CN115475272B - Preparation method of nanofiber membrane with antibacterial anti-blocking function - Google Patents
Preparation method of nanofiber membrane with antibacterial anti-blocking function Download PDFInfo
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- CN115475272B CN115475272B CN202211011564.6A CN202211011564A CN115475272B CN 115475272 B CN115475272 B CN 115475272B CN 202211011564 A CN202211011564 A CN 202211011564A CN 115475272 B CN115475272 B CN 115475272B
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- nanofiber
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- molybdenum sulfide
- microsphere
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 43
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- XDFNWJDGWJVGGN-UHFFFAOYSA-N 2-(2,7-dichloro-3,6-dihydroxy-9h-xanthen-9-yl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C21 XDFNWJDGWJVGGN-UHFFFAOYSA-N 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 2
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Hematology (AREA)
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Abstract
The invention relates to the field of medical materials, and discloses a preparation method of a nanofiber membrane with antibacterial anti-blocking function. The invention applies electrostatic spinning and electrostatic spraying technology to electrostatically spray a layer of polymer microsphere loaded with photodynamic sterilization particles on the surface of Polyacrylonitrile (PAN) nanofiber, wherein the microsphere has an imitated red blood cell structure. The microsphere layer and the PAN layer formed by the microspheres form a Janus structure, have the effect of unidirectional liquid guiding, and can treat excessive wound seepage generated by wounds. The microsphere layer, which serves as a hydrophobic layer, has a high specific surface area, which is conducive to the release of Reactive Oxygen Species (ROS) by the particles. In addition, the hydrophobic layer containing the microspheres has a high rough surface, achieves the effect of being more hydrophobic, and effectively prevents the dressing from adhering to the wound.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a preparation method of a nanofiber membrane with antibacterial anti-blocking function.
Background
The skin is the largest organ of the human body, which covers the whole body, protecting the tissues and organs in the body from physical, mechanical, chemical injury and attack by pathogenic microorganisms. Under the influence of surgery, chronic diseases, burns and scalds and accidents, millions of people worldwide are affected by skin wounds each year, especially for some elderly patients with low immunity. Skin wounds are extremely susceptible to bacterial infection, causing local or systemic infection, and causing sepsis and other related complications. The most effective way to clinically treat bacterial infection is to use antibiotics at present, but with the wide use of antibiotics, more and more bacteria generate drug resistance, and biomedical materials for developing non-antibiotic action mechanisms are imperative.
The inorganic antibacterial agent is widely applied to daily life of people due to good heat resistance, durability, broad spectrum and no drug resistance, and can effectively inhibit bacteria from breeding and maintain human health. However, most of the existing forms exist in the form of dispersion liquid and powder, and the direct use of the existing forms can lead to potential biotoxicity. The electrostatic spinning technology is widely applied to the preparation of polymer nanofibers, and the prepared nanofiber membrane has extremely large specific surface area and porosity, combines the nanofiber membrane with an inorganic antibacterial agent, and can endow the nanofiber with an antibacterial function. However, there is a problem of compatibility between the inorganic nanoparticles and the polymer, and once the compatibility is poor, the inorganic nanoparticles are largely wrapped in the spinning fiber, which greatly affects the therapeutic efficiency, especially some inorganic nanoparticles based on ROS release sterilization mechanism. The particles need to be fully contacted with oxygen, water molecules, hydrogen peroxide and other substances in the air or the microenvironment, and then are excited to generate active oxygen under certain conditions to sterilize. Therefore, the application of the functional particles in the field of nanofiber wound dressings is greatly limited by the common nanofiber structure.
