CN113527676B

CN113527676B - Covalent organic framework material and preparation method and application thereof

Info

Publication number: CN113527676B
Application number: CN202110758986.9A
Authority: CN
Inventors: 董育斌; 姚丙建; 丁罗刚; 胡一宁; 侯承辛; 于颖超
Original assignee: Shandong Normal University
Current assignee: Shandong Normal University
Priority date: 2021-07-05
Filing date: 2021-07-05
Publication date: 2023-05-23
Anticipated expiration: 2041-07-05
Also published as: CN113527676A

Abstract

The present disclosure relates to the field of porous organic framework materials, and in particular provides a covalent organic framework material, and a preparation method and application thereof. The covalent organic framework material has a structure shown in a formula (1),

the preparation method comprises the following steps: in a reaction solvent, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2, 5-dihydroxyl terephthalaldehyde and pyruvic acid are taken as monomers, a crude product is obtained after heating reaction for a period of time under the action of a catalyst, and after cooling to room temperature, the crude product is centrifugally separated, purified and dried in vacuum to obtain a purplish red product. Solves the problems that the COF material is not fully developed and utilized in the prior art; and the prior art mask generally only can block viruses, has little capability of killing bacteria or viruses, and is generally a disposable mask.

Description

Covalent organic framework material and preparation method and application thereof

Technical Field

The present disclosure relates to the field of porous organic framework materials, and in particular provides a covalent organic framework material, and a preparation method and application thereof.

Background

The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.

Due to its permanent porosity, highly ordered and expanded structure, good chemical stability and adjustable functionality, covalent Organic Frameworks (COFs) have important application prospects in the fields of catalysis, separation, sensing, nanomedicine and the like. However, conventional COF materials are mostly formed by dynamic reversible bonds such as imine bonds, and have poor stability in strong acid, strong alkali or reductive chemical environments. In order to expand the bonding type of COF materials and improve the chemical stability of COF materials, more and more linking units and construction methods have been reported. In order to make the synthesis method of Covalent Organic Frameworks (COFs) more complete, developing a new synthesis method, constructing COF materials with high chemical stability, and using potential functionalization sites in the framework to realize their functionalization and high-efficiency application in harsh chemical environments is a challenge to be solved.

The multicomponent reaction is to add three or more raw materials into a reaction system, directly obtain a final product with a complex structure in a one-pot mode without separation and purification of intermediates, and the multicomponent reaction shows high atom economy and is considered as an effective means for synthesizing molecular diversity and complexity. The Doebner reaction is discovered by German chemist Oscar Gustav Doebner, and quinoline-4-formic acid is generated by the reaction of three components of aromatic amine, aromatic aldehyde and alpha-carbonyl acid under the conditions of small heating and acid catalysis. The Doebner reaction can be used as a classical example of constructing the COF material by multi-component reaction to explore the benefit of a huge organic name reaction database, and the obtained COF material has high specific surface area, is rich in carboxylic acid groups, can chelate silver ions, and has important application prospect in the aspect of multifunctional antibiosis.

When a new crown epidemic situation is caused, the mask becomes an essential part of epidemic prevention materials, can provide a barrier for us, and prevents harmful bacteria or viruses from invading human bodies in a manner of spray, close contact and the like. The inventor finds that the existing mask can only meet the basic requirement of blocking bacteria or viruses to a certain extent, but has almost no capability of killing bacteria or viruses, and is mostly used as disposable materials, cannot be used for a plurality of times for a long time, and serious resource waste and waste accumulation are caused.

Disclosure of Invention

Aiming at the problem that the COF material in the prior art is not fully developed and utilized; and the prior art mask generally only can block viruses, has little capability of killing bacteria or viruses, and is generally a disposable mask.

In one or some embodiments of the present disclosure, there is provided a covalent organic framework material having a structure as shown in formula (1),

in one or some embodiments of the present disclosure, there is provided a method of preparing a covalent organic framework material comprising performing the following reaction:

in one or more embodiments of the present disclosure, a COF-Ag material is provided, comprising a supported Ag ⁺ The COF material is the covalent organic framework material or the product prepared by the preparation method of the covalent organic framework material.

