An anti-HPV virus fabric based on a graphene-based hollow sphere structure and a preparation method and application thereof

Abstract

The application provides an anti-HPV virus fabric based on a graphene-based hollow sphere structure and a preparation method thereof. First, low-oxidation-degree graphene oxide nanosheets (carbon-oxygen ratio 3-10) and a sulfonic acid group-containing macromolecular aqueous solution are prepared, the amphiphilicity of the low-oxidation-degree graphene oxide is utilized, and a stable emulsion with graphene oxide as a shell and the sulfonic acid group-containing macromolecular aqueous solution as a core is constructed in n-hexane through ultrasonic shearing. The emulsion is atomized and sprayed on a fabric after low-temperature plasma treatment (so as to make the fabric positively charged), and after slow drying, an open hollow sphere structure is formed. The internal sulfonic acid group acts as a trapping agent to attract viruses, the shell graphene oxide sharp edge physically disturbs and cuts the virus capsid, a three-level synergistic mechanism of "trapping-enrichment-inactivation" is formed, the inactivation rate of the HPV virus is as high as 90% or more, and the washing stability is excellent. The application provides a new solution for upgrading of medical protective textiles and daily hygiene products.

Description

Technical Field

[0001] This invention belongs to the field of functional textile technology, specifically relating to an anti-HPV virus fabric based on a graphene-based hollow sphere structure, its preparation method, and its application. Background Technology

[0002] Human papillomavirus (HPV) is a common DNA virus, and persistent infection with high-risk HPV types is a major cause of cervical cancer and other malignant tumors. Developing fabrics with anti-HPV properties is of great significance for reducing the risk of virus transmission and protecting human health.

[0003] Graphene and its derivatives, due to their unique two-dimensional sheet structure, huge specific surface area, excellent mechanical properties, and abundant surface functional groups, show broad application prospects in the field of antiviral research. Studies have shown that graphene materials can exert antibacterial and antiviral effects through multiple mechanisms, including physical cutting, oxidative stress, and chemisorption by surface functional groups. Currently, graphene oxide is commonly used as an antibacterial material, adsorbent material, or carrier for metal nanoparticles; there are also publications and patents proving its application in antiviral fibers or protective fabrics.

[0004] However, existing technologies still have the following shortcomings: First, existing graphene antiviral fabrics mostly use fiber blending or simple coating methods, and the graphene sheets tend to be laid flat and stacked on the fabric surface, which means that the active edge areas of graphene cannot be fully exposed, thus weakening the physical cutting and contact disturbance effects of graphene.

[0005] Second, existing graphene antibacterial and antiviral technologies are all based on broad-spectrum physical / chemical mechanisms, lacking differentiated structural designs targeting specific virus species. Human papillomavirus (HPV), as a non-enveloped, small DNA virus, has a highly ordered icosahedral capsid structure composed of the L1 protein on its viral particle surface, which is relatively dense and lacks an envelope phospholipid layer. This makes it difficult for graphene's antiviral mechanism to effectively target HPV. More importantly, existing graphene materials cannot achieve selective capture and targeted inactivation of HPV. Therefore, even though graphene-modified textiles have inhibitory effects on various bacteria and some enveloped viruses, their killing efficiency against HPV is significantly insufficient, failing to meet the requirements for efficient and precise disinfection and protection. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides an anti-HPV virus fabric based on a graphene-based hollow sphere structure, its preparation method, and its applications. This invention constructs a core-shell structure of hollow microspheres with a "graphene oxide shell and sulfonic acid-based inner core," combining graphene oxide with HPV-capturing molecules and creating a unique nanoscale structure. This structure not only efficiently captures HPV viruses but also enhances virus contact and capsid disturbance through the exposed edges of the graphene oxide sheets, reducing the possibility of HPV virus escape. Thus, it balances antiviral efficacy, washability, skin-friendly safety, and industrial feasibility.

