WO2023132756A1 - Nanoparticule métallique en suspension - Google Patents

Nanoparticule métallique en suspension Download PDF

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Publication number
WO2023132756A1
WO2023132756A1 PCT/PE2022/050003 PE2022050003W WO2023132756A1 WO 2023132756 A1 WO2023132756 A1 WO 2023132756A1 PE 2022050003 W PE2022050003 W PE 2022050003W WO 2023132756 A1 WO2023132756 A1 WO 2023132756A1
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Prior art keywords
concentration
agent
metal nanoparticles
reaction medium
respect
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PCT/PE2022/050003
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English (en)
Spanish (es)
Inventor
Matías Raúl Lanfranconi
Tobias Salinas LARRECHARTE
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Nairotech Desarrollo E Innovación S.A.
BENITES AGUILAR, Gustavo Enrique
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Application filed by Nairotech Desarrollo E Innovación S.A., BENITES AGUILAR, Gustavo Enrique filed Critical Nairotech Desarrollo E Innovación S.A.
Priority to PCT/PE2022/050003 priority Critical patent/WO2023132756A1/fr
Priority to ARP230100046A priority patent/AR128227A1/es
Publication of WO2023132756A1 publication Critical patent/WO2023132756A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C29/00—Finishing or dressing, of textile fabrics, not provided for in the preceding groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules

Definitions

  • This invention refers to the field of nanotechnology, particularly to obtaining metallic nanoparticles, especially copper nanoparticles.
  • metallic nanoparticles especially copper nanoparticles.
  • copper nanoparticles with biocidal properties for the manufacture of antiviral and antibacterial inputs are particularly interested.
  • Metallic nanoparticles present unique characteristics that make them the object of study and many interesting applications. However, obtaining metallic nanoparticles and their conservation represents a challenge, due to their rapid oxidation.
  • the article “Large-scale synthesis of copper nanoparticles by chemically controlled reduction for applications of inkjet-printed electronics” discloses a method for obtaining copper nanoparticles from pentahydrated copper sulfate, which is reduced to metallic copper by the action of monohydrated sodium hypophosphite in an ethylene glycol medium.
  • ethylene glycol not only acts as a solvent, but is also a reducing and stabilizing agent that contributes to obtaining small particles.
  • polyvinylpyrrolidone is used as a polymer surfactant and dispersing agent that prevents particle aggregation and controls particle growth during the reaction.
  • the reaction must be carried out at high temperatures, in the order of 90 °C, which must be stopped by adding cold deionized water.
  • the high concentrations of reagents used require washing with acetone and water to obtain the copper nanoparticles. All this implies a relatively expensive process due to the amount of reagents and the energy input required, which also has a negative impact on the environment.
  • the nanoparticles obtained have low resistance to oxidation, and the medium in which they are suspended is aggressive when in contact with the skin.
  • the present invention corrects all these drawbacks, managing to obtain metallic nanoparticles with high resistance to oxidation, in a reaction medium with less ecological impact and null cytotoxicity in adequate dilution, which makes washing operations unnecessary if it is desired to separate the nanoparticles obtained. and that it is also carried out at room temperature.
  • An object of the present invention is a nanoparticle of metal, preferably metallic copper in aqueous suspension of great stability with biocidal properties: virucidal and bactericidal, which maintains the metallic state of copper up to a temperature of 210°C and does not oxidize for a period of time. of at least 5 years, which includes a particle size of less than 80 nanometers; a copper core covered by polyvinylpyrrolidone, sodium hypophosphite, ascorbic acid; and it is found suspended in aqueous solution, preferably in the absence of ethylene glycol and any organic solvent.
  • it comprises an antisedimentant in a concentration of up to 3% W/V.
  • Another object of the present invention is a method for obtaining copper nanoparticles that comprises the steps of: preparing a reaction mixture that comprises at least one reaction medium, at least one metal compound, at least one reducing agent, at least one surfactant and surface protector, at least one pH regulating agent; subjecting said reaction mixture to intimate contact at a controlled temperature; optionally, separating the metal nanoparticles formed from the rest of the reaction mixture.
  • reaction medium comprises water.
  • metallic compound comprises a metallic salt, for example, but not limited to, copper sulfate, in a concentration with respect to said reaction medium chosen from the range comprising 20 to 90 g/L.
  • said reducing agent is selected from the set comprised of ascorbic acid, sodium hypophosphite, and their mixtures, in a concentration with respect to said reaction medium chosen from the range comprising 55 to 180 g/L; and in the event that said reducing agent is a mixture, said ascorbic acid comprises a concentration, with respect to said reaction medium, of between 25 and 90 g/L, and said sodium hypophosphite comprises a concentration, with respect to said reaction medium, of reaction, between 30 and 90 g/L.
  • surfactant and surface protective agent comprises polyvinylpyrrolidone in a concentration with respect to said reaction medium chosen from the range comprising 2 to 213 g/L.
  • said pH regulating agent comprises sodium hydroxide in a concentration with respect to said reaction medium chosen from the range comprising 3 to 20 g/L, so that the pH results in the range comprising pH 3 to pH 9.
