CN109487438B - Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine - Google Patents

Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine Download PDF

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CN109487438B
CN109487438B CN201811330410.7A CN201811330410A CN109487438B CN 109487438 B CN109487438 B CN 109487438B CN 201811330410 A CN201811330410 A CN 201811330410A CN 109487438 B CN109487438 B CN 109487438B
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pva
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nanospheres
viscosity
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CN109487438A (en
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王世革
叶长青
罗科义
李金凤
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University of Shanghai for Science and Technology
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    • 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
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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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
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • 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
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • 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
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
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Abstract

The invention provides a method for preparing multifunctional PVA nanospheres by using an electrostatic spinning machine, which is characterized by comprising the following steps of: preparing PVA spinning solution containing photo-thermal material and chemotherapeutic drug, performing electrostatic spinning to obtain multifunctional PVA film, and performing ball milling to obtain multifunctional PVA nanospheres. Compared with the prior art, the multifunctional PVA nanospheres can be prepared in a large scale without complicated test operation steps, addition of a surfactant and harsh reaction conditions, the preparation process is simplified, and the yield is improved remarkably.

Description

Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine
Technical Field
The invention relates to the technical field of PVA nanospheres, in particular to a method for preparing multifunctional PVA nanospheres by using an electrostatic spinning machine.
Background
The polyvinyl alcohol (PVA) is a polyvinyl alcohol (PVA) containing-CH in the molecular main chain2Polymers of-CH (OH) -groups, obtained by alcoholysis of polyvinyl acetate. PVA has excellent hydrophilicity and good reactivity, and the mechanical strength and the chemical stability of PVA are obviously improved and the biodegradation resistance is enhanced through chemical crosslinking or modification treatment. Meanwhile, the PVA material has a series of advantages of no toxicity to bioactive substances, low price, easy obtainment and the like, so that the PVA material becomes a carrier material which can be applied to a plurality of fields such as biological engineering, medical engineering, chemical industry, environmental protection and the like and has development potential.
In recent years, research hotspots on PVA carriers are mainly focused on spherical carriers, and PVA microsphere materials have the advantages of good surface effect, volume effect, functional group characteristics, drug targeting and the like, so that the PVA microsphere materials have special functions which other materials do not have, and therefore the PVA microsphere materials have wide application prospects.
At present, PVA microspheres are prepared by reacting in a water phase, the obtained PVA microspheres are all in a micron grade, high-speed stirring and surfactant addition are needed in the preparation process, and the reaction conditions for preparing the PVA microspheres are harsh, the yield is low and the preparation cost is high.
The electrostatic spinning technology for preparing nano-fiber materials is one of the most important academic and technical activities in the technical field of material science in the last ten years. Electrostatic spinning has become one of the main approaches for effectively preparing nanofiber materials due to the advantages of simple manufacturing device, low spinning cost, various spinnable substances, controllable process and the like. So far, no literature reports about the preparation of PVA microspheres by an electrospinning technique.
Disclosure of Invention
The invention aims to provide a method for preparing multifunctional PVA nanospheres by using an electrostatic spinning machine.
In order to achieve the above object, the present invention provides a method for preparing multifunctional PVA nanospheres using an electrospinning machine, comprising: preparing PVA spinning solution containing photo-thermal material and chemotherapeutic drug, performing electrostatic spinning to obtain multifunctional PVA film, and performing ball milling to obtain multifunctional PVA nanospheres.
Preferably, the preparation method of the PVA spinning solution containing the photothermal material and the drug comprises the following steps: dissolving PVA in distilled water, and stirring at 60-80 ℃ for 2-4 h to obtain a PVA solution, wherein the mass concentration of the PVA is 8-12 wt%; adding a photo-thermal material and a medicament, and stirring for 2-4 h to obtain a PVA spinning solution containing the photo-thermal material and the medicament, wherein the mass ratio of the photo-thermal material to the PVA is 5-10: 100.
More preferably, the PVA consists of high-viscosity PVA and low-viscosity PVA, the mass ratio of the high-viscosity PVA to the low-viscosity PVA is 40-45:5-10, the viscosity of the high-viscosity PVA is 50.0-65.0 mpa.s, and the viscosity of the low-viscosity PVA is 5.0-7.0 mpa.s. Most preferably, the mass ratio of the high viscosity PVA to the low viscosity PVA is 43: 7.
more preferably, the photothermal material is WS2-PVP nanoplate, MoS2-PVP nanoplate, MoS2/Bi2S3-PEG、WS2、MoS2Any one or combination of black phosphorus and gold nanorods.
More preferably, the chemotherapeutic drug is adriamycin, and the mass ratio of the adriamycin to the PVA is 1-5: 100.
