CN109487438A - A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine - Google Patents

A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine Download PDF

Info

Publication number
CN109487438A
CN109487438A CN201811330410.7A CN201811330410A CN109487438A CN 109487438 A CN109487438 A CN 109487438A CN 201811330410 A CN201811330410 A CN 201811330410A CN 109487438 A CN109487438 A CN 109487438A
Authority
CN
China
Prior art keywords
pva
functional
nanosphere
electrostatic spinning
spinning machine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811330410.7A
Other languages
Chinese (zh)
Other versions
CN109487438B (en
Inventor
王世革
叶长青
罗科义
李金凤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN201811330410.7A priority Critical patent/CN109487438B/en
Publication of CN109487438A publication Critical patent/CN109487438A/en
Application granted granted Critical
Publication of CN109487438B publication Critical patent/CN109487438B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M11/07—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 with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—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 with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • 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
    • D06M13/123—Polyaldehydes; Polyketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • 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
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of methods for preparing multi-functional PVA nanosphere with electrostatic spinning machine characterized by comprising prepares the PVA spinning solution containing optothermal material and chemotherapeutics, carry out electrostatic spinning, multi-functional PVA film is obtained, ball milling obtains multi-functional PVA nanosphere.Compared with prior art, multi-functional PVA nanosphere can be largely prepared without many and diverse test operation step, without adding the reaction condition of surfactant and harshness, the technique for simplifying preparation achieves significant progress in the promotion of yield.