[0007] One technical solution of the present invention is to provide an anti-HPV virus fabric based on a graphene hollow sphere structure, comprising a base fabric and a composite antiviral functional layer loaded on at least one surface, fiber surface, and / or fiber gaps of the base fabric; the composite antiviral functional layer comprises graphene oxide hollow microspheres and HPV affinity-capturing components, wherein the graphene oxide hollow microspheres have an open structure, are composed of graphene oxide nanosheets, and at least partially expose the edge regions of the graphene oxide sheets at the edges of the open structure; the hollow microspheres contain HPV affinity-capturing components, which are macromolecules containing sulfonic acid groups; the diameter of the graphene oxide hollow microspheres is 0.5~5 micrometers. The total loading of the composite antiviral functional layer on the base fabric is 0.1~5 g / m².

[0008] Furthermore, the carbon-to-oxygen ratio of the graphene oxide nanosheets is 3 to 10, and the size is 50 to 300 nm.

[0009] Furthermore, the macromolecule containing sulfonic acid groups is one or more of sulfated polysaccharides, sulfated oligosaccharides, fucoidan, chondroitin sulfate, heparin, low molecular weight heparin, heparin analogues, sulfonated chitosan, sulfonated cellulose, sulfonated polyvinyl alcohol, sulfonated polystyrene, or polymers containing sulfonate betaine.

[0010] Furthermore, the base fabric is a fabric formed by weaving or non-woven processes from one or more of the following: cotton, viscose, lyocell, modal, nylon, polyester, polypropylene, polylactic acid fiber, and chitosan fiber.

[0011] The second technical solution of the present invention is to provide a method for preparing the above-mentioned anti-HPV virus fabric, comprising the following steps: (1) Prepare graphene oxide nanosheets with a carbon-to-oxygen ratio of 3 to 10 and a size of 50 to 300 nm, and disperse them in ethanol to obtain a graphene oxide nanosheet dispersion; generally, the modified Hummers method is used to prepare graphene oxide nanosheets. (2) Prepare an aqueous solution of macromolecules containing sulfonic acid groups with a solid content of 5% to 20%; (3) The graphene oxide nanosheet dispersion obtained in step (1) and the aqueous solution of macromolecules containing sulfonic acid groups obtained in step (2) are mixed in n-hexane. Under ultrasonic action, the graphene oxide nanosheets are sheared and dispersed to encapsulate the aqueous solution of macromolecules containing sulfonic acid groups, forming droplets with a diameter of 0.5~5 micrometers. The mixture is then dispersed in n-hexane as an emulsion. The mass ratio of graphene oxide nanosheets to macromolecules containing sulfonic acid groups is 1~10:1. (4) The emulsion obtained in step (3) is atomized and then attached to the base fabric; (5) Place the attached base fabric into an oven, heat it to 90-110℃ at 0.4-1℃ / min and keep it warm for 0.2-1h to obtain anti-HPV virus fabric.

[0012] This invention constructs a core-shell emulsion system of graphene oxide nanosheets encapsulating an aqueous solution containing sulfonic acid macromolecules using an emulsion template method. After atomization and slow drying, hollow graphene oxide microspheres with open structures are formed. This structure is similar to a "fly trap": the sulfonic acid macromolecules are enriched inside the microspheres, generating an initial electrostatic attraction to negatively charged or locally negatively charged virus particles, making it easier for virus particles to enter the interior of the graphene oxide microspheres, acting as a "trapping agent"; the graphene oxide shell, with its sharp edges, physically disturbs, adsorbs, or reduces the activity of the virus capsid structure; at the same time, because the size of the graphene oxide microspheres is only 0.5-5 micrometers, viruses are difficult to detach after entering, thus playing a physical trapping role.

[0013] Further, the sulfonic acid macromolecules mentioned in step (2) are one or more of the following: sulfated polysaccharides, sulfated oligosaccharides, fucoidan, chondroitin sulfate, heparin, low molecular weight heparin, heparin analogues, sulfonated chitosan, sulfonated cellulose, sulfonated polyvinyl alcohol, sulfonated polystyrene, or polymers containing a sulfonic acid betaine structure.

[0014] Furthermore, in step (3), the mass ratio of graphene oxide nanosheets to n-hexane is less than 1:100.

