CN115110209A

CN115110209A - Electrostatic spinning antibacterial film for ancient painting and calligraphy preservation and preparation and application thereof

Info

Publication number: CN115110209A
Application number: CN202210832816.5A
Authority: CN
Inventors: 胡瑜兰; 朱成帅; 吴倩; 潘力伟; 郑梦懿
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2022-07-14
Filing date: 2022-07-14
Publication date: 2022-09-27

Abstract

The invention provides an electrostatic spinning antibacterial film for preserving ancient painting and calligraphy, and preparation and application thereof. The electrostatic spinning antibacterial film comprises the following raw materials: antibacterial nano particles, high-molecular polymer and N, N-dimethylformamide. The invention uses the electrostatic spinning technology to prepare the antibacterial nano particles/nano fibers electrostatic spinning antibacterial film, uses reagents with proper varieties and dosage to prepare the precursor solution of the antibacterial nano particles/nano fibers, uses an electrostatic spinning machine to prepare the antibacterial film, and then applies the antibacterial film on the surface of the painting and calligraphy. The antibacterial nano particle/nano fiber electrostatic spinning antibacterial film prepared by the invention can kill microorganisms growing on paper cultural relics and prevent new microorganism regeneration on common microbial diseases of ancient painting and calligraphy, has slight influence on ancient painting and calligraphy bodies after use, cannot cause secondary damage to the cultural relics, is very convenient to cover and remove, and is suitable for preservation of the ancient painting and calligraphy.

Description

Electrostatic spinning antibacterial film for ancient painting and calligraphy preservation and preparation and application thereof

Technical Field

The invention belongs to the field of cultural relic protection, and particularly relates to an electrostatic spinning nano antibacterial film for preserving ancient painting and calligraphy, and preparation and application thereof.

Background

China has a long and flowing culture source and rich artistic achievements, and ancient calligraphy and painting are unique. Through the related pictures of the ancient painting and calligraphy, later people can intuitively know information of politics, economy, culture, life and the like in the historical period, and the ancient painting and calligraphy painting have high historical value. Ancient painting and calligraphy mostly use paper (rice paper) as a carrier, and the paper mainly contains substances such as cellulose, and is fragile per se and difficult to store for a long time, except illumination, oxidizing gas, acid gas, temperature and humidity, the storage of paper cultural relics can be greatly influenced, and microbial diseases can also be seriously influenced, so that the ancient painting and calligraphy is very important for microbial control.

At present, the sterilization means adopted in China for paper cultural relics are commonly used, such as a chemical agent fumigation method, an alcohol wiping method, a gamma ray irradiation method, a low-temperature freezing method, an anoxic method, a microwave radiation method and the like, and although the methods can achieve the effect of sterilizing and killing insects for a short time, the methods have hidden dangers of damaging paper, polluting the environment and the like. The electrostatic spinning can compound nano-grade materials and various types of matrix fibers to enable the nano-grade materials to have extremely high specific surface area, the process cost is simple and low, and the nano-fibers prepared by electrostatic spinning are widely applied in various fields including food engineering, biological medicine and the like. Therefore, the electrostatic spinning is adopted to prevent and treat the microbial diseases of ancient painting and calligraphy, which is a technical problem to be solved urgently in the field of cultural relic protection at present.

Disclosure of Invention

The invention aims to provide an electrostatic spinning antibacterial film for preserving ancient painting and calligraphy, which is an antibacterial nano particle/nanofiber electrostatic spinning antibacterial film prepared by using an electrostatic spinning technology. The electrostatic spinning antibacterial film comprises the following raw materials: 0.5-4% of antibacterial nano particles, 2-26% of nano electrostatic spinning membrane high-molecular polymer and 70-97% of N, N-dimethylformamide.

As a further step, the antibacterial nanoparticles in the scheme can be selected from: nano silver particles, nano zinc oxide particles or nano titanium dioxide particles.

Further, the nanofiber electrostatic spinning membrane in the scheme selects high molecular polymers as follows: polyacrylonitrile (PAN), polyvinyl alcohol (PVA), Polycaprolactone (PCL), polyvinylpyrrolidone (PVP), Polyurethane (PU).