Description

A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine
Technical field
The present invention relates to PVA nanosphere technical field, in particular to it is a kind of prepared with electrostatic spinning machine it is PVA nanometers multi-functional The method of ball.
Background technique
Polyvinyl alcohol (PVA) is molecular backbone containing-CH2- CH (OH)-group high polymer, by Alcoholysis of Polyvinyl Acetate And it is made.PVA has excellent hydrophily and good reactivity, and by chemical crosslinking or modification, its machinery is strong Degree and chemical stability can significantly improve, antibiont degradation property enhances.Meanwhile PVA material is nontoxic to bioactive substance, valence The honest and clean series of advantages such as be easy to get, making one kind can be applied to bioengineering, pharmaceutical engineering, chemical industry, environmental protection etc. Various fields and the carrier material with development potentiality.
In recent years, in terms of the research hotspot of PVA carrier is concentrated mainly on spheroid carrier, this is because PVA microballoon material Material has many advantages, such as good skin effect, bulk effect, function base characteristic and target-oriented drug, it is made to have other materials institute The specific function not having, thus have a wide range of applications.
The preparation of PVA microballoon at present is made by reacting in water phase, and obtained PVA ball is all micron level, The addition that high-speed stirred and surfactant are needed during preparation, severe reaction conditions needed for preparing PVA microballoon, yield Lowly, preparation cost is high.
It is the most important of world's material science and technology field in recent ten years that electrostatic spinning technique, which prepares nano-fiber material, Science one of with technical activity.Electrostatic spinning and it is simple with its manufacturing device, cost of spinning is cheap, it is numerous to spin substance classes More, the advantages that technique is controllable, it has also become effectively prepare one of main path of nano-fiber material.Up to now, still without text Offer the report that report prepares PVA microballoon by electrostatic spinning technique.
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing multi-functional PVA nanosphere with electrostatic spinning machine.
In order to achieve the above object, the present invention provides a kind of sides that multi-functional PVA nanosphere is prepared with electrostatic spinning machine Method characterized by comprising prepare the PVA spinning solution containing optothermal material and chemotherapeutics, carry out electrostatic spinning, obtain Multi-functional PVA film, ball milling obtain multi-functional PVA nanosphere.
Preferably, the preparation method of the PVA spinning solution containing optothermal material and drug includes: to dissolve PVA In distilled water, 60 DEG C~80 DEG C stirring 2h~4h obtain PVA solution, wherein the mass concentration of PVA is 8-12wt%；Light is added Hot material and drug stir 2h~4h, obtain the PVA spinning solution containing optothermal material and drug, wherein the matter of optothermal material Amount and the mass ratio of PVA are 5~10:100.
It is highly preferred that the PVA is made of high viscosity PVA and low viscosity PVA, high viscosity PVA and low viscosity PVA Mass ratio is 40-45:5-10, and the viscosity of high viscosity PVA is 50.0~65.0mpa.s, the viscosity of low viscosity PVA is 5.0~ 7.0mpa.s.Most preferably, high viscosity PVA and the mass ratio of low viscosity PVA are 43:7.
It is highly preferred that the optothermal material is WS2- PVP nanometer sheet, MoS2- PVP nanometer sheet, MoS2/Bi2S3-PEG、 WS2、MoS2, any one or combination in black phosphorus and gold nanorods.
It is highly preferred that the chemotherapeutics is adriamycin, the mass ratio of adriamycin and PVA are 1~5:100.
Preferably, the step of electrostatic spinning includes: that will be added containing the PVA spinning solution of optothermal material and drug Into syringe pump, electrostatic spinning is carried out, multi-functional PVA film is obtained.
It is highly preferred that the injection flow velocity of the syringe pump is 0.5~0.6mL/h.
It is highly preferred that the operating voltage of the electrostatic spinning is 20kW~21kW.
Preferably, the multi-functional PVA film first passes through crosslinking, obtains multifunctional drainage PVA film, then carry out ball milling, Obtain multi-functional PVA nanosphere.
It is highly preferred that the step of described crosslinking includes: that multi-functional PVA film is immersed in crosslinking agent, the time of immersion It is 1h~1.5h, then is dried in vacuo, vacuum drying temperature is 40 DEG C~50 DEG C, obtains multifunctional drainage PVA film.
Further, the crosslinking agent is made of glutaraldehyde, concentrated hydrochloric acid and acetone, and glutaraldehyde, concentrated hydrochloric acid and acetone Volume ratio be 0.3~0.5:0.01~0.05:15.
Preferably, the Ball-milling Time is 2h~5h.