[0015] Furthermore, in step (4), the atomization method is to atomize using an ultrasonic atomizing device, with an atomization power of 60~110GHz and a flow rate of 1~10mL / min.

[0016] Furthermore, the base fabric described in step (4) undergoes low-temperature plasma treatment to achieve directional anchoring. The low-temperature plasma treatment imparts a positive charge to the fabric surface, allowing electrostatic adsorption to firmly anchor the negatively charged graphene oxide hollow microspheres to the fabric surface. This improves the bonding strength between the functional layer and the fabric, enhancing the fabric's wash resistance. Additionally, after atomized adhesion, a reactive crosslinking agent can be sprayed to covalently bond the graphene oxide hollow microspheres to the fabric surface, further strengthening the bonding.

[0017] Further, in step (4), the base fabric surface is sprayed with a reactive crosslinking agent; the reactive crosslinking agent is selected from silane coupling agents, isocyanate compounds, epoxy compounds, and polyamine compounds. The reactive crosslinking agent is sprayed onto the fabric surface before atomization, allowing the groups on the graphene oxide nanosheets to form covalent bonds with the groups on the fabric substrate. The reactive crosslinking agent forms covalent bonds between the hydroxyl, carboxyl, and epoxy groups on the fabric surface and the oxygen-containing functional groups such as carboxyl, hydroxyl, and epoxy groups in the graphene oxide, without destroying or covering the sulfonic acid macromolecules.

[0018] The third technical solution of the present invention is to provide the application of the above-mentioned anti-HPV virus fabric. Specifically, it can be used in the preparation of underwear crotch fabric, sanitary napkin surface layer, panty liner surface layer, nursing pads, gynecological examination pads, medical nonwoven fabrics, disposable protective fabrics, or public health skin-friendly products.

[0019] The advantages of this invention are: (1) The anti-HPV virus fabric prepared in this invention achieves a virus inactivation rate of more than 90% for HPV through the synergistic effect of sulfonic acid macromolecules trapping HPV, physical disturbance and cutting of graphene oxide nanosheets, and physical interception of graphene oxide microspheres.

[0020] (2) This invention controls the distribution morphology of graphene oxide nanosheets on the fabric surface, thereby fully exposing the edge regions of graphene oxide and avoiding the problem of insufficient active edges caused by excessive flattening of graphene oxide sheets in traditional padding finishing. This edge-exposed structure can significantly increase the contact probability between virus particles and defects, edges, and wrinkles in graphene oxide, thereby improving antiviral efficiency.

[0021] (3) The present invention uses an aqueous system to prepare a macromolecular solution containing sulfonic acid groups, with a small amount of organic solvent used, and the preparation process is mild and does not require high temperature and high pressure, which is in line with the concept of green chemistry and sustainable development. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the method for preparing the anti-HPV virus fabric of the present invention.

[0023] Figure 2 This is a SEM image of the hollow graphene oxide microspheres prepared in Example 1.

[0024] Figure 3 This is a SEM image of the hollow graphene oxide microspheres prepared in Example 2. Detailed Implementation

[0025] The following examples are provided to further illustrate the present invention and are intended to explain the invention, not to limit its scope. Unless otherwise specified, all figures are expressed in parts by weight and weight percentages.

[0026] Unless otherwise specified, the raw materials used in this invention are all conventional commercially available products; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0027] The anti-HPV efficacy was tested according to ISO 18184:2025. The host cell was human embryonic kidney cells (293T cells), passage 5, and the virus was human papillomavirus (HPV-16). The specific steps were as follows: (1) Observe the confluence of cell cultures prepared in 96-well plates under a microscope. If the cells are confluent, remove the growth medium from the culture plate, add 0.1 mL of maintenance medium, and gently rotate to rinse the cell surface. Remove the medium and repeat the washing procedure twice.

[0028] (2) Inoculate 0.1 mL of the test virus elution suspension and the diluted suspension into 8 wells. For example, inoculate the basic virus suspension into the first 8 wells and inoculate the 1 / 10 diluted virus suspension into the second 8 wells. Inoculate the last 8 wells with pure maintenance medium to verify the medium.

