Viral active and / or anti-microbial inks and coatings

Abstract

An ink comprises (i) a carrier; (ii) graphene and / or graphene oxide particles dispersed in the carrier; and (iii) a viral active and / or anti-microbial component adhered to the graphene and / or graphene

Description

08 07 24 Field of Invention The present invention relates to inks comprising a viral active and / or anti-microbial component, articles, methods of manufacture, and use of inks and articles comprising a viral active and / or anti-microbial component. Background to the Invention There have been several major virus outbreaks amongst human populations over the past 20 years, including Ebola, SARS, MERS, Zika and most recently in 2019 / 2020 SARS-CoV-2, amongst others. There has been significant investment in research aimed combating these viruses, including preventing or reducing transmission to humans, preventing human-to-human transmission, developing vaccines and developing anti-virals and treatments for the diseases caused by these viruses. Reducing human-to-human transmission is becoming increasingly more difficult as the world’s population grows and there is increased movement of people. Even where this can be restricted, for example during the lockdowns imposed during the 2019 / 2020 SARS-CoV-2 pandemic, some human-to-human transmission is inevitable, either through human-human contact or through contact with the virus on surfaces. For example, healthcare workers will inevitably come into contact with those infected by the viruses and surfaces on which the virus is present. Similarly, workers in essential supply chains, such as food supply, will be unable to eliminate their exposure entirely. Therefore, it is necessary to provide protection to reduce transmission of the virus where isolation is not possible. Existing protection typically comprises personal protective equipment (PPE), including facemasks for covering the mouth and nose, visors which cover the entire face of the user, gowns and / or gloves. The effectiveness of existing PPE does vary. For example, although certain masks can filter out a significant portion (e.g. 95% for “N95” masks) of harmful bacteria and viruses, few can actually kill viruses, and the coronaviruses in particular. The same is true of other PPE. For example, gloves prevent contact of viruses with the skin, but do not prevent the virus from being passed to other surfaces. Summary of the invention In a first aspect of the invention, there is provided an ink, comprising (i) a carrier; (ii) functionalised graphene and / or functionalised graphene oxide particles dispersed in the carrier; and (iii) a viral active and / or anti-microbial component or additive adhered to the 08 07 24 graphene and / or graphene oxide particles. The functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group. The viral active and / or anti-microbial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent. This combination of materials in the form of an ink provides a particularly effective viral active (virucidal active) and / or anti-microbial (germicidal) system that can easily be applied to surfaces or materials to provide highly effective treatment. For example, where viral active this can be anti-viral (in that it will inhibit the proliferation of the virus) and / or virucidal properties (i.e. it has the capacity to destroy or inactivate viruses) where they are needed. For antimicrobial, this can be anti-bacterial or germicidal component. For example, such an ink can easily be applied to PPE or other surfaces to provide these with anti-viral and / or virucidal properties and thereby reduce the risk of transmission of viruses and infection. The high surface areas of graphene and graphene oxide enable them to be adhered or loaded with high levels of antiviral agents - making them ideal drug carriers. And crucially, the combination of graphene / GO and antiviral agents has been shown to both increase their antiviral performance as well as reduce their toxicity - enabling significantly higher antiviral performance. Indeed, these compositions have been shown to be effective against a number of viruses, including coronaviruses. Embodiments provide a way of enabling these properties to be used practically, for example in manufacturing where the ink can be easily applied to materials and surfaces to provide them with anti-viral or virucidal properties. While these materials can be produced in dried form, for example, the incorporation of these into a delivery mechanism that enables these materials to be applied to substrates (particularly in mass manufacturing) or that provides a stable and robust mechanism by which these materials can be distributed is more difficult. The inks of the present disclosure provide a solution to these problems. For example, this can be applied during manufacture of PPE (e.g. masks and / or gloves) or to surfaces by manufacturers further down the supply chain than would otherwise normally be required. This enables a wider proliferation and adoption of these materials and enables mass production of masks (e.g. particle protection masks), or other garments or equipment currently being used. This is particularly important where a quick response and increase in manufacture is required, for example as seen during the SARS-CoV-2 pandemic, where PPE shortages were commonplace. In some embodiments, the ink can be printed onto the surface of a material to form a layer of graphene and / or graphene oxide particles and a viral active and / or anti-microbial component. 18 02 25 Graphene oxide has anti-viral or anti-microbial properties. The two-dimensional structures, sharp edges, and negatively charged surfaces of graphene oxide (GO) can kill bacteria and viruses by disrupting their plasma membrane (for bacteria) and / or by oxidising them. The inks comprise a viral active and / or anti-microbial component, which means that the ink may comprise at least one of a component that is anti-viral in nature, a component that is virucidal in nature, a component that is anti-microbial (e.g. antibacterial / germicidal), or a combination of these (e.g. a component that is both anti-viral and virucidal in nature) The surfaces and / or edges of the graphene and / or graphene oxide particles are loaded (adhered) with the viral active and / or anti-microbial component. The planar shape of graphene and graphene oxide allows for a relatively low concentration of graphene and / or graphene oxide in a dispersion to be loaded with a high concentration of anti-viral or viricide on the surfaces of the graphene and / or graphene oxide particles. By loading it is meant that the viral active and / or anti-microbial component may be adsorbed onto or otherwise attached to the surface of the graphene and / or graphene oxide particles. In this form, the antiviral performance of the component has been shown to increase, while reducing their toxicity. The viral active and / or anti-microbial component comprises silver nanoparticles. For