Preparation method and application of an anti-pathogen fiber membrane

Abstract

The present invention is applicable to the field of photodynamic antibacterial technology, and provides a preparation method and application of an anti-pathogen fiber membrane. First, the compound shown in formula (I) and the compound shown in formula (II) are prepared. The two compounds have a high reactive oxygen generation efficiency. Secondly, they are applied to the preparation of an antibacterial fiber membrane. The compound shown in formula (I) and the compound shown in formula (II) of the present invention, and the fiber membrane prepared therefrom have strong killing activities against various pathogenic microorganisms including Gram-negative bacteria, Gram-positive bacteria, and coronaviruses. The fiber membrane in the present invention can rapidly kill bacteria and pathogens within 20 minutes under light irradiation. At the same time, the fiber membrane has good mechanical properties, thermal stability and optical transparency, and can be applied to textile raw materials, medical materials and other uses.

Description

Technical Field

[0001] The present invention belongs to the technical field of photodynamic antibacterial technology, and particularly relates to a preparation method and application of an anti-pathogen fiber membrane. Background Art

[0002] Photodynamic therapy refers to the production of reactive oxygen species by a photosensitizer under light irradiation to destroy biological substances such as proteins, achieving the purpose of treatment. Due to its broad-spectrum, high-efficiency, and low-toxicity characteristics, photodynamic therapy (PDT) has been widely applied in the fields of antibacterial (J. Am. Chem. Soc 2019, 141, 16781-16789), anti-tumor (Adv. Mater. 2021, 33, 2007888), and anti-coronavirus (Small 2021, 17, 2101770). Among them, the antibacterial photodynamic inactivation (aPDI) technology refers to the production of toxic reactive oxygen species (ROS) by a photosensitizer when excited by visible light to inactivate bacteria. The reactive oxygen species can diffuse within a certain range and play a role in non-contact inactivation of bacteria. During the process of antibacterial photodynamic inactivation, bacteria cannot resist the bactericidal effect of reactive oxygen by stopping the uptake of photosensitizer small molecules, upregulating the metabolic detoxification rate, or accelerating the efflux of photosensitizer small molecules. Therefore, antibacterial photodynamic inactivation is less likely to cause drug resistance in the body than traditional antibacterial methods, can effectively kill drug-resistant bacteria, cope with the increasing number of drug-resistant bacterial infection solutions, reduce the spread of diseases, and only the bacteria exposed to the light source will be inhibited during the antibacterial process, without affecting the normal flora system of the body, greatly improving the safety and directivity of antibacterial.

[0003] People inevitably come into contact with various microorganisms such as bacteria, fungi, and even viruses in daily life. These microorganisms will rapidly multiply under suitable temperature, humidity, and air conditions to increase their numbers, and bring diseases to the human body in a direct or indirect contact manner. Therefore, in many fields, there is a need for some antibacterial textiles with the function of inhibiting the growth of fungi and maintaining the environmental hygiene and cleanliness of textiles.

[0004] Electrospinning is a technology widely used in fiber preparation, and the diameter of the prepared fibers can reach several micrometers or even several nanometers. Due to the characteristics of high aspect ratio, large specific surface area, controllable porosity, and excellent mechanical properties of the nanofibers prepared by electrospinning, electrospinning has gradually become one of the most common methods for manufacturing nanofibers. In the field of photodynamic antibacterial technology, electrospinning provides infinite possibilities for the application of photosensitive antibacterial fibers due to its good controllability, such as some antiviral personal protective products. However, the current photosensitive antibacterial fiber membranes still have many disadvantages. First, most of these products have high requirements for light conditions and cannot efficiently kill pathogens. Second, the efficiency of generating reactive oxygen species of these products is low, increasing the cost of product development.

[0005] Therefore, the present invention synthesizes two photosensitizers with high reactive oxygen generation efficiency and applies them to fiber membranes to kill pathogens. Summary of the Invention

[0006] To solve the problems that most photosensitive antibacterial fiber membranes mentioned above have high requirements for light conditions and cannot efficiently kill pathogens, and secondly, the efficiency of generating reactive oxygen by such products is low, which increases the cost of product development. Therefore, the present invention provides a photosensitizer with high reactive oxygen generation efficiency and a preparation method of an anti-pathogen fiber membrane, and the specific technical solutions are as follows:

[0007] In the first aspect, the present invention provides compounds represented by formula (I) and formula (II), which are characterized by having high reactive oxygen generation efficiency and being applied to fiber membranes to kill pathogens. The structural formulas of the compounds represented by formula (I) and formula (II) are as follows:

[0008]

[0009]

[0010] In the second aspect, the present invention provides a preparation method of a compound represented by formula (I) and formula (II), which mainly includes the following steps:

[0011] The synthesis of the compound represented by formula (I) is to mix 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde and 1,4-dimethylquinolin-1-ium iodide in a molar ratio of 1:1 to 1:1.2, add a basic reagent (molar ratio to the reactants in formula I is 100:1 to 99:1) to the solution, reflux in a solvent for 12 to 24 hours, and after cooling to room temperature, the crude product is purified by a neutral alumina column to obtain the product.

[0012] The synthesis of the compound represented by formula (II) is to mix 4-(diphenylamino)benzaldehyde and 1,4-dimethylquinolin-1-ium iodide in a molar ratio of 1:1 to 1:1.2, add a basic reagent (molar ratio to the reactants in formula II is 100:1 to 99:1) to the solution, reflux in a solvent for 12 to 24 hours, and after cooling to room temperature, the crude product is purified by a neutral alumina column to obtain the product.

[0013] The solvent for the reaction, preferably, any solvent that has no adverse effect on the reaction can be used, such as methyl chloride, ethanol, chloroform, water, dimethylformamide, tetrahydrofuran, methanol, etc.

[0014] The basic reagent includes: sodium bicarbonate, sodium carbonate, potassium carbonate, triethylamine, pyridine, piperidine, etc. Preferably, other basic reagents are used to improve the reaction rate.

[0015] In a third aspect, the present invention provides a method for preparing an antiviral fiber membrane using the compounds represented by formula (I) and formula (II), comprising:

[0016] ① Preparation of the electrospinning solution: The compounds represented by formula (I) and the compounds represented by formula (II) are formulated into the electrospinning solution according to a ratio of 1 wt% to 20 wt%.

[0017] ② At a certain flow rate, the antiviral fiber membrane is prepared by a high-voltage electrospinning process with a voltage of 10 - 30 kV.

[0018] The solvent of the electrospinning solution can be dichloromethane, ethanol, chloroform, water, dimethylformamide, tetrahydrofuran, methanol, etc., and preferably a solvent that has no effect on the antiviral fiber membrane.

[0019] The polymers used in the electrospinning solution include: polypropylene, polyvinyl chloride, polylactic acid, polyurethane, polystyrene, nylon, polyacrylonitrile, etc., polyvinyl alcohol, polycaprolactone, etc., and preferably polymers that have no functional effect on the antiviral fiber membrane.

[0020] The compounds represented by formula (I) and formula (II) of the present invention, and the fiber membranes prepared therefrom have strong killing activity against various pathogenic microorganisms including Gram-negative bacteria, Gram-positive bacteria, coronaviruses, etc. The fiber membranes in the present invention can rapidly kill bacteria and pathogens within 20 minutes under light. At the same time, the fiber membranes have good mechanical properties, thermal stability and optical transparency, and can be applied to textile raw materials, medical materials and other uses.

[0021] Compared with other antibacterial methods, photodynamic antibacterial mainly has the following characteristics: 1) Strains will not develop drug resistance to it; 2) The antibacterial effect is significant and the antibacterial speed is fast; 3) It has low dark toxicity and side effects; 4) It has strong targeting and a definite action target; 5) It can be applied to the medical field, and local treatment can be carried out to avoid large-scale damage to normal tissues; 6) The antibacterial range is wide, and it generally acts widely on microorganisms such as bacteria and fungi.