[0029] (3) Place the microplate in a CO2 incubator at an appropriate temperature and maintain for 1 hour to allow the cells to absorb the virus. Aspirate the supernatant from the plate. Add 0.1 mL of maintenance medium, use this medium to wash the cell surface, and aspirate any excess maintenance medium.

[0030] (4) Add 0.2 mL of virus trypsin maintenance medium, and place the microplate obtained above in a CO2 incubator and store it at an appropriate temperature for 7 days as required.

[0031] (5) Observe the cytopathic effect, record the results, and calculate TCID. 50 .

[0032] The embodiments of the present invention will be further described below with reference to several examples.

[0033] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0034] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0035] Example 1 (1) Preparation of low-oxidation graphene oxide nanosheets: Graphene oxide nanosheets with a carbon-to-oxygen ratio of 6 and a size of 270~300nm were prepared by the modified Hummers method and dispersed in ethanol at a concentration of 4mg / mL. (2) Preparation of an aqueous solution containing sulfonated chitosan: Dissolve sulfonated chitosan in deionized water to prepare an aqueous solution with a solid content of 20%; (3) Preparation of emulsion: Take 50 mL of graphene oxide nanosheet dispersion obtained in step (1) (containing 200 mg of graphene oxide nanosheet) and 2 mL of sulfonated chitosan aqueous solution obtained in step (2) (containing 200 mg of sulfonated chitosan), add them to 200 mL of n-hexane, and disperse them at 10000 rpm for 10 minutes under the assistance of 200 W ultrasound to form a stable water-in-oil emulsion with a droplet diameter of 0.5~1 micrometer; (4) Atomization Adhesion: The nylon fabric is subjected to low-temperature plasma treatment to make its surface positively charged. The emulsion obtained in step (3) is atomized by an ultrasonic atomization device with a power of 80 GHz and a flow rate of 10 mL / min, and is uniformly adhered to the plasma-treated fabric through an air duct.

[0036] (5) Slow heat treatment: The attached fabric is placed in an oven and slowly heated to 90°C at 0.4°C / min and kept at that temperature for 0.2h to obtain anti-HPV fabric.

[0037] The preparation process of anti-HPV virus fabric is as follows: Figure 1 As shown. The resulting fabric surface is loaded with hollow graphene oxide microspheres with a diameter of 1-2 micrometers. The microspheres contain sulfonated chitosan, and the total loading of the composite antiviral functional layer on the base fabric is 5 g / m². The microstructure of the hollow graphene oxide microspheres is shown in the figure. Figure 2 As shown, the fabric is composed of stacked graphene oxide nanosheets with a wrinkled surface and microspheres containing pores of several hundred nanometers, allowing HPV viruses to enter the hollow spheres. The fabric's antiviral activity against human papillomavirus (HPV-16) was tested, and the results showed that the fabric prepared in Example 1 of this invention had an inactivation rate of 99.95% against HPV-16.

[0038] Example 2 (1) Preparation of low oxidation degree graphene oxide nanosheets: graphene oxide nanosheets with a carbon-to-oxygen ratio of 10 and a size of 50~90nm were prepared by the modified Hummers method and dispersed in ethanol at a concentration of 2mg / mL. (2) Preparation of an aqueous solution containing sulfated oligosaccharides: Dissolve sulfated oligosaccharides in deionized water to prepare an aqueous solution with a solid content of 10%; (3) Preparation of emulsion: Take 50 mL of graphene oxide nanosheet dispersion obtained in step (1) (containing 100 mg of graphene oxide nanosheets) and 2 mL of sulfated oligosaccharide aqueous solution obtained in step (2) (containing 20 mg of sulfated oligosaccharide), add them to 300 mL of n-hexane, and disperse them at 8000 rpm for 8 minutes under ultrasonic assistance of 180 W to form a stable water-in-oil emulsion with a droplet diameter of 2-3 micrometers; (4) Atomization Adhesion: The polyester fabric is subjected to low-temperature plasma treatment to make the surface of the fabric positively charged. The emulsion obtained in step (3) is atomized by an ultrasonic atomization device with a power of 110 GHz and a flow rate of 1 mL / min, and is uniformly adhered to the plasma-treated fabric through the air duct.