example, in one embodiment the ink comprises silver nanoparticle functionalised graphene oxide. The silver nanoparticles may have a particle size of 1 to 40nm, for example 10 to 40 nm. This may be an average particle size (i.e. a number average particle size). This can be measured using SEM. In some embodiments, the graphene and / or graphene oxide particles have a surface coverage of the viral active and / or anti-microbial component of from 5% to 60%. This can be determined using SEM, for example EDS-SEM or EDX-SEM. In some embodiments, the graphene and / or graphene oxide particles and viral active and / or anti-microbial component combined have a weight content of from 5% to 60% wt% viral active and / or anti-microbial component. This can be determined using thermogravimetric analysis (TGA). In some embodiments, the graphene and / or graphene oxide particles have a particle size of between 100 and 2000 nm. The graphene and / or graphene oxide particles have a particle size of between 100 and 2000 nm, for example a number average particle size of 18 02 25 between 100 nm and 2000 nm. This can be a largest dimension (e.g. a diameter). This can be measured by SEM, or by laser light scattering or PCS (photon correlation spectroscopy). In some embodiments, this is a number average particle size. This can be a largest dimension (e.g. a diameter). This can be measured by SEM, by laser light scattering or PCS (photon correlation spectroscopy). In an 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. a number average particle size) in the lateral dimension (i.e. at the greatest width across the face of the platelet) of between 100 and 2000 nm. Number average thickness of the platelets can be less than 200 nm, e.g. less than 100 nm, less than 50 nm, less than 10nm, less than 5nm or less than 1nm. These measurements can all be measured by SEM. The platelets can comprise single or multiple layers of graphene or graphene oxide. In some embodiments, the surfaces and / or edges of the graphene and / or graphene oxide particles are functionalised with the viral active and / or anti-microbial component. Where present, the graphene is functionalised graphene and comprises functional groups selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups. Where present, the graphene oxide is functionalised graphene oxide and comprises a thiol functional group. The presence of the thiol group can help to reduce the size of the nanoparticles (e.g. smaller silver nanoparticles on the surface of the graphene / graphene oxide). In some embodiments, the graphene particles are functionalised with oxygencontaining functional groups and have an oxygen content of from 10 to 30%, for example 10 to 25%. In some embodiment the graphene oxide particles have an oxygen content of from 24 to 40%. For example, greater than 25% to 40%. Oxygen levels have a direct effect on the virucidal efficacy of the product, the higher the better. However, above this level the ink or coating becomes more prone to moisture damage. Oxygen levels can be measured by EDS-SEM or EDX-SEM. In an embodiment, the ink is a solution or suspension and the carrier is a solvent. Alternatively, the ink may be a paste comprising a binder as a carrier; however, it is preferable to have the carrier in the form of a solvent. In embodiments, the ink may comprise 0.1-10 mg / ml of the combined active agent (i.e. graphene / graphene oxide combined with the anti-viral / anti-microbial component) in a solvent, for example, 1-5 or 2-4 mg / ml. In some embodiments, the ink further comprises (i) a binder, optionally selected from cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate) and poly(ethylene glycol ; (ii) a drying agent; and / or (iii) a rheology modifier. In another embodiment, the ink 18 02 25 may further comprise cationic particles, such as cationic polyurethane. This can be, for example, cationic colloidal particles, such as cationic colloidal polyurethane. This enables adhesion using electrostatic properties to negatively charged surfaces, such as polyester or polypropylene. In a second aspect, there is provided a viral active and / or anti-microbial article comprising: a substrate; and a coating provided on the substrate, wherein the coating comprises: (i) functionalised graphene and / or functionalised graphene oxide particles: and (ii) a viral active and / or anti-microbial component adhered to the graphene and / or graphene oxide particles, wherein functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group; and wherein the viral active and / or anti-microbial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent. Such articles can comprise PPE, such as facemasks, gloves, protective clothing or may be in the form of cleaning articles, such as anti-viral or virucidal or antibacterial cleaning fabrics. The presence of the graphene and / or graphene oxide and a viral active and / or antimicrobial component provides the article with all of the advantages described herein associated with the combination of these components in an article. These can be advantageous over existing products, as most approved anti-bacterial or anti-viral compositions include bleach, which is not always appropriate and can be toxic. In some embodiments, the article may comprise the ink of an embodiment disclosed herein. The properties of the graphene and / or graphene oxide, and viral active and / or antimicrobial components are the same as those set out in respect of the inks. In some embodiments, the surfaces and / or edges of the graphene and / or graphene oxide are loaded with the viral active and / or anti-microbial component. The graphene and / or graphene oxide are functionalised graphene and / or functionalised graphene oxide. In particular, the graphene is functionalised graphene and comprises functional groups selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups. The graphene oxide is functionalised graphene oxide and comprises a thiol functional group. 