阅读说明：本技术 一种抗病毒微纳米纤维的制备方法 (Preparation method of antiviral micro-nano fiber ) 是由 季东晓 陈文静 张弘楠 王荣武 覃小红 于 2021-08-26 设计创作，主要内容包括：本发明涉及一种抗病毒微纳米纤维的制备方法。该方法包括：将金属有机框架纳米颗粒加入溶剂,超声分散,加入纺丝聚合物,与金属有机框架混合均匀得到胶体纺丝液,通过静电纺丝制备抗病毒纳米纤维。该方法制备得到的纤维具有有效灭活SARS-COV-2病毒、呼吸道细菌和真菌的功能。该纤维具有高比表面积和孔隙率,适用于病毒防护纺织品和抗病毒过滤等领域。(The invention relates to a preparation method of an antiviral micro-nanofiber. The method comprises the following steps: adding the metal organic framework nano particles into a solvent, performing ultrasonic dispersion, adding a spinning polymer, uniformly mixing with a metal organic framework to obtain a colloidal spinning solution, and preparing the antiviral nano fiber through electrostatic spinning. The fiber prepared by the method has the function of effectively inactivating SARS-COV-2 virus, respiratory bacteria and fungi. The fiber has high specific surface area and porosity, and is suitable for the fields of virus protection textiles, virus resistance filtration and the like.)

1. A preparation method of an antiviral micro-nanofiber comprises the following steps:

(1) adding a solvent into metal organic framework nano particles, performing ultrasonic dispersion, adding a spinning polymer, and uniformly mixing with a metal organic framework to obtain a colloidal spinning solution, wherein the weight ratio of the metal organic framework nano particles to the polymer is 1: 0.5-1: 100, the mass content of the metal organic framework nano particles in a solvent is 0.01-50%;

(2) and (3) performing electrostatic spinning on the spinning solution obtained in the step (1) to obtain the antiviral micro-nano fiber.

2. The method according to claim 1, wherein the metal organic framework nanoparticles in step (1) have a size ranging from 0.01 to 500 nm.

3. The preparation method according to claim 1, wherein the metal organic framework in the step (1) comprises one or more of a silver-based metal organic framework, a zinc-based metal organic framework, a copper-based metal organic framework, a tin-based metal organic framework, an iron-based metal organic framework and a nickel-based metal organic framework.

4. The method according to claim 1, wherein the solvent in the step (1) comprises: one or more of formic acid, tetrahydrofuran, water, dimethylformamide, dimethylacetamide, acetone, chloroform, cresol, dimethyl sulfoxide, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, toluene, methyl pyrrolidone and methyl ethyl ketone.

5. The method according to claim 1, wherein the polymer in the step (1) comprises: one or more of polyvinylidene fluoride, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyvinyl acetate, nylon 6, polyvinyl alcohol, polymethyl methacrylate, polyaniline, polyoxyethylene, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyethylene glycol, polyurethane, fluorinated polyurethane, polysulfone, polyether sulfone and polyvinyl butyral.

6. The preparation method according to claim 1, wherein the electrostatic spinning in the step (2) has the following process parameters: the spinning nozzle comprises: the spinning process is carried out in a high-voltage electrostatic field, the fiber receiver is movable or fixed, the voltage is 0-100kV, the voltage of the receiver is opposite to that of the spinneret, and the distance between the receiver and the spinneret is 5-40 cm.

7. The preparation method according to claim 1, wherein the diameter of the antiviral micro-nano fiber in the step (2) is 10nm-2 um.

8. An antiviral micro-nanofiber prepared by the preparation method of claim 1.

9. The application of the antiviral micro-nano fiber of claim 8 in inactivating SARS-COV-2.

Technical Field

The invention belongs to the field of functional fiber preparation, and particularly relates to a preparation method of an antiviral micro-nanofiber.

Background

The transmission of diseases such as common cold, influenza, tuberculosis and COVID-19 is mainly through biological aerosol in the air. Bioaerosols refer to colloidal systems formed from particulate matter, such as microorganisms, plant or animal debris, suspended in air. These atmospheric particulates include two main types: active bacteria, viruses, pollen, etc.; inactive biological suspensions such as endotoxins, mycotoxins, and allergenic proteins. The size, composition and concentration of aerosol particles in the atmosphere are related to the source of the particle suspension. The spread of bioaerosols with infectious properties has serious adverse effects on health and economic development around the world. For example, the outbreak of the new coronavirus, Severe acute respiratory syndrome coronavirus 2(SARS-CoV-2), in 2020, changed aspects of our daily lifestyle. The alarming increase in the number of infected patients and the rising mortality rate are alarming. The virus is extremely contagious and can be transmitted by respiratory droplets produced by sneezing and coughing by patients. The aerosol of the virus can float in the air for a long time, and the transmission of the virus is increased. And has good thermal stability and pH stability, and can stably survive on inanimate surfaces for several days, and the specific survival time depends on the properties of the substrate surface. These observations are in concert with rapid spread and superdissemination of the virus. Therefore, the use of masks and personal protective equipment to provide a physical barrier to individuals is an effective means of resisting the spread of respiratory aerosols. But the virus will still survive on the personal protective product, making these personal protective products a secondary source of infection. The use of antiviral materials, particularly antiviral materials effective against SARS-CoV-2, in personal protective products can solve this problem well.

By the end of 2020, COVID-19 has caused over 140 million deaths, and over 6000 million infections. The use of antiviral materials to block the pathway of SARS-COV-2 transmission is an effective means to reduce the transmission of COVID-19. However, few reports have been made to date on materials having an inactivating activity against SARS-COV-2 virus, especially fibrous materials. Fiber-based materials are among the most widely used materials. The micro-nano fiber has high specific surface area and adjustable porosity, so that the micro-nano fiber can show better performance in masks and personal protective articles, and is an important development direction. The development of the antiviral fiber material applied to protective articles has important significance for reducing infectious respiratory diseases and preventing and controlling epidemic situations.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of an antiviral micro-nanofiber so as to fill the blank in the prior art.

The invention provides a preparation method of an antiviral micro-nanofiber, which comprises the following steps:

(1) adding a solvent into metal organic framework nano particles, performing ultrasonic dispersion, adding a spinning polymer, and uniformly mixing with a metal organic framework to obtain a colloidal spinning solution, wherein the weight ratio of the metal organic framework nano particles to the polymer is 1: 0.5-1: 100, the mass content of the metal organic framework nano particles in a solvent is 0.01-50%;

(2) and (3) performing electrostatic spinning on the spinning solution obtained in the step (1) to obtain the antiviral micro-nano fiber.

Preferably, in the above method, the metal-organic framework nanoparticles in step (1) have a size ranging from 0.01 to 500 nm.

Preferably, in the above method, the metal-organic framework in step (1) includes one or more of a silver-based metal-organic framework, a zinc-based metal-organic framework, a copper-based metal-organic framework, a tin-based metal-organic framework, an iron-based metal-organic framework, and a nickel-based metal-organic framework.

Preferably, in the above method, the solvent in the step (1) comprises: one or more of formic acid, tetrahydrofuran, water, dimethylformamide, dimethylacetamide, acetone, chloroform, cresol, dimethyl sulfoxide, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, toluene, methyl pyrrolidone and methyl ethyl ketone.

Preferably, in the above method, the polymer in the step (1) comprises: one or more of polyvinylidene fluoride, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyvinyl acetate, nylon 6, polyvinyl alcohol, polymethyl methacrylate, polyaniline, polyoxyethylene, polyvinylpyrrolidone, polyacrylonitrile, polycaprolactone, polyethylene glycol, polyurethane, fluorinated polyurethane, polysulfone, polyether sulfone and polyvinyl butyral.

Preferably, in the above method, the polymer is completely dissolved and uniformly mixed by heating or stirring after the polymer is added in the step (1).

Preferably, in the above method, the process parameters of the electrostatic spinning in the step (2) are as follows: the spinning nozzle comprises: the spinning process is carried out in a high-voltage electrostatic field, the fiber receiver is movable or fixed, the voltage is 0-100kV, the voltage of the receiver is opposite to that of the spinneret, and the distance between the receiver and the spinneret is 5-40 cm.

Preferably, in the above method, the diameter of the antiviral micro-nano fiber in step (2) is 10nm-2 um.

Preferably, in the above method, the anti-virus micro-nanofibers in step (2) can be made into non-woven fabrics or yarns.

The invention also provides the antiviral micro-nano fiber prepared by the preparation method.

The invention also provides an application of the antiviral micro-nano fiber in inactivation of SARS-COV-2, such as preparation of an antiviral fabric, an antiviral filter membrane or an antiviral coating.

The invention uses metal-based materials such as metal organic framework as active materials for inactivating SARS-CoV-2. The loading of the metal-based material is realized by an electrostatic spinning method. The prepared fiber material has low diameter and high activity. The active ingredients have slow release effect, and long-acting protection is achieved. The fiber has light weight, and can greatly reduce the usage amount of antiviral materials.

As an application example, the antiviral micro-nanofiber prepared by the invention can be used as a filter element of an anti-virus mask. The mask has a filtering efficiency of more than 95% for 0.3 μm particles and a low filtering resistance. The micro-nano fiber material is suitable for various fields needing virus protection, and can be used for producing fabrics, filter membranes or antiviral coatings, including personal protection equipment, medical care facility coatings, food protection and the like.

Advantageous effects

(1) The strategy provided by the invention can be used for preparing a micro-nano fiber material for effectively inactivating SARS-COV-2 virus, respiratory bacteria and fungi. At present, reports about micro-nano fibers with inactivated SARS-COV-2 virus are not found. Compared with the traditional fiber material, the material can prevent the spread of virus and bacteria more effectively.

(2) The antivirus micro-nano fiber has high specific surface area and porosity. Their fibrous morphology enables them to be used in various fields where viral protection is required, for the production of fabrics, filtration membranes or antiviral coatings, including personal protective equipment, coatings for health care facilities and for food protection, etc.

Drawings

FIG. 1 is an electron photograph (a) of an anti-viral fiber membrane and the diameter of the fiber and the structure (b) of the fiber membrane under a scanning electron microscope in example 1.

FIG. 2 is the titer data of ZIF-8 micro-nanofiber in example 1 against SARS-COV-2.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Example 1

Preparing an antiviral mask filter element by using anti-SARS-COV-2 micro-nano fibers:

all chemicals were purchased from Sigma-Aldrich.

Synthesis of ZIF-8 metal organic framework nanoparticles: by mixing 17.8g Zn (NO)₃)₂·6H₂Solution A was prepared by dissolving O in 600mL of methanol. Solution B was prepared by dissolving 39.4g of 2-methylimidazole (2-MIM) in 400mL of methanol. Adding the solution A into the solution B, stirring for 1 minute, and then standing at room temperatureFor 24 hours. ZIF-8 nanoparticles were obtained by centrifugation at 8500rpm for 5 minutes and vacuum drying at 60 ℃.

Preparing ZIF-8 nano fibers: 0.6g of the prepared ZIF-8 nanoparticles was added to 5mL of N, N-Dimethylformamide (DMF). And (3) carrying out ultrasonic treatment on the solution to uniformly disperse ZIF-8 in the solution. To prepare the coating solution, 0.4g of polyacrylonitrile (PAN, Mw 150000) was dissolved in the solution by stirring at 60 ℃ for 4 hours. The ZIF-8 nanofibers were made by electrospinning. The high pressure, feed rate, temperature and distance between the spinneret and the collector were fixed at 10kV and 0.2mL h, respectively^-122 ℃ and 15 cm. The needles are moved laterally to increase the uniformity of the resulting nanofiber nonwoven using a conductive flat plate as a collector.

Antiviral testing: SARS-CoV-2(hCoV-19/Singapore/2/2020) was propagated in Vero-E6 cells maintained in Dulbecco's modified Eagle's medium with 5% fetal bovine serum (DMEM-5% FBS). To prepare the viral stock, the confluent cell monolayer was infected with SARS-CoV-2 and incubated at 37 ℃ with 5% CO₂The lower incubation took up to 7 days. When cytopathic effect (CPE) was evident under the microscope, the supernatant was collected, clarified by centrifugation, and stored at-80 ℃.

Inoculating the fabric: pieces of fabric measured 1x 1cm were cut and placed into individual wells of a 24-well plate, including virus-containing control wells without fabric.

For SARS-CoV-2 detection, 50. mu.L of 1x 10 was added⁵TCID50/ml virus was dropped onto the fabric piece. The fabric was exposed to the virus at 4 ℃ for 0, 1 and 24 hours. After the contact time, 1ml of DMEM-5% FBS was added to the wells and the solution was aspirated.

The samples were titrated by limiting dilution, and the titer was calculated using Spearman-Median tissue culture infectious dose (TCID50/mL) for the method.

And (3) antibacterial testing: the following microbial strains were used:

gram-positive bacterial strains: staphylococcus Aureus (SA)29213(ATCC), methicillin-resistant staphylococcus aureus (MRSA) and MRSA21595 (from wounds); gram-negative strains: pseudomonas Aeruginosa (PA)9027(ATCC) and pseudomonas aeruginosa 27853 (ATCC);

fungus strain: aspergillus fumigatus ATCC 90906 and fusarium solani ATCC 46492.

The antimicrobial performance of the various manufactured samples was evaluated according to the Clinical and Laboratory Standards Institute (CLSI) using the Kirby-Bauer radial disk diffusion method. Gram-positive and gram-negative bacterial cultures (0.5 McFarland standard) were spread on the surface of sterile mueller-in-agar (MHA) plates using cotton swabs, using petri dishes with a diameter of 9 cm. To evaluate the antifungal efficacy of the fabric, a fungal culture (concentration of 0.5McFarland standard) was coated on the surface of sterile Sabouraud glucose agar (SDA) plates. A piece of fabric (1 cm. times.1 cm) was placed on top of the culture and incubated in MHA (bacteria) and SDA (fungi) at 35 ℃. + -. 2 ℃ for 24 hours. The antimicrobial activity of these samples was determined by the presence of a significant zone of inhibition. The assay was performed in two separate experiments and the mean zone of inhibition values were calculated.

Testing the filtering performance of the mask: the nanofiber nonwoven was evaluated for filtration efficiency and pressure drop using an automatic filtration tester (model 8130, TSI Group). Aqueous sodium chloride solution was used to generate spray droplets of about 260 nm. The effective area of the aerosol passing through is 100cm²All filtration tests were carried out at room temperature at an air flow rate of 32L/min to 85L/min (NIOSH-42CFR84 Standard specifies that achieving a N95 rating requires achieving it at 85L/min test conditions>Filtration efficiency of 95% and<a pressure drop of 245 Pa).

And (3) testing results: depending on the weight of the fiber, the filtration efficiency of the fiber membranes for particles with a size of 0.3um is in the range of 50-99.999%. The filtration resistance is in the range of 60-400 Pa. The gram weight is 0.36g/m²When the mask is used (the gram weight is adjusted through the spinning time, the spinning time is 10 minutes), the filtering efficiency is more than 95 percent, the filtering resistance is less than 120Pa, and the mask meets the requirements of an N9 mask. The ZIF-8 containing filter membrane showed significant virus inactivation. For SARS-COV-2, the infectious titer was 10 compared to the control sample^4.2TCID50/mL is reduced to 10^2.5TCID 50/mL. In addition, the ZIF-8 fabric can be kept lowWorking at room temperature. After 1 hour and 24 hours of SARS-COV-2 virus inoculation at 4 ℃, the infection titer was further reduced to 10^1.5TCID50/mL and 10TCID 50/mL. The result shows that the ZIF-8 micro-nano fiber filter membrane has the characteristic of well inactivating SARS-CoV-2. Meanwhile, the inhibition zone test proves that the ZIF-8 micro-nano fiber filtering membrane also has broad-spectrum antibacterial property (Table 1).

TABLE 1 antibacterial property of ZIF-8 micro-nanofiber fabric