it. A filtering method is also described, including contacting a gaseous medium with a filtering material, in which the material is used to filter only gaseous media and is not suitable for filtering liquid media, and this is its drawback.

The application [US 2008026041 A1, 2008] proposes a medical structure that we have chosen as a prototype for the proposed collection-bactericidal material as a medical sorbent. The medical structure includes, along with alumina nanofibres, second fibers mixed with alumina nanofibres, and particles dispersed on alumina nanofibres. The aforementioned particles may be a silver bactericidal agent.

Since this medical structure is made using paper technology, i.e. the interfiber pore space is small, it does not have sufficient sorption capacity to absorb and retain wound exudate, which is the most important property of wound dressings.

Thus, it is obvious that there is a need for fundamentally new materials for better cleaning of liquid and gaseous media from particles of the smallest sizes, including pathogenic microflora.

SUMMARY OF THE INVENTION

The technical problem to which the present invention is directed, was the creation of a new sorption material with improved bactericidal properties while maintaining the sorption properties of a material suitable for sterilization of liquid or gas environments and sorption of fine particles, providing the possibility of long-term operation without biofouling, as well as preventing secondary bacterial infection of the filtrate and its contamination with heavy metals.

Another technical challenge facing the developers was the development of a new, less long and laborious way of modifying sorption material.

The next technical objective of the invention was the development of a filtering method, including ensuring contact of liquid and gaseous media with the proposed sorption-bactericidal material.

The next objective of the invention was the expansion of the arsenal of non-woven medical materials with high sorption properties, as well as antibacterial and antiviral activity and, as a result, wound healing ability.

The task in the implementation of the claimed group of inventions on the subject - sorption-bactericidal material is achieved by the fact that the claimed sorption-bactericidal material includes at least one layer of a base of non-woven polymeric fibrous material with particles of aluminum oxide hydrate and an inorganic bactericidal component fixed on its fibers .

The peculiarity lies in the fact that the inorganic bactericidal component is adsorbed on particles of aluminum oxide hydrate.

Moreover, the highly porous particles of alumina hydrate have a substantially plate-like shape with a side of 100-200 nm and a thickness of 5-8 nm.

In addition, at least part of the alumina hydrate particles is grouped into agglomerates of size 0.2-5.0 μm, specific surface area 100-350 m ² / g, porosity 50-95%.

In addition, the number of particles of aluminum oxide hydrate in it is 15-45 wt.%.

Also, a base of non-woven polymeric fibrous material it is formed by cellulose acetate, polysulfone or other bioinert polymer fibers having a diameter of 0.1-10 microns, preferably 1-3 microns.

Moreover, the aforementioned material is obtained, for example, by the method of electroforming or melt-blown technology, which allows to obtain non-woven materials with the mentioned fiber diameter.

It is advisable that the content of the inorganic bactericidal component in the material is 0.05-2.5 mg / g of material.

It is also advisable that colloidal silver particles or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol are selected as the inorganic bactericidal component.

In addition, the particles of colloidal silver have a substantially spherical or nearly spherical shape in size from 5 to 50 nm, mainly 20-30 nm. The task is also achieved by the fact that in the method of producing sorption-bactericidal material on the base layer of non-woven polymer fibrous material, particles of an aluminum-based material are applied in the form of an aqueous or aqueous-alcoholic suspension, followed by hydrolysis of the particles of an aluminum-based material.

What is new is that the base of non-woven polymeric fibrous material with aluminum oxide hydrate particles fixed on its fibers is additionally treated with an inorganic bactericidal component to sorb the latter on particles of aluminum oxide hydrate.

In addition, the treatment is carried out by impregnation with a solution of an inorganic bactericidal component or by spraying the latter onto the material. In addition, the solution is impregnated with an inorganic bactericidal component for 10 minutes to 24 hours, preferably for 30-60 minutes, at room temperature.

Also, the processing time by spraying a solution of an inorganic bactericidal component on the material is determined by the method of applying the solution to the material, for example, manually or automatically.

It is advisable that the treatment is carried out until the content of the inorganic bactericidal component in the material is 0.05-2.5 mg / g of material.

Particles of colloidal silver or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol were selected as the inorganic bactericidal component.

In addition, the particles of colloidal silver are essentially spherical or close to spherical in size from 5 to 50 nm, mainly 20-30 nm.

Preferably, the treated sorption-bactericidal material is dried at a temperature of 80-100 ° C for 2-4 hours.

