CN115998944B - Nano-silver functionalized antibacterial material and preparation method and application thereof - Google Patents
Nano-silver functionalized antibacterial material and preparation method and application thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 25
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- 238000003756 stirring Methods 0.000 claims abstract description 15
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- 239000008103 glucose Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 7
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- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KLGDRWGOXDJNPH-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KLGDRWGOXDJNPH-UHFFFAOYSA-N 0.000 description 1
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- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a nano silver functionalized antibacterial material, a preparation method and application thereof, and relates to the technical field of antibacterial materials. The preparation method of the nano silver functionalized antibacterial material comprises the following steps: s1, uniformly mixing graphene oxide solution and silver ammonia solution, stirring at 40-60 ℃ for reacting for a period of time, adding aqueous solution of glucose, heating to 85-95 ℃ for continuously stirring for reacting, naturally cooling after the reaction is completed, and performing post-treatment to obtain GO/Ag composite nano particles; s2: adding the GO/Ag composite nano particles into a GelMA solution, stirring at room temperature for reaction, and then carrying out ultraviolet crosslinking reaction to obtain the nano silver functionalized antibacterial material. The nano-silver functionalized graphene oxide/methacrylic acylated gelatin prepared by the invention has excellent antibacterial property, and the photo-thermal antibacterial effect of the graphene oxide can be greatly enhanced after silver nano-particles are loaded on the graphene oxide.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a nano-silver functionalized antibacterial material and a preparation method and application thereof.
Background
Bacterial infection wounds are a common clinical problem, and the appearance of drug-resistant bacteria caused by abuse of antibiotics causes poor curative effect and even death, so that the search for new antibacterial means for treating drug-resistant bacteria is necessary. The antibacterial means commonly used in clinic at present mainly comprise: antibiotics, nanoparticles, natural polymers, artificial polymers, etc., nanoparticles are widely used because of their broad-spectrum antibacterial activity and substantially no bacterial resistance. The silver nano-particles are the most widely applied nano-particles, have excellent antibacterial performance, can be metabolically discharged in vivo and have a certain immunoregulatory effect, but the pure silver nano-particles are easy to oxidize and have poor slow release effect.
The Chinese patent publication No. CN113637183A discloses a preparation method of an antibacterial hydrogel, wherein the hydrogel is prepared into a composite hydrogel by using modified graphene, nano silver and polyvinyl alcohol as raw materials by using a freezing-thawing physical crosslinking method, but the repeated freezing method is insufficient in crosslinking strength and easy to break; chinese patent publication No. CN112189672a discloses a preparation method of graphene-loaded silver nanoparticle antibacterial material, but the graphene oxide alone has certain biotoxicity.
Both the above two methods do not fully utilize the photothermal antibacterial effect of graphene oxide, and the antibacterial effect is limited.
Disclosure of Invention
The invention provides a nano silver functionalized antibacterial material, a preparation method and application thereof, and aims to solve the problems in the background technology.
In order to achieve the technical purpose, the invention mainly adopts the following technical scheme:
In a first aspect, the invention provides a preparation method of a nano-silver functionalized antibacterial material, which comprises the following steps:
S1, uniformly mixing graphene oxide solution and silver ammonia solution, stirring at 40-60 ℃ for reacting for a period of time, adding aqueous solution of glucose, heating to 85-95 ℃ for continuously stirring for reacting, naturally cooling after the reaction is completed, and performing post-treatment to obtain GO/Ag composite nano particles;
S2: adding the GO/Ag composite nano particles into a GelMA solution, stirring at room temperature for reaction, and then carrying out ultraviolet crosslinking reaction to obtain the nano silver functionalized antibacterial material.
The graphene oxide is used as an inorganic nano material, contains pi-pi bond adsorbable particles, can adsorb silver nano particles to reduce oxidization, contains abundant hydroxyl, carboxyl and other functional groups, has good photo-thermal effect, and can be combined with antibacterial effect, so that the nano silver nano material has two purposes.