[0022] Advantageous Effects

[0023] Compared with the prior art, a certain embodiment of the present invention has at least one of the following advantageous effects:

[0024] ① A method for synthesizing a photosensitizer provided by the present invention, the compounds represented by formula (I) and the compounds represented by formula (II) have the advantages of clear synthesis route, simple steps and high yield.

[0025] ② The synthesis method of a photosensitizer provided by the present invention, the compound shown in formula (Ⅰ) and the compound shown in formula (Ⅱ) have good bactericidal ability after being made into a photodynamic antibacterial nanofiber membrane.

[0026] ③ The synthesis method of a photosensitizer provided by the present invention, the compound shown in formula (Ⅰ) and the compound shown in formula (Ⅱ) have low systemic toxicity after being made into a photodynamic antibacterial nanofiber membrane. Description of the Drawings

[0027] Figure 1 1H NMR spectrum of the compound shown in formula (Ⅰ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0028] Figure 2 13C NMR spectrum of the compound shown in formula (Ⅰ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0029] Figure 3 Mass spectrum of the compound shown in formula (Ⅰ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0030] Figure 4 1H NMR spectrum of the compound shown in formula (Ⅱ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0031] Figure 5 13C NMR spectrum of the compound shown in formula (Ⅱ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0032] Figure 6 Mass spectrum of the compound shown in formula (Ⅱ) in the preparation method of an anti-pathogen fiber membrane provided by the present invention.

[0033] Figure 7 Antibacterial performance comparison chart of polyurethane@TPP and polyvinyl chloride@TPP nanofabrics of an anti-pathogen fiber membrane provided by the present invention (left figure is Escherichia coli, right figure is Staphylococcus aureus, 60 mW / cm2, 30 min).

[0034] Figure 8 Anti-coronavirus performance comparison chart of polyurethane@TPP and polyvinyl chloride@TPP nanofabrics of an anti-pathogen fiber membrane provided by the present invention (60 mW / cm2, 30 min).

[0035] Figure 9 HE staining comparison images of the back skin after being repeatedly wiped with PBS (20 mL) or 4 mM TPP of the sensitizer compound shown in formula (Ⅰ) for 7 days for an anti-pathogen fiber membrane provided by the present invention.

[0036] Figure 10Schematic diagram of the phototoxicity test on the back skin of healthy mice covered with polyurethane@TPP and polyvinyl chloride@TPP provided by the present invention.

[0037] Figure 11 Image of HE staining of the skin of healthy mice equipped with polyurethane@TPP and polyvinyl chloride@TPP after 1 hour of light irradiation. Scale bar: 100μm.

[0038] Figure 12 Normalized ultraviolet-visible absorption and fluorescence spectra of PU@TPP and PVC@TPP provided by the present invention.

[0039] Figure 13 Fluorescence lifetime curve images of PU@TPP and PVC@TPP provided by the present invention.

[0040] Figure 14 Images of singlet oxygen generation of photodynamic nanofibers in aqueous phase and the blank control group provided by the present invention.

[0041] Figure 15 Images of singlet oxygen signals of PVC@TPP and PU@TPP in air provided by the present invention.

[0042] Figure 16 Schematic diagrams of the optical properties, ROS generation behavior, and theoretical calculation details of two photosensitizers of formula (I) and (II) provided by the present invention.

[0043] Term Explanation

[0044] In the description of the present invention, it should be understood that the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "a plurality" means two or more, unless otherwise specifically defined.

[0045] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples. In addition, without conflict, those skilled in the art may combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0046] In the present invention, "PVC" refers to polyvinyl chloride, abbreviated as PVC in English. It is a polymer formed by the polymerization of vinyl chloride monomer (VCM) under the action of initiators such as peroxides and azo compounds or under the action of light and heat according to the free radical polymerization reaction mechanism. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively called vinyl chloride resins.

