Manufacturing method of photodynamic antibacterial fiber membrane for mask

Abstract

The invention relates to a manufacturing method of a photodynamic antibacterial fiber membrane for masks, which is characterized by comprising the following steps: step 1, preparing 1-methyl-5-(4-methoxyphenyl) quinoline; step 2, preparation of 1-methyl-5-(4-methoxyphenyl) quinolinium hexafluorophosphate; step 2, preparation of 2-methyl-5-(4-methoxyphenyl) quinolinium; and step 3, preparation of an electrostatic spinning fiber membrane: polylactic acid and polyethylene glycol are dissolved in a solvent, the target product is added to form a spinning solution, and the spinning solution is used for electrostatic spinning to form the electrostatic spinning fiber membrane. According to the invention, the photodynamic antibacterial fiber membrane with excellent stability, biodegradability, reusability and antibacterial efficiency can be prepared. Compared with a traditional non-woven fabric mask, the fiber membrane shows higher bacterium adsorption and killing capacity in air containing various bacteria by means of the high specific surface area of the fiber membrane and the synergistic effect of the high-activity antibacterial agent 5-MPQ-Me.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a photodynamic antibacterial fiber membrane that can be used in face masks, belonging to the field of protective equipment technology. Background Technology

[0002] Bacterial infections transmitted through respiratory droplets (including influenza, tuberculosis, and pneumonia) continue to pose a significant threat to public health. As one of the most widely used personal protective equipment, masks effectively block droplets or aerosols containing pathogens from entering the respiratory tract, thereby reducing the risk of disease transmission. However, existing traditional masks have fundamental flaws: they lack inherent antibacterial properties, and prolonged exposure to polluted environments can lead to bacteria adhering to the mask surface, potentially causing cross-infection. This necessitates frequent mask replacement in high-risk environments, generating not only large amounts of polluting waste but also increasing the risk of secondary transmission. More seriously, traditional mainstream masks are made of non-biodegradable polypropylene nonwoven fabric, and most countries still rely on incineration as the primary disposal method, undoubtedly exacerbating the greenhouse effect. Most critically, the fiber diameter of traditional nonwoven masks is typically in the range of 0.5-10.0 μm, making it difficult to effectively filter aerosol particles <0.30 μm, severely limiting protective efficiency. Therefore, developing reusable materials with finer fiber diameters, inherent antibacterial properties, and biodegradability will be a key strategy to overcome the technological bottlenecks of traditional nonwoven fabrics and alleviate the dual pressures on public health and the ecological environment.

[0003] Compared to traditional nonwoven fabrics, nanofiber materials prepared by electrospinning can control fiber diameters to 0.1 μm or even smaller, and their high specific surface area and small pore size significantly improve filtration efficiency. Addressing the issues of non-degradability and incineration of traditional mask materials, biodegradable polymers such as polylactic acid (PLA), polyethylene glycol (PEG), and polyvinyl alcohol (PVA) are used as electrospinning matrices, providing a sustainable solution. Furthermore, by integrating antibacterial agents such as quaternary ammonium compounds, silver nanoparticles, and metal oxide nanoparticles into electrospun fiber membranes, the materials can be endowed with antibacterial activity and reusability, opening new avenues for the development of next-generation masks. Chinese invention patent application CN111838830A, entitled "A Medical Protective Mask Based on Nanophotodynamic Effect," discloses a medical protective mask based on nanophotodynamic effect, comprising an outer layer, an inner layer, and a middle layer disposed between the outer and inner layers. The inner layer has symmetrical tension straps on both the front and back sides of its right sidewall. The middle layer includes a left filter layer that adheres to the right sidewall of the outer layer and a right filter layer that adheres to the left sidewall of the inner layer. A nanomaterial photosensitizer layer is disposed between the left and right filter layers. The material of the nanomaterial photosensitizer layer is Cu-Cy. A silver nanoparticle layer is disposed between the left filter layer and the nanomaterial photosensitizer layer. Chinese invention patent application CN108866820A, entitled "A Method for Preparing and Applying Electrospun Nanofibers," discloses a method for preparing electrospun nanofibers. Under normal temperature and pressure, synthetic and / or natural polymeric materials are dissolved in a volatile solvent, and functional substances are added. Nanofibers are then obtained by electrospinning. The functional substances include one or more of the following: odorants, organic fluorescent compounds, pigments, temperature-sensitive luminescent substances, temperature-sensitive color-changing substances, cell growth factors, hemostatic substances, substances that promote or inhibit or interfere with bodily functions, and nutrients that promote skin regeneration.