18 02 25 The substrate can be any material that can act as a matrix for the graphene and / or graphene oxide particles, and viral active and / or anti-microbial components. The substrate can be a layer of a particular material. The substrate may comprise a cellulosic material (such as cotton or paper) or a material such as polyester or polypropylene. Cellulosic materials are attractive as they are low cost, widely available and straightforward to incorporate into existing PPE. In one embodiment, the substrate comprises polyester or polypropylene. Polyester can be particularly effective as it can be responsible for the entrapment of viruses, including the virus responsible for Covid-19 disease (i.e. SARS-CoV-2). Polyesters form a group of polymers with a high susceptibility to static electricity and a long lifetime of charges generated on surface and in volume. This feature results from a low number of free charges and a low electric conductance. The substrate may be a woven or non-woven. In an embodiment, the article is a filter and the substrate is a filtration membrane provided in the filter to filter particulates passing through the filter; and the coating is provided on at least one surface of the filtration membrane. This can be, for example a filter for a mask or a filter for an air processing unit (e.g. HVAC). In an embodiment, the filter comprises a first filtration layer comprising the substrate and a second filtration layer, wherein the first filtration layer is provided upstream of the second filtration layer. In an embodiment, the filter comprises a first filtration layer comprising the substrate and a second filtration layer, wherein the first filtration layer is provided upstream of the second filtration layer. By upstream it is meant that when the majority of flow in normal use travels in a first direction, the second filtration layer is downstream of the first filtration layer. The second filtration layer may be adapted to prevent passage of the graphene and / or graphene oxide particles. Graphene oxide and graphene can be harmful and so this provides the benefits associated with their use, while ensuring that any that could detach from the substrate are retained within the filter. In an embodiment, the filter comprises at least one fine filtration membrane having a filtration efficiency of at least 95% for particles having a size of 0.3 pm; and the filtration membrane comprising the graphene and / or graphene oxide particles and a viral active and / or anti-microbial component is a coarse filtration membrane. In other words, the substrate / filtration membrane comprising the viral active and / or anti-microbial component (anti-viral / viricide / germicide) is provided outwardly relative to the fine filtration membrane. For example, where the filter is used in a face mask, the fine filtration membrane is provided closest to the user. This is a particularly effective arrangement as the ink traps the exhaled 18 02 25 and inhaled water droplets which carry the viral material and adsorbs them onto the ink where the active viral active ingredient inactivates or kills the virus and / or the antimicrobial active ingredient kills the microbe (e.g. bacteria). Coarse is relative to the fine filtration membrane. For example, the coarse filtration membrane may have a filtration efficiency of at least 95% for particles having a size of 3.0 pm. Moreover, this can reduce the risk of inhalation of graphene and / or graphene oxide particles. In a third aspect, there is provided a face mask comprising an article and / or a filter as disclosed herein. In a fourth aspect, there is provided a method of producing an ink according to the first aspect, comprising a carrier; graphene and / or graphene oxide particles: and a viral active and / or anti-microbial component. The method comprises: (a) dispersing graphene and / or graphene oxide particles in a solvent, wherein functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group; (b) combining the graphene and / or graphene oxide particles with a viral active and / or anti-microbial component to adhere the viral active and / or anti-microbial component to the graphene and / or graphene oxide particles , wherein the capped viral active and / or antimicrobial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent; and (c) dispersing the combined graphene and / or graphene oxide particles and viral active and / or anti-microbial component in a carrier. The step of functionalising the graphene comprises functionalising the graphene, where present, with at least one functional group selected from thiol, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and / or the step of functionalising the graphene oxide, where present, comprises functionalising the graphene oxide with a thiol. For example, this may be achieved by thiolisation using NaSH. In some embodiments, the solvent may be the carrier. Alternatively, the combined graphene and / or graphene oxide and viral active and / or anti-microbial component may transferred into a carrier. In some embodiments, the graphene and / or graphene oxide particles will disperse into a thin layer of nanosheets. These nanosheets may be aligned or misaligned, depending on 08 07 24 the specific viral active and / or anti-microbial component. The solvent is preferably an alcohol (e.g. methanol or ethanol) or water. Sonication of graphene and / or graphene oxide can also be used to reduce the particle size of the graphene / graphene oxide through breakage. In some embodiments, combining the graphene and / or graphene oxide particles with a viral active and / or anti-microbial component comprises loading the viral active and / or antimicrobial component onto the graphene and / or graphene oxide. In some embodiments, the graphene and / or graphene oxide particles may be functionalised with the viral active and / or anti-microbial component. In a fifth aspect, there is provided a method of manufacturing an article as defined herein, the method comprising applying an ink as defined herein to a substrate. In the methods set out herein, the ink can be applied to the substrate by printing. This is particularly advantageous as it allows for straightforward incorporation of this functionality into existing products and in existing manufacturing processes. In embodiments, printing can include spray coating, inkjet printing, dip coating, screen printing, gravure printing, flexographic printing, slot die coating, doctor blade coating. In some embodiments, where the substrate comprises a fabric such as cotton or polyester, the printing comprises spray coating, inkjet printing, dip coating and is adapted to provide a single layer thickness of graphene and / or graphene oxide particles onto the fabric. In other embodiments, where the substrate comprises a cellulosic material, the printing comprises screen printing or gravure printing. This may require higher viscosity ink. In a sixth aspect, the ink as defined herein or an article as defined herein are used as an anti-viral or viricide for Sars-CoV-2. Brief description of the drawings Embodiments of the invention will now be described with reference to the accompanying figures, in which: Figure 1 shows a schematic view of a mask according to an embodiment of the invention; Figure 2 shown an exploded schematic view of a filter according to an embodiment of the invention; and Figure 3 shows a further embodiment of the invention. Detailed description 08 07 24 As set out above, graphene and graphene oxide enhance the anti-viral or virucidal properties of viral active compounds or components. The same is true of a anti-microbial, such as an anti-bacterial. These components may be single components (e.g. a single composition or structure) or multiple, combined components. Where a virucidal material is used, there is a particular advantage over existing methods and anti-virals in general in that the virus is deactivated. Some environments have such high levels of concentrations of a particular virus and a user will be exposed for