In addition, the particles of aluminum oxide hydrate are essentially plate-shaped with a side of 100-200 nm and a thickness of 5-8 nm, at least a portion of the particles of aluminum oxide hydrate are grouped into agglomerates of a size of 0.2-5.0 microns, specific a surface of 150-350 m ² / g, porosity of 50-95%, while the number of particles of aluminum oxide hydrate in the non-woven polymer fibrous material is 15-45 wt.%. The base of the nonwoven polymeric fibrous material is formed by cellulose acetate, polysulfone or other bioinert polymer fibers having a diameter of 0.1-10 microns, preferably 1-3 microns.

Moreover, the above material was obtained, for example, by the method electroforming, Melt-Blown technology, allowing to obtain non-woven materials with the mentioned fiber diameter.

It is advisable that as a material based on aluminum use a material with a particle size of less than 1 μm.

It is preferable that an aluminum powder is used as an aluminum-based material with a specific surface area of 7-28 m ² / g, obtained by the method of electric explosion of wire or another method that allows to obtain aluminum powders of a given size.

It is also preferable that an aluminum-aluminum nitride powder with an AI / AIN percentage ratio of 95: 5 to 5:95, preferably with an AIN content of 30-70% and a specific surface area of at least 7, be used as an aluminum-based material. m ² / g, preferably 11-27 m ² / g. obtained by the method of electric explosion of wire or another method that allows to obtain aluminum powders of a given size and composition.

The problem is also solved by the fact that the method of filtering liquid or gaseous media involves passing a liquid or gaseous medium through a sorption-bactericidal material made according to any one of claims 1 to 9 and obtained by the method according to any one of claims 10-23. Also the fact that the sorption-bactericidal material is part of the filter.

At the same time, sorption-bactericidal material retains electronegative particles, for example, bacteria, viruses, highly dispersed and colloidal particles, humic substances, bacterial endotoxins, nucleic acids, proteins, enzymes, etc.

It is advisable that when filtering liquid media, 8-14 layers of sorption-bactericidal material are used to hold electronegative particles, for example, bacteria, viruses, bacterial endotoxins, nucleic acids, proteins, enzymes, etc. It is advisable that when filtering liquid media, 2-4 layers of sorption-bactericidal material are used to retain highly dispersed and colloidal particles, humic substances.

Moreover, the specified liquid medium is water, an aqueous solution, a biological fluid.

It is advisable that when filtering gaseous media, 2-8 layers of sorption-bactericidal material are used to retain highly dispersed mechanical impurities, bacteria, and viruses.

The problem is also solved by the fact that the medical sorbent includes at least one layer of sorption-bactericidal material made according to any one of claims 1 to 9 and manufactured by the method according to any one of claims. 10-23, for medical and / or hygiene products, including wound dressings.

The invention is illustrated by figures 1-4. Figure 1 shows highly porous particles of aluminum oxide hydrate in the form of unsystematically curved plates of irregular geometric shape (the picture was taken by transmission electron microscopy).

Figure 2 shows an agglomerate of particles of alumina hydrate with sorbed colloidal silver particles, which are visible at the periphery of the agglomerate in the form of denser rounded inclusions (the image was taken by transmission electron microscopy).

Fig. 3 shows agglomerates of alumina hydrate particles attached to a fiber of a nonwoven polymeric material (image taken by scanning electron microscopy).

Figure 4 shows randomly arranged fibers of a nonwoven polymeric material with highly porous particles of aluminum oxide hydrate attached to them (the picture was taken by scanning electron microscopy). W

eleven

BEST MODE FOR CARRYING OUT THE INVENTION

As the sorption material, a non-woven polymeric fibrous material is used, modified by particles of aluminum oxide hydrate, which has high microorganism retention efficiency and, at the same time, low hydrodynamic resistance, has a developed specific surface area, high positive charge on the particle surface and high porosity to provide the necessary speed filtering. Alumina hydrate obtained by hydrolysis of aluminum nanopowders has a high specific surface and an electropositive charge. The advantage of materials made of polymer fibers is their chemical and biological inertness, the ability to maintain mechanical strength even after prolonged exposure to water, and is also able to absorb and retain a large volume of liquid in the interfiber pore space. These materials do not undergo microbiological decomposition, which is very important in the manufacture of filters. The non-woven polymeric material is formed by fibers, for example, from cellulose acetate, polysulfone, just has sufficient porosity and has a fiber diameter of 0.1-10 microns, preferably 1-3 microns. The use of a material with a smaller fiber diameter leads to an increase in the hydrodynamic resistance of the material, and fewer particles of aluminum oxide hydrate are attached to the material with a larger fiber diameter, which reduces the efficiency of cleaning the liquid and gaseous mixture from microorganisms and colloidal particles. Such materials with the desired fiber diameter are obtained by various methods, for example, by the method of electroforming, melt-blown technology, etc.