[0004] Photodynamic therapy (PDT) has become a promising antibacterial strategy due to its advantages such as high selectivity, non-invasiveness, broad-spectrum antibacterial activity, and low toxicity, and it is less likely to induce bacterial resistance. Over the past decade, porphyrin and phthalocyanine photosensitizers have been widely used in PDT, but their planar conjugated backbones are prone to π-π stacking, leading to aggregation-induced quenching (ACQ) effects and significantly reducing the efficiency of reactive oxygen species (ROS) generation. In contrast, photosensitizers with aggregation-induced emission (AIE) properties can effectively suppress non-radiative decay caused by intramolecular motion, thereby increasing ROS production. However, the design and synthesis of AIE-active photosensitizers that can efficiently generate ROS (especially type I ROS) are still in their early stages. Introducing quaternary ammonium salt groups into the organic molecular framework has proven to be an effective strategy for addressing the aforementioned challenges: First, the positively charged quaternary ammonium groups inhibit aggregated π-π stacking through intermolecular electrostatic repulsion, thereby improving fluorescence efficiency and ROS production; second, they promote intramolecular charge transfer, narrowing the singlet-triplet band gap and enhancing intersystem crossing to increase type I ROS generation; furthermore, quaternary ammonium compounds themselves possess antibacterial activity, capable of disrupting bacterial cell wall integrity or increasing membrane permeability through electrostatic interactions, resulting in a synergistic bactericidal effect with photodynamic therapy. Although several highly efficient ROS-generating AIE-active quaternary ammonium salt photosensitizers have been reported, their complex synthesis processes and high costs severely restrict large-scale preparation and practical applications. Therefore, developing structurally simple, low-cost quaternary ammonium salt-based AIE photosensitizers and integrating them into electrospun nanofiber materials to replace traditional nonwoven fabrics still faces significant challenges.

[0005] Based on the above issues, the applicant conducted research, which led to this case. Summary of the Invention

[0006] The purpose of this invention is to provide a method for manufacturing a photodynamic antibacterial fiber membrane that combines stability, biodegradability, reusability, and antibacterial efficacy with a relatively simple process.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A method for manufacturing a photodynamic antibacterial fiber membrane that can be used in face masks, characterized by comprising the following steps: Step 1: Preparation of 1-methyl-5-(4-methoxyphenyl)quinoline 4.00-6.00 mmol of 5-bromoquinoline and 6.00-8.00 mmol of triphenylamine 4-borate were placed in a container and dissolved in 18-22 mL of tetrahydrofuran. Separately, 0.40-0.50 g of potassium carbonate or sodium carbonate was dissolved in 4.0-5.0 mL of water. After the two solutions were mixed, 0.08-0.12 mmol of tetra(triphenylphosphine)palladium was added. The mixture was stirred at 70-80 °C for 42 to 54 hours under nitrogen protection. After the reaction was completed, the organic layer was extracted, concentrated under reduced pressure, and purified to obtain the intermediate product. Step 2: Preparation of 1-methyl-5-(4-methoxyphenyl)quinoline-onium hexafluorophosphate The above intermediate product was dissolved in an organic solvent, and 4.0-6.0 mmol of iodomethane was added. The mixture was stirred at 50-60°C for 42 to 54 hours. After the reaction was completed, the solvent was removed to obtain a yellow solid. The yellow solid was added to 8.0-12.0 mL of saturated ammonium hexafluorophosphate aqueous solution, heated at 75 to 85°C, and anhydrous ethanol was added until the yellow solid was completely dissolved. After cooling the solution to room temperature, yellow transparent crystals were obtained, and the target product was obtained. Step 3: Preparation of electrospun fiber membranes Polylactic acid and polyethylene glycol are dissolved in a solvent, and the target product is added to form a spinning solution. The spinning solution is then used for electrospinning to form an electrospun fiber membrane.