significant periods of time. In these environments, while preventing further replication of the virus can be helpful, the significant levels in the environment mean that the concentration can still lead to a high risk of infection. Virucidal materials in such an environment are useful as they will deactivate or destroy the virus that is present, rather than just preventing replication, for example. By ink, it is meant a liquid (solution or suspension) or paste comprising the graphene and / or graphene oxide particles and viral active and / or anti-microbial component, and a carrier. The carrier may be a solvent, for example water or an alcohol (e.g. ethanol). Therefore, in some embodiments, the ink is a suspension comprising the (i) graphene and / or graphene oxide particles and (ii) the viral active and / or anti-microbial component. The ink need not necessarily be coloured (i.e. may be colourless), but may be coloured (e.g. as a result of the presence of graphene or graphene oxide). Other components of the ink can include additional solvents, rheology modifiers, binders, drying agents and / or polymers. In embodiments, the ink further comprises a binder, for example cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate) and poly(ethylene glycol). Binders can be used as a soluble additive in the dispersion which, upon drying, would precipitate out and adhere the particles to a substrate / matrix (e.g. a fabric). In an embodiment, the ink further comprises a drying agent. These are chemicals which alter the crosslinking rate of the binders (usually react with the oxygen in the air) and contribute to how the inks solvent is absorbed into a material. Embodiments may include mineral-based drying agents, such as alumina and silica. In some embodiments, the ink further comprises a rheology modifier. These adjust the flow properties of the ink. For example, additives are required for screen printing to make the ink shear sensitive which allows the ink to pass through the mesh under shear but then return to a higher viscosity on the surface. In another embodiment, the ink comprises a gel reducers. These improve the properties of the ink for use with cellulosic materials to reduce the tack of the ink which would pick the short cellulosic fibres from the surface. In some embodiments, the ink 08 07 24 can comprise poly(ethylene glycol), which can act as a rheology modifier, a binder, and a drying agent. An additional solvent can include methyl ethyl ketone, which can lower the evaporation temperature. Graphene layer is a two-dimensional allotrope of carbon with a single layer of graphene includes a single planar sheet of sp2-hybridized carbon atoms. Graphene is known for its exceptionally high intrinsic strength, arising from this two-dimensional (2D) hexagonal lattice of covalently-bonded carbon atoms. Further, graphene also displays a number of other advantageous properties including high conductivity in the plane of the layer. Graphene oxide is a layer of graphene which has been functionalised with a number of oxygen-containing groups. For example, the layer may comprise hydroxyl, carboxyl, epoxyl and / or carbonyl groups. Graphene oxide provides advantages in that it has been shown to have anti-viral or anti-bacterial properties. Conversely graphene can be particularly advantageous in that it is easier and more environmentally friendly to manufacture. Oxygen functionalised graphene can be produced using a plasma functionalisation process and can provide graphene with similar functionality to graphene oxide but in an environmentally friendly manner. For example, an example of oxygen functionalised graphene is shown below: An example of graphene oxide is shown below: HsN HsN \ nU NHz 08 07 24 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 e.g. 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. The graphene and / or graphene oxide particles are functionalised. That is, in embodiments, the graphene may be and / or the graphene oxide are treated to incorporate functional groups on the surface and / or edges of the graphene and / or graphene oxide particles (depending on the initial method of manufacture of the graphene oxide, this may be a further functionalisation). The functional groups for the graphene include comprise thiol, hydroxyl, carboxyl, epoxyl and / or carbonyl groups. In one embodiment, thiol functional groups are used to functionalise the graphene and / or graphene oxide particles. Functionalisation can improve compatibility with a solvent or other components and thus improve the qualities of the ink. For example, this can improve the dispersion of the graphene and / or graphene oxide particles in an ink and avoid clumping or agglomeration. This can be, for example, functionalising using plasma treatment. For example, in some embodiments graphene may be functionalised using (additional) carboxyl groups. One example is a plasma treatment of “oxygen” functionalisation using the Haydale HDLPAS process, which is set out in WO 2010 / 142953 A1. Functionalisation can also improve the compatibility and loading of the viral active and / or antimicrobial components. The viral active and / or anti-microbial component comprises silver nanoparticles. For example, in some embodiments the viral active and / or anti-microbial component in the ink is a graphene oxide which is functionalised with silver nano-particles. The silver nanoparticles are chemically bound to the surface of the graphene oxide. This has been shown to be a very effective as both a virucide and an antibacterial agent. In some embodiments, the loading of silver nanoparticles can be up to 60% (by weight and / or surface coverage). By leaving some of the graphene / graphene oxide surface exposed, this allows the trapping of the target materials (e.g. virus of bacteria). For nanoparticles with a particle size of 1-1 Onm, this can in some embodiments be 30-60% loading by weight. For nanoparticles with a particle size of 30-40nm, this can in some embodiments be 30-60% loading by weight, this can be 5-20% loading. A first embodiment of the invention is shown in Figure 1. In this figure, a mask 100 according to an embodiment is shown schematically. The mask comprises a main body 110 and a filter 120. The main body 110 is shaped to fit over a user’s face and cover the user’s 08 07 24 nose and mouth, forming a seal with the face around the edge of the main body. The main body is formed of material that is either substantially impermeable to air or provides a high level of filtration to provide more resistance and filtering than the filter 120. The filter 120 is located in a hole extending through the main body 110. The filter 120 is designed to allow passage of air therethrough and thus provides an airflow pathway (i.e a path of least resistance) through the mask. This arrangement means that, when a user inhales, air is drawn through the filter 120. No air can directly enter the user’s lungs (due to the seal), nor can it pass through the impermeable