Viral active and / or Anti-microbial inks and coatings

Abstract

To provide a particularly effective viral active and / or anti-microbial ink, article, production method, and use of the ink and article, which can be easily applied to surfaces or materials to provide highly effective treatment.SOLUTION: An ink comprising (i) a carrier, (ii) graphene particles and / or graphene oxide particles dispersed in the carrier, and (iii) a viral active component and / or anti-microbial component adhered to the graphene particles and / or graphene oxide particles, wherein the viral active component and / or anti-microbial component comprises metal nanoparticles, and the combination of the graphene particles and / or graphene oxide particles with the viral active component and / or anti-microbial component has a metal nanoparticle weight content of 1 wt.% to 30 wt.%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to inks, articles, methods of manufacture and uses of inks and articles containing virally active and / or antimicrobial components. [Background technology]

[0002] Over the past two decades, there have been several large-scale viral outbreaks in human populations, including Ebola, SARS, MERS, Zika, and more recently SARS-CoV-2 in 2019 / 2020. Considerable investment has been made in research aimed at combating these viruses, including preventing or reducing human transmission, preventing human-to-human transmission, developing vaccines, and developing antivirals and treatments for the diseases they cause.

[0003] As the global population grows and people travel more, it becomes increasingly difficult to reduce human-to-human transmission. Even when people can be restricted from traveling, as was the case during the lockdowns imposed during the 2019 / 2020 SARS-CoV-2 outbreak, some human-to-human transmission is inevitable through person-to-person contact or contact with the virus on surfaces. For example, health care workers inevitably come into contact with infected people and surfaces carrying the virus. Similarly, people working in critical supply chains, such as food supply, will likely not be able to completely eliminate their exposure. For this reason, when isolation is not possible, protection must be provided to reduce transmission of the virus. Summary of the Invention [Problem to be solved by the invention]

[0004] Existing protective gear is generally personal protective equipment (PPE), such as face masks that cover the mouth and nose, visors that cover the user's entire face, gowns, and / or gloves. However, the effectiveness of existing PPE varies widely. For example, some masks can filter out the majority of harmful bacteria and viruses (e.g., 95% in the case of "N95" masks), but few can actually kill viruses, particularly coronaviruses. The same is true for other PPE. For example, gloves can prevent viruses from touching the skin, but cannot prevent the virus from being transferred to other surfaces. [Means for solving the problem]

[0005] In a first aspect of the present invention, there is provided an ink for providing a virally active and / or antimicrobial coating on a substrate, the ink comprising: (i) a carrier; (ii) graphene particles and / or graphene oxide particles dispersed in the carrier; and (iii) a virally active and / or antimicrobial component or additive attached to the graphene particles and / or graphene oxide particles.

[0006] This combination of materials in ink form provides a particularly effective virus-active (virucidal) and / or antimicrobial (bactericidal) system that can be easily applied to surfaces or materials to provide highly effective treatment. For example, in the case of virus-active, this may be antiviral and / or virucidal (i.e., capable of destroying or inactivating viruses) (in the sense of inhibiting viral growth) where necessary. For antimicrobial, this may be an antibacterial or bactericidal component. For example, it is readily feasible to apply such inks to surfaces, such as PPE, to impart antiviral and / or virucidal properties thereto, thereby reducing the risk of viral transmission and infection.

[0007] The large surface area of ​​graphene and graphene oxide makes them ideal drug carriers, allowing for the attachment and loading of high concentrations of antiviral agents. Furthermore, combining graphene / GO with antiviral agents enhances their antiviral performance while reducing the environmental toxicity of the antiviral agents, enabling significantly higher antiviral performance. Indeed, these compositions have been shown to be effective against multiple viruses, including coronaviruses. In embodiments, we provide practical ways to utilize these properties, for example, in manufacturing settings where inks can be easily applied to materials or surfaces to impart antiviral or virucidal / antimicrobial properties. While these materials can be manufactured in dry form, it is more challenging to incorporate them into delivery mechanisms that allow them to be applied to substrates (especially in mass production) or that provide a stable and robust mechanism for dispensing these materials. The inks of the present disclosure provide a solution to these problems. These inks provide a method for depositing these materials in a controlled manner to provide functional and effective coatings. Carriers can be selected to provide stable dispersions that can be applied to materials in a controlled manner and volatilized to provide relatively uniform active coatings. This can be applied to surfaces, for example, during the manufacturing of PPE (such as masks and / or gloves) or by manufacturers further down the supply chain than would normally be required. This allows for wider dissemination and adoption of these materials, enabling mass production of currently used masks (e.g., particulate respirators) or other garments and equipment. This is particularly important when rapid response and increased production volumes are required, such as during the SARS-CoV-2 pandemic, when PPE shortages were chronic. In some embodiments, ink can be printed onto the surface of a material to form a layer of graphene particles and / or graphene oxide particles and antiviral and / or antimicrobial components.

[0008] Graphene oxide possesses antiviral and antimicrobial properties, making it particularly effective in combination with antiviral and / or antimicrobial ingredients. Graphene oxide's two-dimensional structure, sharp edges, and negatively charged surface can be used to kill bacteria and viruses by disrupting lipid membranes (in the case of bacteria) and / or oxidizing the membranes.

[0009] The ink comprises a virally active component and / or an antimicrobial component, which means that the ink may include at least one of a component that is antiviral in nature, a component that is virucidal in nature, a component that is antimicrobial (e.g., antibacterial / bactericidal) or a combination thereof (e.g., a component that is both antiviral and virucidal in nature).

[0010] The graphene particles and / or graphene oxide particles are loaded (attached) to their surfaces and / or edges with a virally active component and / or an antimicrobial component. The planar shape of graphene and graphene oxide allows for high concentrations of antiviral or virucidal agents to be loaded onto the surfaces of the graphene and / or graphene oxide particles, even at relatively low concentrations of graphene and / or graphene oxide in the dispersion. By loaded, we mean that the virally active component and / or antimicrobial component may be adsorbed or otherwise attached to the surface of the graphene and / or graphene oxide particles. For example, this may be a covalent bond to the surface (i.e., the graphene and / or graphene oxide may be functionalized with the virally active component and / or antimicrobial component), or it may be attached via hydrogen bonding, van der Waals, or a combination of bonding mechanisms. In some embodiments, the primary bond involved in attachment is hydrogen bonding. This configuration has been shown to increase the antiviral performance of the components while decreasing their toxicity.

[0011] In some embodiments, the antiviral and / or antimicrobial component comprises metal ions (e.g., silver ions, copper ions), metal nanoparticles (e.g., silver nanoparticles, copper nanoparticles), curcumin, and / or hypericin. These may be provided individually or in combination. For example, in one embodiment, the ink comprises silver nanoparticle functionalized graphene oxide, and in another embodiment, the ink comprises curcumin and silver nanoparticle functionalized graphene oxide. In embodiments where the component is a metal nanoparticle, the nanoparticle may have a particle size of 1-100 nm, e.g., 1-80 nm or 1-40 nm, e.g., 10-40 nm. This may be the average particle size (i.e., number average particle size), calculated based on the particle size when attached to graphene and / or graphene oxide. This can be measured using SEM. Metals used as the ions / nanoparticles described above include transition metals such as V, Ti, Cr, Co, Ni, Cu, Zn, Tb, W, Ag, Cd, Au, and Hg, as well as other metals such as Al, Ga, Ge, As, Se, Sn, Sb, Te, Pb, and Bi. Preferably, the metal of the metal ions or nanoparticles is Ag or Cu. These particles may have a particle size of 1-100 nm, e.g., 1-80 nm or 1-40 nm, e.g., 10-40 nm. In some cases, the particle size is such that at least 80% of the particles are sized between 1 and 100 nm, optionally 80% of the particles are sized between 20 and 60 nm, and optionally 95% are sized between 20 and 60 nm.

[0012] In some embodiments, the graphene particles and / or graphene particles have a surface coverage of the antiviral and / or antimicrobial component of 1% to 60%. This may be 1 to 20%, e.g., 1 to 10% or 3 to 10%, or 10 to 60% or 20 to 60%. This can be determined using SEM, e.g., EDS-SEM or EDX-SEM.

[0013] In some embodiments, the graphene and / or graphene oxide particles and viral active and / or antimicrobial component combined have a viral active and / or antimicrobial component weight content of 1% to 60%, e.g., 1 to 30 wt%, 1 to 20 wt%, 1 to 5 wt%, or 5 to 60% wt%. For metal nanoparticles, in some embodiments, this may be 1 to 20 wt%, e.g., 1 to 10 wt%, 3 to 10 wt%, or 5 to 10 wt%. This can be determined using thermogravimetric analysis (TGA). For example, when using metal ions or metal nanoparticles, TGA may include (i) heating in air to 120°C to remove moisture, followed by heating to 900°C to burn off the graphene / graphene oxide, leaving only the non-combustible material (metal). The metal content (%) can be calculated as follows: Metal content (%) = (mass% at 900°C / mass% at 150°C) × 100.

[0014] In some embodiments, the graphene particles and / or graphene oxide particles have a particle size of 100 to 2000 nm. For example, the number average particle size is 100 nm to 2000 nm. This may be the largest dimension (e.g., diameter), which can be measured by SEM, laser light scattering, or PCS (photon correlation spectroscopy). In some embodiments, this is the number average particle size. This may be the largest dimension (e.g., diameter), which can be measured by SEM, laser light scattering, or PCS (photon correlation spectroscopy). In one embodiment, the graphene and / or graphene oxide is provided in the form of platelets. The graphene or graphene oxide platelets can have an average particle size (i.e., number average particle size) of 100 to 2000 nm in the lateral dimension (i.e., the largest width across the face of the platelet). The number average thickness of the platelets can be less than 200 nm, e.g., less than 100 nm, less than 50 nm, less than 10 nm, less than 5 nm, or less than 1 nm. All of these measurements can be taken by SEM. The platelets may contain a single layer of graphene or graphene oxide, or multiple layers.

