Preparation method and application of antibacterial nanocomposite fiber membrane

Abstract

The application belongs to the technical field of antibacterial nanocomposite fiber materials, and particularly relates to a preparation method and application of an antibacterial nanocomposite fiber film, and comprises the following steps: step 1, preparing imidazole ester skeleton-8; step 2, preparing tungsten-doped ferrite; step 3, using the imidazole ester skeleton-8 and the tungsten-doped ferrite to complete preparation of antibacterial nanomaterial powder; and step 4, using the antibacterial nanomaterial powder prepared in step 3 and TPU particles to prepare TPU spinning solution in which the antibacterial nanomaterial powder is uniformly dispersed; and the obtained spinning solution is subjected to a solution jet spinning method to obtain a composite nanofiber film. The nanocomposite fiber film prepared in the application is expected to be used in the medical and health field to provide new products for medical protection.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial nanocomposite fiber materials, and particularly relates to a preparation method and application of an antibacterial nanocomposite fiber membrane. Background Art

[0002] Medical staff who come into contact with infectious disease patients are required to wear disposable protective equipment to block microparticles from the patient's blood, body fluids, and secretions. Personal protective equipment (PPE) serves as a direct barrier to protect medical staff from the hazards of biological contamination. Thermoplastic elastic polyurethane (TPU) materials have been extensively studied in the medical and health care field due to their excellent biocompatibility, flexibility and elasticity, environmental non-toxicity, and biodegradability. Furthermore, polyurethane nanofibers also possess excellent waterproof, moisture permeability, and breathability.

[0003] Metal-organic framework materials (MOFs) are a type of organic-inorganic porous coordination polymers composed of metal ions or metal clusters and organic ligands. They have a topological three-dimensional network pore structure and are widely used in adsorption and separation, energy storage, sensing, antibacterial and catalysis. As one of the common MOFs materials, imidazolate framework-8 (ZIF-8) is widely used. Although ZIF-8 materials are easy to process, have high chemical stability, good biodegradability and biocompatibility, when used in the field of photocatalysis and antibacterial, due to its large band gap and weak response to visible light, it is difficult to excite internal electrons under visible light conditions, thus affecting its solar radiation efficiency. Tungsten-doped ferrite (FeWO x ) as a magnetic nanomaterial, it has a suitable energy band structure and can form a Z-type heterojunction with ZIF-8, shortening the charge transfer distance, effectively inhibiting the recombination of electrons and holes, and improving the photocatalytic effect of the nanomaterial. At the same time, as a magnetic material FeWO x It can also achieve a synergistic antibacterial effect with ZIF-8 through magnetothermal effect.

[0004] In summary, the present invention designs and develops a nanocomposite fiber membrane with photocatalytic, photothermal and magnetothermal synergistic antibacterial properties. The fiber uses degradable, high-strength and high-hydrophobic TPU as a substrate, into which ZIF-8 / FeWO x (hereinafter referred to as ZF) nanocomposites were prepared by solution jet spinning technology to prepare TPU-ZIF-8 / FeWO x(Hereinafter referred to as T-ZF) nanocomposite fiber membrane. This nanocomposite fiber membrane exhibits synergistic antibacterial properties through photocatalysis, photothermal therapy, and magnetic thermal therapy, achieving a 99.99% kill rate against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), multidrug-resistant E. coli (MDRE. coli), and methicillin-resistant Staphylococcus aureus (MRSA). This nanocomposite fiber membrane could provide a new product for medical protection. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing and applying an antibacterial nanocomposite fiber membrane, and to propose ZIF-8 / FeWO for the first time. x Nanocomposite materials, by constructing Z-type heterojunction, reduce the electron-hole recombination efficiency, make it easier for electrons to jump from the valence band to the conduction band, improve the photocatalytic performance of nanomaterials, and prepare a TPU-ZIF-8 / FeWO x A new type of nanocomposite fiber membrane. The fiber membrane uses TPU as the base material and is made of nano-heterojunction ZIF-8 / FeWO by solution jet spinning technology. x Loaded on the fiber, the fiber promotes photocatalysis through thermal effect to achieve synergistic and efficient antibacterial effects of photocatalysis, photothermal and magnetothermal. The nanocomposite fiber membrane is expected to be used in the medical and health field, providing new products for medical protection.

