CN114796270A

CN114796270A - Meyer sedge nano-silver, preparation and application thereof, nano-silver gel, preparation and application thereof

Info

Publication number: CN114796270A
Application number: CN202210250958.0A
Authority: CN
Inventors: 朱赫男; 姜铁男; 吕茉; 陈宇溪; 朱自豪; 才妍妍; 韩雨桐; 周新宇; 沈启慧; 刘岩
Original assignee: Jilin Institute of Chemical Technology
Current assignee: Jilin Institute of Chemical Technology
Priority date: 2022-03-15
Filing date: 2022-03-15
Publication date: 2022-07-29
Anticipated expiration: 2042-03-15
Also published as: CN114796270B

Abstract

The invention provides a carex meyeriana nano-silver, a preparation method and an application thereof, a nano-silver gel, a preparation method and an application thereof, and belongs to the technical field of medical materials. The Meyer sedge is used as a stabilizer and a reducing agent, the Meyer sedge contains active ingredients such as polysaccharide, flavone and alkaloid, the silver nanoparticles are formed, and the Meyer sedge is split and wraps the nano silver particles in the reduction process, so that the nano silver is prevented from agglomerating, the formed Meyer sedge nano silver has better stability in a solution, and the Meyer sedge nano silver can be kept not to obviously agglomerate within two months; moreover, the carex meyeriana has the performance of resisting bacterial erosion and reproduction, the formed carex meyeriana nano-silver has excellent bacteriostatic activity on gram-positive bacteria and gram-negative bacteria, the use of antibiotics can be avoided, and the method has wide prospects in the aspect of wound healing.

Description

Meyer sedge nano-silver, preparation and application thereof, nano-silver gel, preparation and application thereof

Technical Field

The invention relates to the technical field of medical materials, in particular to wula sedge nano-silver and preparation and application thereof, and nano-silver gel and preparation and application thereof.

Background

The nano silver has unique optical, electronic, catalytic and mechanical properties, good antibacterial activity, biocompatibility, easy surface modification and other advantages, becomes the most important and commercialized nano material, and is generally applied to the fields of biological pesticides, novel biosensors, water purification and the like.

The skin serves as a protective barrier between the external environment and the human body, and the skin barrier can be damaged by overheating and supercooling, so that wounds can be caused. Under natural conditions, the skin has some self-healing capacity, but a slow healing process can cause the skin to enter an inflammatory state. Therefore, it is necessary to promote the healing of the wound by means of external force. The wound curing needs to maintain a slightly moist environment, the hydrogel is a reticular polymer and has very good water absorption and retention performance, the gel absorbs water to swell under the water environment, and the swelling degree is related to the ratio of hydrophobic groups to hydrophilic groups. In addition, the hydrogel has good elasticity and biocompatibility, can provide a moist environment for wounds and is beneficial to wound healing. However, the moist environment of the hydrogel can lead to bacterial growth, and the current method of inhibiting bacterial growth is to add antibiotics, but antibiotic therapy can develop resistance.

Disclosure of Invention

The invention aims to provide the carex meyeriana nano-silver, the preparation and the application of the carex meyeriana nano-silver, the nano-silver gel, the preparation and the application of the nano-silver gel, and the carex meyeriana nano-silver gel has excellent antibacterial activity and can be prepared into antibacterial gel to avoid the use of antibiotics.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of Meyer sedge nano silver, which comprises the following steps:

mixing the carex pennywort herb powder, silver salt and water, and carrying out reduction reaction on the obtained mixed solution to obtain the carex pennywort herb nano-silver.

Preferably, the concentration of the carex meyeriana powder in the mixed solution is 0.5-2 mg/mL, and the concentration of the silver salt in the mixed solution is 0.1-1 mmol/L.

Preferably, the temperature of the reduction reaction is 50-90 ℃ and the time is 1-4 h.

The invention provides the Meyer sedge nano silver prepared by the preparation method in the technical scheme, which comprises nano silver particles and Meyer sedge extract wrapped on the surfaces of the nano silver particles; the average particle size of the nano silver particles is 64.17 nm.

