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Method of inactivating viruses in water media. RU patent 2506232. |
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IPC classes for russian patent Method of inactivating viruses in water media. RU patent 2506232. (RU 2506232):
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FIELD: chemistry. SUBSTANCE: invention can be used for preparation of ultra-pure water, safe for consumption by people, as a result of sorption purification of drinkable water from viruses. Method includes filtration of water through zones with sorption materials, where, at least, one of zones represents porous filtering element based on resins, obtained by condensation of aldehydes with aromatic phenols and amines. Sorption material possesses the following characteristics: ratio of absolute value of zeta potential of porous filtering element to value of effective radius of liquid flow canal constitutes not less than 104 V/m. Porous filtering element, based on resin, obtained by condensation of formaldehyde with resorcin or melamine, is used as such sorption material of, at least, one of zones. Porous filtering element can preferably contain onwashed layer of sorption material, characterised by ratio of absolute value of material zeta potential to value of effective radius of flow canal not less than 105 V/m. EFFECT: method ensures high degree of neutralisation of viruses. 7 cl, 17 ex, 12 tbl
THE TECHNICAL FIELD The invention relates to the field of water purification, mainly drinking water from viruses and can be used in the manufacture of filters designed for preparation of ultrapure water that is safe for human consumption. THE LEVEL OF TECHNOLOGY Virus (lat. virus - poison) - subcellular infectious agent that can be played only within living cells. By nature viruses are Autonomous genetic elements with extracellular stage in the development cycle. Viruses are tiny particles consisting of molecules of nucleic acids - DNA or RNA, prisoners in a protein shell. Viruses can infect living organisms and are obligate parasites, as we are unable to reproduce outside the cell. Outside the cell, the viral particles do not show signs of live and behave as particles of organic polymers. Many viruses that can cause serious disease can enter the human body with drinking water. In water treatment technology removal or inactivation of viruses, special attention is connected with the importance of solving this problem, and with the technical complexity of this solution. Traditional methods of removal of viruses from water can be divided into three groups: 1) Adsorption of viruses on active surfaces; 2) virus Filtering through a porous medium with an effective pore diameter of less than the amount of the virus. 3) Strong chemical and physical influences that destroy the virus. Adsorption methods of virus removal, as a rule, involve the use of fine materials with high surface charge and developed area of contact with water. Fixation of the virus is mainly due to electrostatic interactions. Note, however, that the virus in the water is a particle with a mainly on the protein surface with a low private charge, depending on the pH of the medium. Therefore, the force of binding of the virus on the surface is small, so the virus is not fixed irreversibly in the point of contact with the surface of the adsorbent, but a constant stream of liquid along the surface has a migration of the virus, and when the local fluctuations of the water composition is desorption. In addition to viruses in the water contains substantial amounts of substances of organic origin with the same surface charge: natural polymers (humic acid), man-made substances, microorganisms and products of their vital activity. So committing virus takes the form of the competitive adsorption with substances of a similar nature, the mass content of which is significantly more than the viruses. Virus filtering is possible with the use of a porous medium with a small pore size: osmosis and nanofiltration membranes that entails the application of high pressure, as well as education in the result of the filtering process concentrate containing greater concentration of viruses than in the source water. In addition, the clipping of particles on the membranes is not absolute and there is always a certain probability of passing the virus through the membrane due to the presence of defects in its structure. To chemical and physical influences can be attributed, in particular, the use of General methods for bactericidal treatment of liquid to remove viruses. Such methods are ineffective, because unlike microorganisms viruses are much more resistant to the action of UV radiation, chlorinated bactericides, silver and polymer bactericides. The prior art known to «Filter material, method of