[0008] In a preferred embodiment of the present invention, the mass ratio of polylactic acid to polyethylene glycol in the spinning solution is 20:1-50:1, and the concentration of the target product is 4×10⁻⁶. -6 mol / mL to 6×10 -6 mol / mL.

[0009] In a preferred embodiment of the present invention, in step three, the solvent is a mixture of dichloromethane and N,N-dimethylformamide.

[0010] As a preferred embodiment of the present invention, based on a total mass of 1.2g of polylactic acid and polyethylene glycol, the amount of dichloromethane added is 8 mL, the amount of N,N-dimethylformamide added is 2 mL, and the amount of the target product added is 0.01975g.

[0011] In a preferred embodiment of the present invention, during electrospinning, a voltage of 9.0-9.5 kV is applied to the needle, the receiver voltage is -2.0 kV, the spinning distance is 18 cm, the solution propulsion rate is 0.06 mm / min, and 10 mL of the spinning solution is electrospinned on a 30 cm × 32 cm aluminum foil substrate.

[0012] In a preferred embodiment of the present invention, in step one, after the reaction is completed, water is added for dilution, and the mixture is extracted with ethyl acetate. The organic layer is separated and retained. An equal volume of water is added, the mixture is shaken, allowed to stand for separation, the aqueous layer is discarded, and the organic layer is separated and retained. An equal volume of saturated saline solution is then added, the mixture is shaken, allowed to stand for separation, the saline layer is discarded, and the organic layer is separated and retained. The obtained organic layer is transferred to an Erlenmeyer flask, and sufficient anhydrous sodium sulfate is added for drying. The mixture is filtered, and the filtrate is concentrated under reduced pressure to obtain the crude product. The crude product is purified by silica gel column chromatography. The eluent used for silica gel column chromatography purification is petroleum ether and ethyl acetate in a volume ratio of 10:1.

[0013] In a preferred embodiment of the present invention, in step two, the organic solvent is a mixture of acetonitrile and dichloromethane, the mixture being 16.0-20.0 mL in volume, and the volume ratio of acetonitrile to dichloromethane being 1:1.

[0014] In a preferred embodiment of the present invention, in step two, the mass ratio of polylactic acid to polyethylene glycol is 50:1.

[0015] In a preferred embodiment of the present invention, the loading amount of the target product on the aluminum foil substrate is 0.048 × 10⁻⁶. - 6 mol / cm² to 0.054×10 -6 mol / cm².

[0016] In a preferred embodiment of the present invention, the electrospinning is carried out at a temperature of 20°C to 30°C.

[0017] By employing the technical solution of this invention, a quaternary ammonium salt molecule—1-methyl-5-(4-methoxyphenyl)quinolineonium hexafluorophosphate (i.e., 5-MPQ-Me)—with excellent photodynamic antibacterial activity was successfully prepared via a simple and economical synthetic route. Subsequently, 5-MPQ-Me was loaded onto a polylactic acid (PLA)-polyethylene glycol (PEG) polymer matrix using electrospinning technology to prepare a photodynamic antibacterial fiber membrane possessing excellent stability, biodegradability, reusability, and antibacterial efficacy. Compared with traditional nonwoven masks, this fiber membrane, due to its high specific surface area and the synergistic effect of the highly active antibacterial agent 5-MPQ-Me, exhibits stronger bacterial adsorption and killing capabilities in air containing various bacteria. The research results confirm that this electrospun fiber membrane effectively overcomes the core limitations of traditional nonwoven materials, not only possessing the potential to replace conventional masks but also providing new ideas for designing multifunctional environmentally friendly protective materials. Attached Figure Description

[0018] Figure 1 This is a SEM image of the electrospun fiber membrane obtained when 5-MPQ-Me was not added to the spinning solution in this invention.

[0019] Figure 2 This is a SEM image of the electrospun fiber membrane obtained by adding 5-MPQ-Me to the spinning solution in this invention (the mass ratio of polylactic acid to polyethylene glycol is 50:1).

[0020] Figure 3 This is a SEM image of the electrospun fiber membrane obtained by adding 5-MPQ-Me to the spinning solution in this invention (the mass ratio of polylactic acid to polyethylene glycol is 20:1).

[0021] Figure 4This is a comparative schematic diagram of the contact angles of the electrospun fiber membranes prepared in Examples 1, 2, and 3.

[0022] Figure 5 This is a SEM image of the electrospun fiber membrane from Example 3 after soaking for 1 day.

[0023] Figure 6 This is a SEM image of the electrospun fiber membrane from Example 3 after soaking for 3 days.

[0024] Figure 7 This is an electron microscope (SEM) image of the electrospun fiber membrane from Example 3 after soaking for 5 days.

[0025] Figure 8 This is a SEM image of the electrospun fiber membrane from Example 3 after immersion for 10 days.

[0026] Figure 9 This is a SEM image of the electrospun fiber membrane from Example 3 after immersion for 15 days.

[0027] Figure 10 This is a SEM image of the electrospun fiber membrane from Example 3 after immersion for 20 days.

[0028] Figure 11 This is a SEM image of the electrospun fiber membrane from Example 3 after immersion for 25 days.

[0029] Figure 12 This is a SEM image of the electrospun fiber membrane from Example 3 after immersion for 30 days.

[0030] Figure 13 Comparison of inhibition zone diameters for different strains using 5-MPQ-Me aqueous solution (5 mM / mL), organic solvent (volume ratio DCM:DMF=4:1), fiber membrane of Example 3, and fiber membrane of Example 1 (vertical axis represents inhibition zone diameter, unit is mm).

[0031] Figure 14 This is a schematic diagram comparing the antibacterial activity of the fiber membrane in Example 3 under light and dark conditions (the vertical axis represents the antibacterial rate, and the horizontal axis represents time).

[0032] Figure 15 This is a comparison chart of the antibacterial performance of the fiber membrane in Example 3 after repeated use (the vertical axis represents the antibacterial rate, and the horizontal axis represents the number of cycles).

[0033] Figure 16 This is a SEM image taken under a dark environment 10 minutes after the fiber membrane in Example 3 was reacted with a mixed bacterial suspension.

[0034] Figure 17This is a SEM image taken under a dark environment 30 minutes after the fiber membrane in Example 3 was reacted with a mixed bacterial suspension.

[0035] Figure 18 This is a SEM image taken under a dark environment 60 minutes after the fiber membrane in Example 3 was reacted with a mixed bacterial suspension.

[0036] Figure 19 This is a SEM image taken under a dark environment 120 minutes after the fiber membrane in Example 3 was reacted with a mixed bacterial suspension.

[0037] Figure 20 This is a SEM image taken 10 minutes after the fiber membrane reacted with the mixed bacterial suspension under light conditions in Example 3.

[0038] Figure 21 This is a SEM image taken 30 minutes after the fiber membrane reacted with the mixed bacterial suspension under light conditions in Example 3.

[0039] Figure 22 This is a SEM image taken under an electron microscope 60 minutes after the fiber membrane was reacted with the mixed bacterial suspension under light irradiation conditions in Example 3.

[0040] Figure 23 This is a SEM image taken 120 minutes after the fiber membrane was reacted with the mixed bacterial suspension under light conditions in Example 3. Detailed Implementation

[0041] To better understand the technical solution of the present invention, a more detailed description is provided below with reference to the embodiments.

[0042] The present invention discloses a method for manufacturing a photodynamic antibacterial fiber membrane that can be used in face masks, comprising the following steps: (1) Preparation of 5-MPQ (i.e., 1-methyl-5-(4-methoxyphenyl)quinoline) 4.00-6.00 mmol (5.00 mmol in the example) of 5-bromoquinoline (CAS No.: 4964-71-0) and 6.00-8.00 mmol (7.00 mmol in the example) of triphenylamine 4-borate (CAS No.: 201802-67-7) were placed in a 100 mL flask and dissolved in 20.0 mL of tetrahydrofuran (THF). Separately, 0.40-0.50 g of potassium carbonate or sodium carbonate (potassium carbonate was used in the example, 0.50 g) was dissolved in 4.0-5.0 mL (5 mL in the example) of water. After mixing the two solutions, 0.08-0.12 mmol (0.10 mmol in the example) of tetrakis(triphenylphosphine)palladium (CAS No.: 14221-01-3) was added. The reaction was carried out under nitrogen protection at 70-80 °C with stirring for 42 to 54 hours (75 °C, 48 hours in the example). After the reaction was complete, the mixture was diluted with water and extracted with ethyl acetate. The organic layer was separated and retained. An equal volume of water was added, the mixture was shaken, allowed to stand for separation, the aqueous layer was discarded, and the organic layer was separated and retained. An equal volume of saturated brine was added, the mixture was shaken, allowed to stand for separation, the brine layer was discarded, and the organic layer was separated and retained. The obtained organic layer was transferred to an Erlenmeyer flask, dried with sufficient anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1, v / v). Finally, a colorless powdery intermediate product 5-MPQ was obtained.