main body 110. Although not shown, straps are provided which hold the mask onto a user’s face. In this embodiment, the filter 120 comprises one of the coatings disclosed herein. For example, in one embodiment, the filter 120 comprises a layer comprising a matrix and a silver-functionalised graphene oxide material coated on the matrix. This means that, as a user inhales, any virus present in the environment will pass through the filter 120 and come into contact with the layer comprising the silver-nanoparticle functionalised graphene oxide material. The virucidal properties of this material will deactivate or destroy the virus and thus prevent or reduce the risk of infection of the wearer. One embodiment of the filter 120 is shown in more detail in an exploded schematic view in Figure 2. The filter 120 in this embodiment comprises a number of layers 122, 124, 126, 128 located within a frame (not shown). Outer cover 122 is the outermost layer and is the one that will be exposed to the outside environment during use. This outer cover 128 can be a polyester or polypropylene fluid resistant cover which provides an initial screen to prevent significant water or dirt ingress into the filter 120. The layer behind (i.e. closer to the user) the outer cover is a pre-filter 124. In this embodiment, the pre-filter 124 comprises a layer with a filtration efficiency of greater than or equal to 95% for above 3.0 pm sized particles. This prefilter 124 can comprise a polyester layer (e.g. a non-woven polyester layer). In this embodiment, the pre-filter 124 is also coated with one of the coatings disclosed therein. For example, it can be coated with silver-nanoparticle functionalised graphene oxide material. This can, for example, be manufactured by printing an ink according to an embodiment onto the polyester material, for example on the outer face of the polyester layer to maximise exposure to the water droplets which contain the viral material. Behind the pre-filter 124 is a filter membrane 126. The filter membrane 126 comprises a layer with a filtration efficiency of greater than or equal to 95% for above 0.3 pm sized particles. This layer can comprise a polyester layer. Behind the filter membrane 126 is an inner cover 128. The inner cover 128 forms the innermost layer relative to the user. In some embodiments, this layer is polyester, polypropylene or cotton. 08 07 24 The filter 120 of the embodiment of Figure 2 can be easily manufactured by applying ink according to embodiments of the invention to a base material, such as a polyester, cotton or cellulose layer. This can be incorporated into existing manufacturing processes and without requiring specialist materials or equipment, thereby allowing for mass production of filters 120 and masks 100. For example, the ink can be printed onto a surface of a filter material, such as a polyester, cotton or cellulose layer, for example using an inkjet printer. Advantageously, masks 100 and filters 120 according to the above embodiment allow, the filter layers and coating (formed by applying the ink to a filter material) traps the water droplets which carry the virus (for example, SARS-CoV-2) and adsorbs them onto the ink where the active ingredient inactivates or kills the virus. This arrangement is particularly effective where viruses are transmitted through respiratory droplets. For example, the COVID-19 virus is believed to be transmitted mainly via small respiratory droplets initiated through sneezing, coughing, or when people interact with each other for some time in close proximity (usually less than one metre). These droplets can then be inhaled, or they can land on surfaces that others may come into contact with, who can then get infected when they touch their nose, mouth or eyes. Thus, use of a mask 100 will provide protection for users of the masks and those around them. This is particularly effective when the layer of the filter 120 on which the viral active and / or anti-microbial component is applied is polyester. Polyester fabric provides a very effective mechanism for the entrapment of viruses, including the SARS-CoV-2 virus. Polyesters form a group of polymers with a high susceptibility to static electricity and a long lifetime of charges generated on surface and in volume. This susceptibility to electrostatic charge is utilised in the filters to attract the water droplets to the filter. These virus containing water droplets will then be adsorbed onto the graphene layer coating the filter thus exposing the viral material to the attached viral active and / or anti-microbial compounds (e.g. silver particles). Indeed the electrostatic nature of the fibres will help reduce the penetration of the not only the water droplets but particulates as well. The provision of the ink on a pre-filter is unexpectedly advantageous. Although the first instinct might be to coat the filter membrane 126 having the highest degree of filtration with the ink, the more coarse pre-filter layer is sufficient for the purpose of attracting and trapping the target droplets. Although the COVID-19 virus itself is around 140nm in size, the water droplets carrying the virus have an overall average size distribution of 0.62-15.9pm, with 82% of droplet nuclei centered in 0.74-2.12pm with a mode size of 8.35pm. The size distribution of coughed droplets is multimodal, indicating that the size distribution has three 08 07 24 peaks, at approximately 1pm, 2pm, and 8pm. This makes the droplets an ideal size to be trapped directly in the pre-filter 124 for the coarse droplets, and through electrostatic interaction for the finer droplets, making this an efficient filtering system for droplets of this size range. Although in the embodiment described above with reference to Figure 2, the ink was applied to the pre-filter to form a coating on a matrix, the coating could instead be applied to any of the other layers to provide an effective anit-viral / virucidal filter. For example, application to an inner face of the outer cover 122 would also provide significant contact with viral material. In other embodiments, it may be provided on the inner cover 128 or the filter membrane 126. In some embodiments, the ink could be applied to plural layers of the filter 120. In further embodiments, the ink or coating may be applied to other PPE, such as gloves. In this way, should a user wearing the gloves contact a surface containing a virus, the ink or coating will reduce the risk of infection or transmission by inactivating the virus. Figure 3 shows a schematic view of a fibre 230 of an article that has been coated with particles 240 comprising graphene oxide platelets 241 loaded with Ag nanoparticles 242. The fibre has a width of 12 pm, the Ag nanoparticles 242 have a particle size of 1-2 nm and the graphene oxide platelets 241 have a particle size of 324 nm. Also illustrated are water droplets 250, which range in size from 0.2 to 8.5 pm. The ink and articles disclosed herein can be manufactured in a number of different ways, the ink can be manufactured as follows: (a) (step (a) is optional) functionalising graphene and / or graphene oxide, for example using plasma functionalisation, to provide a functionalised graphene and / or functionalised graphene oxide; (b) dispersing the (functionalised) graphene and / or (functionalised) graphene oxide in a solvent; (c) combining the graphene and / or graphene oxide particles with a viral active and / or anti-microbial component; and (d) dispersing the combined graphene and / or graphene oxide particles with a viral active and / or anti-microbial component in a carrier. Optional step (a) improves the dispersibility of the graphene and / or graphene oxide particles in a solvent. In a preferred embodiment, this comprises thiolisation using Sodium Hydrosulphide (NaSH) to produce thiol functional graphene and / or graphene oxide particles. 