[0006] The technical solutions adopted by the present invention are as follows:

[0007] The preparation method of the antibacterial nanocomposite fiber membrane comprises the following steps:

[0008] Step 1: Preparation of imidazole ester skeleton-8;

[0009] Step 101: adding 2.8-3.5 parts by mass of 2-methylimidazole and 1.2-1.7 parts by mass of zinc nitrate hexahydrate to 65-75 parts by mass of a methanol solution; wherein the concentration of the methanol solution is 40%-60%;

[0010] Step 102: Magnetic stirring is performed at room temperature (25° C.) on a magnetic stirrer for 30 min;

[0011] Step 103: Collect the precipitate by centrifugation and wash it with methanol five times;

[0012] Step 104: drying in a vacuum oven at 60℃ for 12h to complete the preparation of imidazolide skeleton-8.

[0013] Step 2: preparation of tungsten-doped ferrite;

[0014] Step 201: 0.8-0.85 parts by mass of 1,2-dodecanediol, 0.1-0.2 parts by mass of tungsten hexacarbonyl, 0.08-0.09 parts by mass of iron acetylacetone, 0.4-0.5 parts by mass of iron acetylacetone, 75-85 parts by mass of diphenyl ether, 0.35-0.45 parts by mass of oleic acid, and 3.2-4 parts by mass of oleylamine were placed in a round-bottom flask;

[0015] Step 202: slowly heated to 120℃ under argon protection for 10min, then slowly heated to 260℃ and kept for 2.5h, and then immediately quenched;

[0016] Step 203: after the reaction in step 201 cooled to room temperature, the precipitate was collected by centrifugation and washed with ethanol and ultrapure water for 5 times;

[0017] Step 204: vacuum freeze-drying to obtain tungsten-doped ferrite powder.

[0018] Step 3: using imidazolide skeleton-8 and tungsten-doped ferrite to complete the preparation of antibacterial nanomaterial powder;

[0019] Step 301: 45-50 parts by mass of imidazolide skeleton-8 powder and 45-50 parts by mass of tungsten-doped ferrite powder were added to 25-35 parts by mass of ultrapure water,

[0020] Step 302: the solution was treated under ultrasonic conditions for 10min,

[0021] Step 303: the solution was placed in a shaker for 12h,

[0022] Step 304: the precipitate was collected by centrifugation and washed with ultrapure water for 5 times, and vacuum freeze-drying to obtain antibacterial nanomaterial powder.

[0023] Step 4: using the antibacterial nanomaterial powder prepared in step 3 and TPU particles to prepare TPU spinning solution with uniformly dispersed antibacterial nanomaterial powder; the obtained spinning solution was obtained by solution jet spinning method to obtain composite nanofiber membrane.

[0024] Step 401: 0.04-0.05 parts by mass of antibacterial nanomaterial powder was dissolved in 1 part by mass of N,N-dimethylformamide and 2 parts by mass of tetrahydrofuran;

[0025] Step 402: Ultrasonicate for 5 minutes, then add 0.45-0.55 parts by mass of TPU particles;

[0026] Step 403: Magnetic stirring is performed at 40° C. for 12 hours to complete the preparation of a TPU spinning solution in which the antibacterial nanomaterial powder is dispersed;

[0027] Step 404: The obtained spinning solution is subjected to a solution jet spinning method to obtain an antibacterial nanocomposite fiber membrane; the parameters of the jet spinning method in step 404 are: needle specification: 25G, propulsion rate: 0.25mL / h, receiving roller speed: 300rpm, receiving distance: 30cm, and wind pressure: 70MPa.

[0028] Application of the antibacterial nanocomposite fiber membrane in the preparation of medical protective equipment.