[0043] Under the same conditions, the yield of 5-MPQ obtained from the reaction of 5-bromoquinoline (4.00 mmol) and triphenylamine 4-boronate (6.00 mmol) was 83.7%; the yield from the reaction of 5-bromoquinoline (5.00 mmol) and triphenylamine 4-boronate (7.00 mmol) was 90.0%; and the yield from the reaction of 5-bromoquinoline (6.00 mmol) and triphenylamine 4-boronate (8.00 mmol) was 88.3%. The highest yield was obtained from the reaction of 5-bromoquinoline (5.00 mmol) and triphenylamine 4-boronate (7.00 mmol).

[0044] (2) Preparation of 5-MPQ-Me (i.e., 1-methyl-5-(4-methoxyphenyl)quinoline hexafluorophosphate) 5-MPQ (1.0–3.0 mmol, 1.0 mmol in the example) was dissolved in 16.0–20.0 mL (v / v, 1:1) of a mixed solvent of acetonitrile and dichloromethane (20.0 mL in the example), followed by the addition of 4.0–6.0 mmol of iodomethane (5.0 mmol in the example). The reaction was stirred at 50–60 °C for 42–54 hours (55 °C, 48 hours in the example). After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure to obtain a yellow solid. The obtained solid was transferred to a round-bottom flask containing 8.0–12.0 mL of saturated ammonium hexafluorophosphate aqueous solution (10.0 mL in the example), heated at 80 °C, and anhydrous ethanol was added until the solid was completely dissolved. After cooling the solution to room temperature, yellow transparent crystals were obtained. This recrystallization step could be repeated three times to finally obtain the target 5-MPQ-Me.

[0045] Under the same conditions, the product yield of the reaction of 5-MPQ (2.0 mmol) and iodomethane (4.0 mmol) was 70.2%; the product yield of the reaction of 5-MPQ (1.0 mmol) and iodomethane (5.0 mmol) was 76.1%; and the product yield of the reaction of 5-MPQ (3.0 mmol) and iodomethane (6.0 mmol) was 66.7%.

[0046] (3) Preparation of 5-MPQ-Me@PLA-PEG electrospun fiber membrane Prepare a mixed solvent system of 8 mL dichloromethane (CH2Cl2) and 2 mL N,N-dimethylformamide (DMF), and add PLA / PEG blends (mass ratios ranging from 20:1 to 50:1). Add PLA to PEG in a total volume of 1.2 g at a mass ratio of 50:1 (PLA 1.18 g, PEG 0.02 g) or 20:1 (PLA 1.14 g, PEG 0.06 g), and stir at room temperature until completely dissolved. Then add 0.01975 g of 5-MPQ-Me to the polymer solution and disperse by ultrasonication to obtain a spinning solution with a final concentration of 5 × 10⁻⁶ mol / mL for 5-MPQ-Me.

[0047] In this invention, both PLA and PEG are made from existing materials. Specifically, the PLA (CAS: 26100-51-6) is selected with a melt flow index of 12-40 g / 10min and a melting point ≥170℃, for example, it can be purchased from Hubei Qiansheng Biotechnology Co., Ltd.; the PEG can be PEG-6000 (CAS: 25322-68-3).

[0048] In this invention, electrospinning is performed using existing processes, with the following electrospinning parameters set: a voltage of 9.0-9.5 kV applied to the needle, a receiver voltage of -2.0 kV, a spinning distance of 18 cm, and a solution advance rate of 0.06 mm / min. 10.0 mL of the above solution was electrospinned on a 960 cm² (30 cm × 32 cm) aluminum foil substrate. The calculated 5-MPQ-Me loading on the fiber membrane surface was approximately 0.052 μM / cm².