[0015] In some embodiments, the surfaces and / or edges of graphene particles and / or graphene oxide particles are functionalized with virally active and / or antimicrobial components. Functionalization of the edges may improve performance because it is the edges of graphene and / or graphene oxide that are involved in disrupting viral membranes, and having the virally active and / or antimicrobial components at the edges may enhance this. Surface oxygen groups can also oxidize lipid membranes, causing membrane rupture. Functional groups (e.g., polar sites) on the edges of graphene and / or graphene oxide can also be used to facilitate loading of virally active and / or antimicrobial components at the edges.

[0016] In some embodiments, the graphene particles and / or graphene oxide particles are functionalized particles, e.g., containing functional groups selected from thiols, hydroxyl groups, carboxyl groups, epoxyl groups, and / or carbonyl groups. In some embodiments, the graphene oxide is functionalized graphene oxide and contains thiol functional groups. When used in combination with nanoparticles, e.g., virally active nanoparticles and / or antimicrobial nanoparticles, the presence of thiol groups can help reduce the size of the nanoparticles (e.g., smaller silver nanoparticles on the surface of graphene / graphene oxide). Smaller nanoparticles tend to have improved antiviral / microbial activity due to increased effective surface area.

[0017] In some embodiments, the graphene particles are modified with oxygen-containing functional groups and have an oxygen content of 10-30%, e.g., 10-25%. In some embodiments, the graphene oxide particles have an oxygen content of 24-40%, e.g., greater than 25-40%. The oxygen concentration directly impacts the virucidal efficacy of the product, so the higher the oxygen concentration, up to a certain limit, the better. However, above this concentration, the ink or coating becomes susceptible to adverse effects from moisture. It is believed that the improved performance is due, at least in part, to the availability of sufficient spacing between the antiviral / antimicrobial components (e.g., individual silver particles) on the graphene oxide scaffold. Therefore, a larger amount of oxygen species allows for greater spacing. Therefore, reduction of the graphene oxide can result in reduced performance. Therefore, in some embodiments, the material is fabricated to prevent reduction of the graphene oxide. Oxygen concentration can be measured using EDS-SEM or EDX-SEM.

[0018] In one embodiment, the ink is a solution or suspension, and the carrier is a solvent. Alternatively, the ink may be a paste containing a binder as the carrier. However, it is preferred to use a carrier in the form of a solvent. In embodiments, the ink may contain 0.05 to 10 mg / ml, e.g., 0.1 to 10 mg / ml, of the combined active agent (i.e., graphene / graphene oxide combined with an antiviral / antimicrobial component) in the solvent, e.g., 1 to 5 mg / ml or 2 to 4 mg / ml. In some embodiments, the ink further contains (i) a binder selected from cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate), poly(ethylene) glycol, and polyvinylpyrrolidone (PVP), (ii) a drier, and / or (iii) a rheology modifier. In another embodiment, the ink may further contain cationic particles, such as cationic polyurethane. This may be, for example, cationic colloidal particles, such as cationic colloidal polyurethane. This allows for electrostatic adhesion to negatively charged surfaces, such as polyester and polypropylene.

[0019] In one embodiment, the virally active ingredient and / or antimicrobial ingredient includes a capping agent. Capping agents are generally compounds containing a polar moiety and a nonpolar (hydrocarbon) chain. For example, the virally active ingredient and / or antimicrobial ingredient may include a capping agent such as polyvinylpyrrolidone (PVP). For example, in one embodiment, the virally active ingredient and / or antimicrobial ingredient includes capped (e.g., PVP-capped) metal (e.g., silver) nanoparticles. The capping agent may be a polymeric capping agent such as polyethylene glycol (PEG), ethylenediaminetetraacetic acid (EDTA), polyvinylpyrrolidone (PVP), and polyvinyl alcohol (PVA). The capping agent forms a protective shell around the virally active ingredient and / or antimicrobial ingredient and can bond to the graphene and / or graphene oxide surface using hydrogen bonding. While the capping agent can be a mild reducing agent, it has been found that an excess of capping agent used in the solution used to prepare the composition allows for capping of the virally active / antimicrobial agent and hydrogen bonding to the functional groups of the graphene / graphene oxide. In embodiments, the antiviral and / or antimicrobial components are capped metal nanoparticles, where the polar moieties are coordinated to the metal and the non-polar chains extend outward.

[0020] In a second aspect, A support; a coating applied to the substrate; The coating is (i) graphene particles and / or graphene oxide particles; (ii) a virally active component and / or an antimicrobial component attached to the graphene particles and / or graphene oxide particles.

[0021] Such articles can include PPE, such as face masks, gloves, and protective clothing, or they may be in the form of cleaning articles, such as antiviral, virucidal, or antimicrobial cleaning cloths. The presence of graphene and / or graphene oxide and virally active and / or antimicrobial components provides the article with all of the benefits described herein associated with the combination of these components in the article. These may be advantageous over existing products, as most approved antimicrobial or antiviral compositions contain bleaching agents, which are not always suitable and may even be toxic. In some embodiments, the article may comprise the inks of embodiments disclosed herein.

[0022] The properties of the graphene and / or graphene oxide and the virally active ingredient and / or antimicrobial ingredient may be the same as those described for the ink. For example, in some embodiments, the virally active ingredient and / or antimicrobial ingredient includes metal ions, metal nanoparticles, curcumin, and / or hypericin. In some embodiments, the virally active ingredient and / or antimicrobial ingredient is loaded on the surface and / or edge of the graphene and / or graphene oxide. In some embodiments, the graphene particles and / or graphene oxide particles are functionalized particles and may include functional groups selected from thiols, hydroxyl groups, carboxyl groups, epoxyl groups, and / or carbonyl groups. In some embodiments, the graphene oxide is functionalized graphene oxide and includes thiol functional groups.

[0023] The support can be any material that can function as a matrix for the graphene particles and / or graphene oxide particles and the antiviral and / or antimicrobial components. The support can also be a layer of a specific material. The support can include cellulosic materials (e.g., cotton or paper), textiles, or materials such as polyester or polypropylene. Cellulosic materials are attractive because they are low-cost, widely available, and easily incorporated into existing PPE. In one embodiment, the support comprises polyester or polypropylene. Polyesters are particularly effective for containing viruses, including the virus that causes COVID-19 disease (i.e., SARS-CoV-2). Polyesters are a group of polymers that are prone to electrostatic charge generation and have long-lasting charges on their surfaces and in volume. This characteristic is due to their low number of free charges and low electrical conductivity. The support can be a woven or nonwoven fabric.

[0024] In one embodiment, the article is a filter, and the support is a filtration membrane disposed in the filter to filter particulates passing through the filter. The coating may be disposed on at least one surface of the filtration membrane. This may be, for example, a filter for a mask or a filter for an air treatment device (e.g., HVAC). In one embodiment, the filter includes a first filtration layer including the support and a second filtration layer, the first filtration layer being disposed upstream of the second filtration layer.

[0025] In one embodiment, the filter includes a first filtration layer including a support and a second filtration layer, the first filtration layer being upstream of the second filtration layer. By upstream, we mean that the second filtration layer is downstream of the first filtration layer when the majority of the flow during normal use moves in the first direction. The second filtration layer may be adapted to block the passage of graphene particles and / or graphene oxide particles. Because graphene oxide and graphene can be harmful, this provides benefits associated with their use while ensuring that any that may peel off from the support are retained in the filter.

[0026] In one embodiment, the filter includes at least one fine filtration membrane with a filtration efficiency of at least 95% for particles 0.3 μm in size, and the filtration membrane containing graphene particles and / or graphene oxide particles and a virally active ingredient and / or an antimicrobial ingredient is a coarse filtration membrane. That is, the support / filtration membrane containing the virally active ingredient and / or antimicrobial ingredient (antiviral / virucide / bactericide) is located on the outer side of the fine filtration membrane. For example, when the filter is used in a face mask, the fine filtration membrane is positioned closest to the user. This is a particularly effective positioning because the ink captures and adsorbs exhaled or inhaled water droplets carrying viral substances, allowing the virally active ingredient to inactivate or kill viruses and / or the antimicrobial active ingredient to kill microorganisms (e.g., bacteria) in the ink. The term "coarse" refers to its relative relationship to the fine filtration membrane. For example, the coarse filtration membrane may have a filtration efficiency of at least 95% for particles 3.0 μm in size. Furthermore, this may reduce the risk of graphene particles and / or graphene oxide particles being inhaled.

[0027] In a third aspect, there is provided a face mask comprising the articles and / or filters disclosed herein.

[0028] In a fourth aspect, (a) combining graphene particles and / or graphene oxide particles with a virally active ingredient and / or an antimicrobial ingredient to attach the virally active ingredient and / or antimicrobial ingredient to the graphene particles and / or graphene oxide particles; (b) A method of producing an ink is provided, comprising dispersing a combination of graphene particles and / or graphene oxide particles and an antiviral and / or antimicrobial component in a carrier.

[0029] In one embodiment, the method comprises: Dispersing graphene particles and / or graphene oxide particles in a solvent; combining the graphene particles and / or graphene oxide particles with a virally active ingredient and / or an antimicrobial ingredient to attach the virally active ingredient and / or antimicrobial ingredient to the graphene particles and / or graphene oxide particles; The method includes dispersing a combination of graphene particles and / or graphene oxide particles and an antiviral and / or antimicrobial component in a carrier.

[0030] In one embodiment, the method includes combining the graphene particles and / or graphene oxide particles with a virally active component and / or antimicrobial component by dispersing the graphene particles and / or graphene oxide particles in a carrier and then adding the virally active component and / or antimicrobial component to the carrier. In one embodiment, the virally active precursor and / or antimicrobial precursor are added to the solution, and the method includes converting the precursor in situ to the virally active component and / or antimicrobial component. This may be, for example, a metal salt that is converted in situ to metal ions and / or metal particles (e.g., nanoparticles), such as by reduction. In this embodiment, if functionalized graphene and / or (functionalized or non-functionalized) graphene oxide is present, it may be reduced during the reduction of the metal salt (co-reduction).

