RU2426557C1 - Sorption-bactericidal material, method of its obtaining, method of filtering liquid or gaseous media, medical sorbent - Google Patents

Abstract

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to field of elaboration of sorption-bactericidal materials for purification of liquids and gases from highly dispersive particles and microbiological pollutions, including those of medical purpose. Described is sorption material with improved bactericidal properties with simultaneous preservation of sorption properties of material suitable for sterilisation of liquid and gaseous media and sorption of highly dispersive particles, providing possibility of long work without biofouling, as well as preventing secondary bacterial contamination of filtrate and its pollution with heavy metals. Described is method of sorption material modification. Purpose of invention was to extend arsenal of non-woven materials of medical purpose, which possess high sorption properties, as well as antibacterial and antiviral actisvity and, as a result, wound-healing ability. Sorption-bactericidal material contains non-woven polymer fibrous material with fixed on its fibres highly porous particles of aluminium oxide hydrate, inorganic bactericidal component being sorbed on highly porous particles of aluminium oxide hydrate. Method of obtaining sorption-bactericidal material includes material processing with solution of inorganic bactericidal component and processing of non-woven polymer fibrous material, on whose fibres fixed are highly porous particles of aluminium oxide hydrate for period not exceeding 24 hours. Method of filtering liquid or gaseous media includes passing liquid or gaseous medium through sorption-bactericidal material. Medical sorbent includes, at least, one layer of sorption-bactericidal material and is used for therapeutic and/or hygienic products, including wound bandages.

EFFECT: increase of purification efficiency.

31 cl, 8 tbl, 36 ex

Description

The invention relates to the field of development of sorption-bactericidal materials for the purification of liquids and gases from fine particles and microbiological 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 microorganisms 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 μm, serving as a carrier for silver in the form of nitrate salt or metal, according to [GR 3229340 1984] or [SU 971464 A1, 1982] the use of activated carbon impregnated silver salt solution for disinfection of drinking water. For simultaneous disinfection and purification of drinking water, a composition of coarse and fine carbon fibers, including activated ones, is used, on which metal salts, for example silver, are applied as a bactericidal additive in an amount of 0.01-8.0% [SN 556680 A, 1974 ]. Known methods for treating drinking water before serving it using natural sorbents modified with ionic silver [RU 2077494 C1, 1997; RU 2049053 C1, 1995]. In an integrated method for deep purification and conditioning of water [WO 96/20139 A1, 1996], the water to be treated is subjected to preliminary filtration, sorption processing and final microfiltration on filter elements with a pore size of 0.5-10 μm. In this process, numerous sorbents are used in the cleaning process, including a bactericidal sorbent - a silver form of activated carbon. Also, for example, a bactericidal sorbent is known [RU 2221641 C2, 2004], used in pressureless and pressure filters for disinfecting and treating water from a water supply system and freshwater sources. A carbon-containing material is used as the basis (substrate) of the sorbent, and iodine-containing and silver-containing ion-exchange components are used as a bactericidal additive. A known method of disinfection of drinking water [RU 2172720 C1, 2001], in which the used composite materials contain in various combinations uniformly distributed granules of an iodine-containing anion-exchange resin, granular activated carbon, cation-exchange resin and anion-exchange resin with silver-containing sorbent between amphoteric fibers.

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. In the nuclear field, filters are used to purify air and process gases from radioactive iodine. The material [TU 2282-251-2100232-97] was obtained by introducing into the filter material a finely divided activated carbon powder impregnated with silver nitrate. Sorption-filtering material [Gas purification and control of gas emissions of nuclear power plants. / Nakhutin I.E., Ochkin D.V. et al. / M .: Energoatomizdat, 1993] is based on granular activated carbon, including impregnated with potassium iodide (KI), and / or a secondary, tertiary amine, for example triethylenediamine (TEDA), 1,4 diazobicyclo- [2, 2,2] octane (DABCO), hexamethylenetetraamine (HMTA) (urotropine), or silver nitrate.

In the prior art materials with an organic bactericidal additive are known, such as adsorption-bactericidal materials [RU 2070438 C1, 1996; RU 2075196 C1, 1997], containing activated carbon fibers and a bactericidal additive, which is used as organic compounds containing active bactericidal groups in their structure, for example, groups including secondary, tertiary or quaternary nitrogen atoms, as well as groups capable of sorption on matrix surfaces, for example aromatic groups. According to the second patent, activated carbon fibers are modified with organic compounds containing functionally active groups in their structure, for example cation exchange, anion exchange or complexing groups capable of binding substances and compounds to be removed from the liquid being purified.