[0029] The technical effects achieved by the present invention are:

[0030] The present invention discloses a nanocomposite fiber membrane with photocatalytic, photothermal and magnetothermal synergistic antibacterial properties. The fiber uses a degradable, high-strength and highly hydrophobic TPU as a substrate, into which ZIF-8 / FeWO is incorporated. x (hereinafter referred to as ZF) nanocomposites were prepared by solution jet spinning technology to prepare TPU-ZIF-8 / FeWO x (Hereinafter referred to as T-ZF) nanocomposite fiber membrane. This nanocomposite fiber membrane exhibits synergistic antibacterial properties through photocatalysis, photothermal therapy, and magnetic thermal therapy. It boasts a 99.99% kill rate against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), multidrug-resistant Escherichia coli (MDR E. coli), and methicillin-resistant Staphylococcus aureus (MRSA). This nanocomposite fiber membrane could provide a new product for medical protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the preparation of the nanocomposite fiber membrane of the present invention;

[0032] Figure 2 is a SEM image of the ZIF-8 nanomaterial of the present invention;

[0033] Figure 3 is the XRD pattern of the ZIF-8 nanomaterial in the present invention;

[0034] Figure 4 is the Zeta potential diagram of the ZIF-8 nanomaterial in the present invention (n=3);

[0035] Figure 5 FeWO in the present invention x SEM images of nanomaterials;

[0036] Figure 6 FeWO in the present invention x XRD patterns of nanomaterials;

[0037] Figure 7 FeWO in the present invention x Zeta potential diagram of nanomaterials (n=3);

[0038] Figure 8 is a SEM image of the ZF nanomaterial of the present invention;

[0039] Figure 9 is the XRD pattern of the ZF nanomaterial in the present invention;

[0040] Figure 10 The ZIF-8 and FeWO x , FTIR spectrum of ZF;

[0041] Figure 11 The ZIF-8 and FeWO x , UV-Vis-DRS spectrum of ZF;

[0042] Figure 12 The ZIF-8 and FeWO x , ESI spectrum of ZF;

[0043] Figure 13 The ZIF-8 and FeWO x , ZF's photocurrent response spectrum;

[0044] Figure 14 The ZIF-8 and FeWO x , ZF’s 1 ESR spectrum of O2;

[0045] Figure 15 The ZIF-8 and FeWO x 、ESR spectrum of ·OH of ZF;

[0046] Figure 16 The ZIF-8 / FeWO x The band structure diagram of the nanocomposite material;

[0047] Figure 17The ZIF-8 and FeWO x 、ZF simulates sunlight (1000W / m 2 ) and the photothermal cycle curves of ZF under five on / off cycles;

[0048] Figure 18 FeWO in the present invention x , ZF's hysteresis loop;

[0049] Figure 19 The ZIF-8 and FeWO x , the temperature rise curve of ZF under alternating magnetic field and the magnetocaloric cycle curve of ZF under five cycles;

[0050] Figure 20 The present invention is in different groups of ZIF-8, FeWO x and ZF's photos of different plate-coated colonies and bacterial survival quantification diagrams ( Figure 20 Middle: 1: Control; 2: ZIF-8-Dark; 3: FeWO x -Dark; 4: ZF-Dark; 5: ZIF-8-Light; 6: FeWO x -Light; 7: ZF-Light; 8: ZIF-8-Magnetic; 9: FeWO x -Magnetic; 10: ZF-Magnetic; 11: ZIF-8-M+L; 12: FeWO x -M+L; 13: ZF-M+L) (n=3);

[0051] Figure 21 This is a physical diagram of the fiber in the present invention;

[0052] Figure 22 is the SEM image of TPU and T-ZF fibers in the present invention;

[0053] Figure 23 is the contact angle of TPU and T-ZF fibers in the present invention (n=3);

[0054] Figure 24 The TPU, T-ZIF-8, T-FeWO x , T-ZF 1 ESR spectrum of O2;

[0055] Figure 25 The TPU, T-ZIF-8, T-FeWO x , ESR spectrum of ·OH of T-ZF;

[0056] Figure 26The TPU, T-ZIF-8, T-FeWO x 、T-ZF simulates sunlight (1000W / m 2 ) and the photothermal cycle curves of T-ZF fiber under five on / off cycles;

[0057] Figure 27 The TPU, T-ZIF-8, T-FeWO x , the heating curve of T-ZF under alternating magnetic field and the magnetocaloric cycle curve of T-ZF fiber under five thermal cooling cycles;

[0058] Figure 28 This is a diagram showing the antibacterial effect of the present invention on Escherichia coli;

[0059] Figure 29 This is a diagram showing the antibacterial effect of the present invention on Staphylococcus aureus S.aureus;

[0060] Figure 30 This is a diagram showing the antibacterial effect of the present invention on multidrug-resistant Escherichia coli MDRE.coli;

[0061] Figure 31 This is a diagram showing the antibacterial effect of the present invention on methicillin-resistant Staphylococcus aureus (MRSA).