08 07 24 Step (b) comprises dispersing graphene and / or graphene into a solvent. This may comprise dispersing 1-10 wt% (e.g. 1-5, or2-4wt%) graphene and / or graphene oxide particles into a solvent. These concentrations are particularly effective as the graphene and / or graphene oxide particles will disperse into a thin layer a nanosheets. These nanosheets may be aligned or misaligned, depending on the specific viral active and / or anti-microbial component. The solvent is preferably an alcohol (e.g. methanol or ethanol) or water. In the case of water, the concentration is preferably 1-5%, or 2-4% to keep the viscosity relatively low. Step (c), may comprise loading the viral active and / or anti-microbial component onto the graphene and / or graphene oxide particles. For example, loading may comprise further functionalising the graphene and / or graphene oxide particles with the viral active and / or antimicrobial component. After step (c), the combined viral active and / or anti-microbial mixture (i.e. the graphene and / or graphene oxide particles combined with the viral active and / or anti-microbial component(s)) can be dried to provide a dried viral active and / or anti-microbial mixture. However, such a mixture is difficult to handle and use in its dried form. It is therefore necessary to formulate an ink comprising the mixture to effectively use it in the manufacture of anti-viral / virucidal (i.e. viral active and / or anti-microbial) articles. Step (d) therefore comprises dispersing the combined graphene and / or graphene oxide particles with a viral active and / or anti-microbial component in a carrier. This can be achieved using a number of methods. The step of preparing the ink coating may comprise dispersing the graphene oxide and / or graphene combined with the viral active and / or anti-microbial agent in a solvent. The specific properties of the ink may depend on the surface or substrate onto which the ink is to be applied. Examples are provided below. The step of preparing the ink coating may comprise dispersing the graphene oxide and / or graphene combined with the viral active and / or anti-microbial agent in a solvent. The specific properties of the ink may depend on the surface or substrate onto which the ink is to be applied. For example, in some embodiments the graphene oxide and / or graphene combined with the viral active and / or anti-microbial agent can be dispersed in deionised water. Provided the graphene oxide and / or graphene combined with the viral active and / or anti 08 07 24 microbial agent is of the size and has the coverage disclosed herein, such a solution can be used to coat certain materials e.g. having an opposing electrostatic charge. At this stage (step (d)), other components of the ink can be added, for example, rheology modifiers, binders, drying agents and / or polymers. Below are provided some example methods of producing the inks and articles disclosed herein. In some embodiments, the graphene oxide may be manufactured by functionalising graphene with oxygen containing functional groups (e.g. hydroxyl, carboxyl, carbonyl, epoxyl groups). For example, this may be plasma functionalisation. In these embodiments, the step of (i) functionalising graphene oxide may be further functionalisation (e.g. addition of further functional groups, such as a thiol group or additional groups that may already be present). In one embodiment, an article comprises a film or wrap comprising a coating having combined graphene and / or graphene oxide with a viral active and / or anti-microbial component. The film or wrap can be quickly and easily applied to surfaces of any shape to provide protection against viruses and / or microbes. In a specific embodiment, this may be a multi-layer film whereby a (positively-charged) cellulosic film that has been coated with GO / Ag nanoparticles is bonded to a (negatively-charged) film substrate (e.g. PVC, PP, or BOPP, such as a cling film type substrate). The film layer facilitates application to most surfaces (e.g. through use of an adhesive or electrostatic forces) and the cellulosic layer puts the viral active ingredients on the touch surfaces. Examples Preparation of qraphene / graphene oxide combined with a viral agent (precursor to ink and articles formation) Below are examples of how the precursors to the claimed ink and articles can be formed. Precursor Example 1 (not an embodiment) One specific embodiment comprises a silver-nanoparticle graphene oxide ink. Graphene Oxide nanoparticles with a diameter between 100 and 2000 nm loaded with silver nanoparticles of diameters between 1 and 40nm in size. The amount of silver decoration on the graphene oxide is defined by weight (as measured by Thermogravimetric Analysis (TGA)). 08 07 24 The silver-nanoparticle graphene oxide ink can be manufactured according to the methods set out herein. As an initial step, the silver-nanoparticle graphene oxide are manufactured as follows. A thiol grafted graphene oxide (i.e. thiol functionalised graphene oxide) can act as a base on which the silver nanoparticles are attached. The silver nanoparticles are produced via a modified Turkevich method of reducing silver nitrate to silver nanoparticles which are then attached to the graphene oxide plates through the thiol groups pre-attached to the graphene oxide surface. An example method is set out in Vi et al, The Preparation of Graphene OxideSilver Nanocomposites: The Effect of Silver Loads on Gram-Positive and Gram-Negative Antibacterial Activities, Nanomaterials 2018, 8, which is incorporated herein by reference. In this method different molar concentrations of silver nitrate Ag contents of up to 65% were achieved with a size of 1-2nm. This contrasts to the size of the graphene oxide plates which are 1-2pm in size. Another method is disclosed in Kim, J.D.; Yun, H.; Kim, G.C.; Lee, C.W.; Choi, H.C. 