All of the above materials were obtained by treating the carrier material with metal salts, for example, a silver salt solution, similarly to what is claimed in the method for producing a bactericidal sorbent [SU 971464 A1, 1982], in which activated carbon is impregnated, or according to the patent [US 4396512 A, 1983], in which powdered coal and cellulose fiber are impregnated, or in patents [RU 2070438 C1, 1996; RU 2075196 C1, 1997], where the modification of activated carbon fiber is carried out by impregnation with a solution of an organic bactericidal additive. The bactericidal additive is on the surface of these materials either in the form of isolated ions, or in the form of complex compounds with organic molecules.

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 the 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, alumina nanofibres 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.

Known solution "filter material for cleaning liquid and gaseous substances and a bactericidal device" [RU 54811 U1, 2006]. The described filter material includes a porous base with a discrete layer of nanostructured silver particles, the porous base is made of a polymer material with the addition of carbon. The disadvantage of this filter material is insufficient sorption capacity for microorganisms of the porous base.

It is known to obtain filter material for water purification from activated carbon with a surface deposition of silver [SU 1530211 A1, 1989].

This method of obtaining modified activated carbon consists in mechanically applying an additive to a carbon material without firmly fixing it. In addition, this technical solution is not universal for various dissolved pollutants, but is characterized by selective action in relation to dissolved chlorine. As well as its use in the form of fibers that are not formed into a textile structure, complicates the work with the sorbent in the manufacture of the filter and its operation.

The closest in technical essence and the achieved result to the claimed material and the method of its manufacture is a method of modifying the filter element [RU 2135262 C1, 1998]. The method consists in filling a reservoir with an aqueous solution of a modifying composition, placing a preform of a filter element in a solution, keeping the preform in a solution for impregnating it with a solution, and after the impregnation is completed, the preform is removed from the reservoir in which the preform is impregnated with a modifying composition that is an aqueous-organic a solution of nanostructured silver particles, withstand the blank of the filter element formed by a carbon non-woven fabric in solution for 20-120 hours at a temperature of 20 ° С, the optical density of the solution is measured with a spectrophotometer, which changes during the adsorption of silver nanostructured particles from the solution by a carbon nonwoven fabric for a specified period of time every two hours, and when the solution of silver nanostructured particles reaches a predetermined optical density, the resulting filter material is removed, the material is washed 20% solution of alcohol in water, carry out the drying of the material for 3 hours and evaluate the effectiveness of the obtained filter ma terial.

The disadvantage of the prototype is that the material is not effective for the sorption of fine particles and microorganisms, because the material does not provide sterilization of the liquid, and the method for its production is long and laborious.

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. S. S. Block, Lea and Febider 1977 and N. Grier Silver and Its Compounds in Disinfection, Sterilization and Preservation, ed. S. S. 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 use is not always practicable, especially in cases where permanent or implanted medical devices are used.

To solve the problem of slowing down the process of release of silver ions, various technical solutions are proposed. For example, silver-containing complex compounds with low solubility [US 2785153 A, 1957]. This technical solution proposes a protein and colloidal silver-containing compound for the manufacture of a cream. However, the effectiveness of the known compounds due to problems associated with adhesion, abrasion resistance and shelf life during storage is limited by its scope, mainly in the form of cosmetics. 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 it is used as metal particles contains silver nanoparticles from 80 to 99.7%, iron from 0.1 to 20%, aluminum from 0.1 to 20%, edi 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.

A known embodiment of a filter material for a gaseous medium [WO 2009031944 A2, 2009], which contains as a basis a non-woven polymeric fibrous material, on the fibers of which particles of aluminum oxide hydrate are fixed. The material further comprises an antimicrobial additive represented by silver nitrate. The disadvantages of this material include the use of ionic silver.

The application [US 2008026041 A1, 2008] proposes a medical structure that we have chosen as a prototype. The medical structure includes, along with alumina nanofibres, second fibers mixed with alumina nanofibres, and particles dispersed on alumina nanofibres. The above particles can be a bactericidal agent - silver ions.

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.

The technical problem to be solved by the present invention is 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 gaseous media and sorption of highly dispersed particles, which enables long-term operation without biofouling, as well as preventing secondary bacterial contamination 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 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.