[0062] Figure 29-Figure 31 Medium: (1: Control; 2: TPU-Dark; 3: T-ZIF-8-Dark; 4: T-FeWO x -Dark; 5: T-ZF-Dark; 6: TPU-Light+Ice; 7: T-ZIF-8-Light+Ice; 8: T-FeWO x -Light+Ice; 9: T-ZF-Light+Ice; 10: TPU-Light; 11: T-ZIF-8-Light; 12: T-FeWO x -Light; 13: T-ZF-Light; 14: TPU-Magnetic; 15: T-ZIF-8-Magnetic; 16: T-FeWO x -Magnetic; 17: T-ZF-Magnetic; 18: TPU-M+L; 19: T-ZIF-8-M+L; 20: T-FeWO x -M+L; 21: T-ZF-M+L) (n=3). DETAILED DESCRIPTION

[0063] In order to make the purpose and advantages of the present invention more clearly understood, the present invention is described in detail below with reference to the following examples. It should be understood that the following text is only used to describe one or more specific embodiments of the present invention and does not strictly limit the scope of protection of the present invention.

[0064] Example 1:

[0065] The preparation method of the antibacterial nanocomposite fiber membrane comprises the following steps:

[0066] Step 1: Preparation of imidazole ester skeleton-8;

[0067] Step 101: adding 2.8-3.5 parts by mass of 2-methylimidazole and 1.2-1.7 parts by mass of zinc nitrate hexahydrate to 65-75 parts by mass of a methanol solution; wherein the concentration of the methanol solution is 40%-60%;

[0068] Step 102: Magnetic stirring is performed at room temperature (25° C.) on a magnetic stirrer for 30 min;

[0069] Step 103: Collect the precipitate by centrifugation and wash it with methanol five times;

[0070] Step 104: Dry in a vacuum oven at 60° C. for 12 hours to complete the preparation of imidazole ester skeleton-8.

[0071] Step 2: preparing tungsten-doped ferrite;

[0072] Step 201: 0.8-0.85 parts by mass of 1,2-dodecanediol, 0.1-0.2 parts by mass of tungsten hexacarbonyl, 0.08-0.09 parts by mass of ferrous acetylacetonate, 0.4-0.5 parts by mass of ferric acetylacetonate, 75-85 parts by mass of diphenyl ether, 0.35-0.45 parts by mass of oleic acid, and 3.2-4 parts by mass of oleylamine are placed in a round-bottom flask;

[0073] Step 202: slowly heating to 120° C. under argon protection, maintaining for 10 minutes, then slowly heating to 260° C., maintaining for 2.5 hours, and then immediately quenching;

[0074] Step 203: After the reaction in step 201 is cooled to room temperature, the precipitate is collected by centrifugation and washed five times with ethanol and ultrapure water;

[0075] Step 204: vacuum freeze-drying to obtain tungsten-doped ferrite powder.

[0076] Step 3: using imidazolate skeleton-8 and tungsten-doped ferrite to complete the preparation of antibacterial nanomaterial powder;

[0077] Step 301: adding 45-50 parts by mass of imidazole ester framework-8 powder and 45-50 parts by mass of tungsten-doped ferrite powder to 25-35 parts by mass of ultrapure water.

[0078] Step 302: The solution is subjected to ultrasonic treatment for 10 minutes.

[0079] Step 303: Place the solution in a shaker for 12 hours.

[0080] Step 304: The precipitate is collected by centrifugation and washed with ultrapure water for 5 times, and then freeze-dried in vacuum to obtain antibacterial nanomaterial powder.

[0081] Step 4: Use the antibacterial nanomaterial powder and TPU particles prepared in step 3 to prepare a TPU spinning solution in which the antibacterial nanomaterial powder is evenly dispersed; and use a solution jet spinning method to obtain a composite nanofiber membrane.