The present invention also provides the multi-functional PVA nanospheres prepared by the above method as answering in photothermal conversion materiat With.
Compared with prior art, the beneficial effects of the present invention are:
The present invention can make without many and diverse test operation step, without adding the reaction condition of surfactant and harshness Standby a large amount of multi-functional PVA nanosphere, the technique for simplifying preparation obtain the multi-functional PVA ball with nano-scale, and drop The cost of low preparation achieves significant progress in the promotion of yield, is expected to for multi-functional PVA nanosphere being commercialized.
Detailed description of the invention
The SEM that Fig. 1 is the resulting PVA of (a) comparative example 1-2 schemes；(b) comparative example 1-1 is resulting contains MoS2The PVA of-PVP SEM figure；(c) the SEM figure of the resulting multi-functional PVA of embodiment 1.
Fig. 2 is the SEM figure of PVA after the resulting crosslinking of (a) comparative example 2-2；(b) contain after the resulting crosslinking of comparative example 2-1 MoS2The SEM of the PVA of-PVP schemes；(c) SEM of multi-functional PVA schemes after the resulting crosslinking of embodiment 2.
Fig. 3 is the SEM figure of PVA after the resulting ball milling of (a) comparative example 3-2；(b) contain after the resulting ball milling of comparative example 3-1 MoS2The SEM of the PVA of-PVP schemes；(c) SEM of multi-functional PVA schemes after the resulting ball milling of embodiment 3.
Fig. 4 is the resulting MoS of embodiment 32The suspension and comparative example 3-2 of the PVA nanosphere of-PVP are PVA nanometers resulting The UV absorption figure of the suspension of ball.
Fig. 5 is the MoS of (a) different capacity2The PVA nanosphere of-PVP is under 980nm laser emission, and temperature is with radiated time Variation schematic diagram；It (b) is (a) corresponding infrared thermal imaging photo；(c) MoS of different capacity2The PVA nanosphere of-PVP exists Under 808nm laser emission, temperature with radiated time variation schematic diagram；It (d) is (c) corresponding infrared thermal imaging photo.
Fig. 6 is electrostatic spinning machine schematic diagram, and in figure, 1 is syringe pump (syringe), and 2 be spinning solution, and 3 be nozzle (needle), 4 be liquid jet (liquid jet), and 5 be receiver board (collector), and 6 be taylor cone (Taylor cone), 7 be high voltage power supply (DC high voltage)
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
In various embodiments of the present invention it is raw materials used unless otherwise specified, be commercial product, wherein high viscosity PVA's is viscous Degree is 50.0~65.0mpa.s, and the viscosity of low viscosity PVA is 5.0~7.0mpa.s.
MoS2- PVP nanometer sheet is according to ye, document " Preparation of poly that Changqing etc. is delivered (lactic-co-glycolic acid)based composite microfibers for postoperative treatment of tumor in NIR I and NIR II biowindows”(Macromolecular bioscience, Volume: 18 phases: 10, document number: 1800206, publish year: OCT2018, DOI:10.1002/mabi.201800206) in record Preparation method is made.
Embodiment 1
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, adds 50mg MoS2- PVP nanometer sheet and 25mg adriamycin, are stirred for 4h, obtain containing photo-thermal material The PVA spinning solution of material and drug, will obtain being added to containing the PVA spinning solution of optothermal material and drug as shown in FIG. 6 In the syringe pump 1 of electrostatic spinning machine, the flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning machine operating voltage 20kW, electrostatic Spinning machine obtains multi-functional PVA film after having worked, be dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and obtains multi-functional PVA Film；The microscopic appearance of material is observed by SEM: one piece of multi-functional PVA film being taken to be attached to conducting resinl surface, is bonded objective table, It in vacuum metal spraying, by SEM observation, takes pictures, it is 5kV that SEM, which operates voltage,.
Comparative example 1-1
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, 50mg MoS is added2- PVP nanometer sheet is stirred for 4h and obtains mixed solution, mixed solution is added in syringe pump, The flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning machine operating voltage 20kW, and electrostatic spinning machine is contained after having worked MoS2The PVA film of-PVP, is dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and obtains containing MoS2The PVA film of-PVP leads to Cross the microscopic appearance of SEM observation material.
Comparative example 1-2
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, PVA solution is added in syringe pump, the flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning Machine operating voltage 20kW, electrostatic spinning machine obtain multi-functional PVA film after having worked, vacuum drying temperature be 40 DEG C obtain it is more Function PVA film observes the microscopic appearance of material by SEM.
Embodiment 2