  • intimate contact comprises subjecting the reaction mixture to stirring for a period of time chosen from the range comprising 30 to 120 minutes.
  • ambient temperature is chosen from the range comprising 10 °C to 40 °C.
  • said reaction medium comprises water
  • said metallic compound comprises copper sulfate in a concentration of 80 g/L with respect to water
  • said reducing agents comprise ascorbic acid in a concentration of 72 g/L with respect to water and sodium hypophosphite in a concentration of 80 g/L with respect to water
  • said surfactant and surface protector agent comprises polyvinylpyrrolidone in a concentration of 2.2 g/L with respect to water
  • said pH conditioning agent comprises sodium hydroxide in a concentration of 11 .5 g/L with respect to water
  • said intimate contact comprises subjecting the reaction mixture to stirring for a period of 1 hour.
  • the metal nanoparticle in suspension with an average particle size of less than 80 nm, biocide, object of the present invention, comprises a copper core covered by a reducing agent that comprises ascorbic acid and sodium hyposulfite; coated by at least one surface protecting and surfactant agent; and at least one pH regulating agent, in an aqueous medium.
  • said surfactant and surface protector agent is selected from the group comprised of polyvinylpyrrolidone, polyallylamines and polyethylamines and their mixtures and is preferably polyvinylpyrrolidone.
  • said pH regulating agent is sodium hydroxide.
  • it optionally comprises an anti-settling agent in a concentration of up to 3% P/V, selected from the group comprised of guar gum, urea modified in N-methylpyrrolidone and their mixtures.
  • the aqueous suspension of copper nanoparticles, a biocide for the preparation of antiviral and antibacterial products, object of the present invention is stable to oxidation at temperatures greater than 200 °C, and comprises said nanoparticles in aqueous suspension, in the absence of solvent.
  • organic with a particle size of less than 80 nm; a reducing agent comprising ascorbic acid and sodium hyposulfite; a surfactant and surface protective agent; a and a pH regulating agent.
  • it also comprises an anti-settling agent.
  • the method for obtaining metal nanoparticles in aqueous suspension of the present invention comprises the following steps: a. dissolving at least one surfactant and surface protective agent in water, by stirring; b. add to the mixture from point a. ascorbic acid and dissolve by stirring; c. add at least one metal compound to the mixture from point b. and dissolve by stirring; d. add to the mixture from point c. sodium hyposulfite by shaking e. add to the mixture from point d. at least one pH regulating agent; F. subjecting said reaction mixture to intimate contact by stirring the reaction medium at room temperature.
  • reaction medium comprises water in the absence of organic solvents and ethylene glycol; and said metal compound comprises a metal salt, preferably copper sulfate, and is in a concentration with respect to said reaction medium in the range that includes 20 to 90 g/L.
  • said reducing agent comprises ascorbic acid and sodium hypophosphite in a weight/weight ratio of ascorbic acid/sodium hypophosphite between 0.85 and 1.
  • said surfactant and surface protective agent comprises polyvinylpyrrolidone in a preferred embodiment .
  • said pH regulating agent comprises sodium hydroxide, preferably.
  • said reducing agent is found in a concentration with respect to said reaction medium in the range comprising 55 to 180 g/L; and said surfactant and surface protector agent is found in a concentration with respect to said reaction medium in the range from 2 to 200 g/L.
  • said ascorbic acid comprises a concentration, with respect to said reaction medium, of between 25 and 90 g/L, and because said sodium hypophosphite comprises a concentration, with respect to said reaction medium, of between 30 and 90 g /L.
  • said pH regulating agent is found in a concentration with respect to said reaction medium in the range comprising 3 to 20 g/L. Just as its pH is chosen from the range that includes pH 3 to pH 9.
  • said metallic compound comprises copper sulfate in a concentration of between 37 and 82 g/L with respect to the reaction medium
  • said reducing agents comprise ascorbic acid in a concentration of between 32 and 77 g/L with respect to the medium.
  • said surfactant and surface protective agent comprises polyvinylpyrrolidone in a concentration of between 2.3 and 213 g/L with respect to the reaction medium
  • said pH conditioning agent comprises sodium hydroxide in a concentration of between 6 and 12 g/L with respect to the reaction medium.
  • said intimate contact comprises subjecting the reaction mixture to stirring for a period of time chosen from the range comprising 30 to 120 minutes, preferably one hour.
  • Another object of the present invention is a formulation for textile impregnation comprising said suspended metal nanoparticles of the present invention, water, surfactants and anti-settling agents.
  • said suspended metal nanoparticles comprise copper nanoparticles whose concentration is chosen from the range comprising 900 to 1200 ppm.
  • said surfactants comprise non-ionic surfactants, in a concentration chosen from the range comprising 1 g/L to 10 g/L.
  • said anti-settling agents are selected from the group comprised of guar gum, urea modified in N-methylpyrrolidone and their mixtures, in a concentration chosen from the range comprising 5 to 30 g/L.