its production and how you want to filter on the request of the 2005125140 EN from 08.08.2005, the Essence of the method consists in the fact that carry out the modification of polymer fibrous material particles of aluminum oxide hydrate, for which the polymer fibrous material is applied to the source material on the basis of aluminum, then carry out the hydrolysis of the latter, during which the polymer fibrous material are formed and fixed hydrate particles of aluminum oxide. The disadvantage of this solution is that in the process of operation of fine-dispersed aluminium hydroxide dissolves, which leads to loss of the ability of the filter material inactivate viruses. Known solution by the patent USA 7,390,343 from 24.06.2008, serving filtering device, containing at least one fibrous structure, which is a mixture of nanofibers of aluminum hydroxide and other fibers, placed in a matrix to create asymmetric then to filter particles from small to nano size. The claimed device, when passing through the water, is able to suppress bacteria and viruses. In this decision, to achieve the desired result, the active component of inaktiviruyuschy viruses must be applied on an inert carrier. However, because of the physical properties of the inert carrier impossible to apply the active ingredient in the amount required for the removal of viruses in large quantities. Known methods and devices for filtering patent 6,852,224 from USA, 08.02.2005; 7,749,394 USA from 06.07.2010,; 6,783,713 USA from 31.08.2004,; 2237022 EN from 27.09.2004, the essence of water filtration through the dense layers of particles of activated carbon of various size, shape and porosity. Capture pathogens , in particular computer viruses, particles of activated coal, according to the authors, is determined by electrostatic, van der Waals and hydrophobic forces. Thus, the mechanism of action of known solutions is reduced to the physical adsorption of viruses and limited by the amount of adsorption capacity of the material, especially in the conditions of the competitive adsorption of viruses with other admixtures of organic nature. There is a method of purification of drinking water on the application 93050424 EN from 09.11.1993, The essence of the invention lies in the fact that drinking water is filtered through the alternating layers chemisorptive fibers or materials on their basis, containing in the structure a carboxyl group in the H, Na, Ag-forms and ammonium grounds in the Cl and CO-forms with complex compounds of iodine in mass ratio of fibres from 1:3 to 3:1, respectively, and the rate of filtration of up to 20 l/h Active components of the specified decisions are antibacterial and have no specific impact on viruses. The closest solution to the declared is the invention «Method of purification of tap water» by the patent 2049078 EN from 27.11.1995, including sequential transmission of water under pressure through the zone cleaning activated charcoal, cation exchange resin, anion-exchange resin and polymeric membranes, and as ultrafiltration polymeric membranes use of hollow fibers of aromatic polyamide " phenylon", the treated water is served in the internal cavity of hollow fibres and leachate removed from their outer side. Materials in this process of purification are arranged in layers. The size of the particles and the corresponding effective size of the channels of leakage of liquid in the layers of ion exchange resins and activated carbon are too large compared with the size of the virus. Thus, virus removal practically carried out on membranes made of aromatic polyamide, and who have very high hydraulic resistance, which in turn leads to a rapid clogging of membranes in the absence of washing and thereby reduces the efficiency of the process. The technical purpose of the claimed authors solution is to build a highly efficient method of inactivation of viruses in filtering through the environment with moderate hydraulic resistance and high efficiency of properties. The technical result of the invention is a high degree of neutralization of viruses in the filtering process. The technical result is achieved by the method of inactivation of viruses in aquatic environments, including passage of fluid under pressure through the zones of sorption materials, at least one of the zones has the following characteristics: a ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is not less than 10,000 In/m THE ESSENCE OF THE INVENTION According to the available literature data and the results of their own experiments, the authors found that the best results as to the completeness virus removal of water, and conservation of this property over time show polymer materials with a developed surface, and a fairly high density of charge. Assumption purely adsorption mechanism of binding virus allows