Tasks in the implementation of the claimed group of inventions on the subject of sorption-bactericidal material are achieved by the fact that the claimed sorption-bactericidal material includes non-woven fibrous material and an inorganic bactericidal component.

The peculiarity is that it contains a non-woven polymeric fibrous material with highly porous particles of aluminum oxide hydrate fixed to its fibers, while the inorganic bactericidal component is sorbed on highly porous particles of aluminum oxide hydrate.

In this case, the highly porous particles of aluminum oxide 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, 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 aforementioned material was obtained by electrospinning, Melt-Blown technology, or other methods that allow 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 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 problems are solved in that the method for producing the sorption-bactericidal material includes processing the material with a solution of an inorganic bactericidal component.

What is new is that they process a non-woven polymeric fibrous material, on the fibers of which highly porous particles of aluminum oxide hydrate are attached, while the treatment is carried out for a time not exceeding 24 hours.

In this case, 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 of 0.05-2.5 mg / g of material.

As an inorganic bactericidal component, colloidal silver particles were selected.

In this case, a solution of colloidal silver with a concentration of 14 to 140 mg / l is obtained by reducing silver nitrate with tannin in an alkaline medium.

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.

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

In addition, a non-woven polymeric fibrous material, on the fibers of which highly porous particles of aluminum oxide hydrate are attached, are obtained by applying to the base of the non-woven polymeric fibrous material an aqueous or aqueous-alcoholic suspension of aluminum-based material particles, followed by hydrolysis of the aluminum-based material particles for fixing on alumina hydrate particle base fibers.

In this case, 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, at least a portion of the particles of alumina hydrate are grouped into agglomerates with 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 aforementioned material was obtained by electrospinning, Melt-Blown technology, or other methods that allow 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 aluminum powder is used as an aluminum powder with a specific surface area of 7-28 m ² / g, obtained by the method of electric explosion of a 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 Al / AlN percentage ratio of 95: 5 to 5:95 be used as an aluminum-based material. Preferably, the AlN content in the composition is 30-70% and with a specific surface area of at least 7 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 problems are 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 to 25.

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 problems are 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 to 25, for medical and / or hygiene products, including wound dressings.

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 the ability to absorb and retain a large amount 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 electrospinning, 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, randomly curved plates of irregular 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 a bactericidal component, preference is given to colloidal silver. Particles of colloidal silver have a substantially spherical or near-spherical shape ranging in size from 5 to 50 nm, mainly 20-30 nm. Particles of this size are well sorbed and retained by alumina hydrate particles. The content of colloidal silver in the material is 0.05-2.5 mg / g of non-woven material. Such a content of colloidal silver provides a bactericidal effect, and at the same time, the silver content in the filtrate does not exceed the maximum permissible level and there is no secondary contamination of the filtrate with silver.

Obtaining the inventive sorption-bactericidal material is as follows. First of all, an aqueous or aqueous-alcoholic suspension of particles of an aluminum-based material is applied to a nonwoven polymeric fibrous material base, followed by hydrolysis of the aluminum-based material particles to fix aluminum oxide 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 an Al / AlN percentage ratio of from 95: 5 to 5:95, preferably 70: 30% and with a specific surface area of at least 7 m ² / g, preferably 11-27 m, is used 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 aluminitride composition (Al / AlN) 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, by manual or automated method. Processing is carried out until the content of the inorganic bactericidal component in 0.05-2.5 mg / g of non-woven material. It is not by chance that colloidal silver particles are chosen as an inorganic bactericidal component. Particles of colloidal silver are better sorbed and retained by sorption material than 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.

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 drawings shown in 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).

Figure 3 shows agglomerates of particles of alumina hydrate mounted on a fiber of a nonwoven polymeric material (the picture was 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).

The invention is illustrated by the following examples.

Production of sorption and bactericidal material

Example 1

For the manufacture of sorption material, a sheet of nonwoven polymeric fibrous material from cellulose acetate grade FPA-15-2 was used. 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 Al / AlN-60: 40 ratio, kept for 20 minutes, 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 35%.

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, 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 manufactured 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 μm. 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 Al / AlN-70: 30 ratio, kept for 20 min, 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 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.