In addition, the wound can produce excessive wound exudate, wherein inflammatory mediators can increase capillary permeability, resulting in continued exudate production. The protein and other nutritive matters also provide proper growth environment for bacteria to reproduce, and the wound suppuration aggravates infection and slows down the healing process. It has been reported in the literature that excessive wound exudate can be drained by constructing a Janus wound dressing, but if the nanofiber material on the side adjacent to the wound is not sufficiently hydrophobic, adhesion of the dressing to the new tissue and dressing can still be caused, and secondary damage can be caused when the dressing is replaced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a nanofiber membrane with antibacterial anti-blocking function. The invention applies electrostatic spinning and electrostatic spraying technology to electrostatically spray a layer of polymer microsphere loaded with molybdenum sulfide inorganic particles on the surface of PAN nanofiber, and the microsphere is of an imitated red cell structure. The microsphere layer and the PAN layer formed by the microspheres form a Janus structure, have the effect of unidirectional liquid guiding, and can treat excessive wound seepage generated by wounds. In addition, the hydrophobic layer containing the microspheres has a high rough surface, achieves the effect of being more hydrophobic, and effectively prevents the dressing from adhering to the wound. The erythrocyte-like microsphere layer has high specific surface area, is beneficial to the contact of molybdenum sulfide inorganic particles with outside air and moisture in wound microenvironment, and improves the generation efficiency of ROS. Under a near infrared light trigger mechanism, the nano fiber film loaded with molybdenum sulfide can flexibly start or stop generating ROS according to the infection condition, so that the antibacterial time is regulated and controlled, and the efficient and self-adaptive antibacterial treatment is realized.
The specific technical scheme of the invention is as follows: the preparation method of the nanofiber membrane with the antibacterial anti-blocking function comprises the following steps:
(1) Preparation of nanofiber base film: and (3) dissolving polyacrylonitrile in N-N dimethylformamide, heating, stirring and dissolving, and carrying out electrostatic spinning to obtain the nanofiber basement membrane.
The step (1) is to prepare a substrate film through electrostatic spinning, wherein the substrate film mainly plays a role of mechanical support and hydrophilicity.
(2) Preparation of molybdenum sulfide inorganic nano particles: dissolving sodium molybdate in water, performing first ultrasonic treatment, adjusting pH with acid, adding L-cysteine, polyvinylpyrrolidone and water, performing second ultrasonic treatment, transferring to a high-pressure reaction kettle for reaction, and centrifuging to collect molybdenum sulfide inorganic nanoparticles.
As described in the background section, abuse of antibiotics results in the production of resistant bacteria, which in turn reduces the efficacy. The invention prepares molybdenum sulfide inorganic nano particles capable of generating ROS and performs non-antibiotic antibiosis. ROS generated by the particles can effectively kill bacteria, destroy physical structures of the bacteria, such as cell walls, cell membranes, genetic material deoxyribonucleic acid (DNA) and the like, and can not promote the bacteria to generate drug resistance.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: and dissolving or dispersing polycaprolactone and molybdenum sulfide inorganic nano particles in a trifluoroethanol solvent, stirring at room temperature to obtain a polymer spinning solution, performing ultrasonic treatment to obtain a uniform solution, and performing electrostatic spraying on a nanofiber substrate film to obtain the nanofiber film with the antibacterial anti-blocking function.
In the electrostatic spraying process, polycaprolactone (PCL) on which molybdenum sulfide is reloaded forms spherical liquid drops under the repulsive action of the same kind of charges and is sprayed out, and an outer layer solvent volatilizes first to form a thin shell. Thereafter, the internal solvent continues to volatilize, thereby creating an inward compressive force, with the polymer droplets having a tendency to compress inward. If the polymer concentration is in a proper range, the shell formed first can overcome the compression force, and after the internal solvent volatilizes, the shell is recessed inwards, so that the polymer microsphere imitating the red blood cell structure is formed.