The highly porous alumina hydrate particles fixed on the base have a substantially plate-like shape with a side of 100-200 nm and a thickness of 5-8 nm. The term “plate-like shape” of alumina hydrate particles is chosen because they are, most often, irregularly curved irregular plates geometric shape. Part of the particles of aluminum oxide hydrate is grouped into agglomerates with a size of 0.2-5.0 μm, a specific surface area of 100-350 m ² / g, and a porosity of 50-95%. The minimum size of the agglomerates is determined by the size of the individual alumina hydrate plate, and the maximum size is determined by the initial concentration of the suspension of particles of aluminum-based material and their distribution along the length of the fiber of the base of non-woven polymeric material during the impregnation and subsequent hydrolysis of aluminum. The number of particles of alumina hydrate in the material is 15-45 wt.%. With a lower content of alumina hydrate particles in the material, the required sorption efficiency is not provided, and the upper limit of the alumina hydrate particles is determined by the sorption properties of the base of non-woven polymeric fibrous material.

This material described above can be modified with a bactericidal component to give it antibacterial properties. As the bactericidal component, for example, colloidal silver particles or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol, or other drugs can be used. In this case, preference is given to colloidal silver particles. The content of the bactericidal component in the material is justified and amounts to 0.05-2.5 mg / g of non-woven material. Such a content of colloidal silver or iodine provides a bactericidal effect, and at the same time, the content of silver or iodine in the filtrate does not exceed the maximum permissible level and there is no secondary contamination of the filtrate with silver. Particles of colloidal silver are essentially spherical or close to spherical in size from 5 to 50 nm, mainly 20-30 nm. Particles of this size are well sorbed and retained by alumina hydrate particles.

Obtaining the inventive sorption-bactericidal material is as follows. First of all, an aqueous or water-alcohol suspension of particles of an aluminum-based material with subsequent hydrolysis of the particles of the aluminum-based material to fix the alumina hydrate particles to the base fibers. As an aluminum-based material, an aluminum powder with a specific surface area of 7-28 m ² / g obtained by the method of electric explosion of wire or another method that allows to obtain aluminum powders of a given size is used. As an aluminum-based material, an aluminum-aluminum nitride powder with a percentage ratio of AI / AIN from 95: 5 to 5:95, preferably 70: 30% and with a specific surface area of at least 7 m ² / g, preferably 1 1-27, is used m ² / g. obtained by the method of electric explosion of wire or another method that allows to obtain aluminum powders of a given size and composition. The hydrolysis is carried out at a temperature of 30-80 ° C, preferably at 50-60 ° C for 30-90 minutes. The aluminum hydrolysis reaction has a sufficiently long induction period, which requires additional energy costs. The hydrolysis of the aluminum nitride composition (AI / AIN) proceeds with a shorter induction period, and the hydrolysis reaction rate is higher than in the case of aluminum hydrolysis. Next, the basis of non-woven polymeric fibrous material with particles of aluminum oxide hydrate attached to it is squeezed to remove excess moisture under vacuum and dried at a temperature of 20-100 ° C for 2-4 hours. Then, the resulting sorption material is treated with an inorganic bactericidal component. The treatment consists in impregnating a solution of an inorganic bactericidal component for a period not exceeding 24 hours at room temperature, preferably for 30-60 minutes, or spraying the latter onto the material. The processing time by spraying a solution of an inorganic bactericidal component on the material is determined by the method of applying the solution to the material, for example, manually or automatically. Processing is carried out until the content of the inorganic bactericidal component in 0.05-2.5 mg / g of nonwoven material. Particles of colloidal silver or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol are not accidentally selected as an inorganic bactericidal component. In the case of using colloidal particles silver, the latter are better sorbed and retained by sorption material in comparison with silver ions. Silver ions are used mainly for the inactivation of microorganisms in solution and in filtering devices with a short service life. In addition, colloidal silver particles have a higher bactericidal activity compared to larger silver particles and silver ions. Particles of colloidal silver adsorbed on highly porous particles of alumina hydrate destroy microorganisms held by this sorption material. The bactericidal effect of this material with colloidal silver particles persists for a long time due to the fact that silver does not leach into the filtrate.

A method of producing colloidal silver is known [Analytical chemistry of silver. I.V. Pyatnitsky, V.V. Sukhan. M: Science. 1975. S. 60] and is based on the reduction of silver nitrate with tannin in an alkaline environment.