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, adds 50mg MoS2- PVP nanometer sheet and 25mg adriamycin, are stirred for 4h and obtain containing optothermal material With the PVA spinning solution of drug, the PVA spinning solution containing optothermal material and drug is added in syringe pump, setting injection Flow velocity be 0.5mL/h, adjust electrostatic spinning machine operating voltage 20kW, carry out electrostatic spinning, electrostatic spinning machine work after must To multi-functional PVA film, by multi-functional PVA film be immersed in crosslinking agent (by glutaraldehyde, (concentration is (36%~38%)) it is dense Hydrochloric acid and acetone composition, and the volume ratio of glutaraldehyde, concentrated hydrochloric acid and acetone is 0.4:0.03:15) in, the time of immersion is 1h, It is dried in vacuo 12h again, vacuum drying temperature is 40 DEG C, obtains multifunctional drainage PVA film, observes the micro- of material by SEM It sees pattern: one piece of multi-functional PVA film being taken to be attached to conducting resinl surface, be bonded objective table, in vacuum metal spraying, by SEM observation, clap According to it is 5kV that SEM, which operates voltage,.
Comparative example 2-1
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, 50mg MoS is added2- PVP nanometer sheet is stirred for 4h and obtains mixed solution, mixed solution is added in syringe pump, The flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning machine operating voltage 20kW, and electrostatic spinning machine obtains after having worked MoS2The PVA film of-PVP, by MoS2The PVA film of-PVP be immersed in crosslinking agent (by glutaraldehyde, (concentration be (36%~ 38%) concentrated hydrochloric acid and acetone composition), and the volume ratio of glutaraldehyde, concentrated hydrochloric acid and acetone is 0.4:0.03:15) in, immersion Time is 1h, then is dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and obtains hydrophobic MoS2The PVA film of-PVP, passes through SEM Observe the microscopic appearance of material.
Comparative example 2-1
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, PVA solution is added in syringe pump, the flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning Machine operating voltage 20kW, electrostatic spinning machine obtain multi-functional PVA film after having worked, multi-functional PVA film is immersed in crosslinking Agent (is made of, and the body of glutaraldehyde, concentrated hydrochloric acid and acetone glutaraldehyde, the concentrated hydrochloric acid of (concentration is (36%~38%)) and acetone Product ratio is 0.4:0.03:15) in, the time of immersion is 1h, then is dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and is dredged The multi-functional PVA film of water observes the microscopic appearance of material by SEM.
Embodiment 3
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, adds 50mg MoS2- PVP nanometer sheet and 25mg adriamycin are stirred for 4h and obtain containing photo-thermal material The PVA spinning solution of material and drug, the PVA spinning solution containing optothermal material and drug is added in syringe pump, setting note The flow velocity penetrated is 0.5mL/h, adjusts electrostatic spinning machine operating voltage 20kW, electrostatic spinning is carried out, after electrostatic spinning machine has worked Multi-functional PVA film is obtained, multi-functional PVA film is immersed in crosslinking agent (by glutaraldehyde, (concentration be (36%~38%)) Concentrated hydrochloric acid and acetone composition, and the volume ratio of glutaraldehyde, concentrated hydrochloric acid and acetone is 0.4:0.03:15) in, the time of immersion is 1h, then it is dried in vacuo 12h, vacuum drying temperature is 40 DEG C and obtains multifunctional drainage PVA film, multifunctional drainage PVA film It is put into ball milling in ball mill, and Ball-milling Time is 5h, obtains multi-functional PVA nanosphere, the microcosmic shape of material is observed by SEM Looks: taking multi-functional PVA nanosphere to be sprinkling upon conducting resinl surface, is bonded objective table, is blown several times with ear washing bulb, in vacuum metal spraying, passed through SEM observation is taken pictures, and it is 5kV that SEM, which operates voltage,.
Comparative example 3-1
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, 50mg MoS is added2- PVP nanometer sheet is stirred for 4h and obtains mixed solution, mixed solution is added in syringe pump, The flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning machine operating voltage 20kW, and electrostatic spinning machine obtains after having worked MoS2The PVA film of-PVP, by MoS2The PVA film of-PVP be immersed in crosslinking agent (by glutaraldehyde, (concentration be (36%~ 38%) concentrated hydrochloric acid and acetone composition), and the volume ratio of glutaraldehyde, concentrated hydrochloric acid and acetone is 0.4:0.03:15) in, immersion Time is 1h, then is dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and obtains hydrophobic MoS2The PVA film of-PVP, hydrophobic MoS2- The PVA film of PVP is put into ball milling in ball mill, and Ball-milling Time is 5h, obtains MoS2The PVA nanosphere of-PVP, is seen by SEM Examine the microscopic appearance of material.