  • said formulation for impregnating textiles of the invention comprises water, a suspension of metallic nanoparticles obtained at a concentration of 1,000 ppm, nonionic surfactants at a concentration of 3 g/L, and guar gum at a concentration of 20 g/L. .
  • Another object of the present invention is an antimicrobial fabric softener formulation comprising said metal nanoparticles in suspension of the invention and at least one fabric softener. Where 8 ml of metallic nanoparticles in suspension obtained according to the method of the present invention for each liter of said fabric softener.
  • Figure 1 Shows the evolution of the weight percentage (upper curve) and the derivative of the weight percentage with respect to temperature (lower curve) of a sample of metallic copper nanoparticles obtained according to the present invention when subjected to increasing temperatures , during the thermogravimetry test (Example 6).
  • Figure 2 Shows the evolution of the weight percentage (upper curve) and the derivative of the weight percentage with respect to temperature (lower curve) of a sample of metallic copper nanoparticles without polyvinylpyrrolidone coating when subjected to increasing temperatures, during the thermogravimetry test (Example 6).
  • Figure 3 Shows the evolution of the weight percentage (upper curve) and the temperature (lower curve) of a sample of metallic copper nanoparticles obtained according to the present invention over time, during the thermogravimetry test (Example 6).
  • Figure 4 Shows the evolution of the percentage of weight (upper curve) and of the temperature (lower curve) of a sample of metallic copper nanoparticles obtained according to the present invention (sample “NanoCu 210208-01 PVP") over time, during the thermogravimetry test (Example 6).
  • FIG. 5 Shows the result of the Dynamic Light Scattering (DLS) measurement test carried out on the resulting sample of metallic copper nanoparticles obtained according to Example 1 of the present invention (Example 8).
  • DLS Dynamic Light Scattering
  • Figure 6 Shows the graph of absorbance vs. wavelength in a UV-Visible spectrophotometry test of the suspension of example 1, shows the typical curve of metallic copper (Cu°), without the presence of copper oxide (Cu +2 ) .
  • Figure 7 Shows the graph of absorbance vs. wavelength in a UV-Visible spectrophotometry test of a copper sulfate solution (Cu +2 ).
  • % P/V refers to a concentration expressed as a weight/volume percentage
  • % VA/ to a concentration expressed as a volume/volume percentage
  • % P/W to a concentration expressed as a weight/weight percentage
  • a biocide will be understood as having the effect of destroying, counteracting, neutralizing, preventing the action or exerting control of another type on any organism considered harmful to humans, including viruses and bacteria.
  • An object of the present invention is a method for obtaining metallic nanoparticles, which comprises the steps of preparing a reaction mixture and subjecting said reaction mixture to intimate contact at a controlled temperature.
  • the nanoparticles obtained by the present invention can be separated from the remaining reaction mixture.
  • said reaction mixture comprises at least one reaction medium, at least one metal compound, at least a reducing agent, at least one surfactant and surface protective agent, and at least one pH regulating agent.
  • said reaction medium comprises water.
  • water as a reaction medium is an innovative advantage of the present invention, which implies lower costs and less environmental impact compared to organic solvents - such as ethylene liqueur - used in the known methods to obtain metallic nanoparticles.
  • said water is distilled water with a conductivity of less than 1.5 mS.
  • said metallic compound comprises a metallic salt in a concentration with respect to said reaction medium chosen from the range comprising 20 to 90 g/L.
  • said metal salt comprises copper sulfate.
  • said copper sulfate can be found both in its anhydrous form and in its hydrated forms, its hydration not affecting the final result. Therefore, since the use of copper sulfate pentahydrate (CuSO4'5H2O) presents advantages in terms of handling, storage, and costs, it is preferred over its anhydrous variable.
  • said reducing agent comprises ascorbic acid.
  • said reducing agent comprises sodium hypophosphite.
  • said sodium hypophosphite can be found both in its anhydrous form and in its hydrated forms, its hydration not affecting the final result.
  • sodium hypophosphite monohydrate NaH2PO2 H2O
  • anhydrous sodium hypophosphite readily degrades to phosphane gas, a volatile compound and toxic.
  • said reducing agent comprises a mixture of sodium hypophosphite and ascorbic acid.
  • ascorbic acid as a component of the reducing agent constitutes an essential technical characteristic that generates another innovative advantage of the present invention, which reduces the environmental impact compared to the use of sodium hypophosphite as the only reducing agent, and which is also harmless in contact with the skin and non-cytotoxic in concentrations lower than 2.5% VA/, as verified in example 5.
  • the use of a mixture of sodium hypophosphite and ascorbic acid as a reducing agent constitutes an innovative technical characteristic of the present invention, which allows the reduction reaction to be carried out at room temperature while significantly decreasing the concentration. of sodium hypophosphite used compared to known techniques, which is less aggressive for the environment.
  • the reducing agent constituted by the mixture of ascorbic acid and sodium hypophosphite not only achieves the total reduction of Cu++ to Cu 0 , but also forms a stable mixture that remains in the suspension of nanoparticles, being an important factor in the stability of metallic copper. long-term. It is expected to be stable in solution for up to 5+ years, preferably up to 10+ years. Furthermore, the synergistic effect of the reducing agent of the present invention is manifested in that it is not necessary to heat the mixture to obtain the complete reduction reaction. As can be seen in figure 6, the graph of absorbance vs.
