CN110042567B - Preparation method of Ag-ZnO/PLA/beta-CD composite nanofiber membrane - Google Patents

Preparation method of Ag-ZnO/PLA/beta-CD composite nanofiber membrane Download PDF

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CN110042567B
CN110042567B CN201910179831.2A CN201910179831A CN110042567B CN 110042567 B CN110042567 B CN 110042567B CN 201910179831 A CN201910179831 A CN 201910179831A CN 110042567 B CN110042567 B CN 110042567B
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pla
zno
composite nanofiber
nanofiber membrane
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CN110042567A (en
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陈全胜
焦天慧
许艺
王安成
王井井
贺培欢
李欢欢
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Jiangsu University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-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
    • D04H1/72Non-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
    • D04H1/728Non-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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Abstract

The invention belongs to the technical field of membrane material preparation, and relates to a preparation method of a composite nanofiber membrane with surface enhanced Raman and bacteriostatic activity; firstly, preparing silver/zinc oxide nano particles with three-dimensional structures; then dissolving polylactic acid (PLA) and beta-cyclodextrin in dichloromethane to obtain a PLA/beta-CD mixed original solution; adding silver/zinc oxide nano-particles with a three-dimensional structure, and performing ultrasonic stirring to obtain a composite nanofiber stock solution; carrying out electrostatic spinning on the composite nanofiber stock solution at room temperature, and drying to obtain an Ag @ ZnO @ PLA/beta-CD composite nanofiber membrane; according to the invention, polylactic acid and beta-cyclodextrin are used as composite spinning materials, and the relatively loose microstructure is beneficial to the adsorption of a substance to be detected and the seepage of silver ions; not only the Raman enhancement and the bacteriostatic activity are ensured, but also the zinc oxide/silver is firmly combined with the fiber and can be repeatedly utilized, thereby not only widening the application range of the material, but also enhancing the economical efficiency.