Comparative example 3-2
It weighs 0.43g low viscosity PVA and 0.07g low viscosity PVA is dissolved in 5mL distilled water, stirred in 80 DEG C of water-baths 2h is mixed, PVA solution is obtained, PVA solution is added in syringe pump, the flow velocity that injection is arranged is 0.5mL/h, adjusts electrostatic spinning Machine operating voltage 20kW, electrostatic spinning machine obtain multi-functional PVA film after having worked, multi-functional PVA film is immersed in crosslinking Agent (is made of, and the body of glutaraldehyde, concentrated hydrochloric acid and acetone glutaraldehyde, the concentrated hydrochloric acid of (concentration is (36%~38%)) and acetone Product ratio is 0.4:0.03:15) in, the time of immersion is 1h, then is dried in vacuo 12h, and vacuum drying temperature is 40 DEG C and is dredged Water PVA film, hydrophobic PVA film is put into ball milling in ball mill, and Ball-milling Time is 5h, obtains PVA nanosphere, is seen by SEM Examine the microscopic appearance of material.
With Image J 1.40G software (http://rsb.info.nih.gov/ij/download.html, National Institutes of Health, the U.S.) measurement diameter (each sample at least measures 100).
Found out by figure (1a), the PVA fiber with bead structure, PVA nano fibrous membrane, can be from glutaraldehyde cross-linking 1h It receives and directly tears on masking foil, found out by figure (2a), the PVA nano fibrous membrane by crosslinking directly becomes larger, and partial size is 310.8±52.1nm.The PVA nano fibrous membrane naturally dry of crosslinking, puts ball milling 5h in the ball mill, and the product after ball milling is dissolved in In distilled water, find out that the fiber between a beading is interrupted by figure (3a), a beading become the particle of dispersion, and partial size is 422.15±91.9nm。
Found out by figure (2b), pattern variation less, goes out MoS after statistics compared with pure PVA2The grain of the PVA of-PVP Diameter is 342.1 ± 85.9nm, and the product after ball milling is dissolved in distilled water, finds out that the fiber between a beading is beaten by figure (3b) Disconnected, a beading become the particle of dispersion, and partial size is 476.22 ± 121.62nm.
Found out by figure (2c), pattern variation less, goes out multifunctional drainage PVA film after statistics compared with pure PVA Partial size be 402.15 ± 87.91nm, the product after ball milling is dissolved in distilled water, is found out by figure (3c), the fibre between a beading Dimension is interrupted, and a beading become the particle of dispersion, and partial size is 516.6 ± 157.7nm.
Embodiment 4
By the resulting MoS of embodiment 32The PVA nanosphere of-PVP is dispersed in water, and obtains the suspension that concentration is 10mg/L Liquid.The resulting PVA nanosphere of comparative example 3-2 is dispersed in water, the suspension that concentration is 10mg/L is obtained.Use UV-Vis-NIR (Lambda 25, Perkin Elmer company, the U.S.) analyzes its optical absorption property (wave-length coverage 350-1100nm), is received with PVA Rice ball solution is used as control, as can be seen from Figure 4 MoS2The suspension of the PVA nanosphere of-PVP has great number at 800-990nm It absorbs.
Embodiment 5
By the resulting MoS of embodiment 32In the PVA nanosphere disperse water of-PVP, the suspension that concentration is 10mg/L is obtained. With the laser irradiation dispersion liquid of the listed 808nm and 980nm wavelength for presetting power, pass through FLIR E60 infrared thermal imagery Instrument recording materials dispersion liquid temperature under the conditions of different capacity changes with time situation and corresponding infrared thermal imaging photo.From Fig. 5 can be seen that MoS2The PVA of-PVP can be effectively carried out photothermal conversion and increase temperature.The laser intensity of application is higher, energy Amount is bigger, and then water temperature raising is higher.It specifically, is 1w/cm with density2808nm laser irradiation concentration be 10mg/mL MoS2The PVA suspension of-PVP, solution temperature can increase nearly 20 DEG C (18.93 DEG C) in 1min；Continue to laser, solution Temperature tend towards stability, up to 38.53 DEG C when 5min, the temperature in laser-induced temperature-rise period and solution and external world diffusion later reaches Dynamic equilibrium, temperature change are no longer obvious；It is 1w/cm with density2980nm laser irradiation concentration be 10mg/mL MoS2-PVP PVA suspension, heating rate is fast, and solution temperature is up to nearly 35 DEG C (34.54 DEG C) in 1min；Laser is continued to, solution Temperature tends towards stability, and up to 44.32 DEG C when 5min, the temperature in laser-induced temperature-rise period and solution and external world diffusion later reaches dynamic State balance, temperature change are no longer obvious.
In conjunction with attached drawing, the embodiments of the present invention are described in detail above, but the present invention is not limited to described implementations Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.