The invention also aims to provide a preparation method of the electrostatic spinning antibacterial film, which comprises the following steps: the antibacterial nano particle/nano fiber precursor solution is used as a raw material and is obtained by spinning through an electrostatic spinning machine, wherein the antibacterial nano particle/nano fiber precursor is formed by combining antibacterial nano particles and a high molecular polymer. Specifically, 0.5-4% by mass of antibacterial nanoparticles, 2-26% by mass of nano electrostatic spinning membrane high-molecular polymer and 70-97% by mass of N, N-dimethylformamide are taken as raw materials to prepare an antibacterial nanoparticle/nanofiber precursor solution, and an electrostatic spinning machine is used for preparing the antibacterial nanoparticle/nanofiber electrostatic spinning antibacterial membrane.

As a further improvement, the antibacterial nano particle material comprises the following components in percentage by mass: 0.5 to 4 percent.

As a further improvement, the high molecular polymer raw material comprises the following components in percentage by mass: 2 to 26 percent.

As a further improvement, the mass percent of the N, N-dimethylformamide is 70-97%.

The preparation method is realized by the following steps:

1) weighing 1.23-10.61g of high molecular polymer, weighing 20-50ml of N, N-Dimethylformamide (DMF), adding the high molecular polymer into the DMF, and stirring for 20min to ensure that the high molecular polymer is completely dissolved to obtain a high molecular polymer solution.

2) Preparing a precursor solution of the antibacterial nano particles/nano fibers:

the preparation method of the precursor solution of the nano silver particles/nano fibers comprises the following steps:

0.48-0.96g of silver nitrate is weighed, 5ml of DMF is added, and the mixture is stirred and dissolved to obtain a silver nitrate solution.

And pouring the high molecular polymer solution and the silver nitrate solution into a conical flask in sequence, heating in a water bath while magnetically stirring, and heating to 65 ℃ to obtain a high molecular polymer silver nitrate mixed solution. Weighing 0.03-0.15g of Tea Polyphenol (TP), adding 5ml of DMF, stirring for dissolving, dropwise adding the mixture into a high polymer silver nitrate mixed solution, and carrying out constant-temperature magnetic stirring on the mixed solution for 30min to obtain a precursor solution of nano silver particles/nano fibers.

The preparation method of the precursor solution of the nano titanium dioxide particles/nano fibers comprises the following steps:

weighing tetrabutyl orthotitanate Ti (OC) ₄ H ₉ ) ₄ 0.48-0.96g of the nano titanium dioxide solution is added into 5ml of DMF and stirred for about 1 hour to obtain the nano titanium dioxide solution. And dropwise adding the nano titanium dioxide solution into the high molecular polymer solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano titanium dioxide particles/nano fibers.

The preparation method of the precursor solution of the nano zinc oxide particles/nano fibers comprises the following steps:

weighing 0.48-0.96g of zinc oxide (ZnO), adding 5ml of DMF, and stirring to dissolve to obtain a zinc oxide solution. Adding the zinc oxide solution into the high molecular polymer solution. And magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of the nano zinc oxide particles/nano fibers.

3) The 10ml of antibacterial nanoparticle/nanofiber precursor solution was drawn into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed was adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 20kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited for to finish, and the operation is repeated for two times after the machine is reset, so that the thickness of the antibacterial film is ensured, and the antibacterial nano-particle/nano-fiber electrostatic spinning antibacterial film is obtained.

The invention further aims to provide application of the electrostatic spinning bacteriostatic film in protecting ancient painting and calligraphy. The ancient painting and calligraphy are ancient painting and calligraphy cultural relics which need to be prevented from generating microorganisms on the surface or need to be killed after being invaded by the microorganisms.

The application is realized by the following steps:

(1) cutting the antibacterial nano particle/nanofiber electrostatic spinning antibacterial film into a proper size, flatly covering the antibacterial film on the surface of the ancient painting and calligraphy needing to be protected, and standing for 7-14 days.

(2) After the microbial traces on the surfaces of the ancient painting and calligraphy obviously disappear, the ancient painting and calligraphy can be taken off or covered on the surfaces of the ancient painting and calligraphy to prevent the growth of microorganisms.

The working principle of the invention is that the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film which has no destructive effect on the painting and calligraphy is adsorbed on the surface of the painting and calligraphy through the strong adsorption force of the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film, and the antibacterial nano particle can kill the microorganisms on the surface of the painting and calligraphy through the antibacterial and antibacterial effects of the antibacterial nano particle, and can prevent the regeneration of the microorganisms.