The methacryloylated gelatin (GelMA) is a common material for constructing hydrogel, has the characteristic of ultraviolet crosslinking, and the constructed hydrogel with a network structure can simulate extracellular matrix, load and slowly release drugs.
According to the invention, the three materials of nano silver, graphene oxide and GelMA are combined according to a certain proportion, so that the defects of insufficient antibacterial property of pure GelMA, poor biocompatibility of pure graphene oxide, easiness in oxidation of silver nanoparticles and the like are overcome, and meanwhile, the photo-thermal effect of the graphene oxide can be greatly enhanced by the silver nanoparticles, so that the nano silver functionalized graphene oxide/methacryloylated gelatin with excellent antibacterial property is prepared.
In a preferred embodiment of the present invention, in step S1, the preparation method of the graphene oxide solution is as follows: and (3) dissolving graphene oxide in deionized water in an ultrasonic-assisted manner to obtain a graphene oxide solution with the concentration of 0.05-0.2% W/V.
In a preferred embodiment of the present invention, in step S1, the preparation method of the silver-ammonia solution is as follows: and (3) dissolving AgNO3 in deionized water, slowly dripping ammonia water into the AgNO3 solution to precipitate, and continuously dripping ammonia water until the precipitate just disappears to obtain the silver-ammonia solution.
In a preferred embodiment of the present invention, in step S1, the mass ratio of silver to graphene oxide in the GO/Ag composite nanoparticle is ag:go=2:1.
In the preferred embodiment of the present invention, in step S1, after the graphene oxide solution and the silver ammonia solution are reacted for 30 minutes, an aqueous solution of glucose is further added, and then the reaction is continued for 1 hour after the temperature is raised.
In a preferred embodiment of the present invention, in step S1, 30 to 60ml of deionized water contains 0.5 to 2g of glucose in an aqueous solution of glucose.
In a preferred embodiment of the present invention, in step S1, the post-processing includes the steps of: after natural cooling, the product is centrifuged and washed for 3 times by ethanol and deionized water, and then the precipitate is dried in vacuum for 24 hours at the temperature of minus 50 ℃ to obtain the GO/Ag composite nano-particles.
In another preferred embodiment of the present invention, in step S2, the preparation method of the GelMA solution is as follows: and (3) dissolving the GelMA and a photoinitiator LAP in PBS (phosphate buffer solution) in an ultrasonic-assisted manner to obtain a GelMA solution with the concentration of 2-4% W/V, reacting the GelMA solution with the GO/Ag composite nano-particles for 15-30 minutes at room temperature, and then performing ultraviolet crosslinking for 1-3 minutes.
In a second aspect, the invention provides a nano-silver functionalized antibacterial material, which is mainly prepared by the preparation method in the first aspect.
In a third aspect, the present invention provides the use of a nano-silver functionalized antimicrobial material as described in the second aspect for the preparation of an antimicrobial product.
Compared with the prior art, the invention has the following beneficial effects:
(1) The nano-silver functionalized graphene oxide/methacrylic acylated gelatin prepared by the invention has a porous network structure, is obtained by modifying the surface of graphene oxide by silver nano particles and then loading the silver nano particles in a GelMA network structure, and the GelMA is similar to a natural extracellular matrix, and the good biocompatibility of the GelMA solves the defect that the graphene oxide has certain biotoxicity;
(2) The nano-silver functionalized graphene oxide/methacrylic acid gelatin prepared by the invention loads silver in graphene oxide, so that the dispersibility and stability of silver nano-particles can be improved, and the defects of easiness in oxidization and poor sustained-release effect are overcome;
(3) The nano-silver functionalized graphene oxide/methacrylic acylated gelatin prepared by the invention has excellent antibacterial property, and the photo-thermal antibacterial effect of the graphene oxide can be greatly enhanced after silver nano-particles are loaded on the graphene oxide.