Sorption of bacteria E.coli:

Examples 3-8

For testing, a 47 mm disk was cut out, consisting of 14 layers of sorption-bactericidal material, and placed in a Sortorius test cell. The tests were carried out on a pressure filtration unit from Vladisart HE-100.

A 15 L model solution of E. coli in tap water with a concentration of 10 ² -10 ⁴ CFU / ml in the range of filtration rates 0.22-0.64 cm / s was passed through the cell. 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 The effectiveness of water disinfection depending on the concentration of E. coli and the filtration rate Example No. Filtration rate, cm / s Concentration of E. coli, CFU / ml The load on the filter, CFU / cm ² Before filtering After filtering 3 0.22 1.21 × 10 ² 0 1.51 × 10 ⁵ four 1.15 × 10 ⁴ 0 1.44 × 10 ⁷ 5 0.45 1.17 × 10 ² 0 l, 46 × l0 ⁵ 6 1.28 × 10 ⁴ 0 1,60 × 10 ⁷ 7 0.64 1.08 × 10 ² 0 1.35 × 10 ⁵ 8 1.19 × 10 ³ 0 1.49 × 10 ⁶

Sorption of bacteriophage MS2:

Examples 9-13

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 0.04-0.45 cm / s 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 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 Water disinfection efficiency depending on MS2 concentration and filtration rate Example No. Filtration rate, cm / s Coliphage concentration MS2, PFU / ml Filter load, PFU / cm ² Before filtering After filtering 9 0.04 1.07 × 10 ² 0 1.34 × 10 ⁵ 10 1.18 × 10 ⁴ 0 1.48 × 10 ⁷ eleven 0.08 1.19 × 10 ³ 0 1.49 × 10 ⁶ 12 0.22 1.09 × 10 ² 0 1.36 × 10 ⁵ 13 0.45 fourteen 0 1.75 × 10 ⁴

Sorption of bacterial endotoxin:

Examples 14-17

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 was passed through a cell with a 14-layer sorption-bactericidal material in the form of a disk with a diameter of 47 mm, which gave a positive reaction to bacterial endotoxin. 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 The effectiveness of water purification from bacterial endotoxin Example No. Model solution The concentration of endotoxin, EE / ml The volume of filtered water, ml The concentration of endotoxin in the filtrate EE / ml fourteen Endotoxin-positive distilled water 0.24 10 <0.03 fifteen 0.24 120 <0.03 16 0.24 300 <0.03 17 0.24 450 <0.03

Biofouling Prevention:

Example 18

From a sheet of sorption-bactericidal material manufactured analogously to example 1, 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 1.53 × 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 Water disinfection efficiency Exposure time, day Missed Volume, L CFU in 100 ml of filtrate Cartridge load, CFU / cm ² one 200 0 5.00 × 10 ³ 3 400 0 1.00 × 10 ⁴ 10 700 0 1.75 × 10 ⁴ fifteen 1000 0 2,50 × 10 ⁴ eighteen 1600 0 4.00 × l0 ⁴ 23 2100 0 5.25 × 10 ⁴ 28 2500 0 6.50 × 10 ⁴ 31 3100 0 8.00 × 10 ⁴ 37 3500 0 9.00 × 10 ⁴ 44 4100 0 1.05 × 10 ⁵ 51 4600 0 1.28 × 10 ⁵ 57 5200 0 1.43 × 10 ⁵ 60 5600 0 1.53 × 10 ⁵

Sorption of colloidal iron:

Examples 19-22

A model solution of colloidal iron was passed through a cell with a 4-layer sorption-bactericidal material 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 4011-72. Drinking water. Methods for measuring the mass concentration of total iron). Examples No. 19-22 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 the productivity and service life of the filter due to clogging of the sorption-bactericidal material with colloidal particles, which is shown in table 5.

Table 5 The effectiveness of water purification from colloidal iron Example No. The volume of filtered water, l The concentration of iron, mg / l Before filtering After filtering 19 60 0.5 0.1 twenty twenty 1.3 0.1 21 10 3,7 0.1 22 6 5,6 0.1

Washing aluminum and silver from sorption-bactericidal material:

Examples 23-27

Samples of sorption-filtering material with different content of particles of hydrate of aluminum oxide and silver, obtained in example 1, were investigated for leaching of silver particles and aluminum ions. 500 ml of distilled water was 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 elements by inversion voltammetry) and aluminum by the photocolorimetric method with an aluminone indicator (GOST 18165-89. Drinking water. Methods for determination of mass concentration of aluminum). These examples confirm that there is no secondary contamination of the filtrate with components of the sorption-bactericidal material (table 6).