Description

Preparation method of Ag-ZnO/PLA/beta-CD composite nanofiber membrane
Technical Field
The invention belongs to the technical field of film material preparation, and particularly relates to a preparation method of an Ag-ZnO/PLA/beta-CD composite nanofiber film.
Background
The nanofiber has the advantages of high specific surface area, adjustable form and good ductility, and the spun nanofiber membrane has the characteristics of unique network structure, high porosity, light weight and easiness in functional processing, and is widely applied to the fields of food packaging, biological medical treatment, membrane filtration, energy storage and the like.
On the other hand, in order to better satisfy the requirements of different fields for nanofiber membranes, nanomaterials with different functional properties are also introduced into nanofibers. At present, research on the antibacterial performance of the wound dressing made of silver nanoparticles and pectin composite nanofibers and the antibacterial performance of the wound dressing made of the nanofiber surface loaded with the silver nanoparticles has been carried out. Furthermore, noble metal nanoparticles such as silver can enhance the scattering signal and serve as a substrate for surface enhanced raman spectroscopy. However, the nanofiber with the nanofiber/precious metal particle structure has the problem that nanoparticles are loaded on the surface of the fiber, so that the particles are unevenly distributed and easily fall off from the fiber, and further, the performances of bacteriostasis, scattering enhancement and the like are unstable.
The invention content is as follows:
aiming at the defects of the prior art, the invention aims to provide the Ag-ZnO/PLA/beta-CD composite nanofiber membrane which is simple to prepare, has good surface enhanced Raman and bacteriostatic activity, can be recycled and has strong economical efficiency.
In order to achieve the above purpose, the specific steps of the invention are as follows:
(1) preparing silver/zinc oxide nanoparticles (Ag-ZnO NPs) with a three-dimensional structure; first, zinc chloride (ZnCl)2) Adding into distilled water, dissolving, and adding ammonia water (NH)3·H2O), stirring at a certain temperature to obtain white powder; dissolving white powder, polyvinylpyrrolidone K30 and glucose in distilled water, heating and stirring to obtain silver/zinc oxide nanoparticles with three-dimensional structures, and marking as Ag-ZnO NPs;
(2) dissolving polylactic acid (PLA) and beta-cyclodextrin (beta-cyclodextrin, beta-CD) in dichloromethane to obtain a mixed solution, namely a PLA/beta-CD mixed original solution;
(3) adding the Ag-ZnO NPs prepared in the step (1) into the PLA/beta-CD mixed stock solution prepared in the step (2), performing ultrasonic treatment, and then stirring at a certain temperature to prepare a composite stock solution;
(4) setting applied voltage, receiving distance, propelling speed and air humidity, carrying out electrostatic spinning on the composite stock solution at room temperature to obtain fibers, and drying to obtain the Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
Distilled water and ZnCl in the step (1)2And NH3·H2The dosage ratio of O is 200 mL: 2.5 g: 2 mL.
The certain temperature in the step (1) is 60 ℃; the stirring time is 12 h.
The using amount ratio of the white powder in the step (1), polyvinylpyrrolidone K30, glucose and distilled water is 0.5 g: 2 g: 2 g: 50 mL.
The heating and stirring degree of the step (1) is 90 ℃, and the time is 1 h.
The dosage ratio of the polylactic acid, the beta-cyclodextrin and the dichloromethane in the step (2) is 1 g: 0.3-0.8 g: 8-12 mL.
The dosage ratio of the Ag-ZnO NPs to the PLA/beta-CD mixed original solution in the step (3) is 1-4 g: 50 mL.
The ultrasonic treatment time in the step (3) is 15 min; the certain temperature is 40 ℃, and the stirring time is 5-300 min.
And (4) applying 15-30 KV, wherein the receiving distance is 8-12 cm, the propelling speed is 0.5-5 mL/h, and the air humidity is less than or equal to 30%.
And (4) the inner diameter of the needle used for electrostatic spinning is 0.6 mm.
The Ag-ZnO/PLA/beta-CD composite nanofiber membrane prepared by the invention wraps Ag-ZnO NPs in the composite fibers, does not fall off, and has good antibacterial effect and surface enhanced Raman activity.
The invention has the following beneficial effects:
(1) PLA, beta-CD, ZnO and AgNPs contained in the composite membrane prepared by the invention have higher biological safety and environmental friendliness.
(2) The zinc oxide/silver submicron particles with three-dimensional structures are introduced and are wrapped in the zinc oxide/silver submicron particles through simple and feasible one-step spinning, so that the zinc oxide/silver submicron particles cannot fall off and can be recycled, and the economy is improved; the particles with the zinc oxide/silver structure not only have bacteriostatic activity, but also have excellent surface enhanced Raman activity due to the semiconductor/noble metal interface in the particles; the surface enhanced Raman spectroscopy can carry out in-situ detection on the coating, and the bacteriostatic activity of the coating can improve the safety of the coating.
(3) According to the invention, polylactic acid and beta-cyclodextrin are used as composite spinning materials, and the relatively loose microstructure is beneficial to the adsorption of a substance to be detected and the seepage of silver ions; not only the Raman enhancement and the bacteriostatic activity are ensured, but also the zinc oxide/silver is firmly combined with the fiber and can be repeatedly utilized, and compared with the traditional composite nanofiber membrane, the application range is widened, and the economical efficiency is enhanced.
(4) The invention can adjust the mechanical property of the fiber to meet the actual demand by changing the proportion of PLA/beta-CD and the addition of the nano-particles, and has the advantages of low raw material price, simple synthesis and good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