[0039] (5) Slow heat treatment: The attached fabric is placed in an oven and slowly heated to 110℃ at 0.5℃ / min and kept at that temperature for 1 hour to obtain anti-HPV fabric.

[0040] The resulting fabric surface is loaded with hollow graphene oxide microspheres with a diameter of 2-3 micrometers. The microspheres contain sulfated oligosaccharides, and the total loading of the composite antiviral functional layer on the base fabric is 0.1 g / m². The microstructure of the hollow graphene oxide microspheres is as follows: Figure 3 As shown, the fabric is composed of stacked graphene oxide nanosheets with a wrinkled surface and microspheres containing pores of several hundred nanometers, allowing HPV viruses to enter the hollow spheres. The fabric's antiviral activity against human papillomavirus (HPV-16) was tested, and the results showed that the prepared fabric achieved a 94.1% inactivation rate against HPV-16.

[0041] Example 3 (1) Preparation of graphene oxide nanosheets with low oxidation degree: graphene oxide nanosheets with a carbon-to-oxygen ratio of 3 and a size of 270~300nm were prepared by the modified Hummers method and dispersed in ethanol at a concentration of 5mg / mL. (2) Preparation of heparin-containing aqueous solution: Dissolve heparin in deionized water to prepare an aqueous solution with a solid content of 5%; (3) Preparation of emulsion: Take 100 mL of graphene oxide nanosheet dispersion obtained in step (1) (containing 500 mg of graphene oxide nanosheets) and 10 mL of heparin aqueous solution obtained in step (2) (containing 50 mg of heparin), add them to 300 mL of n-hexane, and disperse them at 8000 rpm for 10 minutes under the assistance of 150 W ultrasound to form a stable water-in-oil emulsion with a droplet diameter of 4~5 micrometers; (4) Atomization Adhesion: The nylon fabric is subjected to low-temperature plasma treatment to make its surface positively charged. The emulsion obtained in step (3) is atomized by an ultrasonic atomization device with a power of 60 GHz and a flow rate of 1 mL / min, and is uniformly adhered to the plasma-treated fabric through an air duct.

[0042] (5) Slow heat treatment: The attached fabric is placed in an oven and slowly heated to 90°C at 1°C / min and kept at that temperature for 0.5h to obtain anti-HPV fabric.

[0043] The resulting fabric surface was loaded with hollow graphene oxide microspheres with a diameter of 4-5 micrometers. The microspheres contained heparin, and the total loading of the composite antiviral functional layer on the base fabric was 0.45 g / m². The antiviral activity of the fabric against human papillomavirus (HPV-16) was tested, and the results showed that the prepared fabric had an inactivation rate of 97.65% against HPV-16.

[0044] Example 4 (1) Preparation of low oxidation degree graphene oxide nanosheets: graphene oxide nanosheets with a carbon-to-oxygen ratio of 5 and a size of 150~200nm were prepared by the modified Hummers method and dispersed in ethanol at a concentration of 4mg / mL. (2) Preparation of an aqueous solution containing sulfated polysaccharide: Dissolve sulfated polysaccharide in deionized water to prepare an aqueous solution with a solid content of 5%; (3) Preparation of emulsion: Take 50 mL of graphene oxide nanosheet dispersion obtained in step (1) (containing 200 mg of graphene oxide nanosheets) and 20 mL of sulfated polysaccharide aqueous solution obtained in step (2) (containing 100 mg of sulfated oligosaccharide), add them to 400 mL of n-hexane, and disperse them at 10000 rpm for 15 minutes under ultrasonic assistance of 220 W to form a stable water-in-oil emulsion with a droplet diameter of 0.5~1 micrometer; (4) Atomization Adhesion: The viscose / cotton blended fabric is subjected to low-temperature plasma treatment to make the surface of the fabric positively charged, and then sprayed with a 2% concentration of KH570 aqueous solution and dried. The emulsion obtained in step (3) is atomized by an ultrasonic atomizing device with a power of 100 GHz and a flow rate of 2 mL / min, and uniformly adhered to the plasma-treated fabric through the air duct.