In conclusion, the invention applies electrostatic spinning and electrostatic spraying technology to electrostatically spray a layer of polymer microsphere loaded with molybdenum sulfide inorganic particles on the surface of PAN nanofiber, and the microsphere has an imitated red cell structure. The microsphere layer and the PAN layer formed by the microspheres form a Janus structure, have the effect of unidirectional liquid guiding, and can treat excessive wound seepage generated by wounds. The microsphere layer is used as a hydrophobic layer, has the characteristic of high specific surface area, is beneficial to the contact of molybdenum sulfide inorganic nano particles with outside air and moisture in wound microenvironment, and improves the generation efficiency of ROS. In addition, the hydrophobic layer containing the microspheres has a high rough surface, achieves the effect of being more hydrophobic, and effectively prevents the dressing from adhering to the wound. The prepared nanofiber membrane has a near infrared light trigger mechanism, can freely and flexibly adjust the antibacterial treatment time according to the ' on ' -off ' of near infrared light, and performs the artificial controllable antibacterial treatment process on the infected wound.
Specifically, the invention adopts Polycaprolactone (PCL) as microsphere material, and has the advantages of no immunogenicity, no acid accumulation in the degradation process, good biocompatibility, strong flexibility, high mechanical strength, good blending compatibility, low cost and the like. The invention uses proper PCL to load photodynamic molybdenum sulfide, and utilizes electrostatic spinning technology to electrostatically spray composite microsphere with red blood cell structure on PAN nanofiber membrane to obtain nanofiber membrane with antibacterial anti-blocking function. According to the invention, the red blood cell-like PCL microspheres are utilized, the specific surface area is increased, the contact area between the molybdenum sulfide inorganic nanoparticles and the outside air and wound moisture is increased, the ROS generation efficiency of the molybdenum sulfide inorganic nanoparticles under near infrared light is further improved, the antibacterial performance of the dressing is enhanced, and the efficient, flexible and self-adaptive treatment of an infected part is realized. Meanwhile, the Janus structure is formed by the erythrocyte-like PCL microspheres and the PAN basal membrane, so that the nanofiber membrane is endowed with the property of unidirectional pumping of wound exudate, the aggregation of the exudate on the surface of the wound is effectively avoided, and the excessive hydration of the wound is prevented. In addition, the unique PCL imitation erythrocyte microsphere has high roughness, and the air existing between the microsphere and the microsphere improves the hydrophobicity of one side of the dressing, which is contacted with the wound, so that the adhesion between the dressing and the wound is effectively prevented, and the tearing of the wound during dressing replacement is avoided.
The research shows that the shape and the performance of the microsphere are closely related. Compared with microspheres with other shapes (such as spherical), the red blood cell-like microspheres can remarkably increase the contact area between the microspheres and the substrate film when being sprayed on the surface of the substrate film, thereby improving the adhesiveness of the microspheres. In addition, the polymer microsphere with the structure imitating red blood cells has higher aspect ratio than other microsphere with other shapes, and can effectively prevent the microsphere from being phagocytized by cells when contacting wounds, thereby prolonging the service life.
In the prior art, there have been reported red cell structure-imitating poly (4-styrenesulfonate) and polylactic acid-glycolic acid copolymer microspheres, which have high elastic modulus and can flow through capillaries smaller than the microspheres, so that the microspheres are used as carriers of oxygen, medicines and magnetic particles, and are applied to the fields of oxygen delivery, medicine delivery, medical imaging and the like. However, there is no report on the application of similar structures to wound dressings. If water-soluble poly (4-styrenesulfonate) microspheres are directly applied to the present invention, janus dressing cannot be constructed for exudate management. Although polylactic acid-glycolic acid copolymer has excellent biocompatibility and hydrophobicity, the cost is too high, and if the polylactic acid-glycolic acid copolymer is directly applied to the invention, the preparation cost is greatly increased, and the polylactic acid-glycolic acid copolymer is not suitable for industrial production and market demands.
Preferably, in the step (1), the concentration of the polyacrylonitrile after dissolution is 7-10wt%, and the heating temperature is 50-55 ℃.
Preferably, in the step (1), the parameters of the electrostatic spinning are that the speed is 0.002-0.003 mm/s, the distance between the needle and the needle is 18-20G, the voltage is 10-15 cm, the voltage is 12-15 kV, the temperature is 25-35 ℃, the humidity is 30-50%, and the spinning time is 3-10h.