[0031] In one embodiment, the antiviral and / or antimicrobial component is a metal nanoparticle, which is combined with graphene particles and / or graphene oxide particles.

[0032] In one embodiment, metal ions or metal nanoparticles are used as the virally active and / or antimicrobial component and are formed prior to step (a) (e.g., by reducing a metal salt to form the metal nanoparticles), i.e., before combining with GO. Therefore, the reaction to form the metal ions or nanoparticles (in embodiments, reduction of the metal salt) does not affect the functional groups present on the (functionally modified) graphene and / or graphene oxide. Thus, in one embodiment, the graphene is functionally modified graphene, and step (a) comprises combining the functionally modified graphene and / or (functionally or non-functionally modified) graphene oxide with a virally active precursor and / or antimicrobial precursor, followed by adding a reducing agent to reduce the virally active precursor and / or antimicrobial precursor to form the virally active or antimicrobial component.

[0033] In some embodiments, the method further comprises functionalizing the graphene particles and / or graphene oxide particles prior to step (a), and the functionalizing the graphene and / or graphene oxide may comprise functionalizing the graphene particles and / or graphene oxide particles with at least one functional group selected from a thiol group, a hydroxyl group, a carboxyl group, an epoxyl group, and / or a carbonyl group. In one embodiment, the functional group is a thiol. For example, this may be achieved by thiolation using NaSH.

[0034] In some embodiments, the solvent may be the carrier, or the combination of graphene and / or graphene oxide with antiviral and / or antimicrobial components may be transferred to the carrier.

[0035] In some embodiments, the graphene and / or graphene oxide particles are dispersed in a thin layer of nanosheets. These nanosheets may or may not be aligned, depending on the specific antiviral and / or antimicrobial component. The solvent is preferably alcohol (e.g., methanol or ethanol) or water. Ultrasonic treatment of the graphene and / or graphene oxide can also be used to reduce the particle size of the graphene / graphene oxide by crushing.

[0036] In some embodiments, combining the graphene particles and / or graphene oxide particles with a virally active ingredient and / or an antimicrobial ingredient comprises loading the virally active ingredient and / or antimicrobial ingredient onto the graphene and / or graphene oxide. In some embodiments, the graphene particles and / or graphene oxide particles may be functionalized with the virally active ingredient and / or antimicrobial ingredient.

[0037] In one embodiment, the antiviral and / or antimicrobial component comprises a capping agent.

[0038] In another embodiment, the method may include isolating the combination of graphene particles and / or graphene oxide particles and antiviral and / or antimicrobial components prior to step (b).

[0039] In a fifth aspect, there is provided a method of making an article as defined herein, comprising applying an ink as defined herein to a substrate. In the methods described herein, the ink can be applied to the substrate by printing. This is particularly advantageous because it allows for easy integration of this functionality into existing products and manufacturing processes. In embodiments, printing can include spray coating, inkjet printing, dip coating, screen printing, gravure printing, flexographic printing, slot-die coating, or doctor blade coating. In some embodiments, when the substrate comprises a fabric such as cotton or polyester, the printing includes spray coating, inkjet printing, or dip coating, adapted to provide a monolayer thickness of graphene particles and / or graphene oxide particles on the fabric. In other embodiments, when the substrate comprises a cellulosic material, the printing includes screen printing or gravure printing. In this case, a higher viscosity ink may be required.

[0040] In a sixth aspect, a composition is provided, comprising functionalized graphene particles and / or graphene oxide particles (functionalized or non-functionalized) and a virally active ingredient and / or antimicrobial ingredient attached to the functionalized graphene particles and / or graphene oxide particles, wherein the virally active ingredient and / or antimicrobial ingredient comprises capped metal nanoparticles. Capped metal nanoparticles refer to metal nanoparticles to which a capping agent is attached. This may be added. The specific contents of each of these components of the composition are the same as those disclosed in the other aspects. For example, the capping agent, the properties of the nanoparticles, etc. are the same as those disclosed in the other aspects. For example, in one embodiment, the composition comprises graphene oxide and silver nanoparticles capped with PVP. For example, the capped material may have a metal (e.g., silver) content in the range of 1 to 20 wt%, e.g., 1 to 10 wt%.

[0041] Capping agents (e.g., PVP) added to metals will hydrogen bond with the functional groups on the functionalized graphene and / or GO, especially in areas where oxygen is present (often around the edges). This bonding helps to adhere the particles to the graphene / graphene oxide while promoting spacing between the nanoparticles (defined by the spacing of the functional groups). This spacing can prevent or reduce nanoparticle aggregation. This is one reason why oxygen-containing functional groups are particularly effective.

[0042] In a seventh aspect, a composition (e.g., an ink as defined herein or an article as defined herein) comprising (i) dispersed graphene particles and / or graphene oxide particles and (ii) a virally active ingredient attached to the graphene particles and / or graphene oxide particles is used as an antiviral or virucidal agent against Sars-CoV-2. Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. [Brief explanation of the drawings]

[0043] [Figure 1] FIG. 1 shows a schematic diagram of a mask according to one embodiment of the present invention. [Figure 2] FIG. 2 shows an exploded schematic view of a filter according to one embodiment of the present invention. [Figure 3] FIG. 3 shows another embodiment of the present invention. [Figure 4] FIG. 4 shows the particle sizes of Examples 9 to 11. [Figure 5] FIG. 5 shows an SEM image of Example 9. [Figure 6] FIG. 6 shows the results of a plaque assay performed to measure antiviral potency. [Figure 7] FIG. 7 shows the results of a plaque assay performed to measure antiviral potency. [Figure 8] FIG. 8 shows the results of a plaque assay performed to measure antiviral potency. [Figure 9]FIG. 9 shows the results of a plaque assay performed to measure antiviral potency. [Figure 10] FIG. 10 shows the results of a plaque assay performed to measure antiviral potency. DETAILED DESCRIPTION OF THE INVENTION

[0044] As described above, graphene and graphene oxide enhance the antiviral or virucidal properties of virally active compounds or components. The same applies to antimicrobial agents, such as antibacterial agents. These components may be single components (e.g., a single composition or structure) or multiple composite components.

[0045] The use of virucidal materials is particularly advantageous compared to existing methods and antiviral agents in general in that viruses are inactivated. In some environments, the concentration of a particular virus is very high, and users are exposed to the virus for a significant period of time. In such environments, it may be beneficial to prevent further virus proliferation, but if the level in the environment is high, the concentration may still lead to a high risk of infection. In such environments, virucidal materials are useful not only to prevent virus replication, but also, for example, to inactivate or destroy existing viruses.

[0046] By "ink" is meant a liquid (solution or suspension) or paste comprising graphene particles and / or graphene oxide particles, a virally active component and / or an antimicrobial component, and a carrier. The ink has properties that allow certain components of the ink (in this case, the graphene particles and / or graphene oxide particles and the virally active component and / or antimicrobial component) to adhere to a support. The carrier may be a solvent, such as water or an alcohol (e.g., ethanol). Thus, in some embodiments, the ink is a suspension comprising (i) graphene particles and / or graphene oxide particles and (ii) a virally active component and / or an antimicrobial component. The ink need not necessarily be colored (i.e., it may be colorless), but may be colored (e.g., due to the presence of graphene or graphene oxide).

[0047] Other components of the ink may include additional solvents, rheology modifiers, binders, driers, and / or polymers. In embodiments, the ink also includes a binder, such as cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate), or poly(ethylene glycol). This binder can be used as a soluble additive in the dispersion that precipitates upon drying and adheres the particles to the support / matrix (e.g., fabric). In one embodiment, the ink further includes a drier. These are chemicals that alter the crosslinking rate of the binder (usually reacting with oxygen in the air) and contribute to how the ink's solvent is absorbed into the material. In embodiments, mineral-based driers such as alumina or silica may be included. In some embodiments, the ink also includes a rheology modifier (e.g., hydroxypropyl cellulose, a polyol compound (e.g., glycerol), and / or PVA). These substances adjust the flow characteristics of the ink. For example, in screen printing, additives are needed to make the ink shear-sensitive so that it can return to a viscous state at the surface after passing through a mesh under shear. In another embodiment, the ink includes a gel reducer. The gel reducer improves the ink's properties for cellulosic materials and reduces ink tack, which can cause short cellulose fibers to peel at the surface. In some embodiments, the ink may include poly(ethylene glycol), which can act as a rheology modifier, binder, and drier. Additional solvents can include methyl ethyl ketone, which can lower the evaporation temperature. Other additives that may be present in embodiments (in combination with or instead of the additives mentioned above) include dispersants and / or wetting agents, such as polyethylene oxide-polypropylene oxide (dispersion), polyethylene glycol sorbitan monooleate (dispersion), polyethylene glycol hexadecyl ether (dispersion), polyoxyethylene (40) nonylphenyl ether (dispersion), and silicone additives (wetting).

[0048] In some embodiments, the ink further comprises a film-forming additive or agent. This term refers to an additive that promotes or causes the formation of a film of graphene / graphene oxide particles. These can be particularly advantageous additives because they help provide a uniform coating on the surface of the material to which the ink is applied. This improves coverage, which in turn improves efficacy and reduces waste (e.g., the film may be only a single layer or may have several layers). In embodiments, the film-forming additive is selected from PVP, acrylate, acrylamide, copolymers (e.g., maleic anhydride copolymers), PVA, and / or polyethylene oxide (polyethylene glycol).

[0049] Graphene is a two-dimensional allotrope of carbon, and a graphene monolayer contains sp 2 Graphene contains a planar sheet of bonded carbon atoms. Due to this covalently bonded, hexagonal, two-dimensional (2D) lattice of carbon atoms, graphene is known for its exceptionally high intrinsic strength. Graphene also exhibits several other advantageous properties, such as high in-plane electrical conductivity. Graphene oxide is a graphene layer functionalized with multiple oxygen-containing groups. For example, the layer may contain functional groups such as hydroxyl, carboxyl, epoxy, and / or carbonyl groups. Graphene oxide has the advantage of having demonstrated antiviral and antibacterial properties. Graphene, on the other hand, may be particularly advantageous because it is easy to manufacture and more environmentally friendly. Oxygen-modified graphene can be produced using a plasma functionalization process, providing graphene with similar functionality to graphene oxide but in an environmentally friendly manner. In some embodiments, functionalized graphene and / or graphene oxide (functionalized or non-functionalized) are used. Functionalization can improve the attachment of antiviral and / or antimicrobial components and improve viral activity and / or antimicrobial properties.