In one or some embodiments of the present disclosure, a preparation method of the COF-Ag material described above is provided, including the steps of: and (3) taking the covalent organic framework material or a product prepared by the preparation method of the covalent organic framework material as a raw material, reacting with silver nitrate, and after the reaction is finished, centrifugally separating, purifying and vacuum drying the crude product to obtain the product COF-Ag.

In one or some embodiments of the disclosure, there is provided an application of the COF-Ag material or the product prepared by the preparation method of the COF-Ag material in preparing an antibacterial and antivirus medicament.

In one or some embodiments of the disclosure, an antibacterial and antivirus protective mask is provided, which uses a nonwoven fabric as a substrate, wherein one surface of the nonwoven fabric is covered with the COF-Ag material or a mixture of a product obtained by the preparation method of the COF-Ag material and a polymer organic matter.

In one or some embodiments of the present disclosure, a method for preparing the antibacterial and antivirus protective mask is provided, including the following steps: after the COF-Ag material or the product prepared by the preparation method of the COF-Ag material is evenly doped with high molecular organic matters physically, a stable composite film system is formed on non-woven fabrics by a spraying method, and then the stable composite film system is subjected to vacuum drying treatment to obtain a nano crystal composite film material, and then the nano crystal composite film material is cut to prepare the antibacterial and antivirus protective mask.

One or some of the above technical solutions have the following advantages or beneficial effects:

1) The COF material with high-efficiency and multifunctional antibacterial and antiviral properties is used as a coating, the device is realized, the COF material is used as an antibacterial and antiviral protective mask, and experiments prove that the mask disclosed by the invention has antibacterial and antiviral effects, realizes sterilization and disinfection of the mask instead of simple virus blocking, avoids resource waste caused by using a disposable mask, and provides a new thought for saving resources and realizing multiple functions of epidemic prevention materials.

2) The method for constructing the high-stability COF material by adopting the multi-component reaction of the covalent organic framework material adopts a three-component one-pot Doebner reaction, takes tetraminoporphyrin, aromatic dialdehyde and alpha-carbonyl acid as monomers, and simply synthesizes the COF material containing quinoline-4-formic acid structural units. The reaction can be completed in one step, the method is simple, the cost is low, and a new application of the COF material is opened up.

3) The COF-Ag material realizes the loading of the COF material with Ag ⁺ The COF material has certain activity and can be prepared by one-step reaction, and the method is simple.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate and explain the exemplary embodiments of the disclosure and together with the description serve to explain the disclosure, and do not constitute an undue limitation on the disclosure.

FIG. 1 is a schematic diagram of a synthetic route for small molecules of example 1 of the present disclosure

FIG. 2 is an infrared spectrogram of a small molecule model of example 1 of the present disclosure;

FIG. 3 is a schematic illustration of a model small molecule of example 1 of the present disclosure ¹ H-NMR spectrum;

FIG. 4 is a schematic illustration of a model small molecule of example 1 of the present disclosure ¹³ C-NMR spectrum

FIG. 5 is a HRMS spectrum of a model small molecule of example 1 of the present disclosure;

FIG. 6 is a photograph of a sample of the product COF of example 2 of the present disclosure;

FIG. 7 is an infrared spectrum of the product COF of example 2 of the present disclosure;

FIG. 8 is a powder diffraction PXRD spectrum of product COF of example 2 of the present disclosure;

FIG. 9 is an SEM image of the COF product of example 2 of the present disclosure;

FIG. 10 is a photograph of a sample of the product COF-Ag of example 3 of the present disclosure;

FIG. 11 is a powder diffraction PXRD spectrum of COF-Ag of example 3 of the present disclosure;

FIG. 12 is a SEM image of COF-Ag of example 3 of the present disclosure;

fig. 13 is an XPS diagram of Ag element in COF-Ag of example 3 of the present disclosure;

FIG. 14 is a graph of the DPBF ultraviolet absorbance change spectrum of example 4 of the present disclosure;

FIG. 15 is an image of a staphylococcus aureus colony before and after the COF-Ag antibacterial in example 5 of the present disclosure;

FIG. 16 is a graph showing the bacteriostatic effect of COF-Ag of example 5 of the present disclosure on Staphylococcus aureus;

FIG. 17 is a live/dead activity assay of Staphylococcus aureus before and after COF-Ag antibacterial in example 5 of the present disclosure;

FIG. 18 is immunofluorescence of COF-Ag treated vesicular stomatitis virus of example 6 of the present disclosure;

FIG. 19 is an antiviral effect of COF-Ag in example 6 of the present disclosure before and after treatment of vesicular stomatitis virus;

fig. 20 is a photograph of a COF-Ag type antimicrobial and antiviral adult mask sample of example 7 of the present disclosure.

Fig. 21 is a photograph of a simulation experiment of antibacterial and antiviral activity of a COF-Ag type antibacterial and antiviral adult mask according to example 8 of the present disclosure.

Fig. 22 is a graph showing the bacteriostatic effect of COF-Ag type antimicrobial and antiviral adult masks of example 8 of the present disclosure against staphylococcus aureus.

Fig. 23 shows the antiviral effect of COF-Ag type antimicrobial and antiviral adult mask of example 8 of the present disclosure before and after treatment of vesicular stomatitis virus.

Detailed Description

The following will clearly and fully describe the technical solutions in the embodiments of the present disclosure, and it is apparent that the described embodiments are only some embodiments of the present disclosure, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of this disclosure without making any inventive effort, are intended to be within the scope of this disclosure.

from the reaction equation of the invention, the method for constructing the high-stability COF material by adopting the multi-component reaction of the covalent organic framework material adopts a three-component one-pot Doebner reaction, and adopts tetraminoporphyrin, aromatic dialdehyde and alpha-carbonyl acid as monomers to simply synthesize the COF material containing quinoline-4-formic acid structural units.

Preferably, the method comprises the following steps: in a reaction solvent, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2, 5-dihydroxyl terephthalaldehyde and pyruvic acid are taken as monomers, a crude product is obtained after heating reaction for a period of time under the action of a catalyst, and after cooling to room temperature, the crude product is centrifugally separated, purified and dried in vacuum to obtain a purplish red product.

Preferably, the reaction solvent is one of acetonitrile, dioxane and DMF; preferably, the reaction solvent is acetonitrile;

or, the catalyst is one of p-toluenesulfonic acid, acetic acid and sulfamic acid; preferably, the catalyst is acetic acid;

or, the heating temperature is 100-150 ℃, preferably 120 ℃;

or, the monomer mole ratio of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2, 5-dihydroxyl terephthalaldehyde and pyruvic acid is 1:1-2:3-6;

preferably, the monomer mole ratio of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2, 5-dihydroxyterephthalaldehyde and pyruvic acid is 1:1.5:3.6;

or, the reaction time is 3-7 days, preferably, the reaction time is 5 days;

or, the purification method is to wash in ethanol, tetrahydrofuran and acetone for three times in sequence;

or vacuum drying for 20-30 hr at 50-70deg.C; preferably, the vacuum drying time is 24 hours, and the drying temperature is 60 ℃;

in one or more embodiments of the present disclosure, a COF-Ag material is provided, comprising a supported Ag ⁺ The COF material is the covalent organic framework material or the preparation method of the covalent organic framework materialThe product is prepared.

Preferably, the molar ratio of carboxylic acid groups to silver nitrate in the COF material is 1:1.5-3; preferably, the concentration of silver nitrate in the reaction system is 0.1M;

or, the reaction time is 12 to 36 hours, preferably, the reaction time is 12 hours;

or, the COF material reacts with silver nitrate in a reaction solvent, wherein the reaction solvent is ethanol, methanol, water or one of two mixed solvents;

preferably, the reaction solvent is a mixture of water and ethanol; further preferably, the volume ratio of water to ethanol is 1:1, a step of;

or, the reaction temperature is 0-80 ℃; preferably, the reaction temperature is 25 ℃;

or, the purification method is that ethanol and water are washed in sequence, preferably, 3 times of washing are carried out respectively;

alternatively, the vacuum drying time is 20 to 30 hours, the drying temperature is 70 to 100 ℃, preferably, the vacuum drying time is 24 hours, and the drying temperature is 80 ℃.

Adding the COF-Ag material with certain mass into a culture solution, carrying out ultrasonic treatment until the COF-Ag material is uniformly dispersed, respectively adding the COF-Ag material into the culture solution containing bacteria or viruses with certain concentration, irradiating the culture solution for a certain time under visible light, and then measuring the bacterial liquid OD value and the viral titer of the treated bacterial liquid or virus culture solution to determine the concentration of the bacteria or viruses in the bacterial liquid or virus so as to characterize the antibacterial and virus killing efficiency of the COF-Ag material.

The power density of the test visible light is 10-60mW/cm ² 。

Preferably, the power density of the visible light of the measuring system is 43.5mW/cm ² 。

The test conditions are as follows: sterile, 25℃

Preferably, the bacterium escherichia coli or staphylococcus aureus is one or a mixture of two, and the virus is one or a mixture of two of vesicular stomatitis virus and influenza virus;

further preferably, the bacterium is staphylococcus aureus and the virus is vesicular stomatitis virus.

In one or some embodiments of the disclosure, an antibacterial and antivirus protective mask is provided, which uses a non-woven fabric as a substrate, wherein one surface of the non-woven fabric is covered with the COF-Ag material or a mixture of a product prepared by the preparation method of the COF-Ag material and a polymer organic matter;

preferably, the nonwoven fabric is PET;

preferably, the polymer organic matter is polyurethane.

In one or some embodiments of the present disclosure, a method for preparing the antibacterial and antivirus protective mask is provided, including the following steps:

after the COF-Ag material or the product prepared by the preparation method of the COF-Ag material is evenly doped with high molecular organic matters physically, a stable composite film system is formed on non-woven fabrics by a spraying method, and then the stable composite film system is subjected to vacuum drying treatment to obtain a nano crystal composite film material, and then the nano crystal composite film material is cut to prepare the antibacterial and antivirus protective mask.

Preferably, the polymer organic matter is polyurethane, and the non-woven fabric is PET;

preferably, the PET and COF-Ag materials are mixed according to the mass ratio of 10-80:10-80 parts;

preferably, the physical blending and mixing process is performed in a solvent, wherein the solvent is one or more of azodicarbonamide, dichloromethane, methanol and ethanol, and more preferably, the solvent is dichloromethane;

preferably, the mixing temperature is 10-50 ℃, and more preferably, the mixing temperature is 25 ℃;

or vacuum drying for 20-30 hours at 70-100deg.C, preferably for 24 hours at 80deg.C;

preferably, the mixing process also comprises an ultrasonic dispersion and stirring step;

preferably, the method further comprises the following steps: the three functional layers are sequentially overlapped and stitched from outside to inside, and then four corner bands are stitched to obtain the antibacterial and antivirus protective mask.

The performance test steps of the preferred COF-Ag type antibacterial and antiviral adult mask are as follows: bacterial and viral aerosols were used as model aerosols for evaluating the antibacterial and antiviral properties of COF-Ag protective masks, and the top layer of commercial masks was used as a control group. The method comprises the steps of exposing the top layer of a COF-Ag type antibacterial and antivirus adult mask to an aerosol flow of bacteria or viruses, then irradiating with visible light, and finally fully washing the top layer of the mask with physiological saline solution to obtain a treated bacterial suspension and a treated virus suspension. For bacteria (s.aureus), the antibacterial activity was characterized by measuring the OD value photometrically at 600 nm. For the virus (VSV-GFP), the average titer of the samples was determined and the virucidal activity was characterized. All experiments were repeated 3 times.

Preferably, the model infection aerosol is an aerosol of staphylococcus aureus (s. Aureus) and vesicular stomatitis virus (VSV-GFP) as model infection aerosol.

The power density of the test visible light is 10-60mW/cm ² 。

The test conditions are as follows: sterile, 25 ℃.

Example 1

The preparation method of the model small molecule comprises the following steps:

round bottom flask (50 mL), benzaldehyde (1.0 mmol), aniline (1)2 mmol) and pyruvic acid (1.0 mmol), ethanol (25 mL). After stirring for 10 minutes, p-toluenesulfonic acid (p-TSA 10%0.1 mmol) was added as a catalyst, and the reaction mixture was refluxed (80 ℃ C.) for 3 hours after the catalyst was added. The reaction mixture was monitored by thin layer chromatography (n-hexane: ethyl acetate 1:1). After the reaction was completed, it was cooled to room temperature, and then the reaction mixture was poured into ice water, and the crude product and all the derivatives were collected and purified by chromatography. Obtaining the model small molecule. FIG. 1 shows the synthesis route of model small molecules, and FIGS. 2, 3, 4 and 5 show FT-IR, respectively, of model small molecules, ¹ H-NMR、 ¹³ C-NMR and HRMS spectra. Successful preparation of model small molecules demonstrates the feasibility of the reaction.

Example 2

The preparation method of the covalent organic framework material comprises the following steps:

2, 5-dihydroxyterephthalaldehyde (13.3 mg,0.08 mmol), 5,10,15, 20-tetra (4-aminophenyl) porphyrin (27 mg, 0.04 mmol), o-dichlorobenzene (o-DCB)/n-butanol (n-BuOH) (1/1, 2 mL) in solution, pyruvic acid (14. Mu.L, 0.2 mmol) were sonicated for 10 minutes, p-toluenesulfonic acid monohydrate (0.38 mg,0.02 mmol) was added, acetic acid (6M, 0.3 mL) was added and heated at 120℃for 7 days to obtain a purplish red solid powder, the crude product material obtained was washed three times in ethanol, tetrahydrofuran, acetone, respectively, and centrifuged and dried in vacuo to obtain the product COF-Ag. The characterization of the COF materials thus synthesized proves that the COF materials have a highly crystalline and porous framework structure, as shown in fig. 6, 7, 8 and 9, respectively, are a sample photograph, an infrared spectrum, an XRD spectrum and an SEM photograph of the COF materials.

Example 3

Post-synthesis modification of covalent organic framework materials:

200mg of the COF material and the covalent organic framework material are added into 0.1M AgNO ₃ (H ₂ O/ethanol=1:1) 25mL, and stirred at room temperature for 12h. And then washing the mixture in ethanol and water for three times, and obtaining the product COF-Ag after centrifugal separation and vacuum drying at 80 ℃ for 24 hours. Fig. 10, 11, 12 are XRD spectrum and SEM picture of sample photo of COF material, respectively. Ag (silver) ⁺ The content is 2.31mg/L measured by ICP, and the value of the COF material Ag isThe state is unchanged as shown in fig. 13. The characterization proves that the synthesized COF-Ag material still maintains high crystallization.

Example 4

Photodynamic properties of covalent organic framework materials:

10ml of a 10mM solution of DPBF in DMF was dissolved in 10mM LDMF and the mixture was stirred uniformly by ultrasonic treatment, and the mixture was placed in a stirrer (500W, xenon lamp, 15cm,43.5 mM W/cm) ² ) Under light conditions, 100uL of sample was sampled every 1min, the sampled was calibrated to 5ml with DMF, and 3ml of the DPBF solution after test treatment was sampled for its change in ultraviolet absorbance (at 414 nm). FIG. 14 shows the change in UV absorbance (at 414 nm) with increasing irradiation time for DPBF solutions with addition of COF-Ag (left) and untreated (right), respectively. DPBF photodegradation experiments of the COF-Ag prove that the synthesized COF-Ag material has a good singlet oxygen generation effect, and further proves that the COF-Ag has photodynamic performance.

Example 5

Antibacterial property study of covalent organic framework materials:

represented by Staphylococcus aureus (S.aureus) for evaluating COF-Ag material under visible light (500W, xenon lamp, 15cm,43.5 mW/cm) ² ) The antibacterial activity below. Briefly, a given bacterium was shake-cultured to a desired density in Luria-Bertani medium at 37 ℃. Concentration is set to 10 ⁸

CFU mL

^-1 500. Mu.L of the diluted bacterial solution was spread on a 16-well culture plate, and a PBS solution (1 mg, 500. Mu.L) for sterilizing COF-Ag was added thereto, followed by irradiation with visible light for 30 minutes. After washing with 10mL of a physiological saline solution having a concentration of 0.9% (w/v), the suspension was removed and dispersed in a sterilized tube by a double serial dilution method. Then, 100. Mu.L of the sample was placed in a sterilized solution, 100. Mu.L of the sample in a sterilized tube was inoculated on a nutrient agar plate, incubated at 37℃for 12 hours, and the antibacterial property was visually observed, and the OD value was determined by measuring the photometry at 600 nm. Antibacterial activity is expressed as the percentage of viable bacteria count in the blank. The blank was OD-measured photometrically at 600nm with a sample placed at sterile 25 ℃ for only 30min without any treatment in the absence of light, as shown in fig. 15, 16. All antibacterial experiments were repeated 3 times to eliminateAnd (5) dividing experimental errors. In addition, fluorescence observations of live/dead bacteria before and after irradiation with visible light were performed on COF-Ag experimental groups using Calcein-AM/PI double-stain kit (Everbright inc.) as shown in fig. 17. The antibacterial activity of the COF-Ag on staphylococcus aureus is proved to be as high as 99% by characterization and calculation of the antibacterial activity of the COF-Ag under the illumination condition, so that the COF-Ag has good antibacterial performance.

Example 6

Antiviral property study of covalent organic framework materials:

evaluation of COF-Ag Material on visible light (500W, xenon lamp, 15cm,43.5 mW/cm) typified by vesicular stomatitis Virus ² ) The following virus killing activity. The concentration was set at 4X 10 ⁶ PFU/mL of VSV-GFP virus solution (500. Mu.L) was added to a 12-well plate, followed by addition of sterilized PBS solution of COF-Ag (1 mg, 500. Mu.L), and then irradiated with visible light for 60min. Centrifugation, taking 0.5mL of supernatant, adding to a monolayer-grown HeLa cell dish, after 1h of infection, discarding the inoculum, culturing at 37℃for 12h, and photographing with an Olympus IX73 microscope. After 3 freeze-thawing cycles, the cell debris was removed by centrifugation at 4℃and the average titer of the samples was determined and the virucidal activity was expressed as a percentage of the blank. The blank was photographed with an Olympus IX73 microscope and the average titer of the samples was determined by leaving the samples without any treatment for 60min at 25 ℃ without any light, all experiments were repeated 3 times. As shown in fig. 18 and 19, the characterization and calculation of the virus killing activity of the COF-Ag under the illumination condition prove that the killing rate of the COF-Ag vesicular stomatitis virus is as high as 99%, which proves that the COF-Ag has good virus killing performance.

Example 7

Mechanization of covalent organic framework materials:

polyurethane (1 g) was dissolved in 300mL DCM, stirred at room temperature to a homogeneous solution, 300mL was taken and 300mg of COF-Ag was added and sonicated for 30min until homogeneous. Spraying onto 16.8cm×17.5cm (about 700 mg) nonwoven fabric, standing for 30min, vacuum drying at 80deg.C for 6 hr, taking the nonwoven fabric as the outermost layer, taking commercial polypropylene melt-blown nonwoven fabric as adsorption barrier layer, taking commercial water-repellent and skin-friendly polypropylene spun-bonded nonwoven fabric as inner layer, sequentially stacking and sewing three functional layers from outside to inside, and sewing four corner bands to obtain COF-Ag type antibacterial and antiviral adult mask, as shown in figure 20.

Example 8

Performance study of protective mask:

the antibacterial and antiviral properties of COF-Ag protective masks were evaluated with a sol of staphylococcus aureus (s. Aureus) and vesicular stomatitis virus (VSV-GFP) as model infectious aerosol representations and with the top layer of commercial masks as control group. At a concentration of 10 ⁸ CFU m L ^-1 Bacterial suspension and concentration of 4X 10 ⁶ The PFU/mL virus solutions respectively generate aerosols with diameters of 1-5 μm (median particle diameter of 3.9 μm) as model infection aerosols. Exposing the top layer of COF-Ag type antibacterial and antivirus adult mask to 0.2 mL min ^-1 For 5min in an aerosol stream of bacteria or viruses, then at 43.5mW cm ^-2 The top layer of the mask was washed thoroughly with 20 ml of 0.9% (w/v) physiological saline solution after irradiation with visible light for 90min, and the apparatus was as shown in fig. 21. For bacteria (s. Aureus), the suspension removed is dispersed in sterilized tubes by double serial dilution. Then, 100. Mu.L of the sample was placed in a sterilized solution, and incubated at 37℃for 12 hours in a sterilized tube, and the antibacterial activity was characterized by measuring the OD value by photometry at 600 nm. Antibacterial activity is expressed as a percentage of the number of viable bacteria in the control group. The control group was a commercial mask to photometry OD values at 600nm with the same treatment, as shown in fig. 22. For virus (VSV-GFP), the suspension was removed, centrifuged, and the supernatant was added to 0.5mL of the dish of HeLa cells which had been fully grown with a monolayer, and after 1 hour of infection, the inoculum was discarded, and after 12 hours of incubation at 37℃and 3 freeze-thawing cycles, the cell debris was removed by centrifugation at 4℃and the average titer of the samples was determined, and the virus-killing activity was characterized. The virucidal activity is expressed as a percentage of the control group. The control group was a commercial mask to determine the average titer of the samples under the same treatment as shown in fig. 23. All experiments were repeated 3 times. The characterization and calculation of the antibacterial and antiviral activity of the top layer of the COF-Ag type antibacterial and antiviral adult mask under the 90min illumination condition prove that the COF-Ag type antibacterial and antiviral adult mask is used for treating RNA water bubbles transmitted through sprayThe killing rate of the sexual stomatitis virus is up to 98 percent, and the killing rate of the gram-positive staphylococcus aureus transmitted through the air is up to 99 percent, which indicates that the COF-Ag has good antibacterial and virus killing performance.

The foregoing disclosure is merely illustrative of the presently preferred embodiments of the disclosure and is, of course, not to be construed as limiting the scope of the disclosure, for the purpose of describing and claiming equivalent variations thereto, which fall within the scope of the disclosure.

Claims

1. A covalent organic framework material is characterized in that the structure is shown as a formula (1),

2. a method for preparing a covalent organic framework material, comprising the steps of:

3. the method of preparing a covalent organic framework material of claim 2, comprising the steps of: in a reaction solvent, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2, 5-dihydroxyl terephthalaldehyde and pyruvic acid are taken as monomers, a crude product is obtained after heating reaction for a period of time under the action of a catalyst, and after cooling to room temperature, the crude product is centrifugally separated, purified and dried in vacuum to obtain a purplish red product.

4. The method for preparing a covalent organic framework material according to claim 3, wherein the reaction solvent is one of acetonitrile, dioxane and DMF;

or, the catalyst is one of p-toluenesulfonic acid, acetic acid and sulfamic acid;

or, the heating temperature is 100-150 ℃;

or, the reaction time is 3-7 days;

or vacuum drying for 20-30 hr at 50-70deg.C.

5. The method of preparing a covalent organic framework material of claim 4 wherein the reaction solvent is acetonitrile.

6. The method of preparing a covalent organic framework material of claim 4 wherein the catalyst is acetic acid.

7. The method of preparing a covalent organic framework material of claim 4 wherein the heating temperature is 120 ℃.

8. The method of preparing a covalent organic framework material of claim 4, wherein the monomer molar ratio of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, 2, 5-dihydroxyterephthalaldehyde, and pyruvic acid is 1:1.5:3.6.

9. The method of preparing a covalent organic framework material of claim 4 wherein the reaction time is 5 days.

10. The method of preparing a covalent organic framework material of claim 4 wherein the vacuum drying time is 24 hours and the drying temperature is 60 ℃.

11. A COF-Ag material comprising a carrier of Ag ⁺ The COF material of (2) is as claimed in1 or the product of the method of preparing a covalent organic framework material of any one of claims 2-10.

12. The method for producing the COF-Ag material of claim 11, comprising the steps of: the covalent organic framework material of claim 1 or the product prepared by the preparation method of the covalent organic framework material of any one of claims 2-10 is taken as a raw material to react with silver nitrate, and after the reaction is finished, the crude product is subjected to centrifugal separation, purification and vacuum drying, so that the product COF-Ag is obtained.

13. The method for producing a COF-Ag material according to claim 12, wherein the molar ratio of the carboxylic acid group to silver nitrate in the COF material is 1:1.5 to 3;

or, the reaction time is 12-36 hours;

or, the reaction temperature is 0-80 ℃;

or, the purification method is that ethanol and water are washed in sequence;

or vacuum drying for 20-30 hr at 70-100deg.C.

14. The method for producing a COF-Ag material of claim 13, wherein the concentration of silver nitrate in the reaction system is 0.1M.

15. The method of producing a COF-Ag material of claim 13, wherein the reaction time is 12 hours.

16. The method of preparing a COF-Ag material of claim 13, wherein the COF material reacts with silver nitrate in a reaction solvent, the reaction solvent being a mixture of water and ethanol.

17. The method of producing a COF-Ag material of claim 16, wherein the volume ratio of water to ethanol is 1:1.

18. the method of producing a COF-Ag material of claim 13, wherein the reaction temperature is 25 ℃.

19. The method of producing a COF-Ag material of claim 13, wherein each is washed 3 times.

20. The method of producing a COF-Ag material of claim 13, wherein the vacuum drying time is 24 hours and the drying temperature is 80 ℃.

21. Use of the COF-Ag material of claim 11 or the product of the preparation method of the COF-Ag material of any one of claims 12 to 20 for the preparation of antibacterial and antivirus medicaments.

22. The use according to claim 21, wherein the bacterium escherichia coli or staphylococcus aureus is one or a mixture of both, and the virus is one or a mixture of both of vesicular stomatitis virus and influenza virus.

23. The use according to claim 22, wherein the bacterium is staphylococcus aureus and the virus is vesicular stomatitis virus.

24. An antibacterial and antivirus protective mask, characterized in that a non-woven fabric is used as a substrate, and one surface of the substrate is covered with the mixture of the product prepared by the preparation method of the COF-Ag material according to claim 11 or the COF-Ag material according to any one of claims 12-20 and a polymer organic matter.

25. The antiseptic and protective mask of claim 24, wherein the nonwoven fabric is PET.

26. An antimicrobial and antiseptic protective mask according to claim 24 wherein the polymeric organic material is polyurethane.

27. A method of making an antimicrobial and antiseptic protective mask according to any one of claims 24-26, comprising the steps of:

after the COF-Ag material of claim 11 or the product obtained by the preparation method of the COF-Ag material of any one of claims 12 to 20 is evenly physically doped with high molecular organic matters, a stable composite film system is formed on non-woven fabrics by a spraying method, and then the nano-crystalline composite film material is obtained by vacuum drying treatment, and then the antibacterial and antivirus protective mask is prepared by cutting.

28. The method of claim 27, wherein the polymeric organic material is polyurethane and the nonwoven fabric is PET.

29. The method for producing an antibacterial and disinfecting protective mask according to claim 27, wherein the PET and COF-Ag materials are mixed in a mass ratio of 10 to 80:10-80.

30. The method of claim 27, wherein the physical blending is performed in a solvent selected from the group consisting of azodicarbonamide, methylene chloride, methanol, and ethanol.

31. The method of claim 30, wherein the solvent is methylene chloride.

32. The method of claim 27, wherein the temperature of the mixing is between 10 ℃ and 50 ℃.

33. The method of claim 32, wherein the temperature of mixing is about 25 ℃.

34. The method of claim 27, wherein the vacuum drying time is 20-30 hours and the drying temperature is 70-100 ℃.

35. The method of claim 34, wherein the vacuum drying time is 24 hours and the drying temperature is 80 ℃.

36. The method of claim 27, further comprising the steps of ultrasonic dispersion and agitation during the mixing.

37. The method of manufacturing an antimicrobial and antiseptic protective mask of claim 27 further comprising the steps of: the three functional layers are sequentially overlapped and stitched from outside to inside, and then four corner bands are stitched to obtain the antibacterial and antivirus protective mask.