Drawings
FIG. 1 is a diagram of a nano-silver functionalized graphene oxide/methacrylated gelatin disclosed herein; wherein A is an appearance diagram; b and C are SEM images;
FIG. 2 is a representation of the nano-silver functionalized graphene oxide/methacrylated gelatin disclosed herein; wherein A is an X-ray diffraction pattern of the Ag/GO composite nano-particles; b is a near infrared spectrum chart of pure GelMA, GO-GelMA and GO/Ag-GelMA; c is a Raman spectrum of pure GelMA and GO/Ag-GelMA; d is a thermal weight curve graph of pure GelMA and GO/Ag-GelMA;
FIG. 3 is a graph of the photothermal effect of the nano-silver functionalized graphene oxide/methacrylated gelatin disclosed herein;
Fig. 4 is a graph of photothermal antimicrobial effect of the nano-silver functionalized graphene oxide/methacryloylated gelatin disclosed herein.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The nano silver functionalized antibacterial material is prepared by the following steps:
1. 30-60 mgGO of ultrasonic auxiliary solution is dissolved in 30-60 ml of deionized water to obtain a GO solution with the concentration of 0.05-0.2% W/V;
2. Dissolving 60-120 mg of AgNO 3 in 3-6 ml of deionized water, slowly dripping 3% ammonia water (0.6 ml of 25% high-grade pure ammonia water is prepared to 3-6 ml) into AgNO 3 solution, precipitating in the solution, and then continuously dripping ammonia water until the precipitate just disappears to obtain silver ammonia solution;
3. Mixing the GO solution and the silver ammonia solution in a beaker, placing the beaker in a magnetic stirrer which is heated at 40-60 ℃ for stirring reaction for 30 minutes, adding 30-60 ml of aqueous solution containing 0.5-2 g of glucose, heating to 85-95 ℃ and continuously stirring for 1 hour; after natural cooling, centrifuging and washing the product for 3 times by using ethanol and deionized water, and then placing the precipitate at-50 ℃ for vacuum drying for 24 hours to obtain GO/Ag composite nano particles;
4. 200-800 mgGelMA mg of photoinitiator LAP [ phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate ] and ultrasonic auxiliary are dissolved in 2-4 ml of PBS solution to obtain 2-4% W/V GelMA solution;
5. adding 5-20 mgGO/Ag composite nano particles into GelMA solution, stirring for 15-30 min at room temperature, pouring into a hollow cylinder mould with the inner diameter of 0.8cm and the height of 0.1cm, and then carrying out ultraviolet (500 nm,7mwWcm -2) crosslinking for 1-3 min to obtain the nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA).
In the above embodiment, W/V refers to the weight-to-volume ratio, and in the GO/Ag composite nanoparticle, the mass ratio of silver to graphene oxide is Ag: go=2:1.
Comparative example
The nano silver functionalized antibacterial material is prepared by the following steps:
1. 30-60 mgGO of ultrasonic auxiliary solution is dissolved in 30-60 ml of deionized water to obtain a GO solution with the concentration of 0.05-0.2% W/V;
2. 30-60 mg of AgNO 3 is dissolved in 3-6 ml of deionized water, 3% ammonia water (0.6 ml of 25% high-grade pure ammonia water is prepared to 3-6 ml) is slowly dripped into AgNO 3 solution, precipitation occurs in the solution, and then ammonia water is continuously dripped until the precipitation just disappears, so that silver ammonia solution is obtained;
3. Mixing the GO solution and the silver ammonia solution in a beaker, placing the beaker in a magnetic stirrer which is heated at 40-60 ℃ for stirring reaction for 30 minutes, adding 30-60 ml of aqueous solution containing 0.5-2 g of glucose, heating to 85-95 ℃ and continuously stirring for 1 hour; after natural cooling, centrifuging and washing the product for 3 times by using ethanol and deionized water, and then placing the precipitate at-50 ℃ for vacuum drying for 24 hours to obtain GO/Ag composite nano particles;
4. 200-800 mgGelMA mg of photoinitiator LAP [ phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate ] and ultrasonic auxiliary are dissolved in 2-4 ml of PBS solution to obtain 2-4% W/V GelMA solution;
5. adding 5-20 mgGO/Ag composite nano particles into GelMA solution, stirring for 15-30 min at room temperature, pouring into a hollow cylinder mould with the inner diameter of 0.8cm and the height of 0.1cm, and then carrying out ultraviolet (500 nm,7mwWcm -2) crosslinking for 1-3 min to obtain the nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA).