to explain the lack of saturation filter viruses, as well as small influence the content of organic admixtures in water on the completeness of catching viruses. According to the authors of the invention, neutralization mechanism (inactivation) of the viruses in the process of filtration through a porous medium can be explained as follows. When the filtration of a fluid through a porous medium with a sufficiently high density fixed charge on the pore surface of virus particles near the surface exposed to electrical forces caused by moving of counterions together with the flow of the fluid. With the manifestation of such forces are no known in colloid chemistry electrokinetic phenomena: electro, electrophoresis, the occurrence of a potential difference in flow and sedimentation. In the case of a filtration of a fluid through a porous medium measure of this interaction is the value of the potential leakage. Corresponding own material characteristic is the value of the z-potential, calculated from the values of potential leaks and fluid parameters in equation (1) where Δφ - measured value of the potential flow; P - pressure loss when the flow of a liquid through porous material; η is the dynamic viscosity of liquids; λ S - a private electrical conductivity of porous medium; e and ε 0 is the dielectric constant of the medium and vacuum. In the absence of fluid motion in the pores of the potential flow equal to zero, and the charge of the walls of the pores compensated diffuse layer of counterions. When the flow of fluid in narrow (of the order of microns) pores is a violation of the distribution of mobile ions relative to the walls of the pores due to hydraulic mixing liquid flows down the winding narrow channel. For a completely uniform distribution of mobile ions in a cylindrical pore charged with wall dependence of values of electric field intensity on the distance from the center of the pores x will where r is the radius of the pores, and more precisely - the bearing fixed charge, on which the potential is equal to z, the positive direction of the selected vector from the center to the outer surface of the pores. For pore diameter of 2 mm at the distance of 0.5 microns from the centre when the value of the Zeta-potential 10 mV local value of the electric field is equal to 10,000 In/m=100 V/cm, and the distance of 0.1 microns from the charged surface - 18000 A/m=180/see The natural size of the virus is 50-100 nm, and taking into account the interaction of protein shirts virus water effective size of the virus as colloidal particles in the water can be estimated in tenths of a micron. When driving in the twisting the pores of the viruses get into range of a significant electrical forces. Potential drop along virus particles with effective size will g When injected into the area of action of electric forces virus particle is subjected to polarization and finds himself in a similar process of activation of the virus when approaching to the cage-owner reveal the virus envelope protein and throw nucleic acid of the virus in the body cells transport through the channels of its membrane. Signal to the destruction of the Quaternary protein structure viral shirts can be only electrostatic interaction near the surface of the cell membrane. We can assume that near the charged surface of the pores of the filter media can be a similar violation of the structure of a protein shirts virus, but the virus DNA (or RNA) virus is not in the body of the host cell, and in the water, which does not have the conditions necessary for reduplication. Thus, the virus is , its components remain in the water and on the adsorbing materials surface of pores. For realization of the invention filtered water under pressure through one or more zones, and at least one zone has the necessary combinations of effective pore radius and the porosity of the greatest possible uniformity of these properties on the volume of the zone (the absence of channel effects). Central characteristic of the electric field intensity in the pore can be the having the physical meaning of the values of tension on the distance from the centre, is equal to half the radius of the pores. One of the most homogeneous filter materials are porous resin, obtained by condensation of aromatic aldehydes with phenols, amines. Condensation is held in the form, the porosity of the element sets the number and ratio of the components. The most common porous filtering elements, obtained by condensation of formaldehyde with resorcinol and melamine in an acidic environment. One can obtain the elements of the effective pore radius of 0.5 to 15 microns. The effective range is calculated from the relation where ε - porosity of the medium (the share of the free volume, filled with water), p - the true density of the material, σ - specific surface. Specific surface of the material σ determined by the nitrogen adsorption method Б-Emmett-teller. Porosity ε is calculated from the difference of masses of material saturated with water and after centrifugation, when the water from the pores removed. To determine the z-potential material sample grated in hand a mortar, then stir in water and allow to sit for 30 minutes, after which the suspension of the remaining suspended fine particles is examined for the device «Zetasizer, Malvern». Found that the polymer porous elements on the basis of resorcinol formaldehyde and show considerable (from -25 to -40 mV) negative values of the z-building. Elements on the basis of formaldehyde and melamine, however, show high positive values to +35 mV. Specified behavior associated with the presence on the surface of pores in the materials of significant amounts of weak acid and groups respectively. To strengthen the antiviral activity of filter elements there is a need to create a second filtration zone, which may be formed on the surface of the first in the form of upstream layer. This layer can be made dispersible material with high value of the z-building. One such material is expanded perlite, the resulting thermal processing of mineral on the basis of silicon dioxide with a special crystalline structure. The material has a high specific surface of particles in the presence of their surfaces of numerous weak acid groups. EXAMPLES OF THE IMPLEMENTATION OF THE INVENTION Sustainable value of the z - potential flows of tap water, Saint-Petersburg amounted to 28 mW. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is EXAMPLE 2. Through the filter with filter element in example 1 let in water as viruses. As a viral cultures have used the virus of hepatitis A HAS-15). Used the suspension viral culture of concentration between 10 2 10 10 particles in ml. In each test passed through the filter 10 litres of suspension, have determined the presence of viruses after 2 and 10 liters, the transmission rate was 8 l/min The concentration of virus was determined by PCR (polymerase chain reaction) with the use of reagents « HAV» (made in ), the limit of detection of viruses this method is 10 2 /ml ( - tissue viral-induced cytopathic dose) To control the use enzyme immunoassay using a test system And-Antigen Strip» (made in Vector-best), the limit of detection of the method is 10 6 TDC/ml The results of determining the presence of viruses in the filtered water are given in table 1. Table 1.The concentration of the virus at the entrance /ml PCR method Enzyme-linked immunosorbent assay 2nd liter 10th liter 2nd liter 10th liter 10 2 - - - - 10 3 - - - - 10 4 - - - - 10 5 - - - - 10 6 - - - - 10 7 - - - - 10 8 - - - - 10 9 - + - - 10 10 + + - -Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 7 times. EXAMPLE 3. Through the filter with filter element in example 1 let in water as viruses. As viral culture used rotavirus human HRV/SPb/884/10/05. Used the suspension viral culture of concentration between 10 2 10 10 particles in ml. each test passed through the filter 10 litres of suspension, have determined the presence of viruses after 2 and 10 liters, the transmission rate was 8 l/min The concentration of virus was determined by PCR (polymerase chain reaction) with the use of reagents « Rota viruses group» (made in ), the limit of detection of viruses this method is 10 2 /ml ( - tissue viral-induced cytopathic dose) For control was used enzyme-linked immunosorbent assay with the test-system «Roth AG (SPE ), the limit of detection of the method is 10 6 TDC/ml the Results of determining the presence of viruses in the filtered water are given in table 2. Table 2. The concentration of the virus at the entrance /ml PCR method Enzyme-linked immunosorbent assay 2nd liter 10th liter 2nd liter 10th liter 10 2 - - - - 10 3 - - - - 10 4 - - - - 10 5 - - - - 10 6 - - - - 10 7 - - - - 10 8 - - - - 10 9 - - - - 10 10 + + - -Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 times. EXAMPLE 4. Through the filter with filter element in example 1 let in water as viruses. As viral culture used norovirus (noro-Spb/2005). Used the suspension viral culture of concentration between 10 2 10 10 particles in ml. each test passed through the filter 10 litres of suspension, have determined the presence of viruses after 2 and 10 liters, the transmission rate was 8 l/min The concentration of virus was determined by PCR (polymerase chain reaction) with the use of reagents « Caliciviruses: Noroviruses» (made in ), the limit of detection of viruses this method is 10 2 /ml ( - tissue viral-induced cytopathic dose). The results of determining the presence of viruses in the filtered water are given in table 3. Table 3. The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - - 10 6 - - 10 7 - - 10 8 - - 10 9 + + 10 10 + +Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 6 times. EXAMPLE 5. Porous filtering element was received in the process of condensation of resorcinol formaldehyde in the presence of acid. The linear dimensions of the element - as in example 1. The share of the free volume (porosity) in the filter module was 45%. Specific surface of a material is defined by nitrogen adsorption method BET amounted to 2.4 m 2 /year of the Effective radius of the channel was r EF =0.6 microns. Sustainable value of the z-potential flows of tap water, the St. Petersburg was 38,0 mV. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is EXAMPLE 6. Through the filter with filter element for example 5 missed water as viruses. As a viral cultures have used the virus of hepatitis A HAS-15). Experimental conditions in example 2. Results are shown in table 4. Table 4.The concentration of the virus at the entrance of the TPD/ml PCR method Enzyme-linked immunosorbent assay 2nd liter 10th liter 2nd liter 10th liter 10 2 - - - - 10 3 - - - - 10 4 - - - - 10 5 - - - - 10 6 - - - - 10 7 - - - - 10 8 - - - - 10 9 - - - - 10 10 - - - -EXAMPLE 7. Through the filter with filter element for example 5 missed water as viruses. As viral culture used rotavirus human HRV/SPb/884/10/05. Experimental conditions in example 3. Results are shown in table 5. Table 5. The concentration of the virus at the entrance /ml PCR method Enzyme-linked immunosorbent assay 2nd liter 10th liter 2nd liter 10th liter 10 2 - - - - 10 3 - - - - 10 4 - - - - 10 5 - - - - 10 6 - - - - 10 7 - - - - 10 8 - - - - 10 9 - - - - 10 10 - - - -Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 8 times. EXAMPLE 8. Through the filter with filter element for example 5 missed water as viruses. As viral culture used norovirus (noro-Spb/2005). Experimental conditions in example 4. Results are shown in table 6. Table 6.The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - - 10 6 - - 10 7 - - 10 8 - - 10 9 - - 10 10 + +Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 7 times. EXAMPLE 9. Through the filter with filter element in example 1 let in water as viruses. As viral culture used rotavirus human HRV/SPb/884/10/05. Determination of the content of the virus in the original and filtered water - PCR in example 3. Perform filtering suspensions virus with a concentration of 10 6 TDC/ml at various speeds filtering. The results of the experiment are given in table 7. Table 7.Filtration rate, l/min The concentration of viruses, TDC/ml Time of contact with water, S. Inlet Output 8,7 10 6 - 5,2 9,7 10 6 - 4,7 13,3 10 6 - 3,4 30,2 10 6 10 2 1,5Found that the overshoot of active viruses occurs when a contact time of the filter material with water for at least 2 seconds. EXAMPLE 10. Porous filtering element was received in the process of condensation of resorcinol formaldehyde in the presence of acid. The linear dimensions of the element - as in example 1. The share of the free volume (porosity) in the filter module was 60%. Specific surface of a material is defined by nitrogen adsorption method BET amounted to 0.2 m 2 /year of the Effective radius of the channel was r EF =12.5 mkm. Sustainable value of the z-potential flows of tap water, the St. Petersburg was 25 mV. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is EXAMPLE 11. Through the filter with filter element for example 10 missed water as viruses. As viral culture used norovirus (noro-Spb/2005). The experimental conditions are similar to Example 4. The results of determining the presence of viruses in the filtered water are given in table 8. Table 8. The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - + 10 5 + + 10 6 + + 10 7 + +Found that the filter element in conditions of the experiment provides the reduction of virus concentration not more than 10 times. Thus, the filter element exhibit a low efficiency in inactivation of viruses. EXAMPLE 12. Water as viruses passed through the filter element in example 9, the surface of which was additionally formed alluvial layer, composed by the particles of expanded perlite. Thickness of a layer of perlite amounted to 3 mm, the total weight of it - 155 g, which is in its own particle density 2.65 g/cm 3 corresponds to layer porosity of 0.65. Specific surface of the material determined by BET method amounted to 4 m2 /G. Thus, the effective radius of the channel leakage r EF =0,35 microns. Sustainable value of the z-potential flows of tap water in St. Petersburg was 54 MB. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is As viral culture used norovirus (noro-Spb/2005). The experimental conditions are similar to Example 4. The results of determining the presence of viruses in the filtered water are shown in table 9. Table 9. The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - - 10 6 - - 10 7 - - 10 8 - - 10 9 - + 10 10 + +Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 6 times. EXAMPLE 13. Porous filtering element was received in the process of condensation of melamine formaldehyde in the presence of acid. The linear dimensions of the element - as in example 1. The share of the free volume (porosity) in the filter module was 50%. Specific surface of a material is defined by nitrogen adsorption method BET was 0.6 m 2 /year of the Effective radius of the channel was r EF =5,5 microns. EXAMPLE 14. Through the filter with filter element for example 13 missed water as viruses. As viral culture used norovirus (noro-Spb/2005). The experimental conditions are similar to Example 4. The results of determining the presence of viruses in the filtered water are given in table 10. Table 10. The concentration of the virus at the entrance of the TPD/ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - - 10 6 - - 10 7 - - 10 8 - - 10 9 - - 10 10 + +Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 7 times. EXAMPLE 15. Porous filtering element was received in the process of condensation of urea with formaldehyde in the presence of acid. The linear dimensions of the element - as in example 1. The share of the free volume (porosity) in the filter module was 54%. Specific surface of a material is defined by nitrogen adsorption method BET amounted to 1.5 m 2 /year of the Effective radius of the channel was r EF =1.3 mkm. Sustainable value of the z-potential flows of tap water in St. Petersburg was 12 mV. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is EXAMPLE 16. Through the filter with filter element for example 15 missed water as viruses. As viral culture used norovirus (noro-Spb/2005). The experimental conditions are similar to Example 4. The results of determining the presence of viruses in the filtered water are given in table 11. Table 11. The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - + 10 6 + + 10 7 + +Found that the filter element in conditions of the experiment provides the reduction of virus concentration not more than 10 to 3 times. Thus, the filter element exhibit a low efficiency in inactivation of viruses. EXAMPLE 17 Water as viruses passed through the filter element in example 9, the surface of which was additionally formed alluvial layer, composed of fine-dispersed titanium dioxide particles with an average size of 1 micron. The thickness of the layer of titanium dioxide was 5 mm, the total weight of it - 538 g, which is in its own particle density 4,235 g/cm 3 corresponds to layer porosity 0,55. Specific surface of the material determined by BET method amounted to 1.4 m 2 /and, therefore, the effective radius of the channel leakage r EF =0.4 microns. Sustainable value of the z-potential flows of tap water in St. Petersburg was 42 mW. Thus, the ratio of the absolute values of the Zeta potential of sorption material to the value of the effective radius of the channel of the flow is As viral culture used norovirus (noro-Spb/2005). The experimental conditions are similar to Example 4. The results of determining the presence of viruses in the filtered water are given in table 12. Table 12. The concentration of the virus at the entrance /ml PCR method 2nd liter 10th liter 10 2 - - 10 3 - - 10 4 - - 10 5 - - 10 6 - - 10 7 - - 10 8 - + 10 9 + + 10 10 + +Found that the filter element in conditions of the experiment provides the reduction of the concentration of the virus in at least 10 6 times. 1. The method of inactivation of viruses in aquatic environments, including passing under the pressure of the fluid through the zones of sorption materials, characterized in that in the capacity of sorption material at least one of the zones for use porous filter element based on resins, obtained by condensation of aromatic aldehydes with phenols or amines who has the following characteristics: a ratio of the absolute values of the Zeta potential of porous filter element to the value of the effective radius of the channel of the flow is at least 10 4 In/m 2. The method according to claim 1, characterized in that in the capacity of sorption material at least one of the zones for use porous filter element based resin, obtained by condensation of formaldehyde with resorcinol. 3. The method according to claim 1, characterized in that in the capacity of sorption material at least one of the zones for use porous filter element based on resins obtained by condensation of formaldehyde with melamine. 4. The method according to claim 1, wherein the porous filter element can contain alluvial layer of sorption material, characterized by an attitude of absolute values of the Zeta-potential material to the value of the effective radius of the channel leakage at least 10 5 A/m
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