The team of the invention finds that if the concentration of the polymer is too low and the spinning time is too short, effective mechanical support is difficult to form, so that the mechanical property is poor; if the concentration is too high, the porosity of the base film is too high, and the distribution of the composite microspheres on the base film in the step (2) is affected. If the spinning time is too long, the film is too thick, the air permeability is reduced, the probability of contacting the particles with the outside air is possibly reduced, and the generation of ROS is reduced. Therefore, the concentration of PAN and the spinning time in step (1) need to be strictly controlled.
Preferably, in the step (2), the dosage ratio of the sodium molybdate to the water is 0.25-0.35 g:25-30 mL before the first ultrasonic treatment; the dosage ratio of the L-cysteine, the polyvinylpyrrolidone and the water added for the second time is 0.5-0.6 g:0.025-0.03 g:50-60mL before the second ultrasonic treatment.
Preferably, in the step (2), the pH is adjusted to 6.5-7 by acid, the reaction temperature is 200-230 ℃ and the reaction time is 22-26h.
Preferably, in the step (2), the first ultrasonic time is 3-5min, and the second ultrasonic time is 10-15min.
Preferably, in the step (2), the rotation speed is 11000-13000r/min during centrifugation, and the centrifugation time is 10-20min.
Preferably, in step (3), the concentration of polycaprolactone in the polymer dope is 0.5-5wt%. The mass ratio of the molybdenum sulfide inorganic nano particles to the polycaprolactone is 0.1:1-1.5:1.
The concentration of polycaprolactone is decisive for the effect of the morphology of the erythrocyte-like microspheres. If the concentration is proper, the first polymer crust-like shell formed during electrostatic spraying can overcome the compressive force and maintain the spherical structure. The solvent is continuously volatilized, and the crust-shaped shell is inwards recessed, so that the polymer microsphere imitating the red blood cell structure is formed. If the concentration is too low, the molybdenum sulfide functional particles are agglomerated, the compositing property is poor, and the molybdenum sulfide functional particles are easy to fall off and unstable. If the concentration is too high, the erythrocyte-like composite microspheres cannot be formed, and a common nanofiber structure is formed, so that the inorganic nanoparticles are excessively wrapped, the ROS production efficiency cannot be improved, and the hydrophobicity of the PCL layer is reduced.
Preferably, in the step (3), the stirring time at room temperature is 4-8h.
Preferably, in the step (3), the time of the ultrasonic treatment is 10-30min.
Preferably, in the step (3), the parameters of the electrospinning are: the voltage is 5-30 kV, the propelling speed is 0.0003-0.006 mm/s, the receiving distance is 8-15 cm, the spinning temperature is 20-40 ℃, and the spinning humidity is 40-60%.
Compared with the prior art, the invention has the beneficial effects that: firstly preparing a PAN nanofiber basement membrane, then synthesizing molybdenum sulfide inorganic nano particles with an active oxygen sterilization function, and adopting an electrostatic spraying process to spray red blood cell-like structure microspheres loaded with the molybdenum sulfide inorganic nano particles on the surface of the PAN membrane to obtain the nanofiber membrane with an antibacterial anti-blocking function. The PAN layer and the PCL microsphere layer of the dressing form a Janus structure, and can be used for unidirectionally guiding out wound exudate, so that excessive hydration of a wound is avoided. The molybdenum sulfide inorganic nano particles kill bacteria in a manner of generating ROS, and the generation of drug-resistant bacteria is avoided. The unique red blood cell imitation microsphere structure enlarges the contact area of the molybdenum sulfide inorganic nano particles with air and water molecules, and improves the ROS production efficiency, thereby realizing efficient antibiosis. The microsphere structure also improves the roughness of the PCL layer, is beneficial to improving the hydrophobicity and avoids the adhesion between the dressing and the wound. Compared with microspheres with other morphologies, the microsphere with the simulated red blood cell structure has the advantages of improving the contact area (i.e. adhesiveness) between the microsphere and a basement membrane, preventing the microsphere from being phagocytized by phagocytes in a wound, improving the stability of a Janus structure and prolonging the service life. The nanofiber membrane disclosed by the invention realizes high-efficiency antibacterial and controllable adjustment of treatment time by utilizing the ' on ' -off ' of near infrared light, and meanwhile, performs seepage management, has high-efficiency anti-blocking performance, and has a relatively high application prospect in the field of biomedical materials.