The invention provides application of the carex meyeriana nano-silver in the technical scheme in antibacterial materials.

The invention provides a nano silver gel which is prepared from Meyer sedge nano silver, wherein the Meyer sedge nano silver is the Meyer sedge nano silver in the technical scheme.

The invention provides a preparation method of the nano-silver gel in the technical scheme, which comprises the following steps:

and heating and mixing the adhesive aqueous solution and the carex meyeriana nano-silver, and repeatedly freezing and unfreezing to obtain the nano-silver gel, wherein the carex meyeriana nano-silver is the carex meyeriana nano-silver in the technical scheme.

Preferably, the binder in the aqueous binder solution comprises polyvinyl alcohol; the mass concentration of the adhesive aqueous solution is 7-10%.

Preferably, the content of the Meyer sedge nano silver in the nano silver gel is 4-8 mg/kg.

The invention provides application of the nano-silver gel in the technical scheme or the nano-silver gel prepared by the preparation method in the technical scheme in preparation of a material for treating wound healing.

The invention provides a preparation method of Meyer sedge nano silver, which comprises the following steps: mixing the carex pennywort herb powder, silver salt and water, and carrying out reduction reaction on the obtained mixed solution to obtain the carex pennywort herb nano-silver. The Meyer sedge is used as a stabilizer and a reducing agent, the Meyer sedge contains active ingredients such as polysaccharide, flavone and alkaloid, the silver nanoparticles are formed, and the Meyer sedge is split and wraps the nano silver particles in the reduction process, so that the nano silver is prevented from agglomerating, the formed Meyer sedge nano silver has better stability in a solution, and the Meyer sedge nano silver can be kept not to obviously agglomerate within two months; moreover, the carex nobilis has the performance of resisting bacterial erosion and reproduction, the nano-silver has excellent antibacterial activity, and the formed carex nobilis nano-silver has excellent antibacterial activity on gram-positive bacteria and gram-negative bacteria, can avoid the use of antibiotics, and has wide prospect in the aspect of wound healing.

The invention provides a preparation method of Meyer sedge nano silver, which takes Meyer sedge as a reducing agent, and the synthetic material of the Meyer sedge extract has low price, wide source, safety, environmental protection and high synthetic speed.

The prepared Meyer sedge nano silver is prepared into the nano silver gel, so that the Meyer sedge nano silver gel has the advantages of stability and difficulty in generating drug resistance, can freely enter cell membranes of bacteria at a very low concentration due to small nano silver particle size (the average particle size is 64.17nm), and has very strong binding capacity with the cell membranes to lose activity, so that the Meyer sedge nano silver gel can well inhibit the growth of bacteria and viruses and does not generate drug resistance, and has very good market application prospect.

Drawings

FIG. 1 is a transmission electron microscope image of the Meyer sedge nanosilver prepared in example 10;

FIG. 2 is a graph of the UV-VIS absorption spectra of the Meyer sedge nano-silver prepared in examples 1-4 and the product of comparative example 1;

FIG. 3 is a graph of the UV-VIS absorption spectra of the Meyer sedge nanosilver prepared in examples 4-6 and the product of comparative example 2;

FIG. 4 is a photograph of a Meyer sedge nano-silver solution prepared in example 10;

FIG. 5 is a UV-VIS absorption spectrum of the Meyer sedge nano-silver prepared in examples 4, 7-9;

FIG. 6 is a photograph of the Meyer sedge nano-silver solution prepared in example 10, which was left at room temperature for two months;

FIG. 7 is a graph of the UV-VIS absorption spectra of the Meyer sedge nanosilver prepared in examples 4, 10-11 and the products of comparative examples 3-4;

FIG. 8 shows the results of the zone diameters of Meyer sedge nano-silver and Meyer sedge powders prepared in example 10;

FIG. 9 shows the bacteriostatic ratio results of Meyer sedge nano-silver prepared in example 10 and nano-silver gel prepared in example 12;

FIG. 10 shows the result of Malvern particle size analysis of the silver nanoparticles prepared in example 10;

fig. 11 is a plot of the Zate potential of the nano silver values of Carex meyeriana prepared in example 10.

Detailed Description

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.