  • the reducing agent of the present invention in a preferred version thereof is a mixture of ascorbic acid and sodium hypophosphite in an ascorbic acid/sodium hypophosphite ratio of between 0.85 and 1. This relationship is in P/P.
  • Another object of the present invention is a copper nanoparticle in aqueous suspension with biocidal properties, to be applied to impregnate fabrics, cleaning products such as polishes, rinses, etc.
  • the fact that one of the objects of the present invention is an aqueous suspension of copper nanoparticles implies an enormous advantage, since the fact that the dispersing aqueous solution contains a remaining reducing medium gives it remarkable and surprising stability characteristics.
  • the present invention proposes an aqueous suspension of the same that generates a superlative technical effect in terms of its stability and permanence as Cu 0 when packaging, transporting, and using it for various purposes. uses that are proposed and many other biocidal uses that can be imagined.
  • room temperature is defined as any temperature chosen from the range comprising 10°C to 40°C.
  • said reducing agent is found in a concentration with respect to said reaction medium chosen from the range comprising 55 to 180 g/L.
  • said reducing agent comprises a mixture of ascorbic acid and sodium hypophosphite, where said ascorbic acid comprises a concentration, with respect to said reaction medium, of between 25 and 90 g/L, and where said hypophosphite sodium comprises a concentration, with respect to said reaction medium, of between 30 and 90 g/L.
  • said surfactant and surface protective agent comprises polyvinypyrrolidone in a concentration with respect to said reaction medium chosen from the range comprising 2 to 213 g/L.
  • Other components such as polyallylamines or polyethylamines may also be used.
  • the concentration of the surfactant and surface protection agent used in the present invention is significantly lower than those known in prior art, which constitutes another innovative advantage of the present invention, which not only implies lower surfactant and surface protection agent costs, Rather, it facilitates the subsequent washing and separation of the nanoparticles, and even makes this washing and separation step unnecessary for many applications, thus maximizing the protective effect of the surfactant and surface protection agent and reducing costs, time, and environmental impact associated with these operations, which usually use solvents such as acetone to wash away excess surfactant and surface protection agent.
  • said pH conditioning agent is added to ensure a pH chosen from the range comprising pH 3 to 9.
  • said pH conditioning agent comprises sodium hydroxide.
  • the pH of the reaction mixture is 7.
  • said intimate contact comprises subjecting the reaction mixture to stirring for a period of time chosen from the range comprising 30 to 120 minutes.
  • stirring is understood as any operation that tends to homogenize the reaction mixture, for example, but not limited to, mechanical stirring by means of turbines, mechanical stirring by means of propellers, magnetic stirring, fluid recirculation by means of extraction and reinjection, etc.
  • said controlled temperature is chosen from the range comprising 10°C to 40°C. Room temperature.
  • the range of temperatures to which the reaction mixture is subjected in the present invention is another innovative advantage of the present invention, since said reaction mixture does not have to be heated as in known techniques, thus saving costs and avoiding the potential risks involved in raising the temperature of a reaction mixture.
  • Examples 1, 2 and 3 describe preferred ways of carrying out the method for obtaining metallic copper nanoparticles in aqueous suspension of the present invention.
  • the generated metal nanoparticles are separated from the reaction medium by operations comprising, but not limited to, centrifugation.
  • the antioxidant agents that impregnate them added to the protective action of the surfactant and surface protector agent, considerably increase the useful life of said metallic nanoparticles compared to the useful life of nanoparticles.
  • metals generated by means of the previously known technique which constitutes another innovative advantage of the present invention.
  • thermogravimetry test described in Example 6 shows that while the reducing agents used in the present invention have a positive effect, decreasing the oxidation speed of the metallic nanoparticles; the surfactant agent and surface protector generates a protection on the reducing agents, reducing their losses; and the combination of the reducing agents used, together with the coating provided by the surfactant agent and surface protector generate a protection that completely prevents the oxidation of the metal even at high temperatures.
  • the generated metal nanoparticles are not separated from the reaction medium.
  • useful life is understood as the time during which said metallic nanoparticles remain without oxidizing.
  • useful life of copper nanoparticles produced by the present invention as described in Example 1 is estimated to be at least 5 years, according to the conclusions of the tests of Example 6.
  • the generated metal nanoparticles are kept in suspension with the addition of anti-settling substances, such as, but not limited to, guar gum or modified urea solution in N-methylpyrrolidone.
  • the medium that contains said generated metal nanoparticles to which said anti-settling substances are added is chosen from the set that comprises said reaction medium, water, other solvents, or their mixtures.
  • Example 7 demonstrates that it is possible to achieve stability of aqueous suspensions of metal nanoparticles obtained by means of the present invention for periods of time that depend on the concentration of an added antisedimentant, which represents another advantage of the present invention.