Drawings
FIG. 1 is a transmission electron microscope image of molybdenum sulfide inorganic particles prepared in example 1.
FIG. 2 is a scanning electron microscope image of the PCL side obtained in example 1.
Detailed Description
The invention is further described below with reference to examples.
Example 1
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 10min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: 2.5g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nano particles are dissolved/dispersed in 100mL of trifluoroethanol solvent, the mixed spinning solution is obtained after stirring for 6 hours at room temperature, the mixed spinning solution is subjected to ultrasonic treatment for 20 minutes, so that uniform and consistent solution is formed, electrostatic spraying is carried out on a substrate film, and electrostatic spinning parameters are as follows: the voltage is 10.8kV, the advancing speed is 0.0054mm/s, the receiving distance is 13cm, the spinning temperature is 25 ℃, the spinning humidity is 50%, and the nanofiber membrane with the antibacterial anti-blocking function is obtained.
FIG. 1 is a transmission electron microscope image of molybdenum sulfide inorganic particles prepared in example 1; FIG. 2 is a scanning electron microscope image of the PCL side obtained in example 1.
Example 2
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare a spinning solution with the concentration of 7wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 10min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: 1.25g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nano particles are dissolved/dispersed in 100mL of trifluoroethanol solvent, the mixture is obtained after stirring for 4 hours at room temperature, the ultrasonic treatment is carried out for 20 minutes, so that uniform and consistent solution is formed, electrostatic spraying is carried out on a substrate film, and electrostatic spinning parameters are as follows: the voltage is 9.3kV, the propelling speed is 0.0054mm/h, the receiving distance is 13cm, the spinning temperature is 25 ℃, the spinning humidity is 50%, and the nanofiber membrane with the antibacterial anti-blocking function is obtained.
Example 3
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 13min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: preparing a mixed spinning solution by dissolving/dispersing 2.5g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nano particles in 100mL of trifluoroethanol solvent, stirring for 6 hours at room temperature, performing ultrasonic treatment for 10 minutes to form a uniform solution, and performing electrostatic spraying on a substrate film, wherein the electrostatic spinning parameters are as follows: the voltage is 12.5kV, the propelling speed is 0.003mm/s, the receiving distance is 12cm, the spinning temperature is 25 ℃, the spinning humidity is 40%, and the nanofiber membrane with the antibacterial anti-blocking function is obtained.
Example 4
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.8 with hydrochloric acid (HCl), added with 0.5g of L-cysteine, 0.025g of polyvinylpyrrolidone (PVP) and 50mL of water, sonicated for 10min, transferred to a autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: 1.25g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nano particles are dissolved/dispersed in 100mL of trifluoroethanol solvent, the mixed spinning solution is obtained after stirring for 6 hours at room temperature, the mixed spinning solution is subjected to ultrasonic treatment for 20 minutes, so that uniform and consistent solution is formed, electrostatic spraying is carried out on a substrate film, and electrostatic spinning parameters are as follows: the voltage is 11.2kV, the advancing speed is 0.0054mm/s, the receiving distance is 12cm, the spinning temperature is 25 ℃, the spinning humidity is 50%, and the nanofiber membrane with the antibacterial anti-blocking function is obtained.
Comparative example 1 (PAN base film alone)
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
Comparative example 2 (PCL microsphere layer alone)
(1) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 10min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(2) Compounding of erythrocyte-like microspheres and nanofiber membranes: 2.5g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nano particles are dissolved/dispersed in 100mL of trifluoroethanol solvent, the mixed spinning solution is obtained after stirring for 6 hours at room temperature, the mixed spinning solution is subjected to ultrasonic treatment for 20 minutes, so that uniform and consistent solution is formed, electrostatic spraying is carried out on tin foil paper, and electrostatic spinning parameters are as follows: the voltage is 10.8kV, the advancing speed is 0.0054mm/s, the receiving distance is 13cm, the spinning temperature is 25 ℃, and the spinning humidity is 50%, so that the composite nanofiber membrane is obtained.