According to the invention, through a series of experiments, the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film which is not destructive to ancient calligraphy and painting is prepared, and the electrostatic spinning technology is based on electrostatic electron beam spinning, so that a nano-grade material and matrix fibers can be compounded, and the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film has excellent permeability and extremely high specific surface area, is simple in process and low in cost, is easy to spin by using different polymer sources, and has the advantages of higher tolerance, lower biotoxicity and good antibacterial effect, and nano silver particles contained in the antibacterial film not only improve the defects of poor mechanical property, lack of surface specificity and the like of electrostatic spinning nano fibers. The antibacterial nano particle/nano fiber electrostatic spinning antibacterial film can kill microorganisms growing on the surfaces of paintings and calligraphy and can also prevent the regeneration of the microorganisms. When in use, the paint only needs to cover the surface of the painting and calligraphy, does not produce secondary damage to the painting and calligraphy cultural relics, and is very convenient to remove.

Compared with the prior art, the invention has the following advantages:

(1) the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film adopted by the technology can not only kill the microorganisms growing on the paper cultural relics, but also prevent the regeneration of new microorganisms;

(2) the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film does not cause secondary damage to cultural relics, and is very convenient to cover and remove;

(3) the invention uses the electrostatic spinning technology to prepare the antibacterial nano particle/nano fiber electrostatic spinning antibacterial film, uses reagents with proper varieties and dosage to prepare a precursor solution of the antibacterial nano particle/nano fiber, uses an electrostatic spinning machine to prepare the antibacterial film, and then applies the antibacterial film on the surface of the painting and calligraphy. The bacterial nanoparticle/nanofiber electrostatic spinning antibacterial film has a killing and inhibiting effect on common microbial diseases on ancient painting and calligraphy, and has a slight influence on ancient painting and calligraphy bodies after use. The bacterial nanoparticle/nanofiber electrostatic spinning antibacterial film can kill microorganisms growing on paper cultural relics, can prevent new microorganism regeneration, cannot cause secondary damage to the cultural relics, is very convenient to cover and remove, can be reused in protecting rice paper, and is particularly suitable for repairing and protecting ancient calligraphy and painting.

Drawings

Fig. 1 is a photograph of a nano silver particle/polyacrylonitrile nano fiber bacteriostatic membrane body.

FIG. 2 is a photograph of a bacteriostatic membrane electric mirror of nano silver particles/polyacrylonitrile nano fibers and the analysis result of the diameter. According to the electron microscope picture and the diameter analysis in the figure, the average fiber diameter of the nano silver particles/polyacrylonitrile nano fibers is 770 nm.

FIG. 3 shows the result of EDS mapping element analysis of nano silver particles/polyacrylonitrile nano fiber antibacterial membrane. From the mapping result chart, it can be seen that the Ag element is uniformly distributed on the nanofibers.

FIG. 4 is a photograph showing the growth of the bacteria in the antibacterial test of the nano silver particles/polyacrylonitrile nano fiber antibacterial film. In the figure, the obvious bacteria inhibition zone is generated after the nano silver particle/polyacrylonitrile nano fiber antibacterial film is pasted.

FIG. 5 is a photo of the growth of the microorganism in the antibacterial experiment of the nano silver particles/polyacrylonitrile nanofiber bacteriostatic membrane fungus 1. The figure shows that the obvious fungus inhibition zone is generated after the nano silver particle/polyacrylonitrile nano fiber antibacterial film is pasted.

FIG. 6 is a photo of the growth of the microorganism in the antibacterial experiment of the nano silver particles/polyacrylonitrile nanofiber bacteriostatic membrane fungus 2. In the figure, the obvious fungus inhibition zone is generated after the nano silver particle/polyacrylonitrile nano fiber antibacterial film is pasted.

FIG. 7 is a photo of the growth of the microorganism in the antibacterial experiment of the nano silver particle/polyacrylonitrile nanofiber bacteriostatic membrane fungus 3. The figure shows that the obvious fungus inhibition zone is generated after the nano silver particle/polyacrylonitrile nano fiber antibacterial film is pasted.

FIG. 8 is a photograph showing the growth of the microorganism in the antibacterial test of the nano silver particles/polyacrylonitrile nano fiber antibacterial film fungi 4. The figure shows that the obvious fungus inhibition zone is generated after the nano silver particle/polyacrylonitrile nano fiber antibacterial film is pasted.