The concentration of colloidal silver in the resulting solution determines the particle size of colloidal silver and ranges from 14 to 140 mg / L. This concentration range is selected to obtain colloidal silver particles ranging in size from 5 to 50 nm. It is necessary to process the sorption material with such an amount of a solution of colloidal silver so that after its processing particles of colloidal silver 0.05-2.5 mg / g are adsorbed on it.

Obtaining a complex of iodine with polyvinylpyrrolidone and a complex of iodine with polyvinyl alcohol is also known [Mokhnach V.O. Iodine and problems of life. P., 1974. 254 s].

After processing the sorption material with a complex of iodine and polyvinylpyrrolidone, iodine from 0.05-2.5 mg / g is fixed on it.

The treated sorption-bactericidal material is dried at a temperature of 80-100 ° C for 2-4 hours. The present invention provides a fundamental opportunity to solve these problems by imparting the required sorption and bactericidal properties to the non-woven polymer material. The invention is illustrated by the following examples and tables.

Example 1

For the manufacture of sorption material used a sheet of non-woven polymeric fibrous material from cellulose acetate grade PA-15-2. A sheet of non-woven polymeric fibrous material with a size of 50 * 50 cm was placed in an aqueous suspension of particles of an aluminitride composition with an AI / AIN-60: 40 ratio, kept for 20 minutes, then hydrolysis was carried out in a dry heat oven at a temperature of 60 ° C. Then, the obtained filter material was dried at 100 ° C to constant weight, and the content of alumina hydrate was determined by the gravimetric method. The content of alumina hydrate in the sorption material was 35%.

For the manufacture of sorption-bactericidal material, a sample of sorption material was impregnated with a solution of colloidal silver. A solution of colloidal silver was prepared according to the following procedure: 30 ml of a buffer solution (pH 9.6), 20 ml of a tannin solution of 0.1% concentration, 10 ml of a 0.025 M silver nitrate solution were added to 940 ml of distilled water. In the resulting solution, the content of colloidal silver is 27 mg / L. To prepare a buffer solution, a 0.05 M sodium tetraborate solution was added to 26.8 ml of a 0.1 M sodium hydroxide solution to a volume of 100 ml.

A sample of sorption material was placed in the resulting solution, kept for 30 min at room temperature, squeezed and dried at a temperature of 100 ° С for 4 hours. In the prepared sorption-bactericidal material, the content of colloidal silver was 0.3 mg / g.

Example 2

For the manufacture of sorption material used a sheet of non-woven polymeric fibrous material from polysulfone with an average fiber diameter of 2 microns. A sheet of non-woven polymeric fibrous material measuring 50 * 50 cm was placed in an aqueous suspension of particles of an aluminitride composition with an AI / AIN-70: 30 ratio, kept for 20 min, then hydrolyzed in a dry heat oven at a temperature of 60 ° C. Then, the obtained filter material was dried at 100 ° C to constant weight, and the content of alumina hydrate was determined by the gravimetric method. The content of alumina hydrate in the sorption material was 31%.

For the manufacture of sorption-bactericidal material, a sample of sorption material was impregnated with a solution of colloidal silver. A colloidal silver solution was prepared according to the following procedure: 30 ml of a buffer solution (pH 9.6), 20 ml of a tannin solution of 0.1% concentration, 15 ml of a 0.025 M silver nitrate solution were added to 940 ml of distilled water. In the resulting solution, the content of colloidal silver is 40 mg / L. To prepare a buffer solution, a 0.05 M sodium tetraborate solution was added to 26.8 ml of a 0.1 M sodium hydroxide solution to a volume of 100 ml.

A sample of sorption material was placed in the resulting solution, kept for 60 min at room temperature, squeezed and dried at a temperature of 100 ° С for 4 hours. In the manufactured sorption-bactericidal material, the content of colloidal silver was 0.9 mg / g.

Example 3

For the manufacture of sorption-bactericidal material, a sample of the sorption material according to example 1 or 2 was impregnated with a solution of a complex of iodine with polyvinylpyrrolidone (complex of iodine with polyvinyl alcohol). A solution of the complex of iodine with polyvinylpyrrolidone was prepared according to the following procedure: 140 g of polyvinylpyrrolidone was dissolved in 0.8 l of distilled water, 150 ml of a solution containing 10 g of crystalline iodine and 10 g of potassium iodide was added, then the volume was adjusted to 1 l. Analysis of the obtained aqueous solution of iodine, potassium iodide and polyvinylpyrrolidone showed its compliance with the requirements of the temporary pharmacopoeial article VFS 42-181 1- 88 "Iodovidone solution 200 ml of the resulting solution was applied to a sample of sorption material 50 * 50 cm in size and dried at room temperature to constant weight. The iodine content in the manufactured sorption-bactericidal material was 0.1 mg / g.