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. Precursor Example 2 (not an embodiment) In an alternative method to Precursor Example 1, the silver-nanoparticle graphene oxide ink can be manufactured by manufacturing the silver-nanoparticle graphene oxide particles using addition of a silver salt (e.g. silver nitrate or silver acetate) solution. The silver nanoparticles are then precipitated out of solution by the addition of a reducing agent (e.g. selected from sodium citrate, trisodium citrate, citric acid, sodium borohydride or sodium hydroxide). This method the presence of the thiol group advantageously can lead to a particle size of the precipitate of 1-2nm. After formation, the resultant material is then washed to remove unbound silver and excess salt from solution. Precursor Example 3 In an alternative method to that of Precursor Examples 1 and 2, commercially available silver nanoparticles with a capping agent (polyvinylpyrrolidone (PVP) or a citrated-based agent) can be obtained, and the loading onto the graphene oxide can be achieved by preferentially replacing the capping agent with the thiol groups present on the surface and edges of the graphene oxide. After formation, the resultant material is then washed to remove unbound silver and excess salt from solution. Pre-cursor Examples 4 and 5 (not an embodiment) 08 07 24 In an alternative method to that of Precursor Examples 1 to 3, other groups instead of a thiol group can be used to adhere the silver nano-particles. For example, in a modified version of Pre-cursor Example 3, (poly)ethylene glycol (PEG) (Precursor Example 4) or Polyethylenimine (PEI, CzHsN)^ (Precursor Example 5) can be used to both reduce a silver salt and act as the binder between the silver nano-particle and the graphene oxide. In this instance, different molecular weights of the PEG can give varying reducing / stabilizing effects. The PEG also acts as a buffer in the reaction maintaining a usable pH. Pre-cursor Example 6 In another embodiment, the effectiveness of the ink is further improved by further loading or functionalisation with curcumin, such that in one embodiment an ink comprises a curcumin and silver-nanoparticle graphene oxide ink. This can be manufactured or synthesised by manufacturing a silver-nanoparticle graphene oxide composition as set out above, followed by further functionalisation using curcumin prior to forming 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 DI water and combined with the silver-nanoparticle graphene oxide ink to provide curcumin and silver-nanoparticle graphene oxide ink. In turn, this can then be formulated as an ink, as set out above. Precursor Example 7 (not an embodiment) Prepare Graphene Oxide with Thiol Groups (GO-SH) Graphene Oxide is provided as a 4g in 1000ml dispersion. 125ml of this is reacted is sonicated for 20 minutes to prepare the dispersion. 8.0g of sodium hydrosulfide (NaHS) is added gradually and maintained at 55°C while stirring continuously for 20 hours. The product is filtered and washed with DI water. (Filter using centrifuge at 4000 rpm and wash 5 times with DI water). The product is direct in a vacuum oven at 50°C for 3 hours. Prepare Silver Nitrate Solution To produce 100ml of a 0.1M solution, while stirring 1.6987g of AgNOa is added to 100ml of distilled water. This is stirred for an hour before use. Alternative Silver Nitrate Solutions include a 0.2M solution (100ml of a 0.2M solution is prepared by adding (while stirring) 3.3974g of AgNOa to 100ml of distilled water. This is stirred 08 07 24 for an hour before use) and a 0.25M solution (4.2468g of AgNOa is added to 100ml of distilled water. This is stirred for an hour before use). Preparation of Silver loaded GO particles (GO-Ag) 0.1g of the dried GO-SH particles prepared above are added to 30ml of DI water. This is sonicated for 30 minutes. While stirring the solution, 2ml of the respective silver nitrate solution (0.1M, 0.2M or 0.25M) as produced above is added. While stirring, 20ml of 0.1M solution of sodium Hydroxide (NaOH) is added. This is stirred for 20 hours. The dispersion is then centrifuged at 10,000 rpm multiple times 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 the unreacted salt and loosely bound Ag nanoparticles. For storage, the particles can be added to DI water to limit the oxidation at a concentration of 4g / litre. General Precursor Formation As is apparent from above, numerous combinations of reagents can be used to generate the precursor material (i.e. the viral active and / or anti-microbial graphene / graphene oxide materials or mixtures). Table 1 (below) sets out various combinations according to some embodiments: Graphene Source Silver Source Reducing Agent Binder Graphene Graphene Oxide Silver NPs Silver Salts Oxygen functionalised Graphene Nanoplatelets Oxygen level ranging 10-25% Range of Oxygen levels from 24 to 40% PVP2 Capped, size range 10-40nm Silver Nitrate Sodium Citrate Sodium Hydrosulfide Graphene nanoplatelets Citrate capped, size range 10-40nm Silver acetate Trisodium Citrate PEI Citric Acid Sodium Borohydride PEG Table 1 Formation of inks and articles 08 07 24 Examples of forming inks and / or articles according to the invention are set out below. Silver nanoparticle functionalised graphene oxide particles are negatively charged. The electrostatic nature of these particles can adhere them to a positively charged substrate. Therefore, these particles can be added to DI water and used to coat substrates. Examples of such substrate include cotton (e.g. sateen). Others include, nylon 6,6, wool, glass filaments or spun glass. In another embodiment, the ink may further comprise cationic colloidal particles, such as cationic polyurethane. Such an ink is advantageous in that can be an aqueous solution and rely on electrostatics to coat articles, without being limited to positively charged surfaces. For example, such an ink can be used to coat negatively charged surfaces such as polyesters and polypropylenes. In an embodiment, the colloidal particles are provided and sized so that one colloidal particle retains one flake or particle of silver functionalised graphene oxide to a fibre. This acts as a positive PU particle sandwiched between two negative surfaces. In other embodiments, the inks rely on chemical / mechanical attachment. For example, binders such as cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate) and poly(ethylene glycol) are used as a soluble additive in the dispersion which, upon drying, precipitate out and adhere the particles to a substrate (e.g. a fabric). In one embodiment, the carrier may be a volatile solvent such a isopropanol or ethanol. In methods of forming an article, the substrate can be pre-coated with an adhesive and then an ink containing a solvent can be applied. For example, this ink could be sprayed on using e.g. a volatile solvent. This can adhere the particles to the substrate as the solvent disperse and can use capillary action to orientate the viral active and / or anti-microbial graphene / graphene oxide particles. Although the invention has been described with reference to specific embodiments and examples above, it will be appreciated that modifications can be made to the embodiments and examples without departing from the invention.