FIG. 2 is a Raman spectrum obtained after rhodamine 6G solutions with different concentrations are adsorbed on a nanofiber membrane.
Fig. 3 is a picture of the zone of inhibition formed by the composite fiber membrane in listeria monocytogenes.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1:
(1) preparing Ag-ZnO particles with three-dimensional structures: 2.5g of ZnCl2Adding into 200mL distilled water, dissolving, adding into 2mL NH3·H2O, stirring for 12 hours at the temperature of 60 ℃ to obtain white powder; dissolving 0.5g of white powder, polyvinylpyrrolidone K302 g and 2g of glucose in 50mL of distilled water, and stirring at 90 ℃ for 1h to obtain three-dimensional silver/zinc oxide nanoparticles which are marked as Ag-ZnO NPs;
(2) preparing a PLA/beta-CD mixed original solution: dissolving PLA and beta-CD into dichloromethane together to prepare spinning solution with mass concentration of 18%, wherein the mass ratio of the PLA to the beta-CD is 1: 0.5.
(3) preparing an Ag-ZnO/PLA/beta-CD composite stock solution: adding the Ag-ZnO NPs prepared in the step (1) into the PLA/beta-CD mixed original solution prepared in the step (2), wherein the dosage ratio of the Ag-ZnO NPs to the PLA/beta-CD mixed original solution is 2 g: 50mL, then carrying out ultrasonic treatment for 15min, and keeping the temperature at 30 ℃ and stirring for 300 min;
(4) setting the applied voltage to be 20KV, the receiving distance to be 10cm, the propelling speed to be 2 mL/h and the air humidity to be 25%, carrying out electrostatic spinning on the composite stock solution at room temperature, wherein the inner diameter of a needle used for electrostatic spinning is 0.6mm, obtaining fibers, and drying to obtain the PLA/beta-CD composite nanofiber membrane of the three-dimensional zinc oxide/silver nanoparticles, which is marked as the Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
Example 2:
(1) preparing Ag-ZnO particles with three-dimensional structures: 2.5g of ZnCl2Adding into 200mL distilled water, dissolving, adding into 2mL NH3·H2O, stirring for 12 hours at the temperature of 60 ℃ to obtain white powder; dissolving 0.5g of white powder, polyvinylpyrrolidone K302 g and 2g of glucose in 50mL of distilled water, and stirring at 90 ℃ for 1h to obtain three-dimensional silver/zinc oxide nanoparticles which are marked as Ag-ZnO NPs;
(2) preparing a PLA/beta-CD mixed original solution: dissolving PLA and beta-CD into dichloromethane together to prepare spinning solution with mass concentration of 18%, wherein the mass ratio of the PLA to the beta-CD is 1: 0.3.
(3) preparing an Ag-ZnO/PLA/beta-CD composite stock solution: adding the Ag-ZnO NPs prepared in the step (1) into the PLA/beta-CD mixed original solution prepared in the step (2), wherein the dosage ratio of the Ag-ZnO NPs to the PLA/beta-CD mixed original solution is 1 g: 50mL, then carrying out ultrasonic treatment for 15min, keeping the temperature at 40 ℃ and stirring for 5 min;
(4) setting the applied voltage to be 15KV, the receiving distance to be 8cm, the propelling speed to be 0.5 mL/h and the air humidity to be 25%, carrying out electrostatic spinning on the composite stock solution at room temperature, wherein the inner diameter of a needle used for electrostatic spinning is 0.6mm, obtaining fibers, and drying to obtain the PLA/beta-CD composite nanofiber membrane of the three-dimensional zinc oxide/silver nanoparticles, which is marked as Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
Example 3:
(1) preparing Ag-ZnO particles with three-dimensional structures: 2.5g of ZnCl2Adding into 200mL distilled water, dissolving, adding into 2mL NH3·H2O, stirring for 12 hours at the temperature of 60 ℃ to obtain white powder; dissolving 0.5g of white powder, polyvinylpyrrolidone K302 g and 2g of glucose in 50mL of distilled water, and stirring at 90 ℃ for 1h to obtain three-dimensional silver/zinc oxide nanoparticles which are marked as Ag-ZnO NPs;
(2) preparing a PLA/beta-CD mixed original solution: dissolving PLA and beta-CD into dichloromethane together to prepare spinning solution with mass concentration of 18%, wherein the mass ratio of the PLA to the beta-CD is 1: 0.8.
(3) preparing an Ag-ZnO/PLA/beta-CD composite stock solution: adding the Ag-ZnO NPs prepared in the step (1) into the PLA/beta-CD mixed original solution prepared in the step (2), wherein the dosage ratio of the Ag-ZnO NPs to the PLA/beta-CD mixed original solution is 2 g: 50mL, then carrying out ultrasonic treatment for 15min, keeping the temperature at 50 ℃ and stirring for 100 min;
(4) setting the applied voltage to be 30KV, the receiving distance to be 12cm, the propelling speed to be 5 mL/h and the air humidity to be 25%, carrying out electrostatic spinning on the composite stock solution at room temperature, wherein the inner diameter of a needle used for electrostatic spinning is 0.6mm, obtaining fibers, and drying to obtain the PLA/beta-CD composite nanofiber membrane of the three-dimensional zinc oxide/silver nanoparticles, which is marked as the Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
FIG. 1 is a scanning electron microscope image of the Ag-ZnO/PLA/beta-CD composite nanofiber membrane prepared in example 2; the synthesized Ag-ZnO NPs are wrapped by the nano-fibers and are uniformly distributed in the composite fiber film.
FIG. 2 is 10-8~10-2A raman spectrum obtained after the M-concentration rhodamine 6G solution was adsorbed on the nanofiber membrane prepared in example 2; as can be seen from the figure, the concentration of the fiber membrane in the R6G solution is 10-3M still has weak signals, which indicates that the SERS effect is stronger.
FIG. 3 shows the inhibition zone formed by the Ag-ZnO/PLA/beta-CD composite fiber membrane prepared in example 2 in Listeria monocytogenes; the figure shows that the fibrous membrane has obvious inhibiting capacity on the listeria monocytogenes.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.