[0045] (5) Slow heat treatment: The attached fabric is placed in an oven and slowly heated to 90°C at 1°C / min and kept at that temperature for 0.2h to obtain anti-HPV fabric.

[0046] The resulting fabric surface was loaded with hollow graphene oxide microspheres with a diameter of 0.5–1 micrometer. The microspheres contained sulfated oligosaccharides, and the total loading of the composite antiviral functional layer on the base fabric was 0.42 g / m². The antiviral activity of the fabric against human papillomavirus (HPV-16) was tested, and the results showed that the prepared fabric had an inactivation rate of 97.3% against HPV-16.

[0047] Comparative Example 1 The difference from Example 1 lies in step (3), which uses a conventional dispersion method. Specifically, 50 mL of the graphene oxide nanosheet dispersion obtained in step (1) (containing 200 mg of graphene oxide nanosheets) and 2 mL of the sulfonated chitosan aqueous solution obtained in step (2) (containing 200 mg of sulfonated chitosan) are added to 200 mL of water and stirred until a mixed solution is obtained. The resulting fabric surface is covered with graphene oxide sheets, and the density of exposed edges is low. The antiviral activity of the fabric against human papillomavirus (HPV-16) was tested, and the results showed that the inactivation rate of the prepared fabric against human papillomavirus (HPV-16) was 73.1%, which was significantly lower than that in Example 1.

[0048] Comparative Example 2 The difference from Example 1 is that sulfonated chitosan was not added. The specific steps are as follows: (1) Preparation of low oxidation degree graphene oxide nanosheets: graphene oxide nanosheets with a carbon-to-oxygen ratio of 6 and a size of 270~300nm were prepared by the modified Hummers method and dispersed in ethanol at a concentration of 4mg / mL. (2) Preparation of emulsion: Take 50 mL of graphene oxide nanosheet dispersion obtained in step (1) (containing 200 mg of graphene oxide nanosheets) and 2 mL of water, add them to 200 mL of n-hexane, and disperse them at 10000 rpm for 10 minutes under the assistance of 200 W ultrasound to form a stable water-in-oil emulsion with a droplet diameter of 0.5~1 micrometer; (3) Atomization adhesion: The nylon fabric is subjected to low-temperature plasma treatment to make its surface positively charged. The emulsion obtained in step (2) is atomized by an ultrasonic atomization device with a power of 80 GHz and a flow rate of 1 mL / min, and is uniformly adhered to the plasma-treated fabric through the air duct.

[0049] (4) Slow heat treatment: The attached fabric is placed in an oven and slowly heated to 90°C at 0.4°C / min and kept at that temperature for 0.2h to obtain anti-HPV fabric.

[0050] The resulting fabric surface was loaded with hollow graphene oxide microspheres with a diameter of 0.5-1 micrometer. The antiviral activity of the fabric against human papillomavirus (HPV-16) was tested, and the results showed that the inactivation rate of the prepared fabric against human papillomavirus (HPV-16) was 83.35%, which was significantly lower than that in Example 1.

[0051] Comparative Example 3 The difference from Example 1 is that the slow heating was not performed.

[0052] Step (5) is as follows: The coated fabric is placed in an oven, heated to 90℃ at 10℃ / min and kept at that temperature for 0.2h to obtain an anti-HPV fabric.

[0053] Rapid heat treatment causes the moisture inside the microspheres to evaporate quickly, and the graphene oxide sheets collapse inward due to surface tension, undergoing a process similar to "wrapping a paper ball," encapsulating the HPV affinity-capturing components inside. Although the abundant edges of the graphene oxide sheets can inactivate the virus, the virus capture ability is greatly reduced. Testing the antiviral activity of the fabric against human papillomavirus (HPV-16) showed that the prepared fabric had an inactivation rate of 82.8% against HPV-16, which was still significantly lower than that of Example 1.