A solution of the iodine complex with polyvinyl alcohol was prepared according to the following procedure: 9 g of polyvinyl alcohol was placed in a glass, stainless steel or enameled vessel with a capacity of 1 liter, 700-800 ml of water was poured and left for 0.5-3 hours to swell the polymer in order to increase its solubility. Then the vessel was heated for 0.5-1.5 hours at 90-100 ° C until a clear solution was obtained, after which it was cooled to room temperature. 100-150 ml of an aqueous solution containing 3 g of crystalline iodine and 3 g of potassium iodide was introduced into the resulting solution, after which the volume was adjusted with water to 1 liter. The solution is painted in dark blue. A sample of sorption material measuring 50 * 50 cm was placed in the resulting solution, kept for 60 minutes, squeezed and dried at room temperature to constant weight. In the manufactured sorption-bactericidal material, the iodine content was 0.05-0.08 mg / g. Sorption of bacteria E.coli:

Examples 4-9.

For testing, a 47 mm disk was cut out, consisting of 14 layers of sorption-bactericidal material obtained according to examples 1 or 2, and placed in a Sortorius test cell. The tests were performed on a pressure filtering unit of the Vladisart NE-100 company.

A 15 L model solution of E. coli in tap water with a concentration of 10 ² - 10 ⁴ CFU / ml was passed through the cell in the range of filtration rates 0.22-0.64 cm / s. The filtrate was taken and plated on Petri dishes with culture medium, incubated at 37 ° C for 24 hours, and then the number of colony forming units (CFU) was counted. The efficiency of water treatment in all cases was 100%, which is confirmed by the data indicated in table 1. Table 1

Sorption of bacteriophage MS2:

Examples 10-14.

15 l of a model solution of MS2 virus in tap water with a concentration of 10 ² - 10 ⁴ PFU / ml in the speed range 0.04 was passed through a cell with a 14-layer sorption-bactericidal material obtained according to examples 1 or 2 in the form of a disk with a diameter of 47 mm -0.45 cm / s. The filtrate was collected and plated on Petri dishes with meat peptone agar containing a suspension of E. coli. They were incubated at 37 ° C for 24 hours and then the presence of coliphages was determined by the appearance or absence of lysis zones. The results are shown in table 2.

table 2

Sorption of bacterial endotoxin:

Examples 15-18.

As a result of the death of bacteria, bacterial endotoxin can form, which, when released into water, can cause allergic reactions. A model solution of distilled water, which gives a positive reaction to bacterial endotoxin, was passed through a cell with a 14-layer sorption-bactericidal material obtained according to examples 1 or 2 in the form of a disk with a diameter of 47 mm. The concentration of bacterial endotoxin in model water and filtrates was determined in vitro using the LAL test. The results are shown in table 3.

Table 3

Biofouling Prevention:

Example 19

From a sheet of sorption-bactericidal material obtained according to examples 1 or 2, containing 39% alumina hydrate and 0.27 mg / cm ^{2 of} colloidal silver, a 14-layer cartridge with a height of 10 inches was made. The cartridge was fixed in a filter holder and tap water contaminated with E. coli bacteria was passed for 60 days. The concentration of E. coli throughout the test period was not less than 10 ³ CFU / 100 ml of solution. The efficiency of microbiological treatment during the entire test period was 100%. The maximum filter load was 1, 53x 10 ⁵ CFU / cm ² . During the operation of the filter, bacteria do not grow on the sorption-bactericidal material and wash them into the filtrate, which is confirmed by the data indicated in table 4.

Table 4

Sorption of colloidal iron:

Examples 20-23.

A model solution of colloidal iron was passed through a cell with a 4-layer sorption-bactericidal material obtained according to examples 1 or 2 in the form of a disk with a diameter of 47 mm. The iron content in the filtrate was determined by the photocolorimetric method (GOST 401 1-72 Drinking water. Methods for measuring the mass concentration of total iron). Examples NQ 20-23 prove that an increase in the concentration of colloidal iron in water does not lead to a decrease in filtration efficiency, however, there is a decrease in performance and filter life for due to clogging of the sorption-bactericidal material with colloidal particles, which is reflected in table 5.

Table 5

Washing aluminum and silver from sorption-bactericidal material:

Examples 24-28.