[0050] An example of oxygen-modified graphene is shown below. [ka] An example of graphene oxide is shown below. [ka]

[0051] In some embodiments, the graphene or graphene oxide comprises at least 1 atomic layer of graphene or graphene oxide, at least 5 atomic layers, at least 10 atomic layers of graphene or graphene oxide, for example, up to 15 atomic layers of graphene or graphene oxide. In some embodiments, the graphene or graphene oxide comprises from 1 atomic layer of graphene to 15 atomic layers of graphene or graphene oxide.

[0052] In some embodiments, the graphene and / or graphene oxide particles may be functionalized. That is, in embodiments, the graphene and / or graphene oxide may be treated to incorporate functional groups onto the surface and / or edges of the graphene and / or graphene oxide particles (which may be further functionalized depending on the initial method for producing the graphene oxide). This may be, for example, by covalent bonding. Examples of functional groups include thiol, hydroxyl, carboxyl, epoxyl, and / or carbonyl groups. In one embodiment, a thiol functional is used to functionalize the graphene and / or graphene oxide particles. Functionalization can improve compatibility with solvents or other components, thereby improving ink quality. For example, this can improve dispersion of the graphene and / or graphene oxide particles in the ink, preventing clumping and aggregation. This may be functionalization using, for example, plasma treatment. For example, in some embodiments, the graphene may be functionalized with (additional) carboxyl groups. One example is plasma treatment for "oxygen" functional group modification using the Haydale HDLPAS process described in WO 2010 / 142953 A1, which can improve compatibility and loading of antiviral and / or antimicrobial components.

[0053] In one embodiment, the antiviral and / or antimicrobial component comprises silver nanoparticles. For example, in some embodiments, the antiviral and / or antimicrobial component in the ink is graphene oxide with silver nanoparticles attached. The silver nanoparticles are chemically bonded to the graphene oxide surface, making it highly effective as both a virucide and an antibacterial agent. In some embodiments, when using nanoparticles such as silver nanoparticles, loadings (by weight and / or surface coverage) of up to 80%, e.g., up to 60%, are possible. Leaving a portion of the graphene / graphene oxide surface exposed allows for capture of target substances (e.g., bacterial viruses). For nanoparticles with a particle size of 1-10 nm, this can be a loading of 30-60% by weight in some embodiments. For nanoparticles with a particle size of 30-40 nm, this can be a loading of 5-20% in some embodiments.

[0054] A particularly effective embodiment has been found to be a combination of metal nanoparticles as antiviral and / or antimicrobial components attached to functionalized graphene particles and / or graphene oxide particles. In particular, silver nanoparticles attached to either functionalized (oxygen-containing) graphene or graphene oxide are particularly effective when the nanoparticles are capped with a capping agent such as PVP. A preferred loading (based on the total weight of the combination, as detailed above) is 1-10 wt% silver on the graphene / graphene oxide, e.g., 4-6 wt% silver. This helps ensure good coverage without overloading or aggregation. When present as an ink, these combinations are preferably present at a concentration of 0.5-5% (i.e., 0.5-5 mg / mL) in a liquid vehicle or solvent. In these embodiments, the effective particle size of the silver nanoparticles has been found to be preferably 1-40 nm, more preferably 5-20 nm. This can be even more effective if the ink contains a film-forming agent.

[0055] A first embodiment of the present invention is shown in FIG. 1. This figure shows a schematic representation of a mask 100 according to one embodiment. The mask includes a body 110 and a filter 120. The body 110 is shaped to fit snugly over the user's face, covering the user's nose and mouth, and seals tightly around the edges of the body. The body is made of a material that is substantially impermeable to air or that is more resistant and filtering than the filter 120. The filter 120 is positioned within a hole that penetrates the body 110. The filter 120 is designed to allow air to pass through, providing a path of airflow (i.e., the path of least resistance) through the mask. This arrangement means that when the user inhales, air is drawn through the filter 120. Air cannot enter the user's lungs directly (due to the tight seal) or pass through the impermeable body 110. Although not shown, straps are provided to hold the mask to the user's face. In this embodiment, filter 120 includes one of the coatings disclosed herein. For example, in one embodiment, filter 120 includes a base fabric and a layer including a silver-functionalized graphene oxide material coated onto the base fabric. This means that when a user breathes air, any viruses present in the environment will pass through filter 120 and come into contact with the layer including silver nanoparticle-functionalized graphene oxide. The virucidal properties of this material inactivate or destroy the viruses, preventing or reducing the wearer's risk of infection.

[0056] One embodiment of the filter 120 is shown in greater detail in an exploded schematic view in FIG. 2. In this embodiment, the filter 120 includes multiple layers 122, 124, 126, and 128 arranged within a frame (not shown). The outer cover 122 is the outermost layer and is exposed to the external environment during use. This outer cover 128 may be a fluid-resistant cover made of polyester or polypropylene that acts as a first screen to prevent significant ingress of water or dirt into the filter 120. The layer behind the outer cover (i.e., the layer closest to the user) is the prefilter 124. In this embodiment, the prefilter 124 includes a layer with a filtration efficiency of 95% or greater for particles larger than 3.0 μm. This prefilter 124 includes a polyester layer (e.g., a polyester nonwoven layer). In this embodiment, the prefilter 124 is also coated with one of the coatings disclosed herein. For example, the prefilter 124 may be coated with a silver nanoparticle-functionalized graphene oxide material. This can be produced, for example, by printing an ink according to one embodiment onto a polyester material on the outer surface of the polyester layer to maximize exposure to water droplets containing viral material. Behind the pre-filter 124 is a filter membrane 126. The filter membrane 126 includes a layer with a filtration efficiency of 95% or greater for particles larger than 0.3 μm. This layer may include a polyester layer. Behind the filter membrane 126 is an inner cover 128. The inner cover 128 forms the innermost layer for the user. In some embodiments, this layer is polyester, polypropylene, or cotton.

[0057] 2 can be easily manufactured by applying an ink according to an embodiment of the present invention to a substrate such as a polyester, cotton, or cellulose layer. This can be incorporated into existing manufacturing processes without requiring special materials or equipment, thereby enabling mass production of the filter 120 and mask 100. For example, the ink can be printed onto the surface of a filter material such as a polyester, cotton, or cellulose layer, such as using an inkjet printer.

[0058] Advantageously, the mask 100 and filter 120 according to the above-described embodiment incorporate a filter layer and a coating (formed by applying ink to the filter material) that allows water droplets containing viruses (e.g., SARS-CoV-2) to be trapped and adsorbed to the ink, where the active ingredient inactivates or kills the virus. This configuration is particularly effective when viruses are transmitted through the respiratory system. For example, the COVID-19 virus is believed to be transmitted primarily through small respiratory droplets produced by sneezing or coughing, or by people being together for a period of time in close proximity (typically less than one meter). These droplets can then be inhaled or land on surfaces that other people may come into contact with, potentially causing infection when that person touches their nose, mouth, or eyes. Therefore, using the mask 100 can protect both the mask wearer and those around them.

[0059] This is particularly effective when the layer of filter 120 coated with the virally active and / or antimicrobial components is polyester. Polyester fabrics provide a highly effective mechanism for containing viruses, including the SARS-CoV-2 virus. Polyesters form a family of polymers that readily build up an electrostatic charge, forming a long-lasting charge on their surface and in volume. This tendency to build up an electrostatic charge is utilized by filters to attract water droplets to the filter. Virus-containing droplets are then adsorbed onto the graphene layer covering the filter, exposing the viral material to the attached virally active and / or antimicrobial compounds (e.g., silver particles). In fact, the electrostatic properties of the fabric help to inhibit the penetration of not only water droplets but also particulates.

[0060] Applying ink to the prefilter has unexpected advantages. While one might instinctively want to coat the filter membrane 126 with ink, which has the highest filtration capacity, a coarser prefilter layer is sufficient for attracting and capturing target droplets. While the COVID-19 virus itself is approximately 140 nm in size, virus-containing droplets have an overall mean size distribution of 0.62–15.9 μm, with 82% of droplet nuclei concentrated between 0.74–2.12 μm and a modal size of 8.35 μm. The size distribution of cough droplets has been shown to be multimodal, with three peaks at approximately 1 μm, 2 μm, and 8 μm. This makes larger droplets ideally sized for direct collection by the prefilter 124, while electrostatic interactions with finer droplets make this a highly efficient filtering system for droplets in this size range.

[0061] While the embodiment described above with reference to Figure 2 involves applying ink to a pre-filter to form a coating on a fabric substrate, the coating can also be applied to any other layer to provide an effective antiviral / virucidal filter. For example, application to the inner surface of the outer cover 122 would provide sufficient contact with viral material. In other embodiments, it may be applied to the inner cover 128 or filter membrane 126. In some embodiments, ink may be applied to multiple layers of the filter 120.

[0062] In another embodiment, the ink or coating may be applied to other PPE, such as gloves, so that if a gloved user touches a surface containing the virus, the ink or coating will inactivate the virus, reducing the risk of infection or transmission.

[0063] A schematic diagram of a fiber 230 from the article coated with particles 240 comprising graphene oxide platelets 241 carrying Ag nanoparticles 242 is shown in Figure 3. The fiber is 12 μm wide, the Ag nanoparticles 242 are 1-2 nm in size, and the graphene oxide platelets 241 are 324 nm in size. Also shown are water droplets 250, whose sizes range from 0.2 to 8.5 μm. The graphene oxide 241 platelets form a uniform film across the fiber 230.

[0064] The inks and articles disclosed herein can be prepared as follows.