[0082] Step 401: Weigh 0.04-0.05 parts by mass of antibacterial nanomaterial powder and dissolve it in 1 part by mass of N,N-dimethylformamide and 2 parts by mass of tetrahydrofuran;

[0083] Step 402: Ultrasonicate for 5 minutes, then add 0.45-0.55 parts by mass of TPU particles;

[0084] Step 403: Magnetic stirring is performed at 40° C. for 12 hours to complete the preparation of a TPU spinning solution in which the antibacterial nanomaterial powder is dispersed;

[0085] Step 404: The obtained spinning solution is subjected to a solution jet spinning method to obtain an antibacterial nanocomposite fiber membrane; the parameters of the jet spinning method in step 404 are: needle specification: 25G, propulsion rate: 0.25mL / h, receiving roller speed: 300rpm, receiving distance: 30cm, and wind pressure: 70MPa.

[0086] Example 2:

[0087] Application of the antibacterial nanocomposite fiber membrane in the preparation of medical protective equipment.

[0088] Example 3:

[0089] The preparation method of the antibacterial nanocomposite fiber membrane comprises the following steps:

[0090] Step 1: Preparation of imidazolate framework-8 (abbreviated as ZIF-8):

[0091] 3.3 g of 2-methylimidazole and 1.5 g of zinc nitrate hexahydrate were added to 70 mL of methanol solution and stirred on a magnetic stirrer at room temperature for 30 min. The precipitate was then collected by centrifugation and washed several times with methanol, and then dried in a vacuum oven at 60 °C for 12 h.

[0092] In this embodiment, ZIF-8 is subjected to characterization experiments:

[0093] The morphology of ZIF-8 nanomaterials was obtained by scanning electron microscopy (SEM). Figure 2 As shown in FIG, the obtained ZIF-8 has a rhombic dodecahedral structure and a particle size of about 100 nm. The crystal structure was verified by X-ray powder diffractometer (XRD) analysis. The results are shown in FIG. Figure 3 As shown in the figure, the XRD pattern of ZIF-8 obtained corresponds to the ZIF-8 standard curve, indicating that ZIF-8 was successfully prepared. The Zeta potential of the material was measured by a Zeta potential meter. Figure 4 Shows positive charge.

[0094] Step 2: Preparation of tungsten-doped ferrite (FeWO x ):

[0095] 0.82 g 1,2-dodecanediol, 0.1126 g tungsten hexacarbonyl, 0.0812 g ferrous acetylacetonate, 0.452 g ferric acetylacetonate, 80 mL diphenyl ether, 0.4 mL oleic acid, and 3.6 mL oleylamine were placed in a round-bottom flask. The temperature was slowly raised to 120 °C under argon protection and maintained for 10 min. The temperature was then slowly raised to 260 °C and maintained for 2.5 h. The quenching treatment was then immediately performed. After the reaction was cooled to room temperature, the precipitate was collected by centrifugation and washed several times with ethanol and ultrapure water. FeWO was obtained after vacuum freeze-drying. x powder.

[0096] In this embodiment, FeWO x Conduct characterization exploration experiments:

[0097] FeWO obtained by SEM x The morphology of nanomaterials. Figure 5 As shown, the obtained FeWO x It is spherical and has a particle size of about 80nm. The crystal structure was verified by XRD analysis. The results are as follows Figure 6 As shown, the obtained FeWO x The XRD patterns of FeWO x The standard curve corresponds to FeWO x was successfully prepared. Figure 7 The zeta potential of the material is shown to be negatively charged.

[0098] Step 3: Antibacterial nanomaterial powder (ZIF-8 / FeWO x ) preparation, antibacterial nanomaterial powder (ZIF-8 / FeWO x ) referred to as ZF:

[0099] 50 mg of ZIF-8 powder was mixed with 50 mg of FeWO x The powder was added to 30 mL of ultrapure water, and the solution was first placed under ultrasonic conditions for 10 min, and then the solution was placed in a shaker for 12 h. The precipitate was then collected by centrifugation and washed several times with ultrapure water. After vacuum freeze-drying, the antibacterial nanomaterial powder (ZIF-8 / FeWO x )powder.