FIG. 9 is a photo of the antibacterial property test result of the antibacterial film of nano silver particles/polyacrylonitrile nano fiber to rice paper.

Detailed Description

The technical scheme of the invention is further explained by combining the drawings and the specific embodiments.

Example 1

The preparation method of the electrostatic spinning antibacterial film for ancient painting and calligraphy preservation is realized by the following steps:

1) weighing 1.23g of Polyacrylonitrile (PAN), weighing 50ml of N, N-Dimethylformamide (DMF), adding the PAN into the DMF, and stirring for 20min to ensure that the PAN is completely dissolved to obtain a PAN solution.

2) Weighing silver nitrate (AgNO) ₃ )0.48g, 5ml of DMF was added thereto, and dissolved by stirring to obtain a silver nitrate solution.

3) And sequentially pouring the PAN solution and the silver nitrate solution into a conical flask, heating in a water bath while magnetically stirring, and heating to 65 ℃ to obtain the PAN silver nitrate mixed solution.

4) Weighing 0.03g of Tea Polyphenol (TP), adding 5ml of DMF, stirring and dissolving, dropwise adding the mixture into a PAN silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano-silver particles/polyacrylonitrile nano-fibers.

5) The precursor solution of the above 10ml of nano silver particles/polyacrylonitrile nano fibers was pumped into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y-axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with a positive electrode and a negative electrode. The receiving shaft speed was adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 20kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nano silver particle/polyacrylonitrile nano fiber antibacterial film.

Example 2

1) weighing 10.61g of Polyacrylonitrile (PAN), weighing 20ml of N, N-Dimethylformamide (DMF), adding the PAN into the DMF, and stirring for 20min to ensure that the PAN is completely dissolved to obtain a PAN solution.

3) And pouring the PAN solution and the silver nitrate solution into a conical flask in sequence, heating in a water bath while magnetically stirring, and heating to 65 ℃ to obtain the PAN and silver nitrate mixed solution.

5) The precursor solution of the above 10ml of nano silver particles/polyacrylonitrile nano fibers was pumped into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed was adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 20kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated for two times after the reset so as to ensure the thickness of the antibacterial film. Obtaining the nano silver particle/polyacrylonitrile nano fiber antibacterial film.

Example 3

2) Weighing silver nitrate (AgNO) ₃ )0.96g, 5ml of DMF was added thereto, and dissolved by stirring to obtain a silver nitrate solution.

4) Weighing 0.15g of Tea Polyphenol (TP), adding 5ml of DMF, stirring and dissolving, dropwise adding the mixture into a PAN silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano silver particles/polyacrylonitrile nano fibers.

5) The 10ml of the precursor solution of the nano silver particles/polyacrylonitrile nano fibers is extracted into a syringe by using a 16-gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed is adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 20kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nano silver particle/polyacrylonitrile nano fiber antibacterial film.

Example 4

1) weighing 3g of polyvinyl alcohol (PVA), weighing 25ml of N, N-Dimethylformamide (DMF), adding the PVA into the DMF, and magnetically stirring at 90 ℃ until the polyvinyl alcohol is completely dissolved to obtain a PVA solution.

3) Weighing 0.15g of Tea Polyphenol (TP), adding 5ml of DMF, stirring and dissolving, dropwise adding the mixture into a PVA silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano silver particles/polyvinyl alcohol nanofibers.

4) The 10ml precursor solution of the nano silver particles/polyvinyl alcohol nanofibers was pumped into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed was adjusted to 40. The advancing speed of the Y axis is 0.0015mm/s, and the spinning distance is 15 cm. And then adjusting the positive high-voltage direct current voltage to be 18kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. To obtain the nano silver particle/polyvinyl alcohol nano fiber antibacterial film.

Example 5

1) polyurethane (PU) is weighed to be 10.61g, 40ml of N, N-Dimethylformamide (DMF) is weighed, the PU is added into the DMF, and stirring is carried out for 20min to ensure that the PU is completely dissolved, so as to obtain a PU solution.

3) Weighing 0.15g of Tea Polyphenol (TP), adding 5ml of DMF, stirring and dissolving, dropwise adding the mixture into a PU silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano silver particles/polyurethane nanofiber.

4) The 10ml precursor solution of nano silver particles/polyurethane nanofibers was drawn into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y-axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with a positive electrode and a negative electrode. The receiving shaft speed is adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 35kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nano silver particle/polyurethane nano fiber antibacterial film.