Claims (10)

1. a kind of method for preparing multi-functional PVA nanosphere with electrostatic spinning machine characterized by comprising preparation contains photo-thermal The PVA spinning solution of material and chemotherapeutics carries out electrostatic spinning, obtains multi-functional PVA film, ball milling obtains multi-functional PVA and receives Rice ball.
2. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as described in claim 1, which is characterized in that described The preparation method of the PVA spinning solution containing optothermal material and drug include: that PVA is dissolved in distilled water, 60 DEG C~80 DEG C stirring 2h~4h, obtain PVA solution, wherein the mass concentration of PVA is 8-12wt%；Optothermal material and drug is added, stirs 2h ~4h obtains the PVA spinning solution containing optothermal material and drug, wherein the quality of optothermal material and the mass ratio of PVA are 5 ~10:100.
3. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as claimed in claim 2, which is characterized in that described PVA be made of high viscosity PVA and low viscosity PVA, the mass ratio of high viscosity PVA and low viscosity PVA is 40-45:5-10, and The viscosity of high viscosity PVA is 50.0~65.0mpa.s, and the viscosity of low viscosity PVA is 5.0~7.0mpa.s.
4. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as claimed in claim 2, which is characterized in that described Optothermal material be WS2- PVP nanometer sheet, MoS2- PVP nanometer sheet, MoS2/Bi2S3-PEG、WS2、MoS2, black phosphorus and gold nanorods In any one or combination.
5. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as described in claim 1, which is characterized in that described Chemotherapeutics be adriamycin, the mass ratio of adriamycin and PVA are 1~5:100.
6. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as described in claim 1, which is characterized in that described Electrostatic spinning the step of include: that the PVA spinning solution containing optothermal material and drug is added in syringe pump, carry out electrostatic Spinning obtains multi-functional PVA film.
7. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as claimed in claim 6, which is characterized in that described The injection flow velocity of syringe pump be 0.5~0.6mL/h；The operating voltage of the electrostatic spinning is 20kW~21kW.
8. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as claimed in claim 6, which is characterized in that described Multi-functional PVA film first pass through crosslinking, obtain multifunctional drainage PVA film, then carry out ball milling, obtain multi-functional PVA nanosphere.
9. the method for preparing multi-functional PVA nanosphere with electrostatic spinning machine as claimed in claim 8, which is characterized in that described Crosslinking the step of include: that multi-functional PVA film is immersed in crosslinking agent, the time of immersion is 1h~1.5h, then is dried in vacuo, Vacuum drying temperature is 40 DEG C~50 DEG C, obtains multifunctional drainage PVA film；The crosslinking agent is by glutaraldehyde, concentrated hydrochloric acid It is formed with acetone, and the volume ratio of glutaraldehyde, concentrated hydrochloric acid and acetone is 0.3~0.5:0.01~0.05:15.
10. it is of any of claims 1-9 prepare the method for multi-functional PVA nanosphere with electrostatic spinning machine prepared by Multi-functional PVA nanosphere is as the application in photothermal conversion materiat.
CN201811330410.7A 2018-11-09 2018-11-09 Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine Active CN109487438B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811330410.7A CN109487438B (en) 2018-11-09 2018-11-09 Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811330410.7A CN109487438B (en) 2018-11-09 2018-11-09 Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine

Publications (2)

Publication Number Publication Date
CN109487438A true CN109487438A (en) 2019-03-19
CN109487438B CN109487438B (en) 2021-04-30

Family

ID=65694200

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811330410.7A Active CN109487438B (en) 2018-11-09 2018-11-09 Method for preparing multifunctional PVA nanospheres by using electrostatic spinning machine

Country Status (1)

Country Link
CN (1) CN109487438B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110341257A (en) * 2019-07-26 2019-10-18 南通大学 A kind of multi-functional compound coat fabric and preparation method thereof
CN114541038A (en) * 2020-11-24 2022-05-27 诺一迈尔（苏州）医学科技有限公司 Preparation method of electrostatic spinning membrane for tissue defect repair
CN115138395A (en) * 2022-07-18 2022-10-04 黑龙江工业学院 Preparation method and application of black phosphorus-based photocatalytic composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106267201A (en) * 2016-08-26 2017-01-04 深圳先进技术研究院 A kind of black phosphorus of polymer wrapped and preparation method and application
CN108578384A (en) * 2018-05-16 2018-09-28 华中科技大学 A kind of encapsulating Bi2S3Alginate microsphere of nanoparticle and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106267201A (en) * 2016-08-26 2017-01-04 深圳先进技术研究院 A kind of black phosphorus of polymer wrapped and preparation method and application
CN108578384A (en) * 2018-05-16 2018-09-28 华中科技大学 A kind of encapsulating Bi2S3Alginate microsphere of nanoparticle and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUANYUAN LI ET AL: "Targeted polydopamine nanoparticles enable photoacoustic imaging guided chemo-photothermal synergistic therapy of tumor", 《ACTA BIOMATERIALIA》 *
杨光: "载微/纳颗粒多级结构电纺纤维在肿瘤治疗及诊断中的应用探究", 《中国博士学位论文全文数据库 医药卫生科技辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110341257A (en) * 2019-07-26 2019-10-18 南通大学 A kind of multi-functional compound coat fabric and preparation method thereof
CN114541038A (en) * 2020-11-24 2022-05-27 诺一迈尔（苏州）医学科技有限公司 Preparation method of electrostatic spinning membrane for tissue defect repair
CN114541038B (en) * 2020-11-24 2023-12-12 诺一迈尔（苏州）医学科技有限公司 Preparation method of electrostatic spinning membrane for repairing tissue defect
CN115138395A (en) * 2022-07-18 2022-10-04 黑龙江工业学院 Preparation method and application of black phosphorus-based photocatalytic composite material

Also Published As

Publication number Publication date
CN109487438B (en) 2021-04-30

Similar Documents

Publication Publication Date Title
CN109487438A (en) A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine
El-Newehy et al. Green electrospining of hydroxypropyl cellulose nanofibres for drug delivery applications
EP3190216B1 (en) Method for manufacturing super absorbent polymer fiber
Wongsasulak et al. Electrospinning of food-grade nanofibers from cellulose acetate and egg albumen blends
Crabbe-Mann et al. Ethyl cellulose, cellulose acetate and carboxymethyl cellulose microstructures prepared using electrohydrodynamics and green solvents
CN104845301B (en) A kind of ultraviolet light screener and preparation method thereof and polylactic acid film comprising the ultraviolet light screener and preparation method thereof
Tai et al. A green process for preparing silver nanoparticles using spinning disk reactor
US20050136253A1 (en) Rotary spinning processes for forming hydroxyl polymer-containing fibers
CN107115830A (en) A kind of method that polymer microsphere is prepared based on high-pressure electrostatic ultrasonic atomizatio
KR102284629B1 (en) Water absorbent
Liu et al. Autofluorescent micelles self-assembled from an AIE-active luminogen containing an intrinsic unconventional fluorophore
US20170266124A1 (en) Conjugated Polymer Nanoparticles and Manufacturing Method Thereof
Hao et al. Dialdehyde xylan-based sustainable, stable, and catalytic liquid metal nano-inks
CN106757785B (en) Preparation method of silver-loaded chitosan/polyvinyl alcohol micron belt
CN103435706A (en) Preparation method of starch nanoparticles
CN112898545B (en) Solvent-free green method for preparing polylactic acid nano material
Huang et al. Electrospun nanofibers: from rational design, fabrication to electrochemical sensing applications
Qi et al. Versatile liquid metal/alginate composite fibers with enhanced flame retardancy and triboelectric performance for smart wearable textiles
CN109183277A (en) A kind of conductive fiber flexible membrane and preparation method thereof
CN109338497A (en) A kind of preparation method of hydrophily degradable poly butyrolactam superfine fibre
JP2019147743A (en) Bisamino benzylpiperazine dione, amide acid polymer and polyimide, and hollow polyimide particle and manufacturing method therefor
CN108411401A (en) A kind of nanometer selenium composite fibre and preparation method thereof
Duan et al. Investigation into electrospinning water-soluble xylan: Developing applications from highly absorbent and hydrophilic surfaces to carbonized fiber
Zhang et al. Coaxial two-capillary electrosprayed double-layered shells microcapsules used for in-situ thermally induced coatings
CN109505034A (en) A kind of binary inorganic nano-fiber and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant