CN112899808B - Multifunctional nanofiber and preparation method and application thereof - Google Patents

Multifunctional nanofiber and preparation method and application thereof Download PDF

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CN112899808B
CN112899808B CN202110056717.8A CN202110056717A CN112899808B CN 112899808 B CN112899808 B CN 112899808B CN 202110056717 A CN202110056717 A CN 202110056717A CN 112899808 B CN112899808 B CN 112899808B
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solution
eggshell membrane
membrane
wound
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CN112899808A (en
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刘明焕
陈亚芹
施伟章
杨大鹏
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Quanzhou Xufeng Micro Powder Materials Co ltd
Quanzhou Normal University
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Quanzhou Xufeng Micro Powder Materials Co ltd
Quanzhou Normal University
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Abstract

The invention discloses a multifunctional nanofiber and preparation and application thereof.A dissolved egg membrane solution is used as a soft template to synthesize CuS nanoparticles with good biocompatibility and near infrared absorption. Furthermore, the nano-fiber is mixed with PVP in proportion and is prepared into CuS nano-fiber by means of electrospinning equipment, and the membrane not only reproduces the structural characteristics of the eggshell membrane, but also has the near-infrared absorption heat generation characteristic and the function of promoting wound healing. The in situ electrospinning method can avoid direct contact with the wound, greatly relieve pain, and has better fitting degree on the surface of a rough wound than a bandage and gauze, and can rapidly treat outdoor wounds to prevent bacterial infection. In addition, the eggshell membrane contains a large amount of nutrients required by skin and hair, is hydrolyzed to be used in cosmetics, has the effects of smoothing skin, reducing wrinkles, lightening spots and the like, and is suitable for being used as a beauty mask.

Description

Multifunctional nanofiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a multifunctional nanofiber as well as a preparation method and application thereof.
Background
In outdoor sports, the skin can develop wounds of varying degrees due to burns, surgery and mechanical injury. When the skin is damaged, the open wound becomes a favorable site for microbial colonization. Bacteria that infect wounds are mainly derived from microorganisms (e.g., escherichia coli and staphylococcus aureus) in the air and on the skin near the wound. Proper wound treatment can allow rapid healing; on the contrary, it may cause pyogenic infection, even systemic infection, gangrenous gas and other diseases. Therefore, it is of great research interest to develop a simple method for rapidly treating wounds outdoors to prevent bacterial infections.
Copper sulfide (CuS) is a most important P-type semiconductor in transition metal chalcogenides, and has received much attention from researchers due to its excellent optical, structural, and other physical and chemical properties. It is a novel photo-thermal material. In recent years, photothermal therapy (PTT) having advantages of high selectivity and low invasiveness has attracted extensive attention of researchers. The mechanism is that Near Infrared (NIR) light energy is converted into heat energy by a photo-thermal agent, and the photo-thermal agent can be used for treating diseases such as cancers and bacterial infections. This is a green therapy compared to the use of antibiotics. However, the poor biocompatibility and potentially toxic properties of CuS nanoparticles (CuS NPs) limit their application in biomedicine. Furthermore, due to the high concentration, the rate of photo-generated charge transfer on the surface of the material is reduced, which significantly reduces the performance of the material. An effective option to overcome these disadvantages is to select a suitable support to disperse the nanomaterial, which can increase the surface area and inhibit the recombination of photogenerated charges.
The eggshell membrane is generally regarded as biological waste, and the random disposal not only causes resource waste, but also causes environmental pollution. Through a thorough understanding of the structure and bioactive components of eggshell membrane, we have found that it is a multi-protein complex. As a source of natural collagen, glucosamine, chondroitin and hyaluronic acid, it has great potential in tissue engineering, especially in the process of promoting connective tissue repair.
Disclosure of Invention
The invention aims to provide a multifunctional nanofiber and a preparation method and application thereof aiming at the defects of an outdoor wound treatment means.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to the invention, eggshell membrane solution is used as a soft template, CuS nano particles with a photo-thermal sterilization function are simply combined by adopting a one-step method, and CuS nano fibers are prepared in a green manner by adopting a handheld electrostatic spinning device. The composite CuS nano particle has the advantages of simple preparation method, low cost, good biocompatibility and better photo-thermal sterilization effect; the prepared electrospun CuS nano-fiber can be spun on a wound in situ, can effectively promote the healing of the wound, and can also be used as a beauty mask.