Example 6

1) polyvinylpyrrolidone (PVP) was weighed 3.2g, 40ml of N, N-Dimethylformamide (DMF) was weighed, PVP was added to DMF, and stirring was carried out for 12 hours to obtain a PVP solution.

3) Weighing 0.15g of Tea Polyphenol (TP), adding 5ml of DMF, stirring and dissolving, dropwise adding the mixture into a PVP silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano silver particles/polyvinylpyrrolidone nano fibers.

3) The 10ml precursor solution of nano silver particles/polyvinylpyrrolidone nanofibers was pumped into a syringe using a 16 gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed is adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 15kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nano silver particle/polyvinylpyrrolidone nanofiber antibacterial film.

Example 7

A preparation method of an electrostatic spinning antibacterial film for ancient painting and calligraphy preservation is disclosed, wherein the electrostatic spinning antibacterial film is a nano titanium dioxide particle/polyacrylonitrile nano fiber antibacterial film, and the preparation method is realized by the following steps:

1) weighing 4g of Polyacrylonitrile (PAN), weighing 50ml of N, N-Dimethylformamide (DMF), adding the PAN into the DMF, and stirring for 20min to ensure that the PAN is completely dissolved to obtain a PAN solution.

2) Weighing tetrabutyl orthotitanate Ti (OC) ₄ H ₉ ) ₄ 0.8g of the solution was added to 5ml of DMF, and the mixture was stirred for about 1 hour to obtain a nano titanium dioxide solution.

3) And (3) dropwise adding the nano titanium dioxide solution into the PAN solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano titanium dioxide particles/polyacrylonitrile nano fibers.

4) And (3) pumping the 10ml of the precursor solution of the nano titanium dioxide particles/the polyacrylonitrile nano fibers into a syringe and using a 16-gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed was adjusted to 40. The Y-axis advancing speed was 0.001mm/s and the spinning distance was 15 cm. And then adjusting the positive high-voltage direct current voltage to be 35kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nanometer titanium dioxide particles/polyacrylonitrile nanometer fiber antibacterial film.

Example 8

The preparation method of the electrostatic spinning antibacterial film for ancient painting and calligraphy preservation comprises the following steps:

1) weighing 7.5g of Polycaprolactone (PCL), weighing 50ml of N, N-Dimethylformamide (DMF), adding the PCL into the N, N-Dimethylformamide (DMF), and stirring for 12 hours to obtain a PCL solution.

2) 0.96g of zinc oxide (ZnO) is weighed, 5ml of DMF is added, and the mixture is stirred and dissolved to obtain a zinc oxide solution.

3) The zinc oxide solution was added to the PCL solution. And magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of the nano zinc oxide particles/polycaprolactone nano fibers.

4) And pumping the precursor solution of the 10ml of nano zinc oxide particles/polycaprolactone nano fibers into a syringe, and using a 16-gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The receiving shaft speed was adjusted to 40. The advancing speed of the Y axis was 0.001mm/s, and the spinning distance was 17 cm. And then adjusting the positive high-voltage direct current voltage to be 18kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured. Obtaining the nano zinc oxide particle/polycaprolactone nanofiber antibacterial film.

Example 10 application of Nano silver particle/Polyacrylonitrile nanofiber antibacterial film in Xuan paper

1) Cutting the nano silver particles/polyacrylonitrile nanofiber electrostatic spinning antibacterial film into a proper size, flatly covering the antibacterial film on the surface of the rice paper to be protected, and standing for 7-14 days.

2) After the trace of the microorganisms on the surface of the rice paper obviously disappears, the rice paper can be taken off or covered on the surface of the rice paper which is expected to be protected to prevent the growth of the microorganisms.

In order to facilitate understanding of the present invention, the technical solution of the present invention is further described by the following specific examples:

1) preparing a precursor solution of nano silver particles/polyacrylonitrile nano fibers:

6.371g of Polyacrylonitrile (PAN) was weighed, 40ml of N, N-Dimethylformamide (DMF) was weighed, and PAN was added to DMF and stirred for 20min to ensure complete dissolution of PAN. Weighing silver nitrate (AgNO) ₃ )0.48g, 5ml of DMF was added thereto and dissolved with stirring. Pouring the two solutions into a conical flask in sequence, heating in water bath while magnetically stirring, and heating to 65 ℃. 0.03g of Tea Polyphenol (TP) was weighed, added with 5ml of DMF, dissolved with stirring, and added dropwise to an Erlenmeyer flask. Magnetically stirring the mixed solution at constant temperature for 30min to obtain brownThe color solution is the precursor solution of the nano silver particles/polyacrylonitrile nano fibers.