[0065] (i) (step (i) is optional) functionalizing graphene and / or graphene oxide, e.g., using plasma functionalization, to provide functionalized graphene and / or functionalized graphene oxide; (ii) combining the graphene particles and / or graphene oxide particles with a virally active ingredient and / or an antimicrobial ingredient to attach the virally active ingredient and / or antimicrobial ingredient to the graphene particles and / or graphene oxide particles; (iii) The combination of graphene particles and / or graphene oxide particles and an antiviral and / or antimicrobial component is dispersed in a carrier.

[0066] Optional step (i) can improve the dispersibility of the graphene particles and / or graphene oxide particles in a solvent and can also improve the attachment of components carried on the graphene particles and / or graphene oxide particles, particularly when oxygen-containing groups are functionalized on the surface to which antiviral and / or antimicrobial components can attach (e.g., by hydrogen bonding). In one embodiment, this involves thiolation with sodium hydrosulfide (NaSH) to produce thiol-modified graphene particles and / or graphene oxide particles.

[0067] Step (ii) may involve, for example, dispersing graphene and / or graphene oxide in a solvent or carrier and adding the antiviral and / or antimicrobial component to the graphene and / or graphene oxide particles. This addition may involve dispersing 0.1 to 10 wt% (e.g., 1 to 10, 1.0 to 10.0, 1 to 5, or 2 to 4 wt%) of graphene and / or graphene oxide in the solvent or liquid vehicle. These concentrations are particularly effective because the graphene and / or graphene oxide particles are dispersed into thin layers of nanosheets. These nanosheets may or may not be aligned, depending on the specific antiviral and / or antimicrobial component. The solvent or liquid vehicle is preferably alcohol (e.g., methanol or ethanol) or water. In the case of water, a concentration of 0.1 to 5 wt% (e.g., 1 to 5 wt% or 2 to 4 wt%) can maintain a relatively low viscosity. Alternatively, the method may include adding a virally active precursor and / or antimicrobial precursor to a solvent or carrier, converting the precursor into a virally active component and / or antimicrobial component, and then supporting the precursor on graphene particles and / or graphene oxide particles. Alternatively, the method may include adding the virally active component and / or antimicrobial component to a solvent or carrier, and then adding graphene particles and / or graphene oxide particles to the virally active component and / or antimicrobial component. This may include, for example, adding the virally active precursor and / or antimicrobial precursor to a solvent or carrier, and then converting the precursor into a virally active component and / or antimicrobial component. Graphene and / or graphene oxide can then be added to the solvent or carrier. The precursor may, for example, include a metal salt.

[0068] Step (ii) leads to loading of the graphene particles and / or graphene oxide particles with the virally active component and / or antimicrobial component, for example, loading may include further functionalizing the graphene particles and / or graphene oxide particles with the virally active component and / or antimicrobial component.

[0069] There are several specific methods that can be used to provide step (ii). For example, when metal nanoparticles are used as the virally active and / or antimicrobial component, these methods can include, for example, (i) adding the virally active and / or antimicrobial nanoparticles directly to graphene / graphene oxide (e.g., Ag nanoparticles to GO or Ag nanoparticles to thiolated GO) or (ii) reducing a metal salt (e.g., a silver salt such as silver nitrate) with graphene and / or graphene oxide in situ. When graphene is functionalized or when graphene oxide is present, this can be referred to as co-reduction if the reducing agent reduces the functional groups of the functionalized graphene / graphene oxide. In particular, when functional groups are present on graphene or when graphene oxide (functionalized or unfunctionalized) is used, direct addition has been found to improve the antiviral efficacy, as the functional groups are thought to aid the efficacy of graphene / graphene oxide. Therefore, avoiding the reduction of these groups (especially oxygen-containing groups) maintains high efficacy.

[0070] After step (ii), the combined virologically active and / or antimicrobial mixture (i.e., the graphene particles and / or graphene oxide particles combined with the virologically active and / or antimicrobial component) can be dried to provide a dried virologically active and / or antimicrobial mixture. However, such mixtures are difficult to handle and use in the dried state. Therefore, to effectively use the mixture in the manufacture of antiviral / viricidal (i.e., virologically active and / or antimicrobial) articles, an ink containing the mixture must be prepared.

[0071] Thus, step (iii) involves dispersing the combination of graphene particles and / or graphene oxide particles and the viral active agent and / or antimicrobial agent in a carrier. This can be accomplished using several methods. This may include dispersing the combination of graphene oxide and / or graphene and the viral active agent and / or antimicrobial agent in a solvent or liquid vehicle. The specific properties of the ink may depend on the surface or substrate to which the ink is applied. Some examples are provided below. For example, in some embodiments, the combination of graphene oxide and / or graphene and the viral active agent and / or antimicrobial agent can be dispersed in deionized water. Such a solution can be used to coat a material, such as a material with an opposite electrostatic charge, provided that the combination of graphene oxide and / or graphene and the viral active agent and / or antimicrobial agent has the size and coverage disclosed herein. In some embodiments, step (iii) occurs during the performance of step (ii). That is, step (ii) may be performed in a liquid vehicle or solvent, with the vehicle or solvent forming the carrier for the ink. In other embodiments, the combination of graphene and / or graphene oxide and attached antiviral / antimicrobial component is separated from the solvent or vehicle used in the reaction in step (ii) and then dispersed separately in a carrier.

[0072] Other components of the ink, such as rheology modifiers, binders, driers and / or polymers, can be added, possibly simultaneously with step (iii).

[0073] In some embodiments, graphene oxide may be prepared by modifying graphene with oxygen-containing functional groups (e.g., hydroxyl, carboxyl, carbonyl, or epoxy groups). For example, this may be plasma functionalization. In these embodiments, (i) functionalizing graphene oxide may be further functionalized (e.g., adding additional functional groups, such as thiol groups or additional groups that may already be present).

[0074] In one embodiment, the article includes a film or wrap comprising a coating having a combination of graphene and / or graphene oxide with a virally active ingredient and / or an antimicrobial ingredient. The film or wrap can be quickly and easily applied to any surface shape to provide protection against viruses and / or microorganisms. In certain embodiments, the film or wrap can be a multilayer film, whereby a (positively charged) cellulosic film coated with GO / Ag nanoparticles is attached to a (negatively charged) film support (e.g., PVC, PP, or BOPP, such as a cling film-type support). The film layer facilitates attachment to most surfaces (e.g., using adhesive or electrostatic forces). The cellulosic layer also positions the virally active ingredient at the contact surface.

[0075] Preparation of graphene / graphene oxide combined with viral active agents / antimicrobial agents reduction One embodiment involves preparing a silver nanoparticle graphene oxide ink using a reduction method. Graphene oxide nanoparticles with a diameter of 100-2000 nm are loaded with silver nanoparticles with a diameter of 1-40 nm. The amount of silver decoration on the graphene oxide is determined by weight (as measured by thermogravimetric analysis (TGA)). The silver nanoparticle graphene oxide ink can be prepared according to the methods described herein.

[0076] As a first step, silver nanoparticle graphene oxide is prepared as follows. Thiol-grafted graphene oxide (i.e., thiol-modified graphene oxide) can serve as a base for silver nanoparticle attachment. Silver nanoparticles are prepared by a modified Turkevich method, which reduces silver nitrate to silver nanoparticles. The silver nanoparticles can then be attached to the graphene oxide plate via the thiol groups pre-attached to the graphene oxide surface. An example of this method is described in Vi et al., "The Preparation of Graphene Oxide-Silver Nanocomposites: The Effect of Silver Loads on Gram-Positive and Gram-Negative Antibacterial Activities," Nanomaterials 2018, 8, which is incorporated herein by reference. This method achieved silver nitrate content of up to 65% at different molar concentrations with sizes of 1–2 nm. This is in contrast to the size of graphene oxide plates, which are 1–2 μm in size. Another method is disclosed in Kim, JD; Yun, H.; Kim, GC; Lee, CW; Choi, HC Antibacterial activity and reusability of CNT-Ag and GO-Ag nanocomposites. Appl. Surf. Sci. 2013, 283, 227-233, which is also incorporated herein by reference.

[0077] Co-reduction Alternatively, silver nanoparticle graphene oxide ink can be produced by adding a silver salt (e.g., silver nitrate or silver acetate) solution to a graphene oxide-containing solution to create silver nanoparticle graphene oxide particles. The silver nanoparticles are then precipitated from the solution by adding a reducing agent (e.g., selected from sodium citrate, trisodium citrate, citric acid, sodium borohydride, or sodium hydroxide). This is referred to as co-reduction, since both the silver salt and graphene oxide are reduced. This results in silver nanoparticles on reduced GO (rGO). In this method, the presence of thiol groups can be advantageously linked to the particle size of the precipitates, which can be 1–2 nm. After formation, the resulting material is washed to remove unbound silver and excess salt from the solution.

[0078] direct addition Modified antiviral / antimicrobial ingredients Alternatively, commercially available silver nanoparticles can be loaded onto graphene oxide by capping with a capping agent (polyvinylpyrrolidone (PVP) or a citric acid-based capping agent) that preferentially substitutes with thiol groups present on the surface and edges of the graphene oxide. After formation, the resulting material is washed to remove unbound silver and excess salts from the solution.

[0079] qualification Alternatively, other groups can be used to attach silver nanoparticles instead of thiol groups, for example, in a modified version of the PVP-capped embodiment, (poly)ethylene glycol (PEG) (Precursor Example 4) or polyethyleneimine (PEI, CHN) n PEG can be used to reduce silver salts and act as a binder between silver nanoparticles and graphene oxide. Different molecular weights of PEG can have different reducing / stabilizing effects. PEG also acts as a buffer to maintain a usable pH during the reaction.

[0080] In another embodiment, the efficacy of the ink is further improved by further loading or functionalizing with an organic antiviral / antimicrobial component, such as curcumin, such that in one embodiment the ink comprises curcumin and the silver nanoparticle graphene oxide ink. This can be produced or synthesized by preparing a silver nanoparticle graphene oxide composition as described above, then further functionalizing it with curcumin to form the ink. In this embodiment, curcumin ((E,E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) can be dissolved in deionized water and combined with the silver nanoparticle graphene oxide ink to provide the curcumin and silver nanoparticle graphene oxide ink. This can then be formulated into an ink as described above.