[0054] The above embodiments detail the structure, features, and effects of the present invention. The above descriptions are merely preferred embodiments of the present invention. Any changes made in accordance with the concept of the present invention, or equivalent embodiments modified to have equivalent variations, that do not exceed the scope covered by the specification should be within the protection scope of the present invention.

Claims

1. An anti-HPV virus fabric based on a graphene-based hollow sphere structure, characterized in that, The invention comprises a base fabric and a composite antiviral functional layer loaded on at least one surface, fiber surface, and / or fiber gaps of the base fabric; the composite antiviral functional layer comprises hollow graphene oxide microspheres and HPV affinity-capturing components, wherein the hollow graphene oxide microspheres have an open structure, are composed of graphene oxide nanosheets, and at least partially expose the edge regions of the graphene oxide sheets at the edges of the open structure; the hollow microspheres contain HPV affinity-capturing components, which are macromolecules containing sulfonic acid groups; the diameter of the hollow graphene oxide microspheres is 0.5~5 micrometers; the total loading of the composite antiviral functional layer on the base fabric is 0.1~5 g / m².

2. The anti-HPV virus fabric according to claim 1, characterized in that, The graphene oxide nanosheets have a carbon-to-oxygen ratio of 3 to 10 and a size of 50 to 300 nm.

3. The anti-HPV virus fabric according to claim 1, characterized in that, The macromolecule containing sulfonic acid groups is one or more of the following: sulfated polysaccharides, sulfated oligosaccharides, fucoidan, chondroitin sulfate, heparin or its analogues, sulfonated chitosan, sulfonated cellulose, sulfonated polyvinyl alcohol, sulfonated polystyrene or polymers containing sulfonate betaine.

4. The anti-HPV virus fabric according to claim 1, characterized in that, The base fabric is a fabric formed by weaving or non-woven processes from one or more of the following: cotton, viscose, lyocell, modal, nylon, polyester, polypropylene, polylactic acid fiber, and chitosan fiber.

5. A method for preparing an anti-HPV virus fabric as described in any one of claims 1-4, characterized in that, It includes the following steps: (1) Prepare graphene oxide nanosheets with a carbon-to-oxygen ratio of 3 to 10 and a size of 50 to 300 nm, and disperse them in ethanol to obtain a graphene oxide nanosheet dispersion. (2) Prepare an aqueous solution of macromolecules containing sulfonic acid groups with a solid content of 5% to 20%; (3) The graphene oxide nanosheet dispersion obtained in step (1) and the aqueous solution of macromolecules containing sulfonic acid groups obtained in step (2) are mixed in n-hexane. Under ultrasonic action, the graphene oxide nanosheets are sheared and dispersed to encapsulate the aqueous solution of macromolecules containing sulfonic acid groups, forming droplets with a diameter of 0.5~5 micrometers. The mixture is then dispersed in n-hexane as an emulsion. The mass ratio of graphene oxide nanosheets to macromolecules containing sulfonic acid groups is 1~10:

1. (4) The emulsion obtained in step (3) is atomized and then attached to the base fabric; (5) Place the attached base fabric into an oven, heat it to 90-110℃ at 0.4-1℃ / min and keep it warm for 0.2-1h to obtain anti-HPV virus fabric.

6. The method according to claim 5, characterized in that, In step (3), the mass ratio of graphene oxide nanosheets to n-hexane is less than 1:

100.

7. The method according to claim 5, characterized in that, In step (4), the atomization method is to use an ultrasonic atomizing device with an atomization power of 60~110GHz and a flow rate of 1~10mL / min.

8. The method according to claim 5, characterized in that, The base fabric described in step (4) is treated with low-temperature plasma.

9. The method according to claim 5, characterized in that, The substrate surface in step (4) is sprayed with a reactive crosslinking agent; the reactive crosslinking agent is selected from one or more of silane coupling agents, isocyanate compounds, epoxy compounds and polyamine compounds.

10. The application of the anti-HPV virus fabric as described in claim 1 in the preparation of underwear crotch fabric, sanitary napkin surface layer, and disposable protective fabric.

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