Preparing a nano silver particle/polyacrylonitrile nanofiber bacteriostatic membrane:

the 10ml of the precursor solution of the nano silver particles/polyacrylonitrile nano fibers is extracted into a syringe by using a 16-gauge needle. The needle cylinder is fixed on a Y axis of the electrostatic spinning machine, and the receiving shaft and the metal needle head are respectively connected with the anode and the cathode. The rotating speed of the receiving shaft is adjusted to be 40, the advancing speed of the Y shaft is 0.001mm/s, and the spinning distance is 15 cm. And then adjusting the positive high-voltage direct current voltage to be 20kV, and adjusting the negative high-voltage direct current voltage to be 500V. After the solution in the needle cylinder is stably sprayed out from the needle point, the operation of the machine is waited to be finished, and the operation is repeated twice after the needle cylinder is reset, so that the thickness of the antibacterial film is ensured.

3) Morphological structure characterization of nano-silver particle/polyacrylonitrile nanofiber antibacterial membrane

The morphological characteristics of the nano silver particles/polyacrylonitrile nanofiber antibacterial membrane body are recorded by taking a picture with a camera, and the result is shown in figure 1.

And (3) carrying out comparative analysis on the inclusions and the fiber diameters of the nanofiber membranes of different types by using a scanning electron microscope and Nano Measurer software, and analyzing the distribution condition of the Ag element on the nanofiber membranes by using mapping characterization of EDS attached to the electron microscope. The antibacterial scanning electron microscope photograph and diameter analysis result of the nano silver particles/polyacrylonitrile nano fibers are shown in figure 2.

The EDS mapping elemental analysis results are shown in FIG. 3.

4) Characterization of bacteriostatic condition of nano-silver particle/polyacrylonitrile nanofiber bacteriostatic film by bacteriostatic circle method

2cm multiplied by 2cm of nano silver particles/polyacrylonitrile nano fiber antibacterial membrane is cut by using sterile tweezers, the sterile tweezers are placed in the center of a culture dish uniformly coated with purified single bacterial colony, and the sample is lightly pressed to be flat on the surface of a culture medium. The LB medium colonies were cultured at 37 ℃ for 5 days, and the PDA medium colonies at 28 ℃ for 7 days. And (5) taking out the culture dish after the culture is finished, calculating the radius of each group of inhibition zones by using a vernier caliper, and photographing and recording the condition.

The statistics of the radius of the inhibition zone are shown in table 1, and the growth condition of the microorganism after the treatment of the inhibition membrane is shown in attached figures 4-8.

TABLE 1 radius of zone of inhibition for each experimental group

5) Antibacterial property test of nano silver particle/polyacrylonitrile nano fiber antibacterial film on rice paper

Adding the diluted mixed bacterial liquid with the dilution of 10-5 into a Martin liquid culture medium for culture, and pouring into a sprinkling can. Cutting and taking mildewed rice paper, applying the nano-silver particle/polyacrylonitrile nano-fiber antibacterial film on the surface of the paper, and uniformly spraying a bacteria liquid on the surface by using a spray can. Placing the rice paper into a constant temperature incubator, and standing and culturing at 28 ℃. And (4) standing for 7 days, comparing the mildewing conditions of the group covered with the antibacterial film and the uncovered group of the rice paper, and judging the antibacterial performance of the nano silver/polyacrylonitrile nanofiber antibacterial film. The result that the surface of the rice paper has no light microscopic biological growth traces after 7 days of antibacterial film treatment compared with the blank control group is shown in figure 9.

Of course, the foregoing lists merely illustrate specific embodiments of the invention. It is clear that the invention is not limited to the examples above, to the types of nanoparticles and to the types of nanofibres claimed in the claims and to all variants that can be derived or suggested directly from the disclosure of the invention by a person skilled in the art, which are considered to be within the scope of protection of the invention.

Claims

1. The electrostatic spinning antibacterial film for ancient painting and calligraphy preservation is characterized by being an antibacterial nano particle/nanofiber electrostatic spinning antibacterial film, and comprising the following raw materials in percentage by mass: 0.5-4% of antibacterial nano particles, 2-26% of nano electrostatic spinning membrane high-molecular polymer and 70-97% of N, N-dimethylformamide.