Claims

18 02 251. An ink, comprising:(i) a carrier;(ii) functionalised graphene and / or functionalised graphene oxideparticles dispersed in the carrier; and(iii) a viral active and / or anti-microbial component adhered to the graphene and / or graphene oxide particles,wherein functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group; andwherein the viral active and / or anti-microbial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent.

2. The ink according to claim 1, wherein the silver nanoparticles have a particle size of 1 to40 nm.

3. The ink according to claim 1 or claim 2, wherein the silver nanoparticles have a particle size of from 10 to 40 nm.

4. The ink according to any preceding claim, wherein the silver nanoparticles are capped by polyvinylpyrrolidone (PVP) or a citrate-based capping agent.

5. The ink according to any preceding claim, wherein the graphene and / or graphene oxide particles have a surface coverage of the viral active and / or anti-microbial component of from 5% to 60%.

6. The ink according to any preceding claim, wherein the graphene and / or graphene oxide particles and viral active and / or anti-microbial component combined have a weight content of from 5% to 60% wt% viral active and / or anti-microbial component.

7. The ink according to any preceding claim, wherein the graphene and / or graphene oxide particles have a particle size of between 100 and 2000 nm.

8. The ink of any preceding claim, wherein the surfaces and / or edges of the graphene and / or graphene oxide particles are functionalised with the viral active and / or antimicrobial component.18 02 259. The ink of any preceding claim, wherein the graphene particles are functionalised with oxygen-containing functional groups and have an oxygen content of from 10 to 30%.

10. The ink of any of any preceding claim, wherein the graphene oxide particles have an oxygen content of from 24 to 40%.

11. The ink of any preceding claim, wherein the ink is a solution or suspension and the carrier is a solvent.

12. The ink of any preceding claim, wherein the ink further comprises (i) a binder, optionally selected from cellulose acetate, cellulose acetate butyrate, diethyl phthalate, poly(methyl methacrylate) and poly(ethylene glycol; (ii) a drying agent; and / or (iii) a rheology modifier.

13. A viral active and / or anti-microbial article comprising:a substrate; anda coating provided on the substrate, wherein the coating comprises:(i) functionalised graphene and / or functionalised graphene oxide particles: and(ii) a viral active and / or anti-microbial component adhered to the graphene and / or graphene oxide particles,wherein functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group; andwherein the viral active and / or anti-microbial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent.

14. The article according to claim 13, wherein the substrate comprises polyester, polypropylene or a cellulosic material.

15. The article according to claim 13 or claim 14, wherein the article is a filter and the substrate is a filtration membrane provided in the filter to filter particulates passing through the filter; andwherein the coating is provided on at least one surface of the filtration membrane.18 02 2516. The article according to any of claims 13 to 15,wherein the filter comprises at least one fine filtration membrane having a filtration efficiency of at least 95% for particles having a size of 0.3 pm; andwherein the filtration membrane comprising the graphene and / or graphene oxide particles and a viral active and / or anti-microbial component is a coarse filtration membrane.

17. A face mask, comprising the article of any of claims 13 to 16.

18. A method of producing the ink of any of claims 1 to 12, comprising:(a) dispersing functionalised graphene and / or functionalised graphene oxide particles in a solvent, wherein functionalised graphene particles comprise a functional group selected from thiols, hydroxyl, carboxyl, epoxyl and / or carbonyl groups and wherein functionalised graphene oxide particles comprise a thiol functional group;(b) combining the functionalised graphene and / or functionalised graphene oxide particles with a capped viral active and / or anti-microbial component to adhere the viral active and / or anti-microbial component to the graphene and / or graphene oxide particles, wherein the capped viral active and / or antimicrobial component comprises silver nanoparticles obtained from silver nanoparticles capped by a capping agent; and(c) dispersing the combined graphene and / or graphene oxide particles and viral active and / or anti-microbial component in a carrier.

19. A method of manufacturing an article according to any of claims 13 to 16, the method comprising applying an ink according to any of claims 1 to 12 to a substrate.

20. Use of the ink of any of claims 1 to 12 and / or an article of any of claims 13 to 16 as an anti-viral or viricide for Sars-CoV-2.

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