Comparative example 3 (no supported particles in microspheres)
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Compounding of erythrocyte-like microspheres and nanofiber membranes: 2.5g of Polycaprolactone (PCL) is dissolved in 100mL of trifluoroethanol solvent, the mixture is stirred at room temperature for 6 hours to obtain spinning solution, the spinning solution is subjected to ultrasonic treatment for 20 minutes to form uniform and consistent solution, electrostatic spraying is carried out on a substrate film, and electrostatic spinning parameters are as follows: the voltage is 10.8kV, the advancing speed is 0.0054mm/s, the receiving distance is 13cm, the spinning temperature is 25 ℃, and the spinning humidity is 50%, so that the composite nanofiber membrane is obtained.
Comparative example 4 (PCL too low in concentration)
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 10min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: preparing a mixed spinning solution by dissolving/dispersing 0.2g of Polycaprolactone (PCL) and 0.5g of molybdenum sulfide inorganic nano particles in 100mL of trifluoroethanol solvent, stirring for 6 hours at room temperature, performing ultrasonic treatment for 20 minutes to form a uniform solution, and performing electrostatic spraying on a substrate film, wherein the electrostatic spinning parameters are as follows: the voltage is 11.2kV, the advancing speed is 0.0054mm/s, the receiving distance is 12cm, the spinning temperature is 25 ℃, and the spinning humidity is 50%, so that the composite nanofiber membrane is obtained.
Comparative example 5 (PCL too high concentration)
(1) Preparation of nanofiber base film: polyacrylonitrile (PAN) is dissolved in N-N dimethylformamide to prepare spinning solution with the concentration of 8wt%, and the spinning solution is stirred to be dissolved under the heating condition of 50 ℃, wherein the spinning parameters are as follows: the speed is 0.002mm/s, the needle is 20G, the distance is 13cm, the voltage is 13kV, the temperature is 25 ℃, and the humidity is 30%. Obtaining the nanofiber basement membrane.
(2) Preparation of molybdenum sulfide inorganic nano particles: sodium molybdate (Na) 2 MoO 4 ·2H 2 O) 0.25g was dissolved in 25mL of water, sonicated for 5min, pH adjusted to 6.5 with hydrochloric acid (HCl), L-cysteine 0.5g, polyvinylpyrrolidone (PVP) 0.025g and water 50mL were added, sonicated for 10min, transferred to autoclave, reacted at 200℃for 24h, and then centrifuged at 12000r/min for 15min to collect particles.
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: preparation of a mixed spinning solution obtained by dissolving/dispersing 19g of Polycaprolactone (PCL) and 0.4g of molybdenum sulfide inorganic nanoparticles in 100mL of trifluoroethanol solvent, stirring at room temperature for 6h, carrying out ultrasonic treatment for 20min to form a uniform solution, and carrying out electrostatic spraying on a substrate film, wherein the electrostatic spinning parameters are as follows: the voltage is 13kV, the advancing speed is 0.0054mm/s, the receiving distance is 13cm, the spinning temperature is 25 ℃, and the spinning humidity is 50%, so that the composite nanofiber membrane is obtained.
Performance testing
The materials obtained in each example and comparative example were tested. Wherein the microsphere structure is measured by SEM, the hydrophilicity and hydrophobicity are measured by water contact angle, the unidirectional liquid guiding performance is measured by simulation experiment, the antibacterial effect is measured by dilution coating method, and the specific test method is as follows:
testing the unidirectional liquid guiding performance: the dressing was cut into a 3 x 5cm rectangle, 50 μl of blue ink was added dropwise to the PAN side and PCL side, respectively, and the phenomenon was recorded. If the ink can permeate from the PCL side to the PAN side, but cannot permeate from the PAN side to the PCL side, the dressing has unidirectional liquid guiding performance.