[0047] In the present invention, "PU" refers to polyurethane (PU), whose full name is polycarbamate, which is a high molecular compound. It was prepared by Otto Bayer et al. in 1937. Polyurethanes are divided into two major categories: polyester type and polyether type. They can be made into polyurethane plastics (mainly foam plastics), polyurethane fibers (called spandex in China), polyurethane rubbers and elastomers.

[0048] In the present invention, "HE staining" refers to hematoxylin-eosin staining, abbreviated as HE staining method, which is one of the commonly used staining methods in paraffin section technology. The hematoxylin staining solution is alkaline, mainly making the chromatin in the cell nucleus and the nucleic acid in the cytoplasm stained purple-blue; eosin is an acidic dye, mainly making the components in the cytoplasm and extracellular matrix stained red. The HE staining method is the most basic and widely used technical method in histology, embryology, and pathology teaching and research.

[0049] In the present invention, "PPE" refers to polypropylene ethylene, also called ethylene-propylene rubber (EPR). It is a copolymer rubber with ethylene and propylene as the basic monomers that emerged after the invention of Ziegler-Natta catalysts, the appearance of polyethylene and polypropylene. It is divided into two major categories: ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-diene terpolymer rubber (EPDM). The former is a copolymer of ethylene and propylene, and the latter is a copolymer of ethylene, propylene, and a small amount of non-conjugated dienes.

[0050] In the present invention, "PBS" represents phosphate buffered saline; "ROS" represents reactive oxygen species; "DMSO" represents dimethyl sulfoxide; "SOC" represents SOC coupling constant; "RMSD" represents root mean square error (abbreviated as RMSE), also known as root-mean-square deviation (abbreviated as RMSD), which is a commonly used measure of the difference between numerical values.

[0051] In the present invention, expressions such as "compound of formula (I)", "compound shown in formula (I)", "compound formula (I)", and "compound (I)" have the same meaning, and the naming of other compounds follows the same analogy. Detailed implementation manners

[0052] To enable those skilled in the art to better understand the technical solution of the present invention, some non-limiting embodiments are further disclosed below for a more detailed description of the present invention.

[0053] All the reagents used in the present invention can be purchased from the market or prepared by the methods described in the present invention.

[0054] Example 1: Preparation of the compound shown by photosensitizer formula (I)

[0055] Synthesis of the compound of formula (I) shown in the structural formula as follows

[0056]

[0057] Under N 2 protection, a mixture of 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde (0.1 mmol), 1,4-dimethylquinolin-1-ium iodide (0.12 mmol), and piperidine (0.001 mmol) added in a molar ratio of 100:1 to 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde (0.1 mmol) was used as the reaction solvent with ethanol reagent. Then all the mixtures were stirred at 40 °C for 12 h. The insoluble substances were removed, and the resulting residue was separated by an alumina column (dichloromethane:ethanol = 99:1) to obtain a purple-black powder compound (I) (yield 65%).

[0058] Take the obtained compound (I) and detect its hydrogen spectrum, carbon spectrum, and mass spectrum, as Figure 1 、 2As shown in Figures 3, the structural characterization data of the obtained compound (I) are as follows: 1H NMR (400 MHz, DMSO-d6, δ ppm): 9.30 (s, 1H), 8.95 (s, 1H), 8.42 (s, 2H), 8.26 (s, 1H), 8.15–7.85 (m, 2H), 7.67 (t, J = 36 Hz, 4H), 7.48–6.70 (m, 12H), 4.51 (s, 3H); 13C NMR (101 MHz, DMSO-d6, δ ppm): 44.99, 115.85, 117.90, 119.78, 122.14, 122.63, 124.43, 124.58, 124.92, 125.28, 125.45, 125.96, 126.36, 126.70, 126.77, 127.33, 127.89, 129.62, 130.25, 134.70, 135.37, 136.30, 139.21, 139.52, 140.00, 141.31, 146.87, 147.01, 148.08, 148.39, 148.84, 152.42, 153.38, 184.19; m / z calcd. for C34H27N2S+ ([M]+), 495.18820; found, 413.18895. According to the structural characterization data of compound (I), the target product photosensitizer, the compound shown in formula (I), has been synthesized.