The source of the carex meyeriana powder is not particularly limited in the present invention, and commercially available products well known in the art may be used.

In the present invention, the silver salt preferably comprises silver nitrate; the concentration of the silver salt in the mixed solution is preferably 0.1-1 mmol/L, and more preferably 0.5 mmol/L.

In the invention, the concentration of the carex meyeriana powder in the mixed solution is preferably 0.5-2 mg/mL, and more preferably 1.0-1.5 mg/mL; the invention takes the carex meyeriana as a stabilizer and a reducing agent, the carex meyeriana contains active ingredients such as polysaccharide, flavone and alkaloid, the formation of nano particles is facilitated, and the carex meyeriana wraps the nano silver particles through self splitting, so that the agglomeration of nano silver is prevented, and the stability of the nano silver is better.

The process of mixing the carex meyeriana powder, the silver salt and the water is not particularly limited, and the materials are uniformly mixed according to the well-known process in the field, for example, the carex meyeriana powder is dissolved in the water and then the silver salt is added, or the carex meyeriana and the silver salt are respectively dissolved in the water and then mixed.

In the invention, the temperature of the reduction reaction is preferably 50-90 ℃, more preferably 60-80 ℃, and further preferably 70 ℃; the time is preferably 1 to 4 hours, more preferably 60 to 90min, and further preferably 70 to 80 min.

After the reduction reaction is finished, the method preferably does not carry out any treatment, and directly obtains the carex meyeriana nano-silver solution. The Meyer sedge nano silver exists in the form of solution; the concentration of the carex meyeriana nano-silver solution is not specially limited, and the concentration can be adjusted according to actual requirements.

In the present invention, the binder in the aqueous binder solution preferably includes polyvinyl alcohol; the mass concentration of the adhesive aqueous solution is preferably 7-10%. The invention utilizes the adhesive to play the roles of bonding gel and moisturizing.

In the invention, the process of heating and mixing the adhesive aqueous solution and the carex nigricans nano silver is preferably that the adhesive solution is heated for 5 hours, then the carex nigricans nano silver solution is added, and the heating and stirring are continued for 30 min; the heating temperature is preferably 80-90 ℃; the invention utilizes the heating process to improve the reaction rate, and the silver nitrate and the carex meyeriana plant powder fully react.

The freezing-thawing process is not particularly limited in the present invention, and the gel is obtained according to a process well known in the art; in the examples of the present invention, the freezing was carried out in a refrigerator at-18 ℃ for 2 hours, and the number of repeated freeze-thaw was three.

In the invention, the content of the Meyer sedge nano silver in the nano silver gel is preferably 4-8 mg/kg, and more preferably 8 mg/kg; the dosage of the adhesive aqueous solution and the Meyer sedge nano silver meets the Meyer sedge nano silver content range.

The invention provides application of the nano-silver gel in the technical scheme or the nano-silver gel prepared by the preparation method in the technical scheme in preparation of a material for treating wound healing. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art. The nano-silver gel provided by the invention prevents wound infection by inhibiting pathogenic microorganisms.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Dissolving Meyer sedge powder in water to obtain Meyer sedge solution with concentration of 0.5mg/mL, adding 1mM AgNO ₃ Reducing the water solution at 80 deg.c for 90min to obtain Meyer sedge nano silver solution.

Example 2

The only difference from example 1 is: the concentration of the Meyer sedge solution is 1 mg/mL.

Example 3

The only difference from example 1 is: the concentration of the Meyer sedge solution is 1.5 mg/mL.

Example 4

The only difference from example 1 is: the concentration of the Meyer sedge solution is 2 mg/mL.

Example 5

Adding 0.1mM AgNO into 2mg/mL Meyer sedge solution ₃ Reacting the water solution for 80min at 80 ℃ to obtain the Meyer sedge nano-silver solution.

Example 6

The only difference from example 5 is that: AgNO ₃ The concentration of the aqueous solution was 0.5 mM.

Example 7

Adding 1mM AgNO into 2mg/mL Meyer sedge solution ₃ Reducing the water solution at 70 deg.c for 90min to obtain Meyer sedge nano silver solution.

Example 8

The only difference from example 7 is that: the temperature of the reduction reaction was 60 ℃.

Example 9

The only difference from example 7 is that: the temperature of the reduction reaction was 50 ℃.

Example 10

Adding 1mM AgNO into 2mg/mL Meyer sedge solution ₃ Carrying out reduction reaction on the aqueous solution for 80min at the temperature of 80 ℃ to obtain the Meyer sedge nano silver solution.

Example 11

The only difference from example 10 is that: the time for the reduction reaction was 60 min.

Example 12

Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 10%, heating at 90 ℃ for 5h, adding the Meyer sedge nano-silver solution prepared in the example 10, continuously stirring for 30min, standing at room temperature, freezing in a refrigerator at-18 ℃ for 2h, unfreezing, and repeatedly freezing and unfreezing for three times to obtain nano-silver gel, wherein the content of the Meyer sedge nano-silver in the nano-silver gel is 8 mg/kg.

Comparative example 1

The only difference from example 1 is: the concentration of the Meyer sedge solution is 0 mg/mL.

Comparative example 2

The only difference from example 5 is that: AgNO ₃ The concentration of the aqueous solution was 0 mM.

Comparative example 3

The only difference from example 10 is that: the time for the reduction reaction was 40 min.

Comparative example 4

The only difference from example 10 is that: the time for the reduction reaction was 20 min.

Characterization and Performance testing

1) The transmission electron microscope test is carried out on the Meyer sedge nano silver prepared in the example 10, and the obtained result is shown in figure 1; as can be seen from FIG. 1, most of the nano-silver particles are spherical, the size is 37-122 nm, and the average particle size is 64.17 nm.

2) Carrying out ultraviolet test on the carex meyeriana nano silver prepared in the examples 1-4 and the product of the comparative example 1, wherein the obtained ultraviolet visible absorption spectrum is shown in a figure 2; as can be seen from fig. 2, the sample of comparative example 1, to which no wula sedge was added, had no absorption peak; the obvious absorption peak is generated by adding the Meyer sedge with different concentrations, which proves that the Meyer sedge can induce the formation of the nano-silver.

3) Carrying out ultraviolet test on the carex meyeriana nano silver prepared in the examples 4-6 and the product of the comparative example 2, wherein the obtained ultraviolet visible absorption spectrum is shown in figure 3; as can be seen from FIG. 3, AgNO was added at different concentrations ₃ All show absorption peaks, and prove that AgNO of 0.1mM, 0.5mM and 1mM ₃ All aqueous solutions areCan synthesize nano silver.

4) Fig. 4 is a photograph of the carex was prepared in example 10, and the carex was reddish brown, which illustrates the synthesis of nano-silver.

5) Carrying out ultraviolet test on the carex meyeriana nano silver prepared in the embodiments 4, 7-9, wherein the obtained ultraviolet visible absorption spectrum is shown in figure 5; as can be seen from FIG. 5, absorption peaks appear at different temperatures, indicating that nano-silver can be generated at different temperatures.

6) Fig. 6 is a photograph of the wula sedge nano-silver solution prepared in example 10 after being left at room temperature for two months, and it can be seen from fig. 6 that the wula sedge nano-silver solution is reddish brown, the synthesized nano-silver can be kept stable, and no significant aggregation occurs at room temperature for two months.

7) Carrying out ultraviolet test on the carex nobilis nano silver prepared in the examples 4 and 10-11 and the products of the comparative examples 3-4, wherein the obtained ultraviolet visible absorption spectrum is shown in figure 7; as can be seen from fig. 7, the ultraviolet absorbance of the nano silver is continuously increased along with the extension of the reaction time, and there is no significant change after 90min, which indicates that the synthetic amount of the nano silver is the maximum at 90 min.