[0081] General precursor formation As is evident from the above, various combinations of reagents can be used to generate precursor materials (i.e., virally active and / or antimicrobial graphene / graphene oxide materials or mixtures). Various combinations according to some embodiments are shown in Table 1 (below).

[0082] [Table 1]

[0083] Ink and article formation Examples of forming inks and / or articles according to the present invention are provided below. Silver nanoparticle-functionalized graphene oxide particles are negatively charged. Their electrostatic nature allows them to adhere to positively charged substrates. Therefore, these particles can be added to deionized water and used to coat the substrate. Examples of such substrates include cotton (e.g., satin). Other examples include nylon 6,6, wool, glass filament, or spun glass.

[0084] In another embodiment, the ink may further include cationic colloid particles, such as cationic polyurethane. Such inks can be aqueous solutions and are advantageous in that they rely on electrostatics to coat articles, not just positively charged surfaces. For example, such inks can be used to coat negatively charged surfaces, such as polyester or polypropylene. In one embodiment, colloid particles are prepared and sized so that each colloid particle holds one flake or particle of silver-modified graphene oxide to the fiber. This acts as a positive PU particle sandwiched between two negative surfaces.

[0085] In other embodiments, the inks rely on chemical / mechanical adhesion, for example, binders such as cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate), and poly(ethylene glycol) are used in the dispersion as soluble additives that precipitate upon drying to adhere the particles to the substrate (e.g., fabric).

[0086] In one embodiment, the carrier may be a volatile solvent, such as isopropanol or ethanol. In a method for forming an article, the substrate may be pre-coated with an adhesive, after which a solvent-containing ink may be applied. For example, the ink could be sprayed using, for example, a volatile solvent. This allows the particles to adhere to the substrate as the solvent disperses, and allows capillary action to be used to orient the virally active and / or antimicrobial graphene / graphene oxide particles. [Example]

[0087] Unless otherwise stated, the following reagents were used in the following methods: graphene oxide (1 wt% in water, William Blyth), aqueous silver nanosphere dispersion (Sigma, 10 nm size, PVP functionalized, 0.02 mg / mL), silver nitrate (99%, Alfa), silver acetate (99%, Alfa), sodium citrate (99%, Alfa), trisodium citrate dihydrate (99%, Alfa), citric acid (99%, Alfa), polyethylene glycol (200 Da, Alfa), polyethylene glycol (2000 Da, Alfa), polyethyleneimine (1200 Da, 99%, Alfa), sodium borohydride (97%, Alfa), and cellulose dialysis tubing (33 mm diameter, 100 ft, Sigma).

[0088] Example 1 Preparation of thiol-functionalized graphene oxide (GO-SH) Graphene oxide was prepared as a 4 g dispersion in 1000 ml of water. 125 ml of this was reacted and sonicated for 20 minutes to prepare a dispersion. 8.0 g of sodium hydrosulfide (NaHS) was gradually added and the mixture was maintained at 55°C with continuous stirring for 20 hours. The product was filtered and washed with deionized water (filtered using a 4000 rpm centrifuge and washed five times with deionized water). The product was then directly placed in a vacuum oven at 50°C for 3 hours.

[0089] Preparation of silver nitrate solution To make 100 ml of a 0.1 M solution, add 1.6987 g of AgNO3 to 100 ml of distilled water while stirring. Stir for 1 hour before use. Alternative silver nitrate solutions include a 0.2 M solution (prepare 100 ml of a 0.2 M solution by adding 3.3974 g of AgNO3 to 100 ml of distilled water (while stirring). Stir for 1 hour before use) and a 0.25 M solution (add 4.2468 g of AgNO3 to 100 ml of distilled water. Stir for 1 hour before use).

[0090] Preparation of silver-loaded GO particles (GO-Ag) Add 0.1 g of the dried GO-SH particles prepared above to 30 ml of deionized water and sonicate for 30 minutes. While stirring, add 2 ml of each of the silver nitrate solutions (0.1 M, 0.2 M, or 0.25 M) prepared above. While stirring, add 20 ml of a 0.1 M solution of sodium hydroxide (NaOH). Stir for 20 hours. The dispersion is then centrifuged multiple times at 10,000 rpm to separate the GO-Ag particles. The precipitated GO-Ag particles can then be dried at 60°C for 24 hours and filtered using dialysis tubing to remove unreacted salts and loosely bound Ag nanoparticles. For storage, the particles can be added to deionized water at a concentration of 4 g / L to limit oxidation.

[0091] Examples 2 to 8 Several examples are provided below. General procedures are given, and the specifics of each method are listed below in Table 2. In these examples, the "co-reduction" method is used.

[0092] Graphene oxide dispersion Graphene oxide (1 wt% in water, William Blyth) was diluted 1 / 10 by mass to a concentration of 0.1 wt%. The graphene oxide dispersion was mixed to form a uniform dispersion, which was then dispersed and exfoliated by probe sonication in an ice bath (40%, 300 W, 10 min, 5 s pulses, 5 pauses, 18 mm horn, Q Sonics vibra cell 750 W). During this process, the dispersion changed from opaque brown to transparent brown.

[0093] Co-reduction with silver salt (preparation of Ag / reduced GO) A general description of the synthesis process is provided below. Specific reaction conditions are listed in Table 2. Sonicated graphene oxide (1 mg / mL in deionized water) was added to a round-bottom flask and stirred with a magnetic stirrer. Optionally, the pH was adjusted with either sodium hydroxide solution (0.1 M) or ammonium hydroxide (1 M). The mixture was then heated to 60–90 °C under reflux in an oil bath. Then, either a silver salt or a reducing agent, but not both, was added. The specific aspects of each example are listed in Table 2.

[0094] Once mixed and at the desired temperature, the reducing agent / silver salt was added to the reaction in a minimal amount of water (approximately 2 mL). The reaction was allowed to proceed with stirring for up to 2 hours. The reducing agent was used in amounts ranging from 1 to 10 molar equivalents of silver nitrate. In some cases, a second addition of reducing agent was added and the reaction was continued for an additional 2 hours at 65°C.

[0095] Upon completion, the reaction mixture was left to settle overnight at room temperature. The precipitated Ag and reduced GO particles were collected by vacuum filtration through a 0.2 μm nylon membrane filter (Fisher). The material was then washed with copious amounts of water and stored as a wet powder.

[0096] [Table 2]

[0097] Examples 9-11 (Co-reduction) Using the procedure of Example 7, three solutions containing 20 wt%, 40 wt%, or 60 wt% silver were prepared (Examples 9, 10, and 11, respectively). Graphene oxide was dispersed at 1 mg / mL (0.1 wt%) as outlined in Example 7 above. Next, 100 mL of 0.1 wt% GO was added to a round-bottom flask and the pH was adjusted to 10-11 using ammonium hydroxide (1 M). Ascorbic acid was then added in a 10 molar excess relative to the silver nitrate. The pH was then readjusted to pH 10-11 using ammonium hydroxide (1 M). No signs of precipitation or reduction of the GO were observed at this point. The reaction mixture was vigorously stirred, and silver nitrate was added quickly in a minimal amount of water. The amount of silver nitrate added was sufficient to yield products containing 20 wt%, 40 wt%, or 60 wt% silver (Examples 9, 10, and 11, respectively). For example, to make a 20 wt% solution, 25 mg (0.23 mmol) of silver nanoparticles were required for 100 mg of graphene oxide, so 39 mg (0.23 mmol) of silver nitrate was added. The mixture was then immediately placed in an oil bath set at 90 °C and the reaction was allowed to proceed for 2 hours. Upon completion, the material was allowed to cool overnight to precipitate and then recovered by vacuum filtration (0.2 μm nylon membrane).

[0098] Example 12 (Direct Addition) Graphene oxide was added to silver nanospheres (0.02 mg / mL silver, 25 mL, Sigma, 10 nm size, PVP functionalized) to obtain a 0.75 mg / mL dispersion of GO in the presence of 0.02 mg / mL silver. The graphene oxide was mixed until a uniform dispersion was obtained, and then dispersed and exfoliated by probe sonication in an ice bath (40%, 300 W, 10 min, 5 s pulses, 5 pauses, 18 mm horn, Q Sonics vibra cell 750 W). The material changed from an opaque brown dispersion to a clear brown dispersion, and the Ag / GO product was formed. These dispersions appeared significantly darker and more viscous than comparable graphene oxide dispersions without silver.

[0099] analysis particle size The size of the silver nanoparticles in Examples 2 to 8 was measured using SEM. The solutions prepared in the examples were diluted with water to a volume 10 times that of the original. 10 μL of the solution was dried on a silicon wafer and analyzed by SEM (secondary electron, EDX).

[0100] Among Examples 2 to 8, Example 7 provided the best combination of silver nanoparticle size and distribution characteristics. The average particle size of the resulting silver nanoparticles was approximately 40 nm, with a tight distribution, with 95% of the particles between 20 and 60 nm. SEM and EDX plots showed that silver was uniformly deposited on the GO sheets, with almost no free silver in the system.

[0101] The particle size measurements for Examples 9-11 are shown in Figure 4. The average sizes of the silver nanoparticles for Examples 9-11 were 56 nm, 97 nm, and 106 nm, respectively. These examples demonstrate that increasing the weight level of nanoparticulate silver increases the mean size and modal size of the size distribution, but also increases the breadth. An SEM image of Example 9 is shown in Figure 5.

[0102] In Example 12, the particle size of the PVP-capped nanospheres loaded on graphene oxide ranged from 9 to 18 nm (average particle size 13 nm), which is almost unchanged from the original particle size of the PVP-capped silver nanospheres measured by the same method (10 to 15 nm (average particle size 12 nm) for silver nanoparticles before combination with GO).