  • the metal nanoparticles generated by the present invention have a mean size of 61 nm, with a size less than 80 nm, as demonstrated in Example 8, which represents another advantage of the present invention.
  • Another object of the present invention is a formulation for textile impregnation that gives it antiviral and bactericidal properties.
  • the preferred textile impregnating formulation of the present invention comprises suspended metal nanoparticles obtained according to the present invention, deionized water, surfactants and anti-settling agents.
  • said metallic nanoparticles in suspension are added in such an amount that the concentration value measured with an electroconductivity meter is comprised in the range of 900 to 1200 ppm.
  • said surfactants comprise non-ionic surfactants, such as ethoxylated alcohols and phenols, such as 10 M ethoxylated nonyl phenol, ethoxylated lauryl ether, 7 ethoxylated lauric acid Moles of Ethylene Oxide, among many others known in the state of the art as non-ionic surfactants.
  • said surfactants are in a concentration comprising 1 g/L to 10 g/L.
  • said anti-settling agents comprise guar gum.
  • said anti-settling agents are found in a concentration comprised in the range of 5 to 30 g/L.
  • Examples 9, 10, 11, and 12 illustrate formulations for textile impregnation according to the present invention.
  • test of example 14 shows that the fabrics treated with the formulations for impregnating textiles according to the present invention have bactericidal activity greater than 99.9997%.
  • Example 15 demonstrates that the fabrics treated with the formulations for impregnating textiles according to the present invention have virucidal activity, being effective in producing 99% inactivation (2 logarithmic units) in the infectious titer of a canine coronavirus stock. (ATCC® VR-2068).
  • Example 16 demonstrates that fabrics treated with textile impregnation formulations according to the present invention are not irritating on contact with the skin, and Example 17 demonstrates that fabrics treated with textile impregnation formulations according to the present invention do not cause reaction reactions. sensitization.
  • Another object of the present invention is the preparation of an antimicrobial fabric softener formulation, which comprises at least one commercial fabric softener and metallic nanoparticles in suspension obtained according to the present invention.
  • Example 13 illustrates a preferred antimicrobial fabric softener formulation in accordance with the present invention.
  • Example 18 demonstrates that fabrics treated with the antimicrobial fabric softener formulation of the present invention possess bactericidal activity.
  • Example 1 Obtaining metallic copper nanoparticles.
  • a preferred embodiment of the method for obtaining metallic nanoparticles of the present invention was applied to obtaining copper nanoparticles.
  • a granataria balance with 2 decimal places of precision was used.
  • a 20-liter container 9.5 L of distilled water (reaction medium) were placed at 10 °C. At that temperature, the density of said distilled water is 0.99977 g/cm 3 , therefore 9497.81 g of distilled water were weighed.
  • Example 2 Obtaining metallic copper nanoparticles.
  • a preferred embodiment of the method for obtaining metallic nanoparticles of the present invention was applied to obtaining copper nanoparticles.
  • a granataha scale with 2 decimal places of precision was used.
  • 9.4 L of distilled water (reaction medium) were placed at 25 °C. At that temperature, the density of said distilled water is 0.99713 g/cm 3 , therefore 9 373.02 g of distilled water were weighed.
  • Example 3 Obtaining metallic copper nanoparticles.
  • a preferred embodiment of the method for obtaining metallic nanoparticles of the present invention was applied to obtaining copper nanoparticles.
  • a granataha scale with 2 decimal places of precision was used.
  • 9.4 L of distilled water (reaction medium) were placed at 25 °C. At that temperature, the density of said distilled water is 0.99713 g/cm 3 , therefore 9 373.02 g of distilled water were weighed.
  • Example 4 Quantitative evaluation of viricidal activity.
  • canine coronavirus CCV ATCC® VR-2068
  • 2 Eppendorf-type tubes with a capacity of 1.5 ml were prepared with 0.2 ml of a viral suspension.
  • 0.2 ml of the pure sample were added to a tube, and it was left in contact for 5 min at room temperature.
  • 0.2 ml of culture medium were added to the other tube with virus as a control, and it was incubated under the same conditions.
  • the remaining infectivity in each case was quantified by the Reed-Muench method, calculating the infective dose in tissue culture 50 (TCID 50) in CRFK feline kidney cells (ATCC® CCL-94TM). For this, cell cultures grown in 96-well microplates were inoculated with the decimal dilutions of the samples subjected to each treatment, 40 pl per well, in quadruplicate. After 1 hour of adsorption at 37 °C, the inoculums were removed and DMEM culture medium added with 0.25% trypsin was added. Cultures were incubated at 37 °C in a CO2 oven.
  • the wells were observed daily for 3 days post-infection to record the progression of the cytopathic effect in each well.
  • the remaining ⁇ Affectivity titers were calculated, expressed in TCID50, and based on the results, the virucidal activity of the sample was determined as a % reduction of ⁇ Affectivity with respect to the control not treated with the sample.
  • Inactivation percentage 100 - (Titre of virus treated with the sample / titer of control virus) x 100.