[0100] Antibacterial nanomaterial powder (ZIF-8 / FeWO x ) Characterization Exploration Experiment:

[0101] The morphology of ZF was obtained by SEM, such as Figure 8 As shown, ZIF-8 nanoparticles are tightly bound to FeWO x Around the particles, both rhombic dodecahedral structures and spherical structures can be observed, and the crystal size is about 200nm. The crystal structure of the sample was characterized by XRD analysis, and the diffraction peaks of ZF and its corresponding ZIF-8 and FeWO x The diffraction peaks of Figure 9 The chemical structure and functional groups of the nanomaterials were studied by Fourier transform infrared spectroscopy (FTIR), as shown in Figure 10 As shown, at 421cm -1 The peak at 610 cm is attributed to the Zn-N bond. -1 The peak at 740 cm is attributed to the Fe-O bond. -1 The peak at 1421 cm is attributed to the WO bond. -1 The peak at is attributed to the CN bond. The above characterizations can further illustrate that the antibacterial nanomaterial powder (ZIF-8 / FeWO x )The composite material was successfully prepared.

[0102] Experiments were conducted to explore the photocatalytic performance of ZF:

[0103] In order to evaluate the photocatalytic performance of the materials, the optical properties were first evaluated using ultraviolet-visible diffuse reflectance spectroscopy (UV-VisDRS), such as Figure 11 As shown in Figure 2, ZF exhibits strong absorption ability in the visible light region. In order to evaluate the charge transfer efficiency of the material, we used electrochemical impedance spectroscopy (EIS) to test it. Figure 12 As shown, ZIF-8 and FeWO xCompared with the Nyquist curve of ZF, it shows the smallest arc radius, which means that the migration speed of photogenerated carriers increases. In order to explore whether ZF has faster migration efficiency under the excitation of sunlight, we use transient photocurrent response to detect the situation of the material under simulated sunlight, such as Figure 13 As shown in Figure 2, the photocurrent response intensity of ZF is higher than that of ZIF-8 and FeWO. x , indicating that it will produce more current-carrying electrons under the irradiation of visible light.

[0104] In order to explore the ROS generation ability of the material, we used electron spin resonance (ESR) to detect the types of ROS produced. 2 ) After irradiation, Figure 14 As shown, three characteristic peaks were detected under the condition of adding 2,2,6,6-tetramethylpiperidine (TEMP) capture agent, and the peak intensity of the characteristic peaks was 1:1:1, proving that singlet oxygen (Singletoxygen, 1 O2) is generated, and the peak intensity of the composite material is higher than that of ZIF-8 and FeWO x , further proved that the photocatalytic effect is enhanced. After adding 1% hydrogen peroxide (H2O2) and 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) scavenger, as shown in Figure 15 As shown, four characteristic peaks can be detected, and the peak intensities of the characteristic peaks are 1:2:2:1, which proves that hydroxyl radicals (·OH) are generated, and the peak value of the composite material ZF is higher than that of FeWO x , which once again proves that the photocatalytic performance of ZF is improved.

[0105] In order to clarify the generation mechanism of ROS, ZIF-8 and FeWO were respectively x The band gap and valence band of ZIF-8 / FeWO were tested to calculate the conduction band and obtain the x The band structure of the composite material, such as Figure 16 As shown, ZIF-8, FeWO x The two can form a Z-type heterojunction.

[0106] In this embodiment, the photothermal and magnetothermal properties of ZF are:

[0107] like Figure 17 As shown, at 1000W / m 2 Under simulated sunlight, the photothermal temperature of ZF can reach up to 55℃, which proves that the material has good photothermal performance. Due to the magnetic properties of the material, the hysteresis loop is as follows Figure 18 As shown, under the action of the alternating magnetic field, Figure 19 As shown, the temperature of ZF can also reach 55°C.

[0108] In this embodiment, ZIF-8, FeWO x , Evaluation of the antibacterial properties of ZF:

[0109] In order to evaluate the antibacterial properties of the materials, we chose to explore the antibacterial effects of different nanomaterials on S. aureus and E. coli under different conditions, simulating the antibacterial effects of different nanomaterials on S. aureus and E. coli at 1000W / m 2 Under the conditions of 30 minutes of simulated sunlight irradiation, 10 minutes of alternating magnetic field, and 10 minutes of alternating magnetic field and then 1000W / m 2 The antibacterial ability of the material under the condition of 30 minutes of simulated sunlight exposure. Figure 20 As shown in the figure, under the synergistic effect of photocatalysis and thermal effect, the antibacterial rate of ZF against the two bacteria reached 99.99%.