Table 6 Washing aluminum and silver from sorption-bactericidal material Example No. Sorption and bactericidal material Filtrate Alumina Hydrate,% Silver, mg / cm ² Aluminum, mg / L Silver, mcg / l 23 eighteen 0,07 0,03 3 24 24 0.10 0,07 5 25 29th 0.38 0.11 fifteen 26 38 0.24 0.15 8 27 41 0.42 0.15 21

Air filters. Microorganism Filtration:

Examples 28-35

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 disk of sorption-bactericidal material 100 mm in size 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 apparatus 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 Filtering dry air containing microorganisms Example No. Test samples Productivity, l / min OMCH, CFU / m ³ 28 The control 40 227 29th 2 layers twenty 0 thirty 4 layers fifteen 2 31 8 layers 10 0

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

Table 8 Filtering aerosols containing microorganisms Example No. Test samples Productivity, l / min OMCH, CFU / m ³ 32 The control 40 262 33 2 layers twenty 0 34 4 layers fifteen 0 35 8 layers 10 0

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

Example 36

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

Samples of material were superimposed on the wounds by the size and shape of the wound, or slightly larger. 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.

Claims (31)

1. Sorption-bactericidal material, comprising at least one layer of a base of non-woven polymeric fibrous material with particles of aluminum oxide hydrate attached to its fibers and an inorganic bactericidal component, characterized in that the inorganic bactericidal component is sorbed on particles of aluminum oxide 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 claim 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 non-woven polymer fibrous material is formed by fibers of cellulose acetate, polysulfone or another bioinert polymer having a diameter of 0.1-10 μm, preferably 1-3 μm. 6. The material according to claim 1 or 5, characterized in that the aforementioned material is obtained by electrospinning or melt-blown 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 claim 1 or 7, characterized in that colloidal silver particles are selected as the inorganic bactericidal component. 9. The material of claim 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 polymer 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 gy aluminum oxide drat. 11. The method of obtaining material according to claim 10, characterized in that the treatment is carried out by impregnating a solution of an inorganic bactericidal component or by spraying the latter onto the material. 12. The method of obtaining material according to claim 11, characterized in that the impregnation with a solution of an inorganic bactericidal component is carried out for 10 minutes to 24 hours, preferably for 30-60 minutes, at room temperature. 13. The method of obtaining 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. The method of obtaining the material of 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 are selected as the inorganic bactericidal component. 16. The method of obtaining material according to clause 15, wherein 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. The method of obtaining the material of 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 claim 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 obtaining material according to claim 10, characterized in that the base of 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. 20. The method of obtaining material according to claim 19, characterized in that the aforementioned material is obtained, for example, by electroforming or melt-blown technology. 21. The method of obtaining the material of claim 10, characterized in that as a material based on aluminum using a material with a particle size of less than 1 μm. 22. The method of obtaining the material of claim 10 or 21, characterized in that as the aluminum-based material using aluminum powder with a specific surface area of 7-28 m ² / g, obtained by the method of electric explosion of wire. 23. The method of obtaining the material according to claim 10 or 21, characterized in that the aluminum-alumina powder with an Al / AlN percentage ratio of from 95: 5 to 5:95, preferably with an AlN content in the composition, is used as an aluminum-based material. 30-70% and with a specific surface area of at least 7 m ² / g, preferably 11-27 m ² / g, obtained by the method of 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 to 23. 25. The filtering method according to paragraph 24, where the sorption-bactericidal material is part of the filter. 26. The filtering method according to paragraph 24, where 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 paragraph 24, where 8-14 layers of sorption-bactericidal material are used to hold electronegative particles, for example bacteria, viruses, bacterial endotoxins, nucleic acids, proteins, enzymes, etc. 28. The method of filtering liquid media according to paragraph 24, where 2-4 layers of sorption-bactericidal material are used to hold highly dispersed and colloidal particles, humic substances. 29. The method of filtering liquid media according to paragraph 24, where the specified liquid medium is water, an aqueous solution, a biological fluid. 30. The method of filtering gaseous media according to paragraph 24, where 2-8 layers of sorption-bactericidal material are used to retain highly dispersed mechanical impurities, bacteria, 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 to 23, for medical and / or hygiene products including wound dressings.

Images