Preferably, the step of electrospinning comprises: and adding the PVA spinning solution containing the photo-thermal material and the medicine into an injection pump, and performing electrostatic spinning to obtain the multifunctional PVA film.
More preferably, the injection flow rate of the injection pump is 0.5-0.6 mL/h.
More preferably, the working voltage of the electrostatic spinning is 20kW to 21 kW.
Preferably, the multifunctional PVA film is crosslinked to obtain a hydrophobic multifunctional PVA film, and then ball-milling is carried out to obtain the multifunctional PVA nanospheres.
More preferably, said step of crosslinking comprises: and (2) immersing the multifunctional PVA film into the cross-linking agent for 1-1.5 h, and then carrying out vacuum drying at the temperature of 40-50 ℃ to obtain the hydrophobic multifunctional PVA film.
Furthermore, the cross-linking agent is composed of glutaraldehyde, concentrated hydrochloric acid and acetone, and the volume ratio of the glutaraldehyde to the concentrated hydrochloric acid to the acetone is 0.3-0.5: 0.01-0.05: 15.
Preferably, the ball milling time is 2-5 h.
The invention also provides the application of the multifunctional PVA nanospheres prepared by the method as a photo-thermal conversion material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a large number of multifunctional PVA nanospheres can be prepared without complicated test operation steps, addition of a surfactant and harsh reaction conditions, the preparation process is simplified, the multifunctional PVA spheres with nanometer sizes are obtained, the preparation cost is reduced, the improvement on the yield is remarkable, and the commercialization of the multifunctional PVA nanospheres is expected.
Drawings
FIG. 1 is a SEM photograph of (a) PVA obtained in comparative examples 1 to 2; (b) MoS-containing composition obtained in comparative example 1-12SEM picture of PVA for PVP; (c) method for producing multifunctional PVA obtained in example 1SEM image.
FIG. 2 is a SEM photograph of (a) the crosslinked PVA obtained in comparative example 2-2; (b) comparative example 2-1 resulting crosslinked MoS content2SEM picture of PVA for PVP; (c) SEM image of the resulting crosslinked multifunctional PVA of example 2.
FIG. 3 is a SEM photograph of (a) the resulting ball-milled PVA of comparative example 3-2; (b) MoS-containing after ball-milling obtained in comparative example 3-12SEM picture of PVA for PVP; (c) SEM image of the post-ball-milled multifunctional PVA obtained in example 3.
FIG. 4 shows the MoS obtained in example 32Uv absorption profiles of PVA nanosphere suspensions of PVP and of PVA nanospheres obtained in comparative example 3-2.
FIG. 5 shows (a) MoS at different powers2Schematic representation of PVA nanospheres of PVP as a function of irradiation time under 980nm laser irradiation; (b) is (a) a corresponding infrared thermographic photograph; (c) MoS of different power2Schematic representation of PVA nanospheres of PVP as a function of irradiation time under 808nm laser irradiation; (d) is (c) the corresponding infrared thermographic photograph.
FIG. 6 is a schematic view of an electrospinning machine, in which 1 is an injection pump (syring), 2 is a spinning solution, 3 is a nozzle (needle), 4 is a liquid jet (liquid jet), 5 is a receiver plate (collector), 6 is a Taylor cone (Taylor cone), 7 is a high voltage power supply (DC high voltage)
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used in the embodiments of the present invention are all commercially available products unless otherwise specified, wherein the viscosity of the high viscosity PVA is 50.0 to 65.0mpa.s, and the viscosity of the low viscosity PVA is 5.0 to 7.0 mpa.s.
MoS2PVP nanoplatelets according to the publication "Preparation of poly (lactic-co-glycyl) by ye, Changqing et alolic acid) based composition microorganisms for a biological treatment of tumor in NIR I and NIR II biological sources "(Macromolecular biological, Vol: stage 18: 10, article No.: 1800206, year of publication: OCT2018, DOI: 10.1002/mabi.201800206).
Example 1
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, and stirred in a water bath at 80 ℃ for 2 hours to obtain a PVA solution, and 50mg of MoS was added2Stirring the PVP nanosheet and 25mg of adriamycin for 4 hours to obtain a PVA spinning solution containing the photo-thermal material and the medicine, adding the PVA spinning solution containing the photo-thermal material and the medicine into an injection pump 1 of an electrostatic spinning machine shown in figure 6, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of the electrostatic spinning machine to be 20kW, obtaining a multifunctional PVA film after the electrostatic spinning machine works, and performing vacuum drying for 12 hours at the vacuum drying temperature of 40 ℃ to obtain the multifunctional PVA film; the microscopic morphology of the material was observed by SEM: a multifunctional PVA film is attached to the surface of a conductive adhesive and attached to an objective table, gold is sprayed in vacuum, and observation and photographing are carried out through SEM, wherein the SEM operating voltage is 5 kV.
Comparative examples 1 to 1
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, stirred in a water bath at 80 ℃ for 2 hours, and 50mg of MoS was added2Stirring the PVP nanosheet for 4 hours to obtain a mixed solution, adding the mixed solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, and obtaining the product containing MoS after the electrostatic spinning machine works2PVA film of PVP, vacuum drying for 12h at 40 ℃ to obtain film containing MoS2PVA film of PVP, microscopic morphology of the material observed by SEM.
Comparative examples 1 to 2
Weighing 0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA, dissolving the PVA in 5mL of distilled water, stirring the solution in a water bath kettle at 80 ℃ for 2 hours to obtain a PVA solution, adding the PVA solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, obtaining a multifunctional PVA film after the electrostatic spinning machine works, obtaining the multifunctional PVA film at the vacuum drying temperature of 40 ℃, and observing the microscopic morphology of the material through SEM.
Example 2
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, and stirred in a water bath at 80 ℃ for 2 hours to obtain a PVA solution, and 50mg of MoS was added2-PVP nanosheet and 25mg adriamycin, stirring for 4 hours to obtain PVA spinning solution containing photo-thermal material and medicine, adding the PVA spinning solution containing photo-thermal material and medicine into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, performing electrostatic spinning, obtaining a multifunctional PVA film after the electrostatic spinning machine works, immersing the multifunctional PVA film into a cross-linking agent (consisting of glutaraldehyde and concentrated hydrochloric acid with the concentration of (36-38%)) and acetone at the volume ratio of 0.4:0.03:15), wherein the immersion time is 1 hour, then performing vacuum drying for 12 hours, and the vacuum drying temperature is 40 ℃ to obtain the hydrophobic multifunctional PVA film, and observing the microscopic morphology of the material through SEM: a multifunctional PVA film is attached to the surface of a conductive adhesive and attached to an objective table, gold is sprayed in vacuum, and observation and photographing are carried out through SEM, wherein the SEM operating voltage is 5 kV.
Comparative example 2-1
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, stirred in a water bath at 80 ℃ for 2 hours, and 50mg of MoS was added2Stirring the PVP nanosheet for 4 hours to obtain a mixed solution, adding the mixed solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, and obtaining MoS after the electrostatic spinning machine works2PVA film of PVP, MoS2-soaking PVA film of PVP into cross-linking agent (comprising glutaraldehyde, concentrated hydrochloric acid with concentration of 36-38%) and acetone at a volume ratio of 0.4:0.03:15 for 1h, and vacuum drying at 40 deg.C for 12h to obtain hydrophobic MoS2PVA film of PVP, microscopic morphology of the material observed by SEM.
Comparative example 2-1
Weighing 0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA, dissolving the PVA and the PVA in 5mL of distilled water, stirring the solution for 2 hours in a water bath kettle at 80 ℃ to obtain a PVA solution, adding the PVA solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, obtaining a multifunctional PVA film after the electrostatic spinning machine works, immersing the multifunctional PVA film into a cross-linking agent (consisting of glutaraldehyde and concentrated hydrochloric acid with the concentration of (36-38%)) and acetone at the volume ratio of 0.4:0.03:15), wherein the immersion time is 1 hour, then carrying out vacuum drying for 12 hours, and obtaining the hydrophobic multifunctional PVA film at the vacuum drying temperature of 40 ℃, and observing the microscopic morphology of the material by SEM.
Example 3
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, and stirred in a water bath at 80 ℃ for 2 hours to obtain a PVA solution, and 50mg of MoS was added2Stirring the PVP nanosheet and 25mg of adriamycin for 4 hours to obtain PVA spinning solution containing the photo-thermal material and the drug, adding the PVA spinning solution containing the photo-thermal material and the drug into an injection pump, setting the flow rate of injection to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, carrying out electrostatic spinning, obtaining a multifunctional PVA film after the electrostatic spinning machine works, immersing the multifunctional PVA film into a cross-linking agent (consisting of glutaraldehyde and concentrated hydrochloric acid with the concentration of 36-38%) and acetone, wherein the volume ratio of the glutaraldehyde to the concentrated hydrochloric acid to the acetone is 0.4:0.03:15), the immersion time is 1h, then the vacuum drying is carried out for 12h, the temperature of the vacuum drying is 40 ℃ to obtain the hydrophobic multifunctional PVA film, the hydrophobic multifunctional PVA film is put into a ball mill for ball milling, and the ball milling time is 5h, so that the multifunctional PVA nanospheres are obtained, and the microscopic morphology of the material is observed through SEM: and (3) scattering the multifunctional PVA nanospheres on the surface of the conductive adhesive, attaching to a stage, blowing for several times by using an aurilave, spraying gold in vacuum, observing and photographing by using an SEM (scanning electron microscope), wherein the SEM operating voltage is 5 kV.
Comparative example 3-1
0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA were weighed out and dissolved in 5mL of distilled water, stirred in a water bath at 80 ℃ for 2 hours, and 50mg of MoS was added2Stirring the PVP nanosheet for 4 hours to obtain a mixed solution, adding the mixed solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of the electrostatic spinning machine to be 20kW, and obtaining the PVP nanosheet after the electrostatic spinning machine worksMoS2PVA film of PVP, MoS2-soaking PVA film of PVP into cross-linking agent (comprising glutaraldehyde, concentrated hydrochloric acid with concentration of 36-38%) and acetone at a volume ratio of 0.4:0.03:15 for 1h, and vacuum drying at 40 deg.C for 12h to obtain hydrophobic MoS2PVA film of PVP, hydrophobic MoS2Putting PVA film of-PVP into a ball mill for ball milling for 5h to obtain MoS2PVA nanospheres of PVP, the microscopic morphology of the material was observed by SEM.
Comparative examples 3 to 2
Weighing 0.43g of low-viscosity PVA and 0.07g of low-viscosity PVA, dissolving the PVA and the PVA in 5mL of distilled water, stirring the mixture in a water bath kettle at 80 ℃ for 2 hours to obtain a PVA solution, adding the PVA solution into an injection pump, setting the injection flow rate to be 0.5mL/h, adjusting the working voltage of an electrostatic spinning machine to be 20kW, obtaining a multifunctional PVA film after the electrostatic spinning machine works, immersing the multifunctional PVA film into a cross-linking agent (consisting of glutaraldehyde and concentrated hydrochloric acid with the concentration of (36-38%)) and acetone at the volume ratio of 0.4:0.03:15) for 1 hour, then performing vacuum drying for 12 hours, obtaining a hydrophobic PVA film at the vacuum drying temperature of 40 ℃, placing the hydrophobic PVA film into a ball mill for ball milling for 5 hours to obtain PVA nanospheres, and observing the microscopic morphology of the material by SEM.
The diameter (at least 100 per sample) was measured using Image J1.40G software (http:// rsb. info. nih. gov/ij/download. html, National Institutes of Health, USA).
As shown in the figure (1a), the PVA fiber with a bead structure and the PVA nanofiber membrane are crosslinked by glutaraldehyde for 1h and can be directly torn off from the receiving tinfoil paper, and as shown in the figure (2a), the crosslinked PVA nanofiber membrane is directly enlarged and has the particle size of 310.8 +/-52.1 nm. The cross-linked PVA nanofiber membrane is naturally dried in the air, and is placed in a ball mill for ball milling for 5 hours, the product after ball milling is dissolved in distilled water, and as shown in the figure (3a), the fibers between beads are broken, the beads become dispersed particles, and the particle size is 422.15 +/-91.9 nm.
As can be seen from FIG. 2b, the morphology does not vary much compared to pure PVAAfter statistics, MoS is obtained2PVA for PVP has a particle size of 342.1 + -85.9 nm, the product after ball milling is dissolved in distilled water, and as can be seen from FIG (3b), the fibers between beads are broken, the beads become dispersed particles, and the particle size is 476.22 + -121.62 nm.
As seen from the graph (2c), the shape change is not large compared with that of pure PVA, the particle size of the hydrophobic multifunctional PVA film is 402.15 +/-87.91 nm after statistics, the product after ball milling is dissolved in distilled water, and as seen from the graph (3c), the fiber between beads is broken, the beads become dispersed particles, and the particle size is 516.6 +/-157.7 nm.
Example 4
MoS obtained in example 32PVA nanospheres of PVP were dispersed in water to give a suspension with a concentration of 10 mg/L. The PVA nanospheres obtained in comparative example 3-2 were dispersed in water to give a suspension having a concentration of 10 mg/L. The light absorption properties (wavelength range 350-2The suspension of PVA nanospheres of PVP has a high absorption at 800-990 nm.
Example 5
MoS obtained in example 32PVA nanospheres of PVP were dispersed in water to give a suspension with a concentration of 10 mg/L. The dispersion was irradiated with the listed lasers at 808nm and 980nm with predetermined powers, and the temperature change of the dispersion over time at different powers of the material and the corresponding IR thermographic pictures were recorded by a FLIR E60 IR camera. As can be seen from FIG. 5, MoS2PVA of PVP can effectively perform photothermal conversion to raise the temperature. The higher the laser density applied, the greater the energy and thus the higher the water temperature rise. Specifically, the density of the resin is 1w/cm2(ii) MoS with 808nm laser irradiation concentration of 10mg/mL2-PVA suspension of PVP, the temperature of the solution can be raised by approximately 20 ℃ (18.93 ℃) within 1 min; the temperature of the solution tends to be stable and can reach 38.53 ℃ in 5min by continuously applying the laser, and then the dynamic balance of the laser induced temperature rise process and the temperature diffusion between the solution and the outside is achieved, and the temperature change is not obvious any more; using a density of 1w/cm2980nm laser irradiationMoS with ejection concentration of 10mg/mL2PVA suspension of PVP, the heating rate is fast, and the solution temperature reaches nearly 35 ℃ (34.54 ℃) within 1 min; the temperature of the solution tends to be stable and can reach 44.32 ℃ in 5min after the laser is continuously applied, and then the dynamic balance of the laser-induced temperature rise process and the temperature diffusion between the solution and the outside is achieved, and the temperature change is not obvious any more.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (9)

1. A method for preparing multifunctional PVA nanospheres by using an electrostatic spinning machine is characterized by comprising the following steps: preparing a PVA spinning solution containing a photo-thermal material and a chemotherapeutic drug, performing electrostatic spinning to obtain a multifunctional PVA film, and performing ball milling to obtain multifunctional PVA nanospheres; the preparation method of the PVA spinning solution containing the photothermal material and the medicine comprises the following steps: dissolving PVA in distilled water, and stirring at 60-80 ℃ for 2-4 h to obtain a PVA solution, wherein the mass concentration of the PVA is 8-12 wt%; adding a photo-thermal material and a medicament, and stirring for 2-4 h to obtain a PVA spinning solution containing the photo-thermal material and the medicament, wherein the mass ratio of the photo-thermal material to the PVA is 5-10: 100.
2. The method for preparing multifunctional PVA nanospheres by using an electrospinning machine as claimed in claim 1, wherein the PVA consists of high-viscosity PVA and low-viscosity PVA, the mass ratio of the high-viscosity PVA to the low-viscosity PVA is 40-45:5-10, the viscosity of the high-viscosity PVA is 50.0-65.0 mpa.s, and the viscosity of the low-viscosity PVA is 5.0-7.0 mpa.s.
3. The method of preparing multifunctional PVA nanospheres with electrospinning machine according to claim 1, wherein the photothermal material is WS2-PVP nanoplate, MoS2-PVP nanoplate, MoS2/Bi2 S3-PEG、WS2、MoS2Any one or combination of black phosphorus and gold nanorods.
4. The method for preparing the multifunctional PVA nanospheres with the electrospinning machine according to claim 1, wherein the chemotherapeutic drug is doxorubicin, and the mass ratio of the doxorubicin to the PVA is 1-5: 100.
5. The method of preparing multifunctional PVA nanospheres with electrospinning machine according to claim 1, wherein said step of electrospinning comprises: and adding the PVA spinning solution containing the photo-thermal material and the medicine into an injection pump, and performing electrostatic spinning to obtain the multifunctional PVA film.
6. The method for preparing multifunctional PVA nanospheres with an electrospinning machine according to claim 5, wherein the injection flow rate of the injection pump is 0.5-0.6 mL/h; the working voltage of the electrostatic spinning is 20 kW-21 kW.
7. The method for preparing multifunctional PVA nanospheres with an electrospinning machine according to claim 5, wherein the multifunctional PVA film is crosslinked to obtain a hydrophobic multifunctional PVA film, and then ball-milling is performed to obtain the multifunctional PVA nanospheres.
8. The method of preparing multifunctional PVA nanospheres using an electrospinning machine as claimed in claim 7, wherein said step of crosslinking comprises: immersing the multifunctional PVA film into a cross-linking agent for 1-1.5 h, and then carrying out vacuum drying at the temperature of 40-50 ℃ to obtain a hydrophobic multifunctional PVA film; the cross-linking agent is composed of glutaraldehyde, concentrated hydrochloric acid and acetone, and the volume ratio of the glutaraldehyde to the concentrated hydrochloric acid to the acetone is 0.3-0.5: 0.01-0.05: 15.
9. Use of the multifunctional PVA nanospheres prepared by the method of preparing multifunctional PVA nanospheres with an electrospinning machine according to any one of claims 1 to 8 as a photothermal conversion material.
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