[0110] Step 4: TPU-ZIF-8 / FeWO x Preparation of (T-ZF) antibacterial nanocomposite fiber membrane:

[0111] 0.045g of ZF nanomaterial was weighed and dissolved in 1mL of N,N-dimethylformamide and 1mL of tetrahydrofuran. Ultrasonication was then performed for 5 minutes. 0.5g of TPU particles was then added and magnetic stirring was performed at 40°C for 12 hours to prepare a TPU spinning solution with a uniform dispersion of ZF nanomaterial. The resulting spinning solution was then subjected to solution jet spinning to produce a T-ZF composite nanofiber membrane.

[0112] (Specific parameters are: needle specification: 25G, propulsion rate: 0.25mL / h, receiving roller speed: 300rpm, receiving distance: 30cm, wind pressure: 70MPa)

[0113] In this example, the structural characterization of T-ZF composite nanofibers was investigated:

[0114] like Figure 21 The picture shows TPU and TPU fiber doped with 9% ZF nanomaterials. The nanofiber provides a supporting platform for ZF, evenly fixing the nanomaterial ZF on its surface. Figure 22 As shown in the figure, the SEM images show the surface morphology of TPU and T-ZF nanofibers. The TPU fibers are continuous and smooth in structure. On the fiber membrane containing 9% ZF, ZF nanoparticles attached to the fiber surface can be clearly seen. The hydrophobicity of the fiber can ensure a certain antibacterial effect. Figure 23 The contact angle experiment tested the hydrophobicity of the fiber. The contact angle of the TPU fiber membrane was about 110°, which has high hydrophobicity. After doping with 9% ZF, its hydrophobicity increased to about 120°.

[0115] In this example, the performance characterization of T-ZF composite nanofibers was investigated:

[0116] In this example, the photocatalytic performance of T-ZF composite nanofibers was characterized:

[0117] The present invention detects the type of ROS produced by ESR and simulates sunlight (1000W / m 2 ) After irradiation, Figure 24 As shown, three characteristic peaks were detected under the condition of adding TEMP capture agent, and the peak intensity of the characteristic peaks was 1:1:1, which proved that there was 1 O2 is produced. After adding 1% H2O2 and DMPO scavenger, Figure 25 As shown, four characteristic peaks can be detected, and the peak intensities of the characteristic peaks are 1:2:2:1, which can prove the generation of ·OH.

[0118] In this example, the photothermal and magnetothermal properties of the T-ZF nanocomposite fiber membrane were investigated:

[0119] like Figure 26 As shown, at 1000W / m 2 Under simulated sunlight, the photothermal temperature of the T-ZF nanocomposite fiber membrane can reach up to 39°C, proving that the fiber membrane still has good photothermal properties. Under the action of an alternating magnetic field, Figure 27 As shown, the temperature of the T-ZF nanocomposite fiber membrane can also reach 50 °C.

[0120] In this embodiment, the antibacterial properties of T-ZF composite nanofibers are:

[0121] In order to evaluate the antibacterial properties of the material, we chose to explore the antibacterial effects of the material on E. coli, S. aureus, MDRE. coli, and MRSA under different conditions. The flat coating method intuitively demonstrated the inactivation ability of different groups of fibers on bacteria under different stimulation conditions. 2 Under the conditions of 30 minutes of simulated sunlight irradiation, 10 minutes of alternating magnetic field, and 10 minutes of alternating magnetic field and then 1000W / m 2 The antibacterial ability of the material under the condition of 30 minutes of simulated sunlight exposure. Figures 28-31 As shown, under the synergistic effects of photocatalysis, photothermal and magnetothermal, the antibacterial rate of T-ZF nanofiber membrane against several bacteria can reach 99.99%.