[0059] Example 2: Preparation of the compound shown in formula (II) of photosensitizer

[0060] Synthesis of the compound shown in formula (II) with the structural formula as shown in the following figure

[0061]

[0062] Under N2 protection, a mixture of 4-(diphenylamino)benzaldehyde (0.1 mmol), 1,4-dimethylquinolin-1-ium iodide (0.12 mol), piperidine (molar ratio 100:1), and ethanol (reaction solvent) was stirred at 40 °C for 12 h. Insoluble substances were removed, and the resulting residue was separated by an alumina column (methylene chloride:ethanol = 99:1) to obtain compound (II) (yield 65%).

[0063] Take the obtained compound (II) and detect its hydrogen spectrum, carbon spectrum, and mass spectrum, as Figure 4 、 5, as shown in Figure 6, the structural characterization data of the obtained compound (II) are as follows: 1H NMR (400 MHz, DMSO-d6, δ ppm): 9.26 (d, J = 6.4 Hz, 1H), 9.01 (dd, J = 8.8, 1.6 Hz, 1H), 8.44 (d, J = 6.8 Hz, 1H), 8.41 (dd, J = 8.89, 1.2 Hz, 1H), 8.24 (ddd, J = 8.8, 6.8, 1.2 Hz, 1H), 8.15 (s, 2H), 8.02 (ddd, J = 8.4, 7.2, 1.2 Hz, 1H), 7.91–7.86 (m, 2H), 7.43–7.37 (m, 4H), 7.19 (dt, J = 7.6, 1.2 Hz, 2H), 7.17–7.13 (m, 4H), 6.99–6.94 (m, 2H), 4.50 (s, 3H); 13C NMR (100 MHz, DMSO-d6, δ ppm): 44.93, 115.81, 117.35, 119.77, 120.91, 125.15, 125.98, 126.59, 126.82, 128.88, 129.50, 130.36, 131.04, 135.33, 139.26, 143.39, 146.58, 148.10, 150.28, 153.23; m / z calcd. for C30H25N2+ ([M]+), 413.20123; found, 413.20059. According to the structural characterization data of compound (II), the target product photosensitizer, the compound shown in formula (II), has been synthesized.

[0064] Example 3: Preparation of a nanofiber membrane of a polyurethane-loaded photosensitizer compound of formula (I)

[0065] 1 wt% of compound (I) and polyurethane / polyvinyl chloride were added to a DMF:THF (3:1) solution and stirred for 12 h to obtain a polymer solvent containing the photosensitizer. Under the conditions of 25 °C and 50% humidity, a nanofiber membrane was prepared by electrospinning. Among them, the experimental parameters of electrospinning were a flow rate of 0.0020 mL / min, a voltage of 25 kV, and a spinning distance of 10 cm. Finally, a photodynamic nanofiber membrane: polyurethane@TPP and polyvinyl chloride@TPP nanofabrics were obtained, where TPP refers to the compound shown in formula (I) of the photosensitizer.

[0066] Example 4: Antibacterial performance test of photodynamic nanofibers

[0067] As Figure 7As shown, polyurethane@TPP and polyvinyl chloride@TPP nanofabrics did not exhibit antibacterial properties in the dark, and after 30 min of light irradiation, less than 15% of Escherichia coli and 3% of Staphylococcus aureus survived under light (60 mW / cm2).

[0068] In addition, after the light irradiation was extended to 40 min, almost all bacteria were eliminated, indicating that the photodynamic nanofibers had good bactericidal ability. Under the same experimental conditions, the bactericidal effect of the nanofabric doped with TPP on Staphylococcus aureus was better than that on Escherichia coli.