[0103] Silver content The silver content was measured by thermogravimetric analysis (TGA). The silver content is shown in Table 3 below. The wet powder samples obtained in Examples 9 to 11 were heated in air to 120°C to remove moisture, and then heated to 900°C to burn off the graphene, leaving only the non-combustible material (silver). The silver content (%) was calculated using the following method.

[0104]

number

[0105] Ink formation Examples 13 to 16 Dispersions of silver / graphene oxide nanoparticles in deionized water from Examples 9 to 12 were adjusted to 1 mg / mL by probe sonication (Examples 13 to 16, respectively). For example, the solids content of samples prepared by the method of Example 12 was measured by TGA (Pyris 1, 120 °C for 10 min). The amount needed to achieve a dispersion of approximately 1 mg / mL in deionized water was then weighed. The graphene-water mixture (10 mL) was then sonicated in an ice bath (microtip, 20%, 5 min, 5 s pulse, 5 s pause). The pH of all dispersions was measured and was in the range of 6 to 9.

[0106] Examples 17 and 18 Inks were made from Examples 15 (60 wt% based on Example 11) and 16 (PVP-capped Ag NPs with GO based on Example 12) (corresponding to Examples 17 and 18, respectively). PVP was added in an amount of 20 wt% to the 1 mg / mL dispersions prepared in Examples 15 and 16 above. This was then mixed using a Dual Asymmetric Centrifugal (DAC) mixer. The viscosity of the ink could be increased in this way, providing a viscous material that could be roller coated.

[0107] Examples 19, 20 and 21 A 4 mg / mL dispersion of Ag in reduced graphene oxide material (Example 11) was prepared (Example 19) using the same method as in Example 15, except probe sonication was performed at higher power (40% power, 750 W, 10 min, 5 s pulses). A 0.4 mg / mL dispersion was prepared in a similar manner (Example 20). A 0.4 mg / mL dispersion of Ag in GO (Example 12) was prepared using the method in Example 16, and then diluted 4 / 10 (Example 21).

[0108] Examples 22 and 23 Example 22 is an ink containing thiolated graphene oxide decorated with 10 nm silver nanoparticles at a concentration of 4 g / L, and Example 23 is an ink containing thiolated graphene oxide decorated with 40 nm silver nanoparticles at a concentration of 4 g / L.

[0109] Thiolation of graphene oxide A 4 g / L dispersion of graphene oxide (prepared according to the procedure outlined above) was prepared and sonicated for 20 minutes. 375 ml was transferred to a centrifuge flask. 24.0 g of sodium hydrosulfide (NaHS) (Sigma Aldirch code 161527) was gradually added over 30 minutes at room temperature with stirring (magnetic stirrer). The mixture was heated to 55°C using a glycol bath and maintained at this temperature with continuous stirring for 20 hours. The resulting mixture was centrifuged at 4000 rpm for 45 minutes. The supernatant was decanted. Ultra-high quality (UHQ) water was added, and the contents of the tube were mixed to disperse the solid. The mixture was centrifuged at 4000 rpm for 45 minutes. This was repeated several times to remove unreacted NaHS. For the final wash, as much of the supernatant as possible was removed from the centrifuge tube. The residue was placed in an Erlenmeyer flask and dried overnight under full vacuum in a vacuum oven at 50°C.

[0110] Formation of silver-decorated GO-SH 0.2046 g of the residue (GO-SH) was dispersed in 114 ml of UHQ water using sonication and a high-speed mixer. This was divided into two 57 ml aliquots, each placed in a separate 500 ml centrifuge tube. To one of the 57 ml GO-SH solutions, 250 ml of 10 nm silver nanoparticles (Sigma Aldrich code: 730785-25ML; 1 mg / L) was added (Example 22). To the other 57 ml GO-SH solution, 250 ml of 40 nm silver nanoparticles (Sigma Aldrich code: 730807-25ML; 1 mg / L) was added (Example 23). Both solutions were stirred using a magnetic stir bar and left overnight.

[0111] The dispersion was then separated using a centrifuge at 4000 rpm (10,000 rpm was not possible) for several hours, then left overnight and decanted. This was done several times. The samples were decanted down to 22 ml and 32 ml (10 nm and 40 nm, respectively). Both samples were then made up to 50 ml with UHQ water, resulting in a concentration of approximately 4 g / liter.

[0112] coating The inks of Examples 15, 16, 17 and 18 were successfully coated onto fabrics including Fibertex 100 Pur Trucoat 35 gsm and Fibertex 100-VIS-Flat 50 gsm.

[0113] Wash Coating 50 x 50 mm swatches of Fibertex 100 Pur Trucoat 35 gsm and Fibertex 100-VIS-Flat 50 gsm materials were placed in baths of the inks from Examples 15 and 16 until saturated, then removed and allowed to air dry at ambient temperature on a metal panel. To the naked eye, both coatings appeared uniform and flat across the entire fabric. Both were examined under a microscope. Coating with the ink from Example 16 was found to form a uniform brown coating on the swatch fibers. This is believed to be due to the stability of the material in water and the film-forming properties of GO. A coating was formed with Example 15, but some small agglomerates were observed. This is believed to be due to a slight decrease in film-forming ability due to the reduction in GO.

[0114] Roller Coating 50 x 50 mm swatches of Fibertex 100 Pur Trucoat 35 gsm and Fibertex 100-VIS-Flat 50 gsm materials were aligned on a metal panel, and a line of ink (2-3 mL for each of Examples 17 and 18) was deposited adjacent to them. The ink for each sample was then coated onto each swatch using an ink roller. The coated swatches were then allowed to air dry on the metal panel. The ink for both examples appeared to be deposited quickly and evenly on both fabrics, without completely saturating the fabric. The fabric stiffened with the coating, but remained flexible.

[0115] Antiviral Testing The antiviral efficacy was determined using a plaque assay. The virus strain tested was influenza A virus (IAV). The efficacy of Ag-decorated GO particles in water was measured at 10 3 Low concentrations of plaque-forming units (PFU) and 10 4 Two virus concentrations with high PFU concentrations were measured. In the standard test, 250 μl of each supplied Ag-decorated GO dispersion was mixed with 50 μl of IAV. Viral efficacy was measured 1, 5, and 10 minutes after initial IAV / Ag-decorated GO mixing. After the allotted time, the dispersion was centrifuged to separate the IAV and active particles. Plaque assays were performed using MDCK cells. Diluted dispersions were also tested at both low and high PFU. They were diluted 1:100 in phosphate buffered saline (PBS) (1X phosphate buffered saline, Ca, Mg, phenol red-free, 0.1 micrometer sterile filtered, pH 7.4, Genesee Scientific). The experimental process and results are described below and shown in Figures 6-8.

[0116] GO / Ag NPs treatment The graphene oxide / silver nanoparticle (GO / Ag NP) ink solution (see Table 4) was sonicated for 20 minutes to disperse the particles. The ink solution, vehicle, or 1x PBS (undiluted PBS) was added to a 96-well plate in a volume of 250 μL. For the treatments, the GO / Ag NP ink was tested either undiluted (100% GO / Ag NP; HO vehicle) or diluted 100-fold in 1x PBS (1% GO / Ag NP; 1% HO vehicle).

[0117] 10 3 or 10 4 PFU / mL of influenza A virus (A / WSN / 33(H1N1), IAV) was added to treatment wells in a volume of 50 μL, resulting in a final volume ratio of 5:1 GO / Ag NPs:IAV. 1x PBS (with calcium and magnesium) containing 0.2% bovine serum albumin (BSA) (w / v, Fisher Scientific) vehicle was added to control wells. 1, 5, and 10 minutes after addition of IAV or vehicle, plates were centrifuged at 1650 x g for 5 minutes. Supernatants were transferred to clean 96-well plates. Each treatment condition was tested in triplicate.

[0118] [Table 4]

[0119] Quantification of IAV infectivity Plaque assays were performed to measure IAV infectivity. MDCK cells were grown in DMEM (ThermoFisher Scientific / Gibco) containing 10% FBS (ThermoFisher Scientific / Gibco) and 1% penicillin-streptomycin (ThermoFisher Scientific) in 6-well tissue culture plates to 90-95% confluence. The supernatant from the GO / Ag NP-treated plates was serially diluted in 1x PBS / 0.2% BSA, and 100 μL was seeded onto the MDCK cell monolayer. The inoculated plates were incubated at 37°C for 1 h. After incubation, the inoculum was replaced with 1x Dulbecco's Modified Eagle's Medium (DMEM) containing 1.2% NaHCO3, 0.2% BSA, and 1% bacterial agar (Oxoid). After 72 hours of incubation at 37°C, the 1x DMEM / 1% bacterial agar was removed, and the MDCK cell monolayers were stained with 0.1% crystal violet. The number of plaques per well was counted, and the virus titer was determined.

[0120] Assessment of MDCK cell viability The viability of MCDK cells after exposure to GO / Ag NP supernatant or vehicle was assessed using a Cytotoxicity Detection Kit (Millipore Sigma #11644793001). Prior to testing, GO / Ag NP ink supernatant or vehicle samples were serially diluted in 1x PBS / 0.2% BSA, exactly as performed in the plaque assay preparation. 100 μL of undiluted or diluted GO / Ag NP ink supernatant or vehicle (1x PBS) was seeded onto MDCK cells grown to 90–95% confluence in a 6-well tissue culture plate. The plate was incubated at 37°C for 1 h. The supernatant was then replaced with phenol red-free medium (agar-like medium). Media samples were obtained 1 and 18 h after treatment and tested for the presence of lactate dehydrogenase (LDH). The test involves mixing equal volumes of cell culture supernatant and diaphorase / NAD+ catalyst containing iodotetrazolium chloride and sodium lactate dye solution in the wells of an optically clear 96-well plate. The mixture is then incubated at 25°C for 30 minutes. Cells grown only in the presence of medium served as the low LDH control. Cells lysed with 2% Triton-X served as the high LDH control. Optical density (OD) was measured at 490 nm with a reference wavelength of 650 nm. The percent viability was calculated as follows:

[0121]

number

[0122] result 10 3 or 10 4The GO / Ag NP ink solution (Table 4) was tested for its ability to reduce infectious IAV concentrations by mixing it with either one of the PFU / mL IAVs at a volume ratio of 5:1 and incubating for 1, 5, or 10 minutes. The results are shown in Figures 6A–6D. Plaque assays were then performed to evaluate IAV infectivity after GO / Ag NP exposure by quantifying the viral plaque-forming units (PFU) after treatment. Undiluted (100%) GO / Ag NP Example 12a completely inhibited IAV plaque formation at all exposure time points examined. The 1% GO / Ag NP sample Example 12a was also able to significantly inhibit plaque formation at all exposure time points (Figure 6B). All other ink solutions were able to significantly reduce viral load by up to 0.5 log under certain treatment conditions. The GO / Ag NP aqueous vehicle did not affect IAV viability compared to PBS alone ( Figure 7 ), and the GO / Ag NP ink supernatant was also not found to affect the viability of MDCK cells ( Figure 8 ).