In the above embodiment, W/V refers to the weight-to-volume ratio, and in the GO/Ag composite nanoparticle, the mass ratio of silver to graphene oxide is Ag: go=1:1.
Test examples
Characterization of the appearance and SEM image of the nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA) prepared by the example shows that the results are shown in FIG. 1, and the hydrogel prepared by the invention is clearly seen as a network structure and is attached to the Ag/GO composite nano-particles in FIGS. 1B and C.
The nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA) prepared by the examples was characterized and the results are shown in fig. 2.
Wherein, the A graph is the X-ray diffraction pattern of the Ag/GO composite nano-particle, and the graph shows that the graphene oxide has a unique carbon peak at 40-45 degrees, and the Ag/GO has 4 main peaks at 37.8, 43.8, 64.2 and 77.1 degrees, which correspond to the silver nano-particles with lattice planes (111), (200), (220) and (311) respectively.
The B diagram is a near infrared spectrum diagram of pure GelMA, GO-GelMA and GO/Ag-GelMA, and a reference literature shows that graphene oxide has visible characteristic peaks at 1229, 1163 and 846cm -1 wavelengths, and the GO-GelMA is seen to have peaks at 1188cm -1, namely successful addition of GO is proved; meanwhile, the figure shows that the pure GelMA can see the wave crest at 1033cm -1、1538cm-1, after GO is added, the original wave crest at 1033cm -1 is red shifted to 1047cm -1 and 1045cm -1, and after Ag is added: the original peak at 1538cm -1 undergoes red shifts to 1548cm -1 due to partial destruction of hydrogen bonds by interactions between newly formed CG and Ag, GO nanoparticles, indirectly confirming successful integration of Ag/GO composite nanoparticles with GelMA matrix.
The graph C is a Raman spectrum of pure GelMA and GO/Ag-GelMA, and compared with pure GelMA, the graph shows that the GO/Ag-GelMA has obvious D peak and G peak which are characteristic peaks of graphene oxide, and successful combination of the Ag/GO composite nano particles and the GelMA matrix is verified.
The graph D is a thermal weight graph of pure GelMA and GO/Ag-GelMA, and the graph shows that the residual weight of the hydrogel added with the Ag/GO composite nano particles is slightly higher than that of the pure GelMA hydrogel at the temperature of 600 ℃, so that the thermal stability of the hybrid hydrogel is improved due to the existence of the Ag/GO nano particles.
Examining the photo-thermal effect of nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA) prepared in the examples and comparative examples, the result is shown in FIG. 3, and it can be seen from the graph that after irradiation of 808nm near infrared laser of 0.5w/cm 2 for 5min, the temperature of GO/Ag-GelMA is higher than that of GO-GelMA, which indicates that the addition of Ag nanoparticles enhances the photo-thermal effect of GO; meanwhile, when Ag is GO=2:1, the photo-thermal effect is better than that of hydrogel when Ag is GO is 1:1, so that the invention adopts GO/Ag-GelMA of Ag is GO=2:1.
The photo-thermal antibacterial effect of the nano-silver functionalized graphene oxide/methacryloylated gelatin (GO/Ag-GelMA) prepared by the embodiment of the invention is examined, and the result is shown in figure 4, and the graph shows that the culture dish originally full of staphylococcus aureus and escherichia coli almost has no bacteria survival after being added with GO/Ag-GelMA and irradiated by 808nm near infrared laser, so that the nano-silver functionalized graphene oxide/methacryloylated gelatin prepared by the invention has excellent photo-thermal antibacterial effect.
The present invention uses methacryl group gelatin (GelMA) to construct hydrogel matrix, which is highly similar to extracellular matrix, has excellent biocompatibility, and gelatin itself has a crosslinking property that can be physically crosslinked to form hydrogel at low temperature, and the introduction of methacryl group allows gelatin to have a photocrosslinking property under photoinitiator and light irradiation.
According to the invention, 1-3% of GelMA solution with the concentration of W/V is matched with 0.1-0.3% of light initiator LAP (phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate) with the concentration of W/V, so that a very stable three-dimensional crosslinking structure can be obtained after ultraviolet irradiation for 1-3 minutes.
According to the invention, the mass ratio of Ag to GO is 2:1, a better dispersion ratio can be obtained in the ratio, and the photo-thermal conversion efficiency of the graphene oxide can be better improved by the silver nano particles in the ratio, so that the photo-thermal antibacterial effect of the graphene oxide is fully utilized.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The preparation method of the nano silver functionalized antibacterial material is characterized by comprising the following steps of:
S1, uniformly mixing graphene oxide solution and silver ammonia solution, stirring at 40-60 ℃ for reacting for a period of time, adding aqueous solution of glucose, heating to 85-95 ℃ for continuously stirring for reacting, naturally cooling after the reaction is completed, and performing post-treatment to obtain GO/Ag composite nano particles;
s2: adding the GO/Ag composite nano particles into a GelMA solution, stirring at room temperature for reaction, and then carrying out ultraviolet crosslinking reaction to obtain a nano-silver functionalized antibacterial material;
In step S1, the preparation method of the graphene oxide solution is as follows: dissolving graphene oxide in deionized water in an ultrasonic-assisted manner to obtain a graphene oxide solution with the concentration of 0.05-0.2% W/V;
The preparation method of the silver ammonia solution comprises the following steps: dissolving AgNO 3 in deionized water, slowly dripping ammonia water into AgNO 3 solution to precipitate, and continuously dripping ammonia water until the precipitate just disappears to obtain silver ammonia solution;
In the GO/Ag composite nano-particles, the mass ratio of silver to graphene oxide is Ag:GO=2:1.
2. The method for preparing a nano-silver functionalized antibacterial material according to claim 1, wherein in step S1, after the graphene oxide solution and the silver ammonia solution react for 30 minutes, an aqueous solution of glucose is added, and then the reaction is continued for 1 hour after the temperature is raised.
3. The method for preparing the nano-silver functionalized antibacterial material according to claim 1, wherein in the step S1, 30-60 mL of deionized water contains 0.5-2 g of glucose in the aqueous solution of glucose.
4. The method for preparing a nano-silver functionalized antibacterial material according to claim 1, wherein in step S1, the post-treatment comprises the steps of: after natural cooling, the product is centrifuged and washed for 3 times by ethanol and deionized water, and then the precipitate is dried in vacuum for 24 hours at the temperature of minus 50 ℃ to obtain the GO/Ag composite nano-particles.
5. The method for preparing the nano-silver functionalized antibacterial material according to claim 1, wherein in step S2, the preparation method of the GelMA solution is as follows: and (3) dissolving the GelMA and a photoinitiator LAP in PBS (phosphate buffer solution) in an ultrasonic-assisted manner to obtain a GelMA solution with the concentration of 2-4% W/V, reacting the GelMA solution with the GO/Ag composite nano-particles for 15-30 minutes at room temperature, and then performing ultraviolet crosslinking for 1-3 minutes.
6. A nano silver functional antibacterial material is characterized in that: prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the nano-silver functionalized antibacterial material according to claim 6 for preparing antibacterial products.
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