2. The electrospun anti-bacterial membrane of claim 1, wherein the antimicrobial nanoparticles are selected from the group consisting of: nano silver particles, nano zinc oxide particles or nano titanium dioxide particles.

3. The electrospun bacteriostatic film according to claim 1, wherein the high molecular polymer selected for the nanofiber electrospun film is: polyacrylonitrile, polyvinyl alcohol, polycaprolactone, polyvinylpyrrolidone or polyurethane.

4. The method of claim 1, wherein the antibacterial nanoparticle/nanofiber precursor solution is prepared from 0.5-4% by mass of antibacterial nanoparticles, 2-26% by mass of a polymer of the nano electrostatic spinning membrane, and 70-97% by mass of N, N-dimethylformamide as a raw material, and the antibacterial nanoparticle/nanofiber electrostatic spinning membrane is prepared by an electrostatic spinning machine, wherein the antibacterial nanoparticle/nanofiber precursor is formed by combining the antibacterial nanoparticles with the polymer.

5. The preparation method according to claim 4, which is specifically realized by the following steps:

(1) weighing 1.23-10.61g of high molecular polymer, measuring 20-50ml of N, N-dimethylformamide, adding the high molecular polymer into the N, N-dimethylformamide, stirring to ensure that the high molecular polymer is completely dissolved to obtain a high molecular polymer solution;

(2) preparing a precursor solution of the antibacterial nano particles/nano fibers:

weighing 0.48-0.96g of silver nitrate, adding 5ml of N, N-dimethylformamide, and stirring for dissolving to obtain a silver nitrate solution;

pouring the high-molecular polymer solution and the silver nitrate solution in the step (1) into a conical flask in sequence, heating in a water bath while magnetically stirring, heating to 65 ℃ to obtain a high-molecular polymer silver nitrate mixed solution, weighing 0.03-0.15g of tea polyphenol, adding 5ml of N, N-dimethylformamide, stirring and dissolving, dropwise adding into the high-molecular polymer silver nitrate mixed solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano silver particles/nano fibers;

weighing 0.48-0.96g of tetrabutyl orthotitanate, adding the tetrabutyl orthotitanate into 5ml of N, N-dimethylformamide, stirring for about 1 hour to obtain a nano titanium dioxide solution, dropwise adding the nano titanium dioxide solution into a high molecular polymer solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano titanium dioxide particles/nano fibers;

weighing 0.48-0.96g of zinc oxide, adding the zinc oxide into 5ml of N, N-dimethylformamide, stirring and dissolving to obtain a zinc oxide solution, adding the zinc oxide solution into a high molecular polymer solution, and magnetically stirring the mixed solution at constant temperature for 30min to obtain a precursor solution of nano zinc oxide particles/nano fibers;

(3) extracting 10ml of the antibacterial nanoparticle/nanofiber precursor solution obtained in the step (2) into a needle cylinder, fixing the needle cylinder on a Y axis of an electrostatic spinning machine by using a No. 16 needle, respectively connecting a receiving shaft and a metal needle to a positive electrode and a negative electrode, adjusting the rotating speed of the receiving shaft to be 40, the advancing speed of the Y axis to be 0.001mm/s, the spinning distance to be 15cm, adjusting the positive electrode high-voltage direct-current voltage to be 20kV, the negative electrode high-voltage direct-current voltage to be 500V, after the solution in the needle cylinder is stably sprayed out from the needle point, waiting for the operation of the machine to be finished, and repeating the operation twice after resetting to ensure the thickness of the antibacterial film so as to obtain the antibacterial nanoparticle/nanofiber electrostatic spinning antibacterial film.

6. The use of the electrospun bacteriostatic film of claim 1 in protecting ancient painting and calligraphy.

7. The use of claim 6, wherein the ancient painting and calligraphy is antique which needs to be protected from the generation of microorganisms on the surface or is subjected to the attack of microorganisms and needs to be killed.

8. The application according to claim 6, characterized in that it is implemented by the following steps:

(1) cutting the antibacterial nano particle/nanofiber electrostatic spinning antibacterial film into a proper size, flatly covering the antibacterial film on the surface of the ancient painting and calligraphy needing to be protected, and standing for 7-14 days;