[0123] In Figure 6, the 1% GO / Ag NP ink solution is represented by the blue bar (the center bar of each time set), the 100% GO / Ag NP ink solution is represented by the red bar (the right bar of each time set), and 1x PBS is represented by the black bar (the left bar of each time set). The same colors or bar arrangements are used in Figures 7, 8, and 10. The x-axis represents time (1 min, 5 min, 10 min). The y-axis represents Log(PFU). This is the same for all graphs in Figures 6a-6d, 7, 8, and 10. Figures 6a-6d show the results of plaque assays after treatment with Example 9a, Figure 6b-6c, Example 22a, and Figure 6d show the results of plaque assays after treatment with Example 23a. Data shown are mean ± SD, n = 3 samples per group. * indicates p ≤ 0.05. Significance was determined using a two-way analysis of variance with Tukey's multiple comparison test.

[0124] Figure 7 shows the results of an investigation into whether aqueous vehicles alter IAV infectivity (using GO / Ag NPs). 3 or 10 4PFU / mL of IAV was exposed to 1% HO (diluted in 1x PBS, blue bars) or 100% HO (red bars) vehicle or 1x PBS (black bars) for 10 minutes. Viral PFU were then measured by plaque assay as described above. Data shown are mean ± SD, n = 3 samples per group. Significance was determined by Kruskal-Wallis test.

[0125] Figure 8 shows the results of an investigation into whether the supernatant affected the viability of MDCK cells. MDCK cells were exposed to the supernatant of each GO / Ag NP sample listed in Table 4, vehicle, or 1x PBS. Blue bars represent MDCK cells treated with the supernatant of a 1% solution of GO / Ag NPs or 1% HO vehicle, while red bars represent 100% GO / Ag NPs or 100% HO vehicle. Black bars represent MDCK cells exposed to 1x PBS. LDH concentrations were measured in media collected 1 hour (top) and 18 hours (bottom) after treatment. Viability (%) was determined as described in the Materials and Methods section. Data shown are mean ± SD, n = 3 samples per group. * indicates p ≤ 0.05 compared to the PBS control. Significance was determined using a two-way analysis of variance with Tukey's multiple comparison test. ND = data not available.

[0126] Figures 9 and 10 show the results of Example 12a in more detail. Here, we see that 100% efficacy was achieved undiluted, and even diluted versions had a significant impact on cell viability. Low and high refer to PFU. This is likely due to the synergistic effect of the oxidative potential of GO (the viral lipid membrane) and silver. By using a direct addition method that does not reduce the functional groups of GO, we were able to maximize the oxidative potential of GO and the spacing of silver nanoparticles throughout the GO. Adding PVP-coated silver leaves a significant number of oxygen species on the edges / surface of GO, using only a small number of available oxygen sites (O, COOH, and OH).

[0127] Although the invention has been described with reference to specific embodiments and examples above, it will be understood that modifications can be made to the embodiments and examples without departing from the invention.

Claims

1. 1. An ink for providing a virally active and / or antimicrobial coating on a substrate, comprising: (i) a carrier; (ii) graphene particles and / or graphene oxide particles dispersed in the carrier; (iii) an antiviral and / or antimicrobial component attached to the graphene particles and / or graphene oxide particles, the antiviral and / or antimicrobial component comprises metal nanoparticles; The combination of graphene particles and / or graphene oxide particles with an active ingredient for viruses and / or an antimicrobial ingredient has a weight content of metal nanoparticles of 1 wt % to 30 wt %.

2. The ink of claim 1, wherein the metal nanoparticles have a particle size of 1 to 40 nm.

3. The ink according to any one of claims 1 to 2, wherein the graphene particles and / or graphene oxide particles have a surface coverage of the antiviral and / or antimicrobial component of 5% to 60%.

4. The ink according to any one of claims 1 to 3, wherein the surfaces and / or edges of the graphene particles and / or graphene oxide particles are functionalized with the antiviral and / or antimicrobial component.

5. The ink according to any one of claims 1 to 4, wherein the graphene particles and / or graphene oxide particles are functional group-modified particles and contain a functional group selected from thiols, hydroxyl groups, carboxyl groups, epoxyl groups, and / or carbonyl groups.

6. 6. The ink of claim 1, further comprising: (i) a binder optionally selected from cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate), poly(ethylene) glycol, and polyvinylpyrrolidone (PVP); (ii) a drying agent; and / or (iii) a rheology control agent.

7. The ink according to any one of claims 1 to 6, wherein the combination of the graphene particles and / or graphene oxide particles and the antiviral agent and / or antimicrobial agent in the carrier has a concentration of 0.05 mg / ml to 10 mg / ml.

8. The ink according to any one of claims 1 to 7, wherein the antiviral and / or antimicrobial component comprises a capping agent.

9. The ink according to any one of claims 1 to 8, wherein the combination of graphene particles and / or graphene oxide particles with an active ingredient for viruses and / or an antimicrobial ingredient has a weight content of metal nanoparticles of 1 wt% to 10% wt%.

10. A support; a coating applied to the substrate; The coating comprises: (i) graphene particles and / or graphene oxide particles; (ii) an antiviral and / or antimicrobial component attached to the graphene particles and / or graphene oxide particles, the antiviral and / or antimicrobial component comprises metal nanoparticles; A virally active and / or antimicrobial article, wherein the combination of the graphene particles and / or graphene oxide particles with a virally active ingredient and / or antimicrobial ingredient has a weight content of metal nanoparticles of 1 wt % to 30% wt %.

11. The article of claim 10 , wherein the substrate comprises polyester, polypropylene, a woven fabric, or a cellulosic material.

12. the article is a filter, and the support is a filtration membrane provided in the filter for filtering particulates passing through the filter; Optionally, the coating is applied to at least one surface of the filtration membrane.

13. the filter comprises at least one microfiltration membrane having a filtration efficiency of at least 95% for particles having a size of 0.3 μm; The article of any one of claims 10 to 12, wherein the filtration membrane comprising the graphene particles and / or graphene oxide particles and an active viral component and / or an antimicrobial component is a coarse filtration membrane.

14. (a) combining graphene particles and / or graphene oxide particles with a virally active ingredient and / or an antimicrobial ingredient to attach the virally active ingredient and / or antimicrobial ingredient to the graphene particles and / or graphene oxide particles; the antiviral and / or antimicrobial component comprises metal nanoparticles; The combination of the graphene particles and / or graphene oxide particles with the antiviral component and / or antimicrobial component has a weight content of metal nanoparticles of 1 wt % to 30 wt %; (b) A method for producing an ink, comprising dispersing the combination of the graphene particles and / or graphene oxide particles and an antiviral and / or antimicrobial component in a carrier.

15. 15. The method of claim 14, wherein combining the graphene particles and / or graphene oxide particles with the virally active ingredient and / or antimicrobial ingredient comprises dispersing the graphene particles and / or graphene oxide particles in a carrier and then adding the virally active ingredient and / or antimicrobial ingredient to the carrier.

16. 16. The method of claim 15, wherein a virally active and / or antimicrobial precursor is added to the carrier, and the method comprises converting the precursor to the virally active and / or antimicrobial component in situ.

17. The method of claim 14 , wherein the metal nanoparticles are formed prior to step (a).

18. 17. The method of any one of claims 14 to 16, wherein the graphene is functionally group-modified graphene, and wherein step (a) comprises combining functionally group-modified graphene and / or graphene oxide with a virally active precursor and / or an antimicrobial precursor, and then adding a reducing agent to reduce the virally active precursor and / or antimicrobial precursor to form the virally active component and / or antimicrobial component.

19. 19. The method according to any one of claims 14 to 18, further comprising, prior to step (a), a step of functionally modifying the graphene particles and / or graphene oxide particles, wherein optionally, the step of functionally modifying the graphene particles and / or graphene oxide particles comprises functionalizing the graphene particles and / or graphene oxide particles with at least one functional group selected from a thiol group, a hydroxyl group, a carboxyl group, an epoxyl group, and a carbonyl group.

20. The method according to any one of claims 14 to 19, wherein the antiviral and / or antimicrobial component comprises a capping agent.

21. The method of any one of claims 14 to 20, optionally comprising isolating the combination of graphene particles and / or graphene oxide particles and antiviral and / or antimicrobial components prior to step (b).

22. A method for producing an article according to any one of claims 10 to 13, comprising applying an ink according to any one of claims 1 to 9 to a substrate.

23. functional group-modified graphene particles and / or graphene oxide particles; an antiviral component and / or an antimicrobial component attached to the functional group-modified graphene particles and / or graphene oxide particles, the antiviral and / or antimicrobial component comprises capped metal nanoparticles; The combination of the functional group-modified graphene particles and / or graphene oxide particles with the antiviral and / or antimicrobial component has a weight content of capped metal nanoparticles of 1 wt % to 30% wt %.

24. 24. The composition of claim 23, wherein the combination of the functional group-modified graphene particles and / or graphene oxide particles with the antiviral and / or antimicrobial component has a weight content of capped metal nanoparticles of 1 wt % to 10% wt %.

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