Samples of sorption-filtering material with different content of particles of hydrate of aluminum oxide and silver, obtained according to examples 1 or 2, were investigated for leaching of silver particles and aluminum ions. 500 ml of distilled water were passed through a cell with a 14-layer sorption-bactericidal material in the form of a disk with a diameter of 47 mm. The silver content was determined in the filtrate (GOST R 52180-2003 Drinking water. Determination of the content of elements by inversion voltammetry) and aluminum by the photocolorimetric method with an aluminone indicator (GOST 18165-89 Drinking water. Methods for determination of aluminum mass concentration). These examples confirm that there is no secondary contamination of the filtrate with the components of the sorption-bactericidal material (table 6). Table 6

Air filters. Microorganism Filtration:

Examples 29-36

The total bacterial contamination of the air or the microbial number (CFU / m ³ ) was determined by taking an air sample on Petri dishes with nutrient medium using the Krotov apparatus. For this, a Petri dish with a thin layer of nutrient medium was mounted on a rotating table of the Krotov apparatus. The lid with a wedge-shaped slit for sucking air was lowered from above and closed hermetically. A disc of sorption-bactericidal material obtained in Examples 1 or 2 with a size of 100 mm was placed over the lid. Air sucked into the device and containing microorganisms first passed through layers of sorption-bactericidal material, then through a wedge-shaped slot in the lid of the device and hit the surface of the nutrient medium in the Petri dish. In this case, microorganisms adhered to the nutrient medium. After passing 1 m ^{3 of} air, the Petri dish was removed, closed with a lid and placed in a thermostat at 37 ° C. After 24 hours, colony counts were performed. The results are shown in table 7. Table 7

An aerosol containing microorganisms was pumped through Krotov’s apparatus with sorption-bactericidal material. The results are shown in table 8.

Table 8

The use of sorption-bactericidal material as a medical sorbent:

In examples 37-39 used samples of a sorption-filter material with different content of particles of hydrate of aluminum oxide and silver, obtained in example 1 or 2.

Tests of the wound healing effect of sorption and bactericidal material were carried out at the GOU VPO SibGMU in Tomsk. The animals were kept in accordance with the rules adopted by the European Convention for the Protection of Vertebrate Animals used for experimental and other scientific purposes (Strasbourg, 1986).

Example 37

Healing of an uninfected wound. In animal experiments, a dressing was used, consisting of 14 layers of sorption-bactericidal material in an atraumatic membrane made of polypropylene non-woven fabric located on the side of the wound and a mesh knitted polyester fabric on the opposite side of the wound. White nonlinear mice weighing 19-21 g were used as objects of study.

Tests were carried out on 3 groups of animals:

1. Group with experimental wound without treatment (control 1) - 20 mice;

2. Group with an experimental wound with a gauze dressing (control

2) - 20 mice;

3. A group with an experimental wound with the claimed sorption-bactericidal material - 20 mice.

The effect of sorption-bactericidal material on the healing of a wound defect was studied using a “skin flap” model. A skin flap 10x10 mm in size was cut out on a depilated back area in mice under ether anesthesia. The use of sorption-bactericidal material contributed to a 79% reduction in wound diameter on the 14th day of observation in comparison with control 2, where the animals were applied a gauze bandage. Acceleration of healing time under the action of sorption-bactericidal material was 11% compared with both control 1 and control 2. By 14 days, 73.3% of animals from experimental group 3 showed complete wound healing, while in control group 1 such animals were 1, 6 times less, and only 53.8% of the control group 2 recorded complete healing of wounds in this period.

The inventive sorption-bactericidal material has a positive effect on the healing of skin flap wounds, reducing the healing time of wound damage, increasing the number of animals with complete epithelization of the wound defect, the layer of epithelial cells is thinner and more even. When using sorption-bactericidal material, more active maturation of granulation tissue occurs.

Example 38

Healing an infected wound. As the objects of study, we used 2 groups of white not purebred sexually mature male rats weighing 200-220 grams of 5 rats per group. The choice of animals was due to the fact that in many respects the skin in rats morphologically approaches human skin.

Animals under anesthesia performed shaving of the skin on the back in the interscapular region. 1 ml of suspension of bacteria Pseudomonas aeruginosa at a concentration of 10 ⁸ microbial bodies and 1 ml of suspension of Staphylococcus aureus at a concentration of 5><10 ⁸ microbial bodies were introduced into this place. After a day, the abscesses were opened and the wounds were sown with tampons. Sorption-bactericidal material (group 1 — 5 animals) or gauze balls (group 2 — 5 animals) of a similar volume were injected into the cavity and sutured tightly. Samples of smears taken from rats from an experimental wound of the skin were examined. Samples were seeded on Petri dishes with blood agar and placed in a thermostat at a temperature of + 37 ° C. Colony counting was performed after 24 hours (table 9).

Table 9

Studies of the antimicrobial properties of sorption-bactericidal material in relation to the pathogenic microflora of the wound surface, which were carried out on white outbred adult rats, showed that when using the developed sorption-bactericidal material, there is a decrease in bacterial contamination of wound surfaces when infected with Pseudomonas aeruginosa for 3-4 days. When wounds were infected with staphylococcus, the use of the material tended to reduce bacterial contamination.

Example 39

A dressing based on sorption-bactericidal material (including colloidal silver particles) was tested on 9 volunteers. Of these, 3 people with torn corns, 2 people with torn knees, 1 person with weeping neurodermatitis in their hands, 2 people with cut wounds in their hands and 1 person with a lacerated purulent wound to their legs.

Samples of material were superimposed on the wounds in size and shape slightly larger than the wound. The dressing was changed 1 time per day. According to the subjective feelings of all volunteers, the material does not have an irritating and allergic effect.

Sorption-bactericidal material effectively absorbs and retains wound exudate and purulent discharge of an infected wound, which creates favorable conditions for wound healing. The mechanism of this effect is associated with a high sorption capacity of the fibrous material, the holding ability and antibacterial properties of the material. The use of material allows you to create optimal moisture conditions in the wound. The material accelerates wound healing, having a positive effect on tissue regeneration processes in the wound.

Example 40. We used samples of a sorption-filter material with different content of particles of aluminum oxide hydrate and iodine complex, obtained in example 3.

A dressing based on sorption-bactericidal material was tested on 3 volunteers with purulent wounds of various localization.

Material wounds were superimposed on the wounds in size and shape a little more than the wound was fixed with adhesive tape or a sterile bandage. The dressing was changed 1 time per day. According to the subjective feelings of all volunteers the material does not have irritating and allergic effects.

Sorption-bactericidal material effectively absorbs and retains wound exudate and purulent discharge of an infected wound, which creates favorable conditions for wound healing, in addition, iodine from the complex is gradually released into the wound, having an antiseptic effect. The material accelerates wound healing, having a positive effect on tissue regeneration processes in the wound.

INDUSTRIAL APPLICABILITY

The proposed sorption-bactericidal material possesses, along with high sorption properties, improved bactericidal properties, while it provides the possibility of long-term operation without biofouling, prevents secondary bacterial infection of the filtrate and its contamination with heavy metals, which allows it to be effectively used for sterilization of liquid or gas media and sorption of highly dispersed particles in various industrial and medical facilities where high purity requirements are required ear, in domestic, industrial liquids purification systems, in particular water, as well as in medicine as a sorbent for the medical treatment, hygiene products, including wound dressings.

Claims

CLAIM

1. Sorption-bactericidal material, comprising at least one base layer of non-woven polymeric fibrous material with particles of alumina hydrate attached to its fibers and an inorganic bactericidal component, characterized in that the inorganic bactericidal component is sorbed on particles of alumina hydrate.

2. The material according to claim 1, characterized in that the particles of alumina hydrate are essentially plate-shaped with a side of 100-200 nm and a thickness of 5-8 nm.

3. The material according to claims 1 or 2, characterized in that at least a portion of the alumina hydrate particles are grouped into agglomerates of a size of 0.2-5.0 μm, a specific surface area of 100-350 m ² / g, a porosity of 50- 95%

4. The material according to claim 1, characterized in that the number of particles of aluminum oxide hydrate in it is 15-45 wt.%.

5. The material according to claim 1, characterized in that the base of the non-woven polymeric fibrous material is formed by fibers of cellulose acetate, polysulfone or another bioinert polymer having a diameter of 0.1-10 microns, preferably 1-3 microns.

6. The material according to claims 1 or 5, characterized in that the aforementioned material is obtained, for example, by the method of electroforming or meltblown technology.

7. The material according to claim 1, characterized in that the content of the inorganic bactericidal component in the material is 0.05 -

2.5 mg / g of material.

8. The material according to paragraphs. 1 or 7, characterized in that as the inorganic bactericidal component selected particles colloidal silver or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol.

9. The material according to p. 8, characterized in that the particles of colloidal silver having a substantially spherical or close to spherical shape ranging in size from 5 to 50 nm, mainly 20-30 nm.

10. A method of producing a sorption-bactericidal material, in which particles of an aluminum-based material in the form of an aqueous or aqueous-alcoholic suspension are applied to a base layer of non-woven polymeric fibrous material, followed by hydrolysis of particles of an aluminum-based material, characterized in that the non-woven base a polymeric fibrous material with aluminum oxide hydrate particles fixed on its fibers is additionally treated with an inorganic bactericidal component to sorb the latter on particles of g the squared alumina.

11. The method of obtaining the material according to claim 10, characterized in that the treatment is carried out by impregnation with a solution of an inorganic bactericidal component or by spraying the latter onto the material.

12. The method of obtaining the material according to claim 11, characterized in that the solution is impregnated with an inorganic bactericidal component for 10 minutes to 24 hours, preferably for 30-60 minutes, at room temperature.

13. The method of obtaining the material according to claim 11, characterized in that the processing time by spraying a solution of an inorganic bactericidal component on the material is determined by the method of applying the solution to the material, for example, manually or automatically.

14. A method of obtaining a material according to claim 10, characterized in that the treatment is carried out until the content of the inorganic bactericidal component in the material is 0.05-2.5 mg / g of material.

15. The method of producing material according to claim 10, characterized in that colloidal silver particles or complexes of iodine with polyvinylpyrrolidone or polyvinyl alcohol are selected as the inorganic bactericidal component.

16. The method of obtaining the material according to p. 15, characterized in that the colloidal silver particles having a substantially spherical or close to spherical shape ranging in size from 5 to 50 nm, mainly 20-30 nm.

17. A method of obtaining material according to claim 10, characterized in that the treated sorption-bactericidal material is dried at a temperature of 80-100 ° C for 2-4 hours.

18. The method of obtaining material according to p. 10, characterized in that the particles of aluminum oxide hydrate are essentially plate-shaped with a side of 100-200 nm and a thickness of 5-8 nm, at least a portion of the particles of aluminum oxide hydrate are grouped into agglomerates the size of 0.2-5.0 microns, a specific surface area of 150-350 m ² / g, porosity of 50-95%, while the number of particles of aluminum oxide hydrate in the non-woven polymer fibrous material is 15-45 wt.%.

19. The method of producing material according to claim 10, characterized in that the base of non-woven polymeric fibrous material is formed by cellulose acetate, polysulfone or other bioinert polymer fibers having a diameter of 0.1 -10 microns, preferably 1-3 microns.

20. The method of obtaining the material according to claim 19, characterized in that the aforementioned material is obtained, for example, by electrospinning or melt-blown technology.

21. A method of obtaining a material according to claim 10, characterized in that a material with a particle size of less than 1 μm is used as an aluminum-based material.

22. The method of obtaining material according to paragraphs. 10 or 21, characterized in that as the material based on aluminum using powder aluminum with a specific surface of 7-28 m ² / g, obtained by the method of electric wire explosion.

23. The method of obtaining material according to paragraphs. 10 or 21, characterized in that the aluminum-aluminum powder is used as an aluminum-based material with an AI / AIN percentage ratio of 95: 5 to 5:95, preferably with an AIN content of 30-70% in the composition and with a specific surface not less than 7 m ² / g, preferably 11-27 m ² / g. obtained by electric explosion of wire.

24. A method of filtering liquid or gaseous media, comprising passing a liquid or gaseous medium through a sorption-bactericidal material made according to any one of claims 1 to 9 and obtained by the method according to any one of claims. 10-23.

25. The filtering method according to p. 24, where the sorption-bactericidal material is in the filter.

26. The filtering method according to claim 24, wherein the sorption-bactericidal material holds electronegative particles, for example, bacteria, viruses, highly dispersed and colloidal particles, humic substances, bacterial endotoxins, nucleic acids, proteins, enzymes, etc.

27. The method of filtering liquid media according to claim 24, wherein 8-14 layers of sorption-bactericidal material are used to retain electronegative particles, for example, bacteria, viruses, bacterial endotoxins, nucleic acids, proteins, enzymes and

^D R-

28. A method for filtering liquid media according to claim 24, wherein 2-4 layers of sorption-bactericidal material are used to hold highly dispersed and colloidal particles, humic substances.

29. A method for filtering a liquid medium according to claim 24, wherein said liquid medium is water, an aqueous solution, a biological liquid.

30. A method for filtering gaseous media according to claim 24, wherein 2-8 layers of sorption-bactericidal material are used to retain highly dispersed solids, bacteria, and viruses.

31. Medical sorbent, characterized in that it includes at least one layer of sorption-bactericidal material made according to any one of claims 1 to 9 and manufactured by the method according to any one of claims 10-23, for medical and / or hygiene products, including wound dressings.