Claims (7)

1. A preparation method of an Ag-ZnO/PLA/beta-CD composite nanofiber membrane is characterized by comprising the following steps:
(1) preparing silver/zinc oxide nano-particles with three-dimensional structures, and marking as Ag-ZnO NPs;
(2) dissolving polylactic acid and beta-cyclodextrin in dichloromethane to obtain a mixed solution, namely a PLA/beta-CD mixed original solution;
(3) adding the Ag-ZnO NPs prepared in the step (1) into the PLA/beta-CD mixed stock solution prepared in the step (2), performing ultrasonic treatment, and then stirring at a certain temperature to prepare a composite stock solution; the dosage ratio of the Ag-ZnO NPs to the PLA/beta-CD mixed original solution is 1-4 g: 50 mL;
(4) setting applied voltage, receiving distance, propelling speed and air humidity, carrying out electrostatic spinning on the composite stock solution at room temperature to obtain fibers, and drying to obtain the Ag-ZnO/PLA/beta-CD composite nanofiber membrane.
2. The method for preparing Ag-ZnO/PLA/beta-CD composite nanofiber membrane as claimed in claim 1, wherein the dosage ratio of polylactic acid, beta-cyclodextrin and dichloromethane in step (2) is 1 g: 0.3-0.8 g: 8-12 mL.
3. The method for preparing Ag-ZnO/PLA/beta-CD composite nanofiber membrane as claimed in claim 1, wherein the time of the ultrasonic treatment in the step (3) is 15 min.
4. The preparation method of the Ag-ZnO/PLA/beta-CD composite nanofiber membrane as claimed in claim 1, wherein the certain temperature in the step (3) is 40 ℃, and the stirring time is 5-300 min.
5. The preparation method of the Ag-ZnO/PLA/beta-CD composite nanofiber membrane as claimed in claim 1, wherein the voltage applied in step (4) is 15-30 KV, the receiving distance is 8-12 cm, the advancing speed is 0.5-5 mL/h, and the air humidity is less than or equal to 30%.
6. The method for preparing Ag-ZnO/PLA/beta-CD composite nanofiber membrane as claimed in claim 1, wherein the inner diameter of the needle used in the electrostatic spinning in the step (4) is 0.6 mm.
7. The Ag-ZnO/PLA/beta-CD composite nanofiber membrane prepared by the preparation method of the Ag-ZnO/PLA/beta-CD composite nanofiber membrane according to any one of claims 1-6, wherein the Ag-ZnO NPs are wrapped in the PLA/beta-CD nanofibers by the composite nanofiber membrane.
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