8) a, biological activity of nano silver

The antibacterial activity of the carex was measured for the selected strains using escherichia coli and bacillus subtilis as pathogen models by a paper diffusion method (DDM) as described in example 10: a commercially available LB agar medium was autoclaved at 121 ℃ for 15min, a test strain was inoculated on the medium and cultured for 12h, the culture solution was subjected to antibacterial assay, and finally, the inhibition zone was observed using a microscope, and three or more times of antibacterial activity assay were carried out, and compared with the carex niveus powder, and the obtained results are shown in FIG. 8. As can be seen from FIG. 8, on the solid culture medium, the carex nobilis nano-silver particles have significant antibacterial effects on both gram-positive bacteria (Bacillus subtilis) and gram-negative bacteria (Escherichia coli), and the sizes of the inhibition zones of the carex nobilis nano-silver on the Escherichia coli and the Bacillus subtilis are respectively 10.48 +/-1 mm and 11.59 +/-0.25 mm; the Meyer sedge powder has no antibacterial zone, which indicates that the Meyer sedge powder has no antibacterial ability.

b. Bioactivity of nano silver gel

Escherichia coli and Bacillus subtilis were inoculated into LB medium and placed on a shaker at 37 ℃ for 12 hours. Then diluting the two bacteria to 108CFU/mL by using a culture medium; placing 1 cm-diameter nano silver gel or Meyer sedge nano silver into a conical flask, culturing at 37 deg.C for 6h, taking 100 μ L of gel-treated bacterial solution, coating on LB solid culture medium, placing in 37 deg.C incubator, culturing for 12h, observing the growth condition of the strain, and comparing with polyvinyl alcohol hydrogel, the obtained result is shown in FIG. 9. Fig. 9 shows the results of the bacteriostatic rates of the carex nobilis nano-silver prepared in example 10 and the nano-silver gel prepared in example 12 against bacillus subtilis and escherichia coli, and as can be seen from fig. 9, both the bacteriostatic rates of the carex nobilis nano-silver and the nano-silver gel against gram-positive bacteria and gram-negative bacteria can reach 99.9%, indicating that the antibacterial effect on bacterial growth is significantly inhibited.

c. The particle size of the wula sedge nano-silver prepared in example 10 was measured using a malvern particle sizer, and the experimental results are shown in fig. 10; as can be seen from FIG. 10, the average particle size of the silver nanoparticles of carex was 64.17nm and the particle size distribution of 25% of the silver nanoparticles was 60nm, both of which were measured at 1mM by the Malvern particle size analyzer and prepared at 80 ℃.

d. Potential analysis was performed on the wula sedge nanosilver prepared in example 10, and the obtained result is shown in fig. 11, and it can be seen from fig. 11 that the potential analysis is-19.2 mV, indicating that the nanosilver particles have excellent stability.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of Meyer sedge nano silver comprises the following steps:

2. The method of claim 1, wherein the concentration of the Meyer sedge powder in the mixed solution is 0.5-2 mg/mL, and the concentration of the silver salt in the mixed solution is 0.1-1 mmol/L.

3. The preparation method according to claim 1 or 2, wherein the temperature of the reduction reaction is 50-90 ℃ and the time is 1-4 h.

4. The carex nobilis nano-silver prepared by the preparation method of any one of claims 1 to 3 comprises nano-silver particles and a carex nobilis extract coated on the surfaces of the nano-silver particles; the average particle size of the nano silver particles is 64.17 nm.

5. The use of the Meyer sedge nano-silver of claim 4 in bacteriostatic materials.

6. A nano silver gel, which is characterized by being prepared from Meyer sedge nano silver, wherein the Meyer sedge nano silver is the Meyer sedge nano silver disclosed by claim 4.

7. The method for preparing nano silver gel of claim 6, comprising the steps of:

heating and mixing the adhesive aqueous solution and the carex meyeriana nano-silver, and repeatedly freezing and unfreezing to obtain the nano-silver gel, wherein the carex meyeriana nano-silver is the carex meyeriana nano-silver in claim 4.

8. The method of claim 7, wherein the binder in the aqueous binder solution comprises polyvinyl alcohol; the mass concentration of the adhesive aqueous solution is 7-10%.

9. The preparation method of claim 7, wherein the nano silver gel contains Meyer sedge nano silver in an amount of 4-8 mg/kg.

10. Use of the nano-silver gel of claim 6 or the nano-silver gel prepared by the preparation method of any one of claims 7 to 9 in preparation of a material for healing wounds.