[0049] Under otherwise identical conditions, Example 1 used PLA and PEG (total amount constant 1.2 g), without the addition of 5-MPQ-Me. The resulting electrospun fiber membrane had a contact angle of 131.5° and an average diameter of 1.9 μm, which was insufficient for effectively filtering fine aerosol particles, and its significant hydrophobicity was unfavorable for bacterial adhesion. Example 2 used a PLA / PEG blend (mass ratio 50:1, total amount constant 1.2 g), with the addition of 5-MPQ-Me. The resulting electrospun fiber membrane had a contact angle of 59.5° and an average diameter of 0.75 μm. Example 3 used a PLA / PEG blend (mass ratio 20:1, total amount constant 1.2 g), with the addition of 5-MPQ-Me. The resulting electrospun fiber membrane had a contact angle of 36.1° and an average diameter of 0.18 μm. The electrospun fiber membrane prepared in Example 3 not only uniformly disperses 5-MPQ-Me, but also endows the material with ideal hydrophilicity (contact angle <40°) and submicron fiber diameter (<0.3 μm), giving it the potential to filter aerosols <0.3 μm.

[0050] (4) Stability, antibacterial properties and recyclability of 5-MPQ-Me@PLA-PEG electrospun fiber membrane Firstly, an ultrapure water immersion experiment was conducted. The 5-MPQ-Me@PLA-PEG electrospun fiber membrane was immersed in ultrapure water, and samples were collected on days 1, 3, 5, 10, 15, 20, 25, and 30. The water stability of the 5-MPQ-Me@PLA-PEG electrospun fiber membrane was evaluated using SEM characterization. The results showed that the fiber morphology remained intact even after 30 days of immersion, confirming the material's excellent resistance to aqueous environments.

[0051] The inhibitory effect of the fiber membrane on various pathogens was systematically evaluated using the agar diffusion method (Chinese National Standard GB / T 20468—2006). Tested strains included *Escherichia coli*, *Enterobacter cloacae*, *Klebsiella pneumoniae*, *Pseudomonas aeruginosa*, *Staphylococcus aureus*, two methicillin-resistant *Staphylococcus aureus* strains (MRSA1 and MRSA2; MRSA1 was the ATCC 43300 standard strain, and MRSA2 was isolated from Quanzhou First Hospital), and *Bacillus subtilis*. Due to the introduction of 5-MPQ-Me, the fiber membrane exhibited significant antibacterial activity against both Gram-positive and Gram-negative bacteria, especially showing strong inhibition against the two MRSA strains.

[0052] To further investigate the photodynamic antibacterial effect, a fiber membrane was mixed with a bacterial suspension (1×10⁻⁶). 7 CFU / mL of a solution containing *Escherichia coli*, *Klebsiella pneumoniae*, *Staphylococcus aureus*, and MRSA was incubated under light and dark conditions for different times (10 / 30 / 60 / 120 minutes). The antibacterial efficiency was quantified using the CFU plate count method. Under dark conditions, the antibacterial rate reached 69.48% after 10 minutes of incubation, while the antibacterial rate in the light-illuminated group significantly increased to 87.46% due to ROS generation. At 30 minutes, the antibacterial rate in the dark group reached 91.04%, while the antibacterial rate in the light-illuminated group further increased to 98.16%. With prolonged incubation, the difference between light and dark conditions gradually decreased: at 60 minutes, the two groups reached 97.54% and 99.63%, respectively, and after 120 minutes, both exceeded 99.80%, confirming that light exposure significantly enhances the antibacterial effect in short-term exposure, highlighting the photodynamic antibacterial advantages of the material.

[0053] (5) Antibacterial mechanism Dark conditions: Contact sterilization dependent on quaternary ammonium cations (Zeta potential +28.5mV). Excellent hydrophilicity and high zeta potential jointly promote the strong binding of 5-MPQ-Me to the bacterial membrane, achieving sterilization by disrupting the membrane potential and causing intracellular leakage. Light conditions: Synergistic photodynamic sterilization (ROS flux reaches 4.2μmol / cm²·h), ROS generation accelerates membrane damage.

[0054] The scope of protection of this invention is not limited to this embodiment. Any similar modifications made to it, such as scaling up the components proportionally, are considered to be within the scope of protection of this invention.

Claims

1. A method for manufacturing a photodynamic antibacterial fiber membrane suitable for use in face masks, characterized in that, The steps include: Step 1: Preparation of 1-methyl-5-(4-methoxyphenyl)quinoline 4.00-6.00 mmol of 5-bromoquinoline and 6.00-8.00 mmol of triphenylamine 4-borate were placed in a container and dissolved in 18-22 mL of tetrahydrofuran. Separately, 0.40-0.50 g of potassium carbonate or sodium carbonate was dissolved in 4.0-5.0 mL of water. After the two solutions were mixed, 0.08-0.12 mmol of tetra(triphenylphosphine)palladium was added. The mixture was stirred at 70-80 °C for 42 to 54 hours under nitrogen protection. After the reaction was completed, the organic layer was extracted, concentrated under reduced pressure, and purified to obtain the intermediate product. Step 2: Preparation of 1-methyl-5-(4-methoxyphenyl)quinoline-onium hexafluorophosphate The above intermediate product was dissolved in an organic solvent, and 4.0-6.0 mmol of iodomethane was added. The mixture was stirred at 50-60°C for 42 to 54 hours. After the reaction was completed, the solvent was removed to obtain a yellow solid. The yellow solid was added to 8.0-12.0 mL of saturated ammonium hexafluorophosphate aqueous solution, heated at 75 to 85°C, and anhydrous ethanol was added until the yellow solid was completely dissolved. After cooling the solution to room temperature, yellow transparent crystals were obtained, and the target product was obtained. Step 3: Preparation of electrospun fiber membranes Polylactic acid and polyethylene glycol are dissolved in a solvent, and the target product is added to form a spinning solution. The spinning solution is then used for electrospinning to form an electrospun fiber membrane.

2. The method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 1, characterized in that, In the spinning solution, the mass ratio of polylactic acid to polyethylene glycol is 20:1-50:1, and the concentration of the target product is 4×10⁻⁶. -6 mol / mL to 6×10 -6 mol / mL.

3. The method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 2, characterized in that, In step three, the solvent is a mixture of dichloromethane and N,N-dimethylformamide.

4. The method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 3, characterized in that, Based on a total mass of 1.2 g for polylactic acid and polyethylene glycol, the amount of dichloromethane added was 8 mL, the amount of N,N-dimethylformamide added was 2 mL, and the amount of the target product added was 0.01975 g.

5. A method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 4, characterized in that, In the electrospinning process, a voltage of 9.0-9.5 kV is applied to the needle, the receiver voltage is -2.0 kV, the spinning distance is 18 cm, the solution propulsion rate is 0.06 mm / min, and 10 mL of the spinning solution is electrospinned on a 30 cm × 32 cm aluminum foil substrate.

6. The method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 1, characterized in that, In step one, after the reaction is complete, water is added for dilution, and the mixture is extracted with ethyl acetate. The organic layer is separated and retained. An equal volume of water is added, the mixture is shaken, allowed to stand for separation, the aqueous layer is discarded, and the organic layer is separated and retained. An equal volume of saturated saline solution is then added, the mixture is shaken, allowed to stand for separation, the saline layer is discarded, and the organic layer is separated and retained. The obtained organic layer is transferred to an Erlenmeyer flask, and sufficient anhydrous sodium sulfate is added for drying. The mixture is filtered, and the filtrate is concentrated under reduced pressure to obtain the crude product. The crude product is purified by silica gel column chromatography. The eluent used for silica gel column chromatography purification is petroleum ether and ethyl acetate in a volume ratio of 10:

1.

7. The method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 1, characterized in that, In step two, the organic solvent is a mixture of acetonitrile and dichloromethane, with a volume ratio of 16.0-20.0 mL.

8. A method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 7, characterized in that, In step two, the mass ratio of polylactic acid to polyethylene glycol is 50:

1.

9. A method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 8, characterized in that, The loading of the target product on the aluminum foil substrate is 0.048 × 10⁻⁶. -6 mol / cm² to 0.054×10 -6 mol / cm².

10. A method for manufacturing a photodynamic antibacterial fiber membrane for use in face masks as described in claim 9, characterized in that, The electrospinning is carried out at 20°C to 30°C.

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