  • the sample of metallic copper nanoparticles produced according to the present invention was effective to produce 99.99% inactivation (4 log units) in the infectious titer of a canine coronavirus stock (ATCC® VR-2068), after 5 minutes. contact.
  • Example 5 MTT cytotoxicity assay according to ISO 10993-5:2009.
  • the assay was performed using L-929 cells grown in the exponential phase of growth.
  • Sample dilutions were made and added to a culture of L-929 cells.
  • the sample and controls were prepared according to ISO 10993-12 ( 4th edition, corrected 2012) and added to a culture of L-929 cells. After 24 hours at 37 °C and 5% CO2, cytotoxicity was evaluated.
  • the sample and the extracts were prepared based on the ISO 10993-12 standard ( 4th edition, corrected 2012).
  • the extraction conditions were: closed, sterile and chemically inert containers; 24 h at 37 ⁇ 2 °C with shaking. Due to the presence of particles in suspension in the highest concentration tested (20% V/V), it was centrifuged before diluting it and placing it in contact with the cell monolayer.
  • the pH of the extracts carried out was determined: the blank resulted with pH 8.0 and without change in color or turbidity; the sample extract resulted with pH 8.0 without color modification and with particles in suspension; the negative control resulted with pH 8.0 and no change in color or turbidity; the positive control resulted with pH 7.5 and no change in color or turbidity.
  • the positive and negative controls were chosen based on the suggestions of the ISO 10993-12 standard.
  • Positive cytotoxicity control sterile latex, and DMSO.
  • Negative cytotoxicity control sterile polypropylene tested.
  • the cell line used is a line derived from normal mouse areolar and adipose subcutaneous connective tissue (Mus musculus). This is an established and well characterized cell line, which has shown reproducible results. It is commonly used for toxicity tests.
  • L-929 cells were cultured in sterile GIBCO Minimum Essential Medium.
  • the sample was tested in 6 different concentrations: 20%, 10%, 5%, 2.5%, 1.25% and 0.625%.
  • sterile culture medium supplemented with 5% FBS was used, extracted for 24 hours at 37 ⁇ 2 °C with shaking.
  • the medium was replaced with MTT (3-(4, 5-dimethylthiazolyl-2)-2, 5-diphenyltetrazolium bromide), and incubated with the cells. for 2 more h (37 °C and 5% CO2). Subsequently, the optical density at 570 nm (ref 650 nm) was quantified as a measure of metabolic activity and cell viability.
  • the viability percentage was calculated according to the formula:
  • % Viability less than 70% is considered potentially cytotoxic.
  • Table 1 summarizes the results obtained. As can be seen, the cell viability of the cultures that were in contact with the different dilutions of the sample is greater than 70% (non-cytotoxic) from the 1/40 dilution (2.5% V/V concentration).
  • Test 20% dilution 1/5 0.009 0.0022 0.7
  • Test 10% dilution 1/10 0.049 0.00741 3.8
  • Test 5% dilution 1/20 0.085 0.00404 6.55
  • Test 2.5% dilution 1/40 1 .1049 0.03041 80.49
  • Test 0.625% dilution 1/160 1 , 190 0.0363 91 ,26
  • Example 6 Thermogravimetry test.
  • Thermogravimetry tests were carried out on two samples of copper nanoparticles in aqueous suspension, using a TA Q500 unit.
  • the sample from Example 1 had a polyvinylpyrrolidone coating (surfactant and surface protective agent that provides a polymeric protective layer to the nanoparticles), while the sample named BETA was prepared as described in Example 1 but without use polyvinylpyrrolidone. Both samples with the protection of reducing agents (sodium hypophosphite and ascorbic acid).
  • the samples were kept under a nitrogen flow of 30 ml/min (inert atmosphere), heated at 10 °C/min up to 90 °C, maintaining this temperature for 60 minutes to completely eliminate the water contained in them. .
  • the atmosphere was changed to an air atmosphere (oxidative), maintaining a flow of 30 ml/min, and a heating ramp was applied at 10 °C/min up to 500 °C ( Figures 1 to 4). This temperature was maintained for 1 hour.
  • the reducing agent of the present invention (ascorbic acid/sodium hypophosphite) have a positive effect, slowing down the oxidation rate of copper; and a synergistic effect is noted between said reducing agent with polyvinylpyrrolidone that generates protection over the reducing agents, reducing their losses and increasing resistance to oxidation, achieving unusual stability at temperature and a protection that completely prevents the oxidation of copper up to temperatures close to 200 °C.
  • the synergy between polyvinylpyrrolidone and the reducing agent of the present invention constituted by the mixture of ascorbic acid and sodium hypophosphite is demonstrated.
  • thermo gravimetric analysis TGA
  • Example 7 Stability in suspension.
  • Example 2 To carry out this test, an aliquot of a suspension of copper nanoparticles prepared according to Example 1 of the present invention was taken, and 8 samples of suspensions thereof were prepared in various media. The time elapsed until a phase separation began to be noted was taken as the stability time. The results over time and the description of the media are detailed in Table 2.
  • the copper concentration in all samples was 0.1% weight by volume.