[0069] To test the anti-coronavirus ability of the nanofabric, we loaded murine coronavirus: murine hepatitis virus strain A59 (MHV-A59) droplets (1.316×106 copies / μL) on the nanofabric and examined the infectivity under light. The results showed that 99.9997% of the coronaviruses were inactivated after only 20 min (60 mW / cm2) of light irradiation on the polyurethane@TPP nanofabric (as Figure 8 shown), and its killing efficiency was about 10.5 times higher than that of polyvinyl chloride@TPP (99.9973%). The higher anti-coronavirus efficiency was due to the higher ROS production of polyurethane@TPP. In contrast, control experiments in the dark group (polyurethane@TPP or polyvinyl chloride@TPP in the dark) and the light group (polyurethane or polyvinyl chloride matrix under the same light) showed negligible coronavirus inactivation function. These results together indicate that the photosensitizer-doped nanofabric has excellent anti-coronavirus effect in the presence of light.

[0070] Example 4: In vitro and in vivo biocompatibility tests of TPP

[0071] First, the in vitro dark cytotoxicity of TPP was measured using the CCK8 assay. The survival rate of murine lung epithelial cells (MLE-12) co-cultured with TPP at 4 mM for 24 h was still higher than 90% (much higher concentration compared to TPP in the photodynamic nanofibers), indicating that the side effects of TPP were negligible on normal lung cells. For in vivo evaluation, healthy mice were intranasally injected with PBS or TPP. After 7 days of treatment, the results of body weight, blood tests, and HE staining images of major organs showed that there were no significant changes in the TPP treatment group compared to the PBS-treated control group. Considering the application scenario of antiviral PPE, it should be of low toxicity to normal skin during daily use. We first evaluated the safety of TPP on the bare skin of mice. The skin appearance and pathological analysis together confirmed that no abnormalities were observed after continuous wiping with 4 mM TPP solution in PBS on the back skin for one week ( Figure 9as shown). In addition, to evaluate whether TPP would cause any phototoxicity when used in PPE (such as masks), the dorsal skin of healthy mice covered with PVC@TPP and PU@TPP was continuously irradiated for 1 h (60 mW / cm2) Figure 11 as shown. The following histochemical analysis showed that the treated skin maintained its normal morphology after light exposure. Therefore, the photodynamic nanofibers have low systemic toxicity when used as PPE.

[0072] Example 5: Optical properties and ROS generation performance tests of polyurethane@TPP and polyvinyl chloride@TPP

[0073] As Figure 12 shown, the normalized UV-visible absorption and fluorescence spectra of PU@TPP and PVC@TPP are shown. It can be seen from the UV-visible absorption spectrum that the maximum absorption wavelength of PU@TPP is around 690 nm, and the maximum absorption wavelength of PVC@TPP is around 790 nm. As Figure 13 shown, the fluorescence lifetime curves of PU@TPP and PVC@TPP are shown. According to the display results of the images, the fluorescence lifetime of PVC@TPP is better than that of PU@TPP. As Figure 14 shown, the singlet oxygen generation images of the photodynamic nanofibers in the aqueous phase are shown. It can be seen from the images that the A / A0 intensity of singlet oxygen of PVC@TPP is closer to the blank control group over time. As Figure 15 shown, the singlet oxygen signals of PVC@TPP and PU@TPP in air are shown, demonstrating that the two photodynamic nanofibers can generate 1O2, that is, excited state oxygen molecules, in air. These results together indicate that the photosensitizer-doped nanofabrics have high reactive oxygen generation efficiency and can be applied to fiber membranes to kill pathogens.

[0074] Finally, the properties and theoretical calculation details of photosensitizer formula (I) and photosensitizer formula (II), where TPP refers to the photosensitizer shown in compound formula (I), and TP refers to the photosensitizer shown in compound (II). As Figure 16 shown in 16a, the normalized absorption spectra and fluorescence spectra of TP and TPP in DMSO are shown. 16b shows the 1O2 generation ability determined by ABDA (20 mW / cm2). 16c shows the generation of 1O2 through TPP, and TP is determined using ESR. 16d shows the molecular orbitals of TP and TPP in the S0 state (SMD, water) at the PBE0 / 6-31g(d) level by Gaussian. 16e shows the hole-electron analysis of TP and TPP by Multiwfn. 16f and g show the SOC constants of TPP and TPP by ORCA software under the same conditions. 16h shows the RMSD between S1 and T1 of TP and TPP.