The antibacterial effect test method comprises the following steps: the materials in each of the above examples were placed in a test tube containing 5mL of Staphylococcus aureus (the content of Staphylococcus aureus was 10) 7 CFU/mL), and then placing the test tube into a shake incubator, shaking at 150rpm for 4 hours at 37 ℃, taking out the bacterial liquid, diluting to different gradient concentrations, and plating on a solid medium. Then placing the mixture into a constant temperature and humidity incubator, culturing for 24 hours at 37 ℃, and selecting a proper culture plate to count bacteria. And calculating the antibacterial rate.
Detection of ROS: firstly preparing DCFH-DA solution with 1mmol/L prepared by DMSO, then mixing DCFH-DA solution (1 mmol/L) and NaOH solution (10 mmol/L) in a volume ratio of 1:4, and continuously stirring for 30min under the dark condition to obtain DCFH solution with 0.25 mmol/L. The DCFH-DA solution was then diluted to working concentration (1. Mu. Mol/L) with a neutral sodium phosphate solution (25 mmol/L, pH=7). Under the irradiation of near infrared light, the nanofiber membrane which can generate active oxygen and non-fluorescent DCFH (1 mu mol/L) are subjected to oxidation reaction to quickly generate fluorescent 2',7' -Dichlorofluorescein (DCF). The fluorescence intensity of the reaction at different times was measured by a fluorescence spectrophotometer, and the fluorescence spectrum was recorded to investigate whether the membrane was able to generate active oxygen.
The test results were as follows:
as shown in the table, the simulated red blood cell PCL microsphere (examples 1-4) with molybdenum sulfide loaded on the surface of the PAN film is compounded to form the dressing with the Janus structure, and the contact area between the molybdenum sulfide and the outside air and moisture is enlarged due to the unique structure of the PCL simulated red blood cell microsphere, so that the efficiency of generating active oxygen is increased, and the antibacterial rate of more than 90% can be realized.
If only the PAN basal membrane is present in the dressing structure (comparative example 1), the structure of the pseudo red blood cell microsphere is not provided, the Janus structure cannot be constructed, the unidirectional liquid guiding performance and the ROS antibacterial performance are not provided, sterilization is not possible, and it can be calculated that the antibacterial rate is probably due to the fact that when the bacterial liquid is cultured with the nanofiber membrane, a very small part of bacteria is adsorbed on the PAN nanofiber membrane, so that the colony quantity grown by the experimental group of the control group is different.
If the dressing structure has only a PCL layer (comparative example 2), the base film is lacking, the film cannot be removed from the tinfoil, and the dressing which cannot form the Janus structure is subjected to unidirectional liquid guiding.
If no particles are loaded in the PCL microspheres (comparative example 3), the nanofiber membrane cannot generate ROS under near infrared light and cannot sterilize, and it can be calculated that the antibacterial rate may be attributed to the fact that very little bacteria adsorb on the membrane when the bacterial liquid is cultured with the nanofiber membrane, thereby leading to the difference in the number of colonies grown in the experimental group of the control group.
If the PCL concentration is too low (comparative example 4), the pseudo red blood cell microspheres cannot be formed, and the molybdenum sulfide is exposed and easily falls off from the membrane.
If the PCL concentration is too high (comparative example 5), a nanofiber structure is formed, the hydrophobicity is reduced, the adhesion between the dressing and the wound is not easily prevented, in addition, the fiber structure completely wraps the particles, and the contact between the particles and the outside air and the water molecules are reduced, so that the generation of ROS is reduced, and the antibacterial rate is obviously reduced.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the nanofiber membrane with the antibacterial anti-blocking function is characterized by comprising the following steps of:
(1) Preparation of nanofiber base film: dissolving polyacrylonitrile in N-N dimethylformamide at a concentration of 7-10wt%, heating, stirring, dissolving, and performing electrostatic spinning to obtain a nanofiber substrate film; the parameters of the electrostatic spinning are as follows: the speed is 0.002-0.003 mm/s, the needle is 18-20G, the distance is 10-15 cm, the voltage is 12-15 kV, the temperature is 25-35 ℃, the humidity is 30-50%, and the spinning time is 3-10h;
(2) Preparation of molybdenum sulfide inorganic nano particles: dissolving sodium molybdate in water, performing first ultrasonic treatment, adjusting pH with acid, adding L-cysteine, polyvinylpyrrolidone and water, performing second ultrasonic treatment, transferring to a high-pressure reaction kettle for reaction, and centrifuging to collect molybdenum sulfide inorganic nanoparticles;
(3) Compounding of erythrocyte-like microspheres and nanofiber membranes: and dissolving or dispersing the polycaprolactone and molybdenum sulfide inorganic nano particles in a trifluoroethanol solvent, stirring at room temperature to obtain a polymer spinning solution, carrying out ultrasonic treatment on the polymer spinning solution to obtain a uniform solution, and carrying out electrostatic spraying on a nanofiber substrate film to obtain the nanofiber film with the antibacterial anti-blocking function.
2. The method of manufacturing according to claim 1, wherein: in the step (1), the heating temperature is 50-55 ℃.
3. The method of manufacturing according to claim 1, wherein: in the step (2), the dosage ratio of the sodium molybdate to the water before the first ultrasonic treatment is 0.25-0.35 g/25-30 mL.
4. A method of preparation as claimed in claim 3, wherein: in the step (2), the dosage ratio of the L-cysteine, the polyvinylpyrrolidone and the second water addition before the second ultrasonic treatment is 0.5-0.6g, 0.025-0.03g and 50-60mL.
5. The method of claim 1, 3 or 4, wherein: in the step (2), the pH is regulated to 6.5-7 by acid, the reaction temperature is 200-230 ℃, and the reaction time is 22-26h.
6. The method of claim 1, 3 or 4, wherein: in the step (2), the step of (C),
the first ultrasonic time is 3-5min, and the second ultrasonic time is 10-15min;
the rotation speed is 11000-13000r/min during centrifugation, and the centrifugation time is 10-20min.
7. The method of manufacturing according to claim 1, wherein: in the step (3), the mass ratio of the molybdenum sulfide inorganic nano particles to the polycaprolactone is 0.1:1-1.5:1.
8. The method of claim 1 or 7, wherein: in the step (3), the step of (c),
the stirring time at room temperature is 4-8 h;
the ultrasonic treatment time is 10-30min.
9. The method of claim 1 or 7, wherein: in the step (3), the parameters of the electrostatic spraying are as follows: the voltage is 5-30 kV, the propelling speed is 0.0003-0.006 mm/s, the receiving distance is 8-15 cm, the temperature is 20-40 ℃, and the humidity is 40-60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202211011564.6A CN115475272B (en) | 2022-08-22 | 2022-08-22 | Preparation method of nanofiber membrane with antibacterial anti-blocking function |
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| CN111228040A (en) * | 2020-01-08 | 2020-06-05 | 河南亚都实业有限公司 | Absorbable anti-adhesion dressing and preparation method thereof |
| CN113265763A (en) * | 2021-05-12 | 2021-08-17 | 广西医科大学 | Near-infrared light response electrostatic spinning PCL/MoS2Nanofiber membrane and preparation method thereof |
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| CN109734132A (en) * | 2019-03-12 | 2019-05-10 | 中国矿业大学 | A method of controlling synthesis of carbon/molybdenum disulfide particle in mixed solvent system |
| CN111228040A (en) * | 2020-01-08 | 2020-06-05 | 河南亚都实业有限公司 | Absorbable anti-adhesion dressing and preparation method thereof |
| CN113265763A (en) * | 2021-05-12 | 2021-08-17 | 广西医科大学 | Near-infrared light response electrostatic spinning PCL/MoS2Nanofiber membrane and preparation method thereof |
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