The preparation method of the multifunctional nanofiber comprises the following steps:
(1) egg shell membrane pretreatment: collecting waste eggshells, peeling off an eggshell membrane from the eggshells, repeatedly washing the eggshells with deionized water, soaking the eggshell membrane in a hydrochloric acid solution for 5-24 hours, then cleaning and drying the eggshell membrane, and finally crushing the eggshell membrane to obtain the eggshell membrane;
(2) preparing an eggshell membrane solution: preparing 20-100 mL of 0.5-2 mol/L sodium hydroxide solution, adding 0.5-2.5 g of eggshell membrane, stirring and mixing uniformly, heating the obtained mixed solution at 50-70 ℃, continuously stirring for 3-6 h, and after stirring, performing suction filtration to obtain light yellow clear liquid, namely eggshell membrane solution;
(3) and (3) synthesis of CuS nano particles: preparing 10-60 mL egg shell membrane solution, and adding 1-6 mL copper nitrate trihydrate (CuNO) 3 ·3H 2 O), stirring for 10-60 min at normal temperature; using HNO 3 Adjusting the pH value of the solution to 6-10, and then slowly adding 1-6 mL thioacetamide (CH) while stirring 3 CSNH 2 ) And stirring uniformly; finally, placing the obtained solution in an oil bath at the temperature of 60-100 ℃ for heating for 0.5-2 h, wherein the solution is changed into dark greenish black, synthesizing materials, and finally, freeze-drying the liquid into powder to obtain CuS nano particles;
(4) green preparation of CuS nanofibers: preparing a polyvinylpyrrolidone (PVP) solution with the mass fraction of 10-30%, adding the prepared CuS nano particles to prepare an electrostatic spinning solution with the mass fraction of CuS of 0.1-0.5%, and then performing electrospinning by adopting an electrostatic spinning instrument and adjusting parameters to obtain the CuS nano fibers.
The egg shell membrane in the step (1) comprises any one of egg shell membrane, duck egg shell membrane, quail egg shell membrane, ostrich egg shell membrane and turkey egg shell membrane, but the egg shell membrane is not limited to the above types, and various poultry egg shell membranes can be used as raw materials.
CuNO described in the above step (3) 3 ·3H 2 The concentration of O is 0.1-0.5M.
HNO described in the step (3) 3 The concentration of (A) is 30-100%.
CH described in the above step (3) 3 CSNH 2 The concentration of (A) is 0.1-0.3M.
The electrostatic spinning parameters of the step (4) are as follows: the voltage is 10 kV, and the receiving distance is 5-20 cm.
The CuS nano particles prepared in the step (3) are applied to photo-thermal sterilization, the CuS nano fibers prepared in the step (4) are used for repairing skin wounds, the wound healing can be effectively promoted, and the CuS nano fibers can be applied to a beauty mask.
The method for applying the CuS nanoparticles to photo-thermal sterilization comprises the following steps:
(1) culturing the bacteria in a broth culture medium for 18-24 h, and adjusting the concentration of the bacteria to 1 × 10 5 ～1×10 9 CFU/mL；
(2) Adding 5-20 mg of CuS nano particles into 0.2-2 mL of bacterial solution and fully mixing;
(3) setting an illumination group and a non-illumination group, wherein the illumination group is to make the bacterial liquid (test group) added with the CuS nano particles and the bacterial liquid (control group) not added with the CuS nano particles in 1-3W/cm 2 Irradiating for 2-10 minutes under near-infrared laser;
(4) and (4) respectively introducing the bacterial liquid obtained in the step (3) into a culture dish to be cultured together with agar, culturing for 18-24 h at 37 ℃, and then testing the antibacterial performance of the material by a colony counting method.
The above bacteria are any of Escherichia coli, Staphylococcus aureus, Streptococcus, and Proteus, but the species of the bacteria are not limited to the above species.