[0075] In summary, compared with the prior art, one embodiment of the present invention has at least one of the following beneficial effects:

[0076] ① The synthesis method of a photosensitizer provided by the present invention has the advantages that the compounds shown in formula (Ⅰ) and the compounds shown in formula (Ⅱ) have a clear synthesis route, simple steps and a relatively high yield.

[0077] ② The synthesis method of a photosensitizer provided by the present invention has good bactericidal and antibacterial abilities after the compounds shown in formula (Ⅰ) and the compounds shown in formula (Ⅱ) are made into a photodynamic antibacterial nanofiber membrane.

[0078] ③ The synthesis method of a photosensitizer provided by the present invention has a low systemic toxicity after the compounds shown in formula (Ⅰ) and the compounds shown in formula (Ⅱ) are made into a photodynamic antibacterial nanofiber membrane.

[0079] ④ The preparation of a photosensitizer and an antibacterial fiber membrane provided by the present invention has good mechanical properties, better thermal stability and optical transparency, and can be widely used in textile raw materials, medical materials and other applications.

[0080] The method of the present invention has been described through preferred embodiments. It is obvious that relevant personnel can make changes or appropriate modifications and combinations to the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can draw on the content of this article and appropriately improve the process parameters to achieve it. It should be particularly noted that all such substitutions and modifications are obvious to those skilled in the art and are all considered to be included in the present invention.

Claims

1. A compound represented by formula (I), characterized in that it has a high reactive oxygen generation efficiency and is used to kill pathogens in a fiber membrane. The structural formula of the compound represented by formula (I) is as follows:

2. A preparation method of a compound represented by formula (I) according to claim 1, characterized in that it includes: In a solution of 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde and 1,4-dimethylquinolin-1-ium iodide, the molar ratio of 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde to 1,4-dimethylquinolin-1-ium iodide is 1:1 to 1:1.

2. An alkaline reagent is added, and the mixture is refluxed in a solvent for 12 to 24 hours. After cooling to room temperature, the crude product is purified to obtain the compound represented by formula (I).

3. A preparation method of a compound represented by formula (I) according to claim 2, characterized in that the solvent uses an ethanol solution as the reaction solvent.

4. A preparation method of a compound represented by formula (I) according to claim 2, characterized in that the alkaline reagent includes: sodium bicarbonate, sodium carbonate, potassium carbonate, triethylamine, pyridine, piperidine, which are used to improve the reaction rate. Among them, the alkaline reagent is added to the solvent in a molar ratio of 100:1 to 99:1 with 5-(4-(diphenylamino)phenyl)thiophene-2-carbaldehyde.

5. A preparation method of a compound represented by formula (I) according to claim 1 for an antiviral fiber membrane, characterized in that it includes: ① Preparation of the electrospinning solution: The compound represented by formula (I) is formulated into the electrospinning solution according to a ratio of 1 wt% to 20 wt%. ② Under a flow rate set to 0.0010 mL / min to 0.0030 mL / min, an antiviral fiber membrane is prepared by a high-voltage electrospinning process at 10 to 30 kV.

6. A preparation method of a compound represented by formula (I) according to claim 5 for an antiviral fiber membrane, characterized in that the solvent of the electrospinning solution is dichloromethane, ethanol, chloroform, water, dimethylformamide, tetrahydrofuran or methanol.

7. A preparation method of a compound represented by formula (I) according to claim 5 for an antiviral fiber membrane, characterized in that the polymers used in the electrospinning solution include: polypropylene, polyvinyl chloride, polylactic acid, polyurethane, polystyrene, nylon, polyacrylonitrile, polyvinyl alcohol, polycaprolactone.

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