CN116041884A - Preparation method and application of photo-curing 3D printing hydrogel metamaterial - Google Patents
Preparation method and application of photo-curing 3D printing hydrogel metamaterial Download PDFInfo
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- CN116041884A CN116041884A CN202310014482.5A CN202310014482A CN116041884A CN 116041884 A CN116041884 A CN 116041884A CN 202310014482 A CN202310014482 A CN 202310014482A CN 116041884 A CN116041884 A CN 116041884A
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Abstract
The invention discloses a preparation method and application of a photo-curing 3D printing hydrogel metamaterial, wherein the method comprises the following steps of: step 1, dissolving an unsaturated monomer, a water-based photoinitiator, a crosslinking agent and a light absorber in a solvent to prepare photosensitive 3D printing hydrogel ink; step 2, establishing a three-dimensional metamaterial structure model by using software, placing photosensitive 3D printing hydrogel ink into a trough, and performing photo-curing 3D printing to obtain a covalent cross-linked hydrogel metamaterial structure; step 3, putting the covalent cross-linked hydrogel metamaterial into a metal salt solution for soaking and cross-linking; and 4, carrying out water dialysis balancing on the covalent cross-linked double-network hydrogel metamaterial structure to obtain the photocuring 3D printing hydrogel metamaterial. The mechanical property of the hydrogel metamaterial biological antibacterial scaffold is regulated by regulating and controlling the coordination concentration of the photosensitive hydrogel ink component and the metal ion, and the hydrogel metamaterial biological antibacterial scaffold has good support property and softness.
Description
Technical Field
The invention belongs to the field of photo-curing hydrogel materials and medical instruments, and particularly relates to a preparation method and application of a photo-curing 3D printing hydrogel metamaterial.
Background
With the prolongation of the service life, the risks of cardiovascular diseases, esophageal cancer and bronchogenic cancer of people are also rapidly increased, and the patients become the main diseases threatening the life health of people. The stent is used as a medical instrument commonly used in interventional operations and is the most common and effective treatment measure for treating the diseases at present. However, most of the stents used in clinic at present are made of metal and high molecular polymer materials. The metal stent can cause various serious complications after being implanted into a human body, such as massive hemorrhage caused by the damage of the structure and the function of cells in the skin and erosion of the tracheal mucosal blood vessels, displacement and deformation caused by the improper stent selection or placement, and the like. In addition, the metal stent implant cannot support differently according to the stenosis degree of esophagus, trachea and blood vessel, and insufficient supporting force or overlarge supporting force can be caused. In recent years, with the rapid development of 3D printing technology, researchers have been working on developing personalized custom 3D printing polymer scaffolds with complex structures, and materials currently available for 3D printing polymer scaffolds are mainly engineering plastics such as ABS, PLA, PA and photosensitive resins. However, these polymer stents have poor mechanical properties and flexibility, which easily cause problems such as restenosis, thrombosis, wall loss, etc. when the tube wall with a large bending degree and a long area is in service, and the stent has serious axial shortening phenomenon when being expanded, so that a good therapeutic effect is difficult to realize. Therefore, from the clinical practical requirements, the biological stent must have certain flexibility and support, be able to be sutured and attached to the body tissue, be able to withstand surgical procedures without breaking, and have mechanical properties that do not cause mechanical damage to the body tissue.
Among the many flexible polymeric materials, hydrogels have attracted attention by virtue of their properties similar to biological tissues. The hydrogel is used as a hydrophilic polymer material with a three-dimensional cross-linked network structure, and is widely applied in the fields of tissue engineering, medicine slow release and cell culture scaffolds due to good biocompatibility, substance exchange capacity, adjustable mechanical properties, flexibility and elasticity. However, the existing hydrogel has the main problems of insufficient mechanical strength, poor swelling property, poor elasticity and processability and unsatisfactory stability, so that the application of the hydrogel in the biomedical field is restricted.
In recent years, photo-curing 3D printing hydrogels have been widely used for scaffold construction in the biological field because of their more accurate construction of highly complex three-dimensional structures that mimic human soft tissues. However, for in vivo biological scaffolds, the requirements for material properties and dimensional accuracy are relatively high. However, the existing photocuring 3D printing hydrogel has the disadvantages of poor mechanical property, low printing resolution, easy swelling and poor functionality, and is not suitable for constructing a complex three-dimensional in-vivo biological stent with ultrahigh precision. Functionally, the transplantation of hydrogels in vivo is at risk of bacterial infection, and therefore, there is a need to design hydrogel scaffold materials with antibacterial function. An important feature of hydrogel bioscaffold in terms of mechanical properties is that it must be elastic, flexible and well supportive, thus requiring the desired material properties to be obtained by engineering from molecular networks and geometries. The light-cured 3D printing high-strength swelling-resistant hydrogel system with good biocompatibility, good flexibility and elasticity, higher mechanical strength and safety is sought and developed, and is one of the problems to be solved at present.
Disclosure of Invention
The invention aims to provide a preparation method and application of a photo-curing 3D printing hydrogel metamaterial, and solves the problems of poor mechanical property, low printing resolution, easiness in swelling and poor functionality of the existing photo-curing 3D printing hydrogel.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a preparation method of a photo-curing 3D printing hydrogel metamaterial comprises the following steps:
and step 1, dissolving an unsaturated monomer, an aqueous photoinitiator, a crosslinking agent and a light absorber in a solvent to prepare the photosensitive 3D printing hydrogel ink.
And 2, establishing a three-dimensional metamaterial structure model by using software, and placing the photosensitive 3D printing hydrogel ink in the step 1 into a trough for photo-curing 3D printing to obtain a covalent cross-linked hydrogel metamaterial structure.
And 3, soaking the covalent cross-linked hydrogel metamaterial in the step 2 in a metal salt solution, and performing solvent replacement and metal coordination cross-linking.
And 4, carrying out water dialysis balancing on the covalent cross-linked and metal coordination cross-linked double-network hydrogel metamaterial structure in the step 3 to obtain the high-strength and high-toughness photo-cured 3D printing hydrogel metamaterial.
Further, the unsaturated monomer in the step 1 is one or two of acrylamide, hydroxyethyl acrylamide, dimethylacrylamide, N-isopropyl acrylamide, acryloylmorpholine, acrylic acid, vinylimidazole and N-vinylpyrrolidone; the mass percentage of the unsaturated monomer in the photosensitive 3D printing hydrogel ink is 30-60%.
Further, the aqueous photoinitiator in the step 1 is one of phenyl 2,4, 6-trimethyl benzoyl lithium phosphate, azo diisobutylamidine hydrochloride, phenyl bis 2,4, 6-trimethyl benzoyl sodium phosphate, phenyl bis 2,4, 6-trimethyl benzoyl lithium phosphate and polyethylene glycol/phenyl bis 2,4, 6-trimethyl benzoyl phosphine oxide; the mass percentage of the photoinitiator reagent and the unsaturated monomer is 0.1-1%.
Further, the cross-linking agent in the step 1 is one of N, N' -methylene bisacrylamide, polyethylene glycol dimethacrylate, zinc acrylate, zinc methacrylate and urea-based cross-linking agent containing double bonds; the mass percentage of the cross-linking agent and the unsaturated monomer is 0.2-2%.
Further, the light absorbent in the step 1 is one of lemon yellow, riboflavin, 2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonate; the mass percentage of the light absorber and the photosensitive 3D printing hydrogel ink is 2-6 per mill.
Further, in the step 1, the solvent is a mixed solvent of water and dimethyl sulfoxide; the mass ratio of water to dimethyl sulfoxide is (7-3) to (3-7).
Further, the light source wavelength of the photo-curing 3D printing in the step 2 is 385-405 nm; the intensity of the light source is 300-800 mW; the exposure time of the single layer is 5-60 s; the thickness of the single slice is 0.05-0.2 mm.
Further, in the step 3, the metal salt solution is one of zinc nitrate, zinc complex acid and zinc chloride; the concentration of the metal salt solution is 0.1-1.0 mol/L; the soaking time of the hydrogel metamaterial structure in the metal salt solution is 3-14 days; the time required for the equilibrium of the hydrogel metamaterial structure through water dialysis is 3-14 days.
The invention adopts another technical scheme as follows: a photocuring 3D printing hydrogel metamaterial obtained by the preparation method.
The invention adopts another technical scheme as follows: the application of the photo-curing 3D printing hydrogel metamaterial in the aspect of manufacturing a biological antibacterial stent is one or more than two of a heart stent, a vascular stent, a tracheal stent and an esophageal stent.
The invention has the beneficial effects that:
1. the photo-curing 3D printing hydrogel metamaterial prepared by the method has adjustable mechanical properties and an adjustable mechanical metamaterial structure;
2. the method provided by the invention can be used for preparing the hydrogel metamaterial structure with high mechanical strength, good biocompatibility, good flexibility and elasticity and designable structure.
3. The double-network structure hydrogel formed by the metal organic coordination structure not only improves the mechanical property of the hydrogel, but also endows the hydrogel with excellent antibacterial property. The hydrogel metamaterial has the advantages of high printing resolution, difficult swelling and the like, and is suitable for constructing a complex three-dimensional in-vivo biological stent with ultrahigh precision;
4. the advantage of photo-curing 3D printing is utilized, and personalized and rapid manufacturing of the hydrogel metamaterial biological antibacterial stent can be realized.
5. Compared with the traditional metal stent and the polymeric stent, the biological antibacterial stent prepared from the hydrogel metamaterial prepared by the method has excellent mechanical property and flexibility, can not cause the problems of restenosis, thrombosis, wall damage and the like of the wall of the tube when the tube wall with larger bending degree and longer area is in service, can not generate serious axial shortening phenomenon when the stent is expanded, and has very good application prospect.
Drawings
FIG. 1 is a schematic flow chart of the preparation of a photo-cured 3D printing hydrogel metamaterial according to the present invention;
FIG. 2 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 1;
FIG. 3 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 2;
FIG. 4 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 3;
FIG. 5 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 4;
FIG. 6 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 5;
FIG. 7 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 6;
FIG. 8 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 7;
FIG. 9 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in example 8;
FIG. 10 is a block diagram of a hydrogel metamaterial biological antibacterial stent in example 9;
FIG. 11 (a) is a graph showing the antibacterial property of the hydrogel metamaterial biological antibacterial scaffold in example 9 before an antibacterial test;
FIG. 11 (b) is a graph showing the antibacterial property of the hydrogel metamaterial biological antibacterial scaffold according to example 9 after antibacterial test;
FIG. 12 is a block diagram of a photo-cured 3D printed hydrogel metamaterial in comparative example 1;
FIG. 13 is a graph showing the mechanical properties of the photo-cured 3D printed hydrogel metamaterials of examples 1-4;
FIG. 14 is a graph showing the mechanical properties of the photo-cured 3D printed hydrogel metamaterials of examples 5-8.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
The preparation method of the photocuring 3D printing hydrogel metamaterial has the key steps that the printing performance of the hydrogel is regulated and controlled by using a mixed solvent, and the metal ion coordination and water balance post-treatment are the key steps for enhancing the mechanical properties, and the excellent antibacterial performance is endowed by using the metal ion coordination component.
The following describes in detail the preparation method of a photo-curable 3D printing hydrogel metamaterial provided by the invention through examples 1-9 and comparative examples.
Example 1
As shown in FIG. 1, the preparation method of the photo-curing 3D printing hydrogel metamaterial comprises the following steps:
step 1 photosensitive 3D printing hydrogel ink was prepared from 35.54g acrylamide, 9.41g vinylimidazole, 0.22g water-soluble photoinitiator LAP,0.34g urea-based crosslinker, and 0.06g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 7:3).
Step 3, soaking the covalent cross-linked hydrogel metamaterial in 0.1mol/L zinc nitrate solution for solvent replacement and metal coordination reaction for 7 days;
and 4, balancing the hydrogel metamaterial structure subjected to solvent replacement and metal coordination through slow water dialysis for 7 days to obtain the photo-curing 3D printing double-network hydrogel metamaterial.
Example 2
Step 1 photosensitive 3D printing hydrogel ink was prepared from 34.12g acrylamide, 11.29g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g urea-based crosslinker, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 7:3).
And 3, soaking the covalent cross-linked hydrogel metamaterial in a zinc nitrate solution with the concentration of 0.1mol/L for carrying out solvent replacement and metal coordination reaction for 10 days.
And 4, balancing the hydrogel metamaterial structure subjected to solvent replacement and metal coordination through slow water dialysis for 10 days to obtain the photo-curing 3D printing double-network hydrogel metamaterial.
Example 3
Step 1 photosensitive 3D printing hydