CN115852699B - Preparation method of photodynamic chargeable antibacterial antiviral nanofiber membrane - Google Patents
Preparation method of photodynamic chargeable antibacterial antiviral nanofiber membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a photodynamic chargeable antibacterial antiviral nanofiber membrane. According to the invention, the fiber membrane is used as a base membrane, and the photosensitizer TDPA and the antibacterial agent CA are grafted on the PAN@PDA nanofiber membrane in a dipping mode to form the composite antibacterial agent, so that the defect of poor effect of a single antibacterial agent is overcome, and the chargeable nanofiber membrane capable of being stored and high-efficiency and lasting in antibacterial and antiviral effects is obtained. The TDPA contains a double diphenyl ketone structure which can release active oxygen after absorbing energy, has antibacterial and antiviral properties, and is reduced to diphenyl ketone again in a hydrogen abstraction and oxygen quenching mode, so that the problems of irreversible consumption of antibacterial materials, short release period, bacterial resistance induction after long-term use and the like are solved, and efficient and durable antibacterial and antiviral effects are realized.
Description
Technical Field
The invention belongs to the technical field of fiber membranes, and particularly relates to a preparation method of a photodynamic chargeable antibacterial antiviral nanofiber membrane.
Background
Infectious diseases are diseases caused by a wide variety of pathogens, one that can be transmitted inter-between humans, animals, or humans and animals. While personal protection equipment worn by medical personnel can significantly reduce the transmission of pathogens, the risk of infection is not completely eliminated. In the case of the current antibacterial materials, the consumption is irreversible, the release period is short, and the risk of inducing bacterial resistance after long-term use exists.
Photodynamic technology generates Reactive Oxygen Species (ROS) by irradiation with visible light to bind to targets on bacteria, thereby inhibiting protein synthesis, causing dissolution and death of bacteria. Considering genetic flexibility of bacteria and viruses, the multi-target inactivation mode enables photodynamic therapy to have a broad spectrum of biocidal activity so as to avoid the bacteria and viruses from generating drug resistance. Document Dayleight-Driven Photosensitive Antibacterial Melt-blown Membranes for Medical Use grafts terephthaloyl diphthalic acid and epigallocatechin gallate onto hydrophilically modified PPCL meltblown films, but the ROS yield of this study is low. Therefore, it is important to prepare a photodynamic antibacterial and antiviral material which can work under light and dark conditions and can be charged and has high ROS release amount.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a photodynamic chargeable antibacterial antiviral nanofiber membrane.
The technical scheme for solving the technical problems is that the invention provides a preparation method of a photodynamic chargeable antibacterial antiviral nanofiber membrane, which is characterized by comprising the following steps:
1) Immersing the fiber membrane in a PDA solution, wherein the PDA is self-polymerized and deposited on the fibers of the fiber membrane; taking out after the deposition is finished, washing, removing impurities, and drying to remove the detergent to obtain the PAN@PDA nanofiber membrane;
2) Dissolving TDPA and polyphosphoric acid in a solvent to obtain a homogeneous TDPA/polyphosphoric acid solution; then soaking the PAN@PDA nanofiber membrane in a TDPA/polyphosphoric acid solution for grafting reaction, wherein the TDPA is grafted to the fibers of the PAN@PDA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the PAN@PDA/TDPA nanofiber membrane;
3) Dissolving CA and polyphosphoric acid in a solvent to obtain a homogeneous CA/polyphosphoric acid solution; then soaking the PAN@PDA/TDPA nanofiber membrane in a CA/polyphosphoric acid solution for grafting reaction, and grafting CA onto TDPA of the PAN@PDA/TDPA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the photodynamic chargeable antibacterial antiviral nanofiber membrane.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the fiber membrane is used as a base membrane, and the photosensitizer TDPA and the antibacterial agent CA are grafted on the PAN@PDA nanofiber membrane in a dipping mode to form the composite antibacterial agent, so that the defect of poor effect of a single antibacterial agent is overcome, and the chargeable nanofiber membrane capable of being stored and high-efficiency and lasting in antibacterial and antiviral effects is obtained.
(2) The TDPA contains a double diphenyl ketone structure which can release active oxygen after absorbing energy, has antibacterial and antiviral properties, and is reduced to diphenyl ketone again in a hydrogen abstraction and oxygen quenching mode, so that the problems of irreversible consumption of antibacterial materials, short release period, bacterial resistance induction after long-term use and the like are solved, and efficient and durable antibacterial and antiviral effects are realized.
(3) The nanofiber membrane prepared by the invention has excellent killing effect on escherichia coli and staphylococcus aureus, and the sterilizing rate on the escherichia coli and the staphylococcus aureus is more than 95% under the conditions of illumination and darkness. The nanofiber membrane has chargeable and storable properties, and the charging capacity is maintained to be 65% -75% of the original charging capacity after 7-cycle testing. The nanofiber membrane has structural stability, and LAT structural stability is 65% -70%. OH and H of nanofiber membranes 2 O 2 The amounts of the components are 5900-6300 mug/g and 780-850 mug/g respectively, and the composition has excellent antiviral property.
(4) The base film of the invention has wide material selection, and can adopt an electrostatic spinning film, a melt-blown film or an SMS composite non-woven film. The PAN nanofiber membrane prepared by the electrostatic spinning technology has a high specific surface area, a porous structure and potential pathogen interception capability.
Drawings
FIG. 1 is a Fourier infrared spectrum of the nanofiber membranes prepared in example 1 and comparative examples 1-4 of the present invention;
FIG. 2 is a moisture permeability test of nanofiber membranes prepared in example 1 and comparative examples 1-4 of the present invention;
FIG. 3 is a graph showing the release amount of hydroxyl radical (. OH) under dark conditions after 1 hour of sunlight irradiation of the nanofiber membranes prepared in example 1 and comparative examples 3-4 of the present invention;
FIG. 4 shows the nanofiber membranes prepared in example 1 and comparative examples 3-4 according to the present invention after 1H of sunlight irradiation under dark conditions with hydrogen peroxide (H 2 O 2 ) Is a graph of the release amount of (2);
FIG. 5 is a graph showing the release amount of hydroxyl radicals versus time for the nanofiber membrane prepared in example 1 of the present invention;
FIG. 6 is a graph showing the release amount of hydrogen peroxide versus time for the nanofiber membrane prepared in example 1 of the present invention;
FIG. 7 is a chart showing the rechargeable cycle test of the nanofiber membrane prepared in example 1 of the present invention;
FIG. 8 is a graph showing the LAT structure of the nanofiber membrane prepared in example 1 of the present invention as a function of storage time;
FIG. 9 shows colony formation of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with E.coli (E.coli) for 1 hour under Light (+);
FIG. 10 shows colony formation of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with Staphylococcus aureus (S.aureus) for 1 hour under light conditions;
FIG. 11 shows colony formation of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with E.coli for 1 hour under dark (Light (-)) condition;
FIG. 12 shows colony formation of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with Staphylococcus aureus for 1 hour under dark conditions;
FIG. 13 is a graph showing the sterilization rate of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with E.coli and S.aureus for 0min, 10min, 30min, and 60min, respectively, under the illumination condition;
FIG. 14 is a graph showing the sterilization rate of the nanofiber membrane prepared in example 1 of the present invention after co-culturing with E.coli and S.aureus for 0min, 10min, 30min, and 60min, respectively, under dark conditions;
FIG. 15 is a graph showing antiviral properties of comparative example 1 and example 1 of the present invention.
Detailed Description
The invention provides a preparation method (abbreviated as method) of a photodynamic chargeable antibacterial antiviral nanofiber membrane, which is characterized by comprising the following steps:
1) Immersing the fibrous membrane in a PDA (polydopamine) solution, wherein the PDA self-aggregates and deposits on the fibers of the fibrous membrane; taking out after the deposition is finished, washing, removing impurities, and drying to remove the detergent to obtain the PAN@PDA nanofiber membrane;
preferably, in step 1), the fibrous membrane is an electrospun membrane, a melt blown membrane or an SMS composite nonwoven membrane; the polymer material of the electrostatic spinning film is selected from PAN (polyacrylonitrile), PVA (polyvinyl alcohol), PCL (polycaprolactone), PVP (polyvinylpyrrolidone), TPU (thermoplastic polyurethane elastomer rubber) or PVA-co-PE (polyvinyl alcohol copolymer); the polymer material of the melt-blown film is selected from PP (polypropylene), PP/PCL (polypropylene/polycaprolactone), PTFE/PP (polytetrafluoroethylene/polypropylene) or PP/PC (polypropylene/polycarbonate); the polymer material of the SMS composite non-woven film is PP.
Preferably, in step 1), the specific process of electrospinning is: sucking the polymer solution into a syringe, controlling the extrusion flow of the polymer solution by using a syringe pump under the voltage of 15-20 kV, and collecting the fiber film formed by electrostatic spinning on a metal roller covered with release paper to obtain a polymer nanofiber film; the speed of the injection pump is 1-2 ml/h, the collection time is 5-7 h, and the rotating speed of the roller is 60-100 rpm.
Preferably, in step 1), the PAN electrospun film is prepared by: dissolving PAN powder in a PAN good solvent to obtain a homogeneous PAN solution as a spinning solution, and obtaining a PAN nanofiber membrane by an electrostatic spinning method; the concentration of the PAN solution is 8-14 wt% (preferably 10-12 wt%); the dissolution temperature of PAN is 30-60 ℃, stirring is adopted for dissolution, and the stirring time is 3-7 h. As a good solvent for PAN, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or Dimethylsulfoxide (DMSO) can be used.
Preferably, in step 1), the PDA solution is prepared specifically by: dissolving dopamine hydrochloride and tris hydrochloride in deionized water, mixing 3-aminopropyl triethoxysilane and absolute ethyl alcohol, pouring, and stirring to obtain PDA solution.
Preferably, in the step 1), the ratio of the mass of dopamine hydrochloride, the mass of tris hydrochloride, the volume of deionized water and the volume of 3-aminopropyl triethoxysilane to the volume of absolute ethyl alcohol in the PDA solution is 0.1-0.4 g to 0.06-0.24 g to 50-200 ml to 0.2-0.8 g to 10-40 ml; the temperature of the self-polymerization deposition is room temperature and the time is 8-16 h.
Preferably, in step 1), the drying temperature is 40-60 ℃ and the drying time is 2-6 h.
Preferably, in step 1), the washing impurity is removed by washing the PDA solution with detergent a; the detergent A adopts deionized water.
2) Dissolving TDPA (4, 4' -terephthaloyl diphthalic anhydride) and polyphosphoric acid in a solvent to obtain a homogeneous TDPA/polyphosphoric acid solution; then soaking the PAN@PDA nanofiber membrane in a TDPA/polyphosphoric acid solution for grafting reaction, wherein the TDPA is grafted to the fibers of the PAN@PDA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the PAN@PDA/TDPA nanofiber membrane;
preferably, in step 2), the mass of TDPA, the mass of polyphosphoric acid and the volume ratio of solvent are 0.1-0.4 g:0.1-0.4 g:10-40 ml; stirring is continuously carried out in the grafting reaction process, the grafting temperature is 30-70 ℃, and the grafting time is 1-3 h.
Preferably, in the step 2), the drying is performed by vacuum drying, the temperature is 30-50 ℃, and the time is 1-3 hours.
3) Dissolving CA (natural polyphenol chlorogenic acid) and polyphosphoric acid in a solvent to obtain a homogeneous CA/polyphosphoric acid solution; then soaking the PAN@PDA/TDPA nanofiber membrane in a CA/polyphosphoric acid solution for grafting reaction, and grafting CA onto TDPA of the PAN@PDA/TDPA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the PAN@PDA/TDPA/CA nanofiber membrane, namely the photodynamic chargeable antibacterial antiviral nanofiber membrane (nanofiber membrane for short).
Preferably, in step 3), the ratio of the mass of CA, the mass of polyphosphoric acid to the volume of the solvent is 0.1-0.4 g:0.1-0.4 g:10-40 ml; stirring is continuously carried out in the grafting reaction process, the grafting temperature is 30-70 ℃, and the grafting time is 1-3 h.
Preferably, in step 2) and step 3), the solvent is a good solvent for TDPA, CA and polyphosphoric acid, in particular DMF, tetrahydrofuran (THF) or 1, 4-dioxane.
Preferably, in step 2), the washing impurity is removed by washing with detergent B to remove polyphosphoric acid, solvent and unreacted TDPA; in the step 3), washing and impurity removing are carried out by adopting a detergent B to wash away polyphosphoric acid, solvent and unreacted CA; the detergent B is acetone or ethanol.
Preferably, in the step 3), the drying is performed by vacuum drying, the temperature is 40-60 ℃, and the time is 1-3 hours.
The photodynamic chargeable antibacterial antiviral nanofiber membrane prepared by the invention can be used as a protective material.
Specific examples of the present invention are given below. The specific examples are provided only for further details of the present invention and do not limit the scope of the claims.
Example 1
(1) 2g of PAN powder is dissolved in 14.67ml of DMF and stirred for 6 hours, the stirring temperature is 45 ℃, and the PAN powder is fully and uniformly mixed to obtain a PAN solution with the concentration of 12 weight percent; sucking the PAN solution into a 10ml injector, controlling the extrusion flow of the PAN solution at a speed of 2ml/h by using an injection pump under a voltage of 15kV, and collecting a fibrous membrane formed by electrostatic spinning on a metal roller covered with release paper to obtain a PAN nanofiber membrane;
dissolving 0.2g of dopamine hydrochloride and 0.12g of tris hydrochloride in 100ml of deionized water, mixing 0.4g of 3-aminopropyl triethoxysilane with 20ml of absolute ethyl alcohol, pouring, and stirring to obtain a PDA solution;
immersing the PAN nanofiber membrane into a PDA solution, and performing self-polymerization deposition for 12 hours at room temperature; taking out after the deposition is finished, washing with deionized water, and drying for 4 hours to obtain the PAN@PDA nanofiber membrane;
(2) Dissolving 0.2g of TDPA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous TDPA/polyphosphoric acid solution; then 0.1g of PAN@PDA nanofiber membrane is soaked in TDPA/polyphosphoric acid solution for grafting reaction, and stirred at 60 ℃ for 2h; taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA nanofiber membrane;
(3) Dissolving 0.2g of CA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous CA/polyphosphoric acid solution; then soaking 0.1g of PAN@PDA/TDPA nanofiber membrane in a CA/polyphosphoric acid solution for grafting reaction, and stirring at 60 ℃ for 2h; and taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA/CA nanofiber membrane.
In FIG. 5, white represents irradiation, gray represents darkness, and 20min interval bright-dark fatigue test was performed on example 1. As can be seen from fig. 5, OH is generated when light is irradiated and stopped when dark. However, the activity of example 1 did not decrease during this period, and the amount of ROS released after each cycle remained steadily increasing.
In FIG. 6, white represents irradiation, gray represents darkness, and 20min interval bright-dark fatigue test was performed on example 1. As can be seen from fig. 6, H 2 O 2 Generated when illuminated and stopped when dark. However, the activity of example 1 did not decrease during this period, and the amount of ROS released after each cycle remained steadily increasing.
Fig. 7 evaluates chargeability of the nanofiber membrane prepared in example 1 by repeating charging and quenching for seven cycles. As can be seen from fig. 10, example 1 was first illuminated for 1h in each cycle and quenched with an excess of thiosulfate solution after measuring ROS release. After seven cycles, the charging capacity is not obviously reduced, 70.32% and 71.28% of the original charging capacity are respectively reserved, and the nanofiber membrane can be repeatedly utilized.
As can be seen from fig. 8, the LAT structure-dependent absorption peaks exhibit a slow decay. The test shows that example 1 still retains more than 67% of the original LAT structure, thus highlighting the stability of the structure.
As can be seen from FIG. 9, the colony count was significantly reduced compared with the blank colony count when example 1 and E.coli were co-cultured for 30min under the light condition, and almost no colony appeared after 1h of co-culture, and example 1 showed higher bactericidal activity.
As can be seen from FIG. 10, the colony count was significantly reduced compared with the blank colony count when example 1 and S.aureus were co-cultured for 30min under the light condition, and almost no colony appeared after 1h of co-culture, and example 1 showed higher bactericidal activity.
As can be seen from FIG. 11, in the dark, the colony count was significantly reduced compared with the blank colony count when example 1 was co-cultured with E.coli for 30min, and the colony count was smaller after 1h of co-culture, and example 1 showed higher bactericidal activity.
As can be seen from FIG. 12, in the dark, the colony count was significantly reduced compared with the blank colony count when example 1 was co-cultured with S.aureus for 30min, and the colony count was smaller after 1h of co-culture, and example 1 showed higher bactericidal activity.
As can be seen from fig. 13, example 1 has a greater bactericidal rate against staphylococcus aureus than escherichia coli in the same contact time. Mainly because of the difference in cell wall structures between E.coli and Staphylococcus aureus, which in turn affects the sensitivity of the bacteria to ROS. When example 1 was co-cultured with bacteria for 60min, the sterilization rate under light conditions could reach 99% or more.
As can be seen from FIG. 14, when example 1 was co-cultured with bacteria for 60 minutes, the sterilization rate under dark conditions could reach 99% or more.
According to the basic structure of viruses, ROS have three main targets with viruses: nucleic acids, viral proteins, and viral lipids. To evaluate the antiviral performance of example 1, the challenge of example 1 was performed with H3N2 influenza virus. As can be seen from fig. 15, the antiviral activity value of example 1 can reach 3.6, mainly due to the oxidation of the RNA and lipid membrane of H3N2 by ROS generated in example 1. In addition, ROS cross-link with the protein capsids of the viruses, resulting in inactivation of specific binding sites of the viruses to host cells.
Comparative example 1
The PAN nanofiber membrane obtained in step (1) of example 1 was used.
Comparative example 2
The PAN@PDA nanofiber membrane obtained in step (1) of example 1 was used.
Comparative example 3
0.2g of CA and 5g of CDI (N, N-carbonyldiimidazole) were dissolved in 20ml of THF to obtain a homogeneous CA/CDI solution; then 0.1g of PAN@PDA nanofiber membrane in the step (1) of the example 1 is soaked in a CA/CDI solution to carry out grafting reaction, and the reaction is stirred at 60 ℃ for 2 hours; and taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/CA nanofiber membrane.
Comparative example 4
The PAN@PDA/TDPA nanofiber membrane obtained in step (2) of example 1 was used.
As can be seen from FIG. 1, all samples were at 3647, 3564, 2932, 2865, 2241, 1732, 1665, 1451cm -1 Characteristic absorption peaks of PAN appear there. Comparative example 2 was conducted at 3679-2938, 1614 and 1519cm -1 New characteristic peaks appear here, mainly due to the O-H, N-H and C-NH group stretching vibrations of PDA. After PDA grows on PAN nanofiber membrane in situ, PAN characteristic peak does not change, indicate that poly dopamine in situ growth is physical phenomenon. Since example 1 and comparative examples 3-4 were both PDA-modified, the absorption peak of PDA was not changed on the fibrous films of these three examples. Wherein 501cm -1 、773cm -1 、1114-1455cm -1 Vibration at the peak indicates that example 1 and comparative examples 3-4 are not physical but chemical grafts, indicating successful grafting.
As can be seen from fig. 2, there is a certain difference between the moisture permeability of example 1 and comparative examples 1 to 4, mainly because the hydrophilic groups contained therein have an increased attraction to water molecules after the nanofiber membrane is treated with hydrophilic polydopamine. The modified nanofiber membrane shows good moisture permeability.
As can be seen from fig. 3, the rate of release of OH of example 1 was maximum during the first 5min, and the ROS concentration increased slowly with time, and finally exhibited a saturated state. It can be seen from the test that the maximum release OH of example 1 was 6188.56. Mu.g/g. Corresponding to a charge rate of 103.14 μg/g/min, indicating that a large amount of light energy can be fully utilized by the nanofiber membrane.
As can be seen from FIG. 4, example 1 releases H during the first 5 minutes 2 O 2 The rate of (2) is greatest, and as time increases, the concentration of ROS slowly increases, eventually assuming a saturated state. It can be seen from the test that example 1 releases H at maximum 2 O 2 In an amount of 842.00 μg/g. Corresponding to a charge rate of 14.03 μg/g/min, indicating that a large amount of light energy can be fully utilized by the nanofiber membrane.
Example 2
(1) 1.63g of PAN powder is dissolved in 14.67ml of DMF and stirred for 6 hours, the stirring temperature is 45 ℃, and the PAN powder is fully and uniformly mixed to obtain a PAN solution with the concentration of 10 weight percent; sucking the PAN solution into a 10ml injector, controlling the extrusion flow of the PAN solution at a speed of 2ml/h by using an injection pump under a voltage of 20kV, and collecting a fibrous membrane formed by electrostatic spinning on a metal roller covered with release paper to obtain a PAN nanofiber membrane;
dissolving 0.2g of dopamine hydrochloride and 0.12g of tris hydrochloride in 100ml of deionized water, mixing 0.4g of 3-aminopropyl triethoxysilane with 20ml of absolute ethyl alcohol, pouring, and stirring to obtain a PDA solution;
immersing the PAN nanofiber membrane into a PDA solution, and performing self-polymerization deposition for 8 hours at room temperature; taking out after the deposition is finished, washing with deionized water, and drying for 4 hours to obtain the PAN@PDA nanofiber membrane;
(2) Dissolving 0.2g of TDPA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous TDPA/polyphosphoric acid solution; then 0.1g of PAN@PDA nanofiber membrane is soaked in TDPA/polyphosphoric acid solution for grafting reaction, and stirred at 40 ℃ for reaction for 3 hours; taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA nanofiber membrane;
(3) Dissolving 0.2g of CA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous CA/polyphosphoric acid solution; then 0.1g of PAN@PDA/TDPA nanofiber membrane is soaked in the CA/polyphosphoric acid solution for grafting reaction, and stirred at 70 ℃ for reaction for 1h; and taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA/CA nanofiber membrane.
Example 3
(1) 2.39g of PAN powder is dissolved in 14.67ml of DMF and stirred for 6 hours, the stirring temperature is 45 ℃, and the PAN powder is fully and uniformly mixed to obtain 14wt% PAN solution; sucking the PAN solution into a 10ml injector, controlling the extrusion flow of the PAN solution at a speed of 2ml/h by using an injection pump under a voltage of 17kV, and collecting a fibrous membrane formed by electrostatic spinning on a metal roller covered with release paper to obtain a PAN nanofiber membrane;
dissolving 0.2g of dopamine hydrochloride and 0.12g of tris hydrochloride in 100ml of deionized water, mixing 0.4g of 3-aminopropyl triethoxysilane with 20ml of absolute ethyl alcohol, pouring, and stirring to obtain a PDA solution;
immersing the PAN nanofiber membrane into a PDA solution, and performing self-polymerization deposition for 16 hours at room temperature; taking out after the deposition is finished, washing with deionized water, and drying for 4 hours to obtain the PAN@PDA nanofiber membrane;
(2) Dissolving 0.2g of TDPA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous TDPA/polyphosphoric acid solution; then 0.1g of PAN@PDA nanofiber membrane is soaked in TDPA/polyphosphoric acid solution for grafting reaction, and stirred at 70 ℃ for reaction for 1h; taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA nanofiber membrane;
(3) Dissolving 0.2g of CA and 0.2g of polyphosphoric acid in 20ml of 1, 4-dioxane to obtain a homogeneous CA/polyphosphoric acid solution; then soaking 0.1g of PAN@PDA/TDPA nanofiber membrane in a CA/polyphosphoric acid solution for grafting reaction, and stirring at 40 ℃ for 3 hours; and taking out after the reaction is finished, washing with acetone, and drying in a vacuum oven at 40 ℃ for 2 hours to obtain the PAN@PDA/TDPA/CA nanofiber membrane.
The invention is applicable to the prior art where it is not described.
Claims (9)
1. The preparation method of the photodynamic chargeable antibacterial antiviral nanofiber membrane is characterized by comprising the following steps of:
1) Immersing the fiber membrane in a PDA solution, wherein the PDA is self-polymerized and deposited on the fibers of the fiber membrane; taking out after the deposition is finished, washing, removing impurities, and drying to remove the detergent to obtain the PDA nanofiber membrane;
the fiber membrane adopts an electrostatic spinning membrane, a melt-blown membrane or an SMS composite non-woven membrane; the polymer material of the electrostatic spinning film is PAN, PVA, PCL, PVP, TPU or PVA-co-PE; the polymer material of the melt-blown film is selected from PP, PP/PCL compound, PTFE/PP compound or PP/PC compound; the polymer material of the SMS composite non-woven membrane is PP;
2) Dissolving TDPA and polyphosphoric acid in a solvent to obtain a homogeneous TDPA/polyphosphoric acid solution; then soaking the PDA nanofiber membrane in TDPA/polyphosphoric acid solution for grafting reaction, and grafting the TDPA to the fibers of the PDA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the PDA/TDPA nanofiber membrane;
the TDPA is 4,4' -terephthaloyl diphthalic anhydride;
3) Dissolving CA and polyphosphoric acid in a solvent to obtain a homogeneous CA/polyphosphoric acid solution; then soaking the PDA/TDPA nanofiber membrane in a CA/polyphosphoric acid solution for grafting reaction, and grafting the CA onto the TDPA of the PDA/TDPA nanofiber membrane through esterification reaction; taking out after the reaction is finished, washing, removing impurities, and drying to remove the detergent to obtain the photodynamic chargeable antibacterial antiviral nanofiber membrane;
the CA is natural polyphenol chlorogenic acid.
2. The method for preparing the photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in the step 1), the specific process of electrospinning is as follows: sucking the polymer solution into a syringe, controlling the extrusion flow of the polymer solution by using a syringe pump under the voltage of 15-20 kV, and collecting the fiber film formed by electrostatic spinning on a metal roller covered with release paper to obtain a polymer nanofiber film; the speed of the injection pump is 1-2 ml/h, the collection time is 5-7 h, and the rotating speed of the roller is 60-100 rpm.
3. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in step 1), the PDA solution is prepared specifically by: dissolving dopamine hydrochloride and tris hydrochloride in deionized water, mixing 3-aminopropyl triethoxysilane and absolute ethyl alcohol, pouring, and stirring to obtain PDA solution.
4. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in step 1), the ratio of the mass of dopamine hydrochloride, the mass of tris hydrochloride, the volume of deionized water and the volume of 3-aminopropyl triethoxysilane to the volume of absolute ethyl alcohol in a PDA solution is 0.1-0.4 g:0.06-0.24 g:50-200 ml:0.2-0.8 g:10-40 ml; the temperature of the self-polymerization deposition is room temperature and the time is 8-16 h.
5. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in step 1), the PDA solution is washed away by using a detergent a for washing and impurity removal; the detergent A adopts deionized water.
6. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in the step 2), the mass of TDPA, the volume ratio of the mass of polyphosphoric acid to the solvent is 0.1-0.4 g:0.1-0.4 g:10-40 ml; stirring is continuously carried out in the grafting reaction process, the grafting temperature is 30-70 ℃, and the grafting time is 1-3 h.
7. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in the step 3), the ratio of the mass of CA to the mass of polyphosphoric acid to the volume of the solvent is 0.1-0.4 g:0.1-0.4 g:10-40 ml; stirring is continuously carried out in the grafting reaction process, the grafting temperature is 30-70 ℃, and the grafting time is 1-3 h.
8. The method for preparing the photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein the solvent in the step 2) and the step 3) is good solvent of TDPA, CA and polyphosphoric acid, and specifically DMF, tetrahydrofuran or 1, 4-dioxane.
9. The method for preparing a photodynamic chargeable antibacterial and antiviral nanofiber membrane according to claim 1, wherein in the step 2), the polyphosphoric acid, the solvent and the unreacted TDPA are washed away by using a detergent B for washing and impurity removal; in the step 3), washing and impurity removing are carried out by adopting a detergent B to wash away polyphosphoric acid, solvent and unreacted CA; the detergent B is acetone or ethanol.
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| CN108517582A (en) * | 2018-04-10 | 2018-09-11 | 天津工业大学 | A kind of degradable antibacterial nano fiber and preparation method thereof |
| CN109137264A (en) * | 2018-07-07 | 2019-01-04 | 东莞市联洲知识产权运营管理有限公司 | A method of antibacterial medical dressing is prepared using electrostatic spinning |
| CN113123017A (en) * | 2021-04-19 | 2021-07-16 | 天津工业大学 | Photodynamic filtering antibacterial composite membrane and preparation method and application thereof |
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| CN108517582A (en) * | 2018-04-10 | 2018-09-11 | 天津工业大学 | A kind of degradable antibacterial nano fiber and preparation method thereof |
| CN109137264A (en) * | 2018-07-07 | 2019-01-04 | 东莞市联洲知识产权运营管理有限公司 | A method of antibacterial medical dressing is prepared using electrostatic spinning |
| CN113123017A (en) * | 2021-04-19 | 2021-07-16 | 天津工业大学 | Photodynamic filtering antibacterial composite membrane and preparation method and application thereof |
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