The steps of using the CuS nano fiber for repairing skin wounds are as follows:
(1) preparing a sufficient amount of mice, anesthetizing the animals with 4-10% chloral hydrate, and then cutting into circular areas (about 5-10 mm in diameter) on both sides of the back and shoulders of each mouse with surgical scissors;
(2) then 50-100. mu.L MRSA bacterial suspension (1X 10) is used 7 ～1×10 8 CFU/mL) infected mouse tissue, and 24 hours later, pus was observed on the infected wound;
(3) mice were divided into 4 groups: the control group is a near infrared laser (NIR) irradiation group, the electrostatic spinning solution group (marked as CuS group) with CuS mass fraction of 0.1-0.5%, and the electrostatic spinning solution + NIR group (marked as CuS + NIR group) with CuS mass fraction of 0.1-0.5%. The wounds were treated differently:
control group: no treatment was performed on the wound;
NIR group:carrying out near-infrared laser irradiation on the wound, wherein the irradiation condition is 980 nm and 1-3W/cm 2 NIR of 5-20 minutes;
and (4) CuS group: in-situ electrospinning the electrostatic spinning solution on the wound by using a handheld electrostatic spinning instrument without infrared laser irradiation;
CuS + NIR set: in-situ electrospinning solution on a wound by using a handheld electrospinning instrument, and performing laser irradiation under the illumination condition of 980 nm and 1-3W/cm 2 NIR of 5-20 minutes;
(4) the recovery of the wound was observed in mice and skin samples were taken for analysis.
The invention adopts a simple method to dissolve the eggshell membrane and uses the eggshell membrane as a soft template to synthesize the CuS nano-particles with good biocompatibility and near-infrared absorption characteristic. The CuS nano particles show excellent photo-thermal antibacterial performance. In addition, the CuS nano particles are mixed with PVP, and the CuS nano fibers are synthesized in a green mode by using a handheld electrostatic spinning device, so that the CuS nano fibers not only reproduce the microstructure of an eggshell membrane, but also have the functions of photo-thermal antibiosis and promotion of wound rapid healing, and can be used as a beauty mask or for rapidly treating outdoor wounds to prevent bacterial infection.
Compared with the prior art, the invention has the following beneficial effects:
1. the nano material prepared by the invention uses the waste eggshell membrane as the raw material, has low cost and wide raw material source, and can realize the recycling of biological waste.
2. The nano material prepared by the invention is synthesized by adopting a one-step method, the preparation method is simple, and the reaction condition is mild.
3. The nano material prepared by the invention has stronger near infrared absorption and can be applied to photo-thermal sterilization.
4. The composite nanofiber prepared by the invention can be electrospun on a wound in situ, so that the direct contact with the wound is avoided, and the adhesion degree with a rough wound is better than that of a bandage and a dressing.
5. The eggshell membrane contains a large amount of nutrients required by skin and hair, is hydrolyzed to be used in cosmetics, and has the effects of smoothing skin, reducing wrinkles, lightening spots and the like, so the CuS nanofiber is suitable for being used as a beauty mask.
Drawings
FIG. 1 is a diagram of UV-vis of the CuS nanoparticle of the invention.
FIG. 2 is a graph showing the heating curves of different concentrations of materials and water under 980 nm Near Infrared (NIR) irradiation in a CuS nanoparticle solution of the present invention over time.
FIG. 3 is a statistical graph of the antibacterial efficiency of the CuS nanoparticles of the present invention against Escherichia coli (A) and Staphylococcus aureus (B) at different concentrations.
FIG. 4 is an SEM image of CuS composite nanofibers and natural eggshell membrane of the present invention. The picture A is natural eggshell membrane, and the picture B is CuS composite nanofiber.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A preparation method of CuS nano particles and CuS nano fibers comprises the following steps:
(1) egg shell membrane pretreatment: collecting waste eggshells, peeling off an eggshell membrane from the eggshells, repeatedly washing the eggshells with deionized water, soaking the eggshell membrane in a hydrochloric acid solution for 10 hours, then cleaning and drying the eggshell membrane, and finally crushing the eggshell membrane to obtain the eggshell membrane;
(2) preparing an eggshell membrane solution: preparing 40 mL of 1 mol/L sodium hydroxide solution, adding 1 g of eggshell membrane, stirring and mixing uniformly, heating the mixed solution at 50 ℃, continuously stirring for 4 hours, and after stirring is finished, performing suction filtration to obtain light yellow clear liquid, namely eggshell membrane solution;
(3) and (3) synthesis of CuS nano particles: 10 mL of eggshell membrane solution was prepared, and 1mL of 0.25M copper nitrate trihydrate (CuNO) was added 3 ·3H 2 O), normal temperatureStirring for 30 min; using 40% HNO 3 The pH of the solution was adjusted to 6 and then 1mL of 0.12M thioacetamide (CH) was added slowly with stirring 3 CSNH 2 ) And stirring uniformly; finally, placing the obtained solution in an oil bath at 90 ℃ for heating for 1 h, wherein the solution becomes dark greenish black, synthesizing materials, and finally, freeze-drying the liquid into powder to obtain CuS nano particles;
(4) green preparation of CuS nanofibers: preparing a polyvinylpyrrolidone (PVP) solution with the mass fraction of 10%, adding the prepared CuS nano particles to prepare an electrostatic spinning solution with the mass fraction of CuS of 0.1%, and then carrying out electrospinning by adopting an electrostatic spinning instrument and adjusting parameters to obtain the CuS nano fiber. Wherein the voltage is 10 kV, and the receiving distance is 8 cm.
The CuS nano particles prepared by the method are applied to photo-thermal sterilization, and the prepared CuS nano fibers are used for in-situ repair of skin wounds and can be applied to beauty masks.
The method for applying the CuS nano particles to photo-thermal sterilization comprises the following steps:
(1) staphylococcus aureus (A), (B), (C)S. aureus) Culturing in broth for 18 h, and adjusting the bacterial concentration to 1X 10 6 CFU/mL；
(2) Adding 5 mg of CuS nano particles into 0.5 mL of bacterial solution and fully mixing;
(3) setting an illumination group and a non-illumination group, wherein the illumination group is prepared by adding the bacterial liquid (test group) containing CuS nano particles and the bacterial liquid (control group) containing no CuS nano particles at 1.5W/cm 2 Irradiating for 5 minutes under near-infrared laser;
(4) and (4) respectively introducing the bacterial liquid obtained in the step (3) into a culture dish to be cultured together with agar, culturing for 18 h at 37 ℃, and then testing the antibacterial performance of the material by a colony counting method.
A method for in situ repair of skin wounds with CuS nanofibers, comprising the steps of:
(1) a sufficient amount of mice were prepared, the animals were anesthetized with 4% chloral hydrate, and then cut into circular areas (about 7 mm in diameter) on both sides of the back and shoulders of each mouse with surgical scissors;
(2) then 50. mu.L of MRSA bacterial suspension (1X 10) was used 7 CFU/mL) infected mouse tissue. After 24 hours, pus was observed on the infected wound;
(3) mice were divided into 6 groups: control, near infrared laser (NIR) irradiated, 0.1% CuS + NIR, wounds were treated differently as follows:
control group: no treatment was performed on the wound;
NIR group: irradiating the wound with near infrared laser at 980 nm and 1.5W/cm 2 NIR 5 min of (a);
and (4) CuS group: in-situ electrospinning the electrostatic spinning solution on the wound by using a handheld electrostatic spinning instrument without infrared laser irradiation;
CuS + NIR group: electro-spinning the electro-spinning solution on the wound in situ by using a handheld electro-spinning instrument, and carrying out laser irradiation under the illumination condition of 980 nm and 1.5W/cm 2 NIR 5 min of (1);
(4) wound recovery was observed and skin samples were taken for analysis.
Example 2
A preparation method of CuS nano particles and CuS nano fibers comprises the following steps:
(1) egg shell membrane pretreatment: collecting waste eggshells, peeling off an eggshell membrane from the eggshells, repeatedly washing with deionized water, soaking in a hydrochloric acid solution for 12 h, then cleaning and drying, and finally crushing to obtain an eggshell membrane;
(2) preparing an eggshell membrane solution: preparing 80 mL of 1 mol/L sodium hydroxide solution, adding 2 g of eggshell membrane, stirring and mixing uniformly, heating the mixed solution at 60 ℃, continuously stirring for 5 hours, and performing suction filtration after stirring to obtain light yellow clear liquid, namely eggshell membrane solution;
(3) and (3) synthesis of CuS nano particles: 20 mL of eggshell membrane solution was prepared, and 2 mL of 0.25M copper nitrate trihydrate (CuNO) was added thereto 3 ·3H 2 O), stirring for 30 min at normal temperature; using 50% HNO 3 The pH of the solution was adjusted to 6.8, then adjusted2 mL of 0.12M thioacetamide (CH) was slowly added with stirring 3 CSNH 2 ) And stirring uniformly; finally, placing the obtained solution in an oil bath at the temperature of 80 ℃ for heating for 1 h, wherein the solution becomes dark greenish black, synthesizing materials, and finally freeze-drying the liquid into powder, namely the CuS nano particles;
(4) green preparation of CuS nanofibers: preparing a polyvinylpyrrolidone (PVP) solution with the mass fraction of 10%, adding the prepared CuS nano particles to prepare an electrostatic spinning solution with the mass fraction of CuS of 0.2%, and then carrying out electrospinning by adopting an electrostatic spinning instrument and adjusting parameters to obtain the CuS nano fiber. Wherein the voltage is 10 kV, and the receiving distance is 10 cm.
The CuS nano particles prepared by the method are applied to photo-thermal sterilization, and the prepared CuS nano fibers are used for in-situ repair of skin wounds and can be applied to beauty masks.
The CuS nano particles are applied to photo-thermal sterilization and comprise the following steps:
(1) escherichia coli (A), (B) and (C)E. coli) And Staphylococcus aurora: (S. aureus) Culturing in broth for 18 h, and adjusting the bacterial concentration to 1X 10 7 CFU/mL；
(2) Adding 10 mg of CuS nano particles into 1mL of bacterial solution and fully mixing;
(3) setting an illumination group and a non-illumination group, wherein the illumination group is to make the bacterial liquid (test group) added with CuS nano particles and the bacterial liquid (control group) not added with CuS nano particles at 2.5W/cm 2 Irradiating for 8 minutes under near-infrared laser;
(4) and (4) respectively introducing the bacterial liquid obtained in the step (3) into a culture dish to be cultured together with agar, culturing for 18 h at 37 ℃, and then testing the antibacterial performance of the material by a colony counting method.
A method for in situ repair of skin wounds with CuS nanofibers, comprising the steps of:
(1) preparing a sufficient amount of mice, anesthetizing the animals with 8% chloral hydrate, and then cutting into circular areas (about 7 mm in diameter) on both sides of the back and shoulders of each mouse with surgical scissors;
(2) then 50. mu.L of MRSA bacteria were usedSuspension (1.75X 10) 7 CFU/mL) infected mouse tissue. After 24 hours, pus was observed on the infected wound;
(3) mice were divided into 6 groups: control, near infrared laser (NIR) irradiated, 0.2% CuS + NIR. The wounds were treated differently as follows:
control group: no treatment was performed on the wound;
NIR group: near infrared laser irradiation is carried out on the wound, and the irradiation condition is 980 nm and 2.5W/cm 2 NIR 8 min of (1);
and (4) CuS group: in-situ electrospinning the electrostatic spinning solution on the wound by using a handheld electrostatic spinning instrument without infrared laser irradiation;
CuS + NIR set: electro-spinning the electro-spinning solution on the wound in situ by using a handheld electro-spinning instrument, and carrying out laser irradiation under the illumination condition of 980 nm and 2.5W/cm 2 NIR 8 min of (1);
(4) wound recovery was observed and skin samples were taken for analysis.
Example 3
A preparation method of CuS nano particles and CuS nano fibers comprises the following steps:
(1) egg shell membrane pretreatment: collecting waste egg shells, peeling off egg membranes from the egg shells, repeatedly washing with deionized water, soaking in a hydrochloric acid solution for 20 h, cleaning and drying, and finally crushing to obtain the egg shell membranes;
(2) preparing an eggshell membrane solution: preparing 100 mL of 1.5 mol/L sodium hydroxide solution, adding 2.5 g of eggshell membrane, stirring and mixing uniformly, heating the mixed solution at 60 ℃, continuously stirring for 6 hours, and after stirring, performing suction filtration to obtain light yellow clear liquid, namely eggshell membrane solution;
(3) and (3) synthesis of CuS nano particles: 50 mL of eggshell membrane solution was prepared, and 5 mL of 0.4M copper nitrate trihydrate (CuNO) was added thereto 3 ·3H 2 O), stirring for 20 min at normal temperature; using 50% HNO 3 The pH of the solution was adjusted to 7 and 5 mL of 0.19M thioacetamide (C) was then added slowly with stirringH 3 CSNH 2 ) And stirring uniformly; finally, placing the obtained solution in an oil bath at 100 ℃ for heating for 1 h to ensure that the solution becomes dark greenish black, synthesizing materials, and finally freeze-drying the liquid into powder, namely the CuS nano particles;
(4) green preparation of CuS nanofibers: preparing a polyvinylpyrrolidone (PVP) solution with the mass fraction of 15%, adding the prepared CuS nano particles to prepare an electrostatic spinning solution with the mass fraction of CuS of 0.5%, and then carrying out electrospinning by adopting an electrostatic spinning instrument and adjusting parameters to obtain the CuS nano fiber. Wherein the voltage is 10 kV, and the receiving distance is 10 cm.
The CuS nano particles prepared by the method are applied to photo-thermal sterilization, and the prepared CuS nano fibers are used for in-situ repair of skin wounds and can be applied to beauty masks.
The method for applying the CuS nano particles to photo-thermal sterilization comprises the following steps:
(1) escherichia coli (A), (B) and (C)E. coli) Cultured in broth for 18 h, and the bacterial concentration was adjusted to 1X 10 8 CFU/mL；
(2) Adding 15 mg of CuS nano particles into 1mL of bacterial solution and fully mixing;
(3) an illumination group and a non-illumination group were established, wherein the illumination group was prepared by mixing the bacteria solution (test group) containing CuS nanoparticles and the bacteria solution (control group) containing no CuS nanoparticles at 3W/cm 2 Irradiating for 10 minutes under near-infrared laser;
(4) and (3) respectively introducing the bacterial liquid obtained in the step (3) into a culture dish to be cultured together with agar, culturing for 20 h at 37 ℃, and then testing the antibacterial performance of the material by a colony counting method.
A method for in situ repair of skin wounds with CuS nanofibers, comprising the steps of:
(1) a sufficient amount of mice were prepared, the animals were anesthetized with 10% chloral hydrate, and then cut into circular areas (about 10 mm in diameter) on both sides of the back and shoulders of each mouse with surgical scissors;
(2) then 50. mu.L of MRSA bacterial suspension (1X 10) was used 8 CFU/mL) infected mouse tissue. After 24 hours, wound after infectionPus was observed on the mouth;
(3) mice were divided into 6 groups: control, near infrared laser (NIR) irradiated, 0.5% CuS + NIR. The wounds were treated differently as follows:
control group: no treatment was performed on the wound;
NIR group: irradiating the wound with near infrared laser at 980 nm and 3W/cm 2 NIR 10 min of (a);
and (4) CuS group: in-situ electrospinning the electrostatic spinning solution on the wound by using a handheld electrostatic spinning instrument without infrared laser irradiation;
CuS + NIR set: electro-spinning the electro-spinning solution on the wound in situ by using a handheld electro-spinning instrument, and carrying out laser irradiation under the illumination condition of 980 nm and 3W/cm 2 NIR 10 min;
(4) wound recovery was observed and skin samples were taken for analysis.
An UV-vis graph measured by the CuS nanoparticle solution prepared in the example 2 is shown in FIG. 1, which shows that the CuS nanoparticle material has strong near infrared absorption and has the potential of photo-thermal sterilization.
Example 2 the heating curves of the prepared CuS nanoparticle solution under 980 nm Near Infrared (NIR) light irradiation with different concentrations of materials and water are shown in fig. 2. It can be seen that higher concentrations of CuS nanoparticles can bring higher temperatures. The temperature rises more and more slowly with increasing time. Within 10 minutes, the temperature of water rose only from 25 ℃ to 39 ℃, while the concentration of CuS nanoparticles rose from 25 ℃ to 56 ℃ (600 mg/L). The result shows that the CuS nano particles have good photo-thermal performance and can be used as a good photo-thermal agent for sterilization.
A statistical chart of the antibacterial efficiency of the CuS nanoparticles prepared in example 2 against Escherichia coli (A) and Staphylococcus aureus (B) at different concentrations is shown in FIG. 3. It is directly seen from the figure that the antibacterial effect is gradually enhanced as the concentration of the material is increased; and the antibacterial effect of the near infrared laser (NIR) added is higher at each concentration than the case where no laser is used. FIG. 3A shows the antibacterial properties of the material against E.coli, with NIR added material sterilization being almost 100% and no laser addition only 55% at a concentration of 600 mg/L. A similar phenomenon was observed at a concentration of 300 mg/L for Staphylococcus aureus (FIG. 3B) (95% NIR and 86% no NIR). The material is shown to have excellent photothermal effect which can be used for sterilization.
Example 2 SEM images of the resulting CuS composite nanofibers and natural eggshell membrane prepared are shown in fig. 4. The picture A is natural eggshell membrane, and the picture B is CuS composite nanofiber. The CuS nano composite fiber prepared is similar to a natural eggshell membrane structure and has a three-dimensional layered porous network structure. The unique three-dimensional network structure of eggshell membrane is reported to promote oxygen exchange in wounds, thereby promoting wound healing and serving as a wound dressing. Therefore, the multifunctional nanofiber simulating the eggshell membrane can effectively promote the healing of skin wounds.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. The preparation method of the multifunctional nanofiber is characterized by comprising the following steps of:
(1) egg shell membrane pretreatment: collecting waste eggshells, peeling off an eggshell membrane from the eggshells, repeatedly washing the eggshells with deionized water, soaking the eggshell membrane in a hydrochloric acid solution for 5-24 hours, then cleaning and drying the eggshell membrane, and finally crushing the eggshell membrane to obtain the eggshell membrane;
(2) preparing an eggshell membrane solution: adding 0.5-2.5 g of eggshell membrane into 30-100 mL of 0.5-2 mol/L sodium hydroxide solution, stirring and mixing uniformly, heating the obtained mixed solution at 50-70 ℃, continuously stirring for 3-6 h, and after stirring, performing suction filtration to obtain an eggshell membrane solution;
(3) and (3) synthesis of CuS nano particles: adding 1-6 mL of CuNO with concentration of 0.1-0.5M into 10-60 mL of eggshell membrane solution 3 ·3H 2 O, stirring for 10-60 min at normal temperature, adjusting the pH of the solution to 6-10, and then slowly adding the solution into the solution for 1-6 min while stirringmL of CH with a concentration of 0.1-0.3M 3 CSNH 2 Uniformly stirring, finally placing the obtained solution in an oil bath at the temperature of 60-100 ℃ for heating for 0.5-2 h, and finally freeze-drying the liquid into powder to obtain CuS nano particles;
(4) preparing CuS nano fibers: adding CuS nano particles into 10-30% of PVP solution by mass fraction to prepare an electrostatic spinning solution with the CuS mass fraction of 0.1-0.5%, then adopting an electrostatic spinning instrument, adjusting the voltage to 10 kV, enabling the receiving distance to be 5-20 cm, and carrying out electrospinning to obtain the CuS nano fiber.
2. The method of claim 1, wherein the eggshell membrane comprises any one of eggshell membrane, duck eggshell membrane, quail eggshell membrane, ostrich eggshell membrane, and turkey eggshell membrane.
3. The method for preparing multifunctional nano fiber according to claim 1, wherein HNO is adopted in the step (3) 3 Adjusting the pH of the solution, said HNO 3 The concentration of (A) is 30-100%.
4. CuS nanoparticles obtainable by the preparation process according to any one of claims 1 to 3.
5. Use of the CuS nanoparticles of claim 4 in photo-thermal sterilization, or in a cosmetic mask.
6. CuS nanofibers obtained by the production method according to any one of claims 1 to 3.
7. Use of the CuS nanofibers of claim 6 in a cosmetic mask.
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