[0122] The foregoing is merely a preferred embodiment of the present invention. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications are also within the scope of protection of the present invention. Structures, devices, and operating methods not specifically described or explained herein shall, unless otherwise specified or limited, be implemented in accordance with conventional means in the art.

Claims

1. A method for preparing an antibacterial nanocomposite fiber membrane, characterized in that: The following steps are involved: Step 1: Preparation of imidazole ester skeleton-8; Step 2: preparing tungsten-doped ferrite; Step 3: using imidazolate skeleton-8 and tungsten-doped ferrite to complete the preparation of antibacterial nanomaterial powder; Step 4: using the antibacterial nanomaterial powder and TPU particles prepared in step 3, preparing a TPU spinning solution in which the antibacterial nanomaterial powder is evenly dispersed; the obtained spinning solution is subjected to a solution jet spinning method to obtain an antibacterial nanocomposite fiber membrane; In the step 1, the specific steps of preparing the imidazole ester skeleton-8 are as follows: Step 101: adding 2.8-3.5 parts by mass of 2-methylimidazole and 1.2-1.7 parts by mass of zinc nitrate hexahydrate to 65-75 parts by mass of a methanol solution; Step 102: Stirring on a magnetic stirrer for 30 minutes; Step 103: Collect the precipitate by centrifugation and wash it with methanol five times; Step 104: Drying in a vacuum oven to complete the preparation of imidazole ester skeleton-8; In step 2, the specific steps of preparing tungsten-doped ferrite are as follows: Step 201: 0.8-0.85 parts by mass of 1,2-dodecanediol, 0.1-0.2 parts by mass of tungsten hexacarbonyl, 0.08-0.09 parts by mass of ferrous acetylacetonate, 0.4-0.5 parts by mass of ferric acetylacetonate, 75-85 parts by mass of diphenyl ether, 0.35-0.45 parts by mass of oleic acid, and 3.2-4 parts by mass of oleylamine are placed in a round-bottom flask; Step 202: slowly heating to 120° C. under argon protection, maintaining for 10 minutes, then slowly heating to 260° C., maintaining for 2.5 hours, and then immediately quenching; Step 203: After the reaction in step 201 is cooled to room temperature, the precipitate is collected by centrifugation and washed five times with ethanol and ultrapure water; Step 204: vacuum freeze-drying to obtain tungsten-doped ferrite powder; Described step 3 comprises the following specific steps: Step 301: adding 45-50 parts by mass of imidazole ester framework-8 powder and 45-50 parts by mass of tungsten-doped ferrite powder to 25-35 parts by mass of ultrapure water; Step 302: subjecting the solution to ultrasonic treatment for 10 minutes; Step 303: placing the solution in a shaker for 12 hours; Step 304: collecting the precipitate by centrifugation and washing it with ultrapure water five times, and freeze-drying it in a vacuum to obtain an antibacterial nanomaterial powder; Described step 4 comprises the following specific steps: Step 401: Weigh 0.04-0.05 parts by mass of antibacterial nanomaterial powder and dissolve it in 1 part by mass of N,N-dimethylformamide and 2 parts by mass of tetrahydrofuran; Step 402: Ultrasonicate for 5 minutes, then add 0.45-0.55 parts by mass of TPU particles; Step 403: Magnetic stirring is performed at 40° C. for 12 hours to complete the preparation of a TPU spinning solution in which the antibacterial nanomaterial powder is dispersed; Step 404: The obtained spinning solution is subjected to a solution jet spinning method to obtain an antibacterial nanocomposite fiber membrane.

2. The method for preparing the antibacterial nanocomposite fiber membrane according to claim 1, characterized in that: In step 101, the concentration of the methanol solution is 40%-60%; in step 102, magnetic stirring is performed at room temperature of 25°C; in step 104, drying is performed in a vacuum oven at 60°C for 12 hours.

3. The method for preparing the antibacterial nanocomposite fiber membrane according to claim 1, wherein: The parameters of the jet spinning method in step 404 are: needle specification: 25G, propulsion rate: 0.25 mL / h, receiving roller speed: 300 rpm, receiving distance: 30 cm, and wind pressure: 70 MPa.

4. Use of the antibacterial nanocomposite fiber membrane according to any one of claims 1 to 3 in the preparation of medical protective equipment.

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