  • the medium used for sample 1 was distilled water.
  • the medium used for sample 2 was a 50% volume by volume solution of ethylene glycol in distilled water.
  • the medium used for samples 3, 4, 5, and 6 was a solution of an antisedimentant in distilled water, with different concentrations.
  • a solution of urea modified in N-methylpyrrolidone with the trade name Rheobyk-420 was used as an antisedimentant, in different concentrations shown in Table 2.
  • Example 8 Measurement of particle size.
  • Dynamic Light Scattering (DLS) measurements were carried out in triplicate in a Malvern brand equipment, Zetasicer model. To carry out this test, an aliquot of a sample of copper nanoparticles prepared according to Example 1 of the present invention was taken and the measurement was carried out. The result obtained (Fig. 5) shows that the particles coated with polivini ipirrolidone have a mean size of 61 nm. It is observed that the size of the particles is less at 80 nm.
  • Example 9 Formulation for impregnation of non-woven textiles.
  • a formulation for impregnation of non-woven textiles was prepared.
  • Example 2 In a 20 L capacity container, 15 L of deionized water were placed. A suspension of metallic nanoparticles obtained according to Example 1 of the present invention was added, in such an amount that the concentration value measured with an electroconductivity meter was approximately 1000 ppm. Nonionic surfactant (10 M nonyl phenol ethoxylate) was then added to a final concentration of 3 g/L. Finally, guar gum (anti-settling agent) was added to a final concentration of 20 g/L.
  • Example 10 Formulation for impregnation of cotton textiles.
  • a formulation for impregnating cotton textiles was prepared.
  • Example 11 Formulation for textile impregnation.
  • a formulation for textile impregnation was prepared.
  • 15 L of deionized water were placed.
  • 100 ml of a suspension of metallic nanoparticles obtained according to example 3 of the present invention was added.
  • Non-ionic surfactant (10 M nonyl phenol ethoxylate) was then added to a final concentration of 6 g/L, to a final concentration of 10 g/L.
  • guar gum antioxidant-settling agent
  • Example 12 Formulation for textile impregnation.
  • a formulation for textile impregnation was prepared.
  • a 20 L capacity container 15 L of deionized water were placed. 200 ml of a suspension of metallic nanoparticles obtained according to example 1 of the present invention were added. Non-ionic surfactant (10 M ethoxylated nonyl phenol) was then added to a final concentration of 8 g/L. Finally, guar gum (anti-settling agent) was added to a final concentration of 20 g/L.
  • Example 13 Antimicrobial fabric softener formulation.
  • a fabric softener formulation with antimicrobial capabilities was prepared. To 1 L of commercial fabric softener was added 8 ml of a suspension of copper nanoparticles obtained according to Example 2 of the present invention.
  • Example 14 Antimicrobial activity test of non-woven fabrics.
  • Example 9 Three textile samples of non-woven fabric used to make chinstraps treated with the formulation of Example 9 (samples A, B, and C) of the present invention, and an untreated sample of the same textile (Blanco sample) were tested.
  • K12 strain RP437 The gram-negative Escherichia coli (K12 strain RP437) bacterium, grown and maintained in a Luha-Bertani (LB) culture medium, was used for the tests.
  • LB Luha-Bertani
  • a bactericidal effect was observed in the analyzed textile samples A, B, and C (treated with the formulation of example 9 of the present invention), obtaining a bactericidal effect on E. coli greater than 99.9997% after 24 hours of incubation. .
  • Table 3 summarizes the test results. Table 3: Antimicrobial activity test of non-woven fabrics
  • Example 15 Quantitative evaluation test of virucidal activity on fabrics.
  • control (untreated) fabric and the fabric impregnated with the formulation of Example 12 of the present invention were sterile cut into 20mm x 20mm pieces.
  • the virucidal capacity of each cloth sample was measured by direct contact for 30 minutes with 200 pl of the viral stock (1x10 8 TCID50/ml), determining the quantity of remaining infective virus after washing for 20 minutes with 2 ml of physiological solution. .
  • the remaining infectivity was quantified in each case by the quantal method of end point and Reed-Muench transformation, calculating the infective dose in tissue culture 50 (TCID 50) in CRFK feline kidney cells (ATCC® CCL-94TM).
  • TCID 50 tissue culture 50
  • ATCC® CCL-94TM CRFK feline kidney cells
  • cell cultures grown in 96-well microplates were inoculated with the decimal dilutions of the samples subjected to each treatment, 40 pl per well, in quadruplicate. After 1 h of adsorption at 37 °C, the inoculums were removed and DMEM culture medium added with 0.25% trypsin was added. Cultures were incubated at 37 °C in a CO2 oven. The wells were observed daily for 3 days post-infection (pi) to record the progression of the cytopathic effect in each well.
  • the remaining infectivity titers were calculated, expressed in TCID50, and based on the results, the virucidal activity of the sample was determined as a % reduction in infectivity with respect to the control (control cloth).
  • SBA_Cu Fabric (treated with the formulation of Example 12 of the present invention) was effective in producing 99% inactivation (2 log units) in the infectious titer of a canine coronavirus stock (ATCC® VR-2068).
  • Example 16 Determination of the Primary Dermal Irritation Index.
  • the test was carried out according to the ISO 10993-10 standard and the patch test in rabbits according to Draize J.H Resolution No. 288 / 90, for samples that do not alter the color of the skin.
  • the animals were kept throughout the test period in individual cages at a temperature of 22°C + / - 2 oC and relative humidity between 30% and 70%.
  • the sample obtained an index of 0.00 (it is considered satisfactory if its index is between 0.0 and 0.9), therefore it is classified as non-irritating.
  • Example 17 Topical Sensitization Assay.
  • Example 12 of the present invention A sample of fabric treated with the formulation of Example 12 of the present invention was tested, using the methodology according to ISO 10993-10.
  • the sample under study was applied 10 times, every other day (inductive phase) and then the treatment was suspended. Twelve days later, the sample is applied again (triggering phase) and readings of the skin reactions were taken at 1, 6, 24, and 48 hours after the sample was withdrawn. The sample is withdrawn every 48 hours after its application.
  • the animals treated with the study sample had NO skin reactions.
  • Example 18 Determination of antimicrobial properties of fabrics treated with Antimicrobial Fabric Softener Formulation.
  • Example 13 The Antimicrobial Fabric Softener Formulation of Example 13 was used in an automatic washing machine wash with 3 fabric samples: one cotton (Alg-TP-Suav sample), one acetate (Acet-Suav sample), and one polyester. (sample Polies-Suav). These 3 samples were tested along with 3 other untreated samples used as blanks, one cotton (Alg-TP-Blank sample), one acetate (Acet-Blank sample), and one polyester (Polies-Blank sample).
  • F Mb -Ma
  • Ma the mean logarithm of the number of live bacteria on the control cloth at time 0.
  • Mb the mean logarithm of the number of live bacteria on the control cloth after 24h of incubation.
  • the test When the growth value is greater than 1.5, the test is considered effective, and when the growth value is 1.5 or less, the test is considered ineffective.
  • Me is the average of the logarithm of the number of live bacteria on the cloths after 24 h of incubation in an antimicrobial-treated sample.
  • K12 strain RP437 The gram-negative Escherichia coli (K12 strain RP437) bacterium, grown and maintained in a Luha-Bertani (LB) culture medium, was used for the tests.
  • LB Luha-Bertani
  • Spectrophotometric analyzes were carried out in the entire range of the UV-Visible spectrum to determine the oxidation state of the copper particles of the formulation of Example 9, as seen in Figure 6, which shows the absorbance vs. wavelength.
  • a solution of Cu+2 was analyzed (copper sulphate as a comparative control).

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Abstract

Nanoparticules métalliques biocides en suspension et méthode d'obtention de ces nanoparticules métalliques à partir d'un mélange réactionnel à température ambiante comprenant des composés métalliques, des agents réducteurs, des agents tensioactifs et des agents régulateurs de pH ; notamment pour obtenir des nanoparticules de cuivre à partir d'eau, d'acide ascorbique, d'hypophosphite de sodium, de polyvinylpyrrolidone, de sulfate de cuivre et d'hydroxyde de sodium, qui possèdent une activité virucide au moins contre le coronavirus canin.
PCT/PE2022/050003 2022-01-07 2022-01-07 Nanoparticule métallique en suspension WO2023132756A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880493A (zh) * 2010-07-01 2010-11-10 中国科学院宁波材料技术与工程研究所 一种纳米铜导电墨水的制备方法
WO2014196881A1 (fr) * 2013-06-03 2014-12-11 Eko-Styl Sp. Z O. O. Procédé de lavage par voie humide pour produire des textiles biocides
US20150166810A1 (en) * 2013-12-16 2015-06-18 Nano And Advanced Materials Institute Limited Metal Nanoparticle Synthesis and Conductive Ink Formulation
CN110115272A (zh) * 2019-03-28 2019-08-13 中山大学 一种Cu纳米粒子耦合石墨烯水凝胶复合材料及其制备方法和应用
CN112442893A (zh) * 2020-11-26 2021-03-05 甘肃省科学院实验工厂 一种特高效纳米铜抗菌剂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880493A (zh) * 2010-07-01 2010-11-10 中国科学院宁波材料技术与工程研究所 一种纳米铜导电墨水的制备方法
WO2014196881A1 (fr) * 2013-06-03 2014-12-11 Eko-Styl Sp. Z O. O. Procédé de lavage par voie humide pour produire des textiles biocides
US20150166810A1 (en) * 2013-12-16 2015-06-18 Nano And Advanced Materials Institute Limited Metal Nanoparticle Synthesis and Conductive Ink Formulation
CN110115272A (zh) * 2019-03-28 2019-08-13 中山大学 一种Cu纳米粒子耦合石墨烯水凝胶复合材料及其制备方法和应用
CN112442893A (zh) * 2020-11-26 2021-03-05 甘肃省科学院实验工厂 一种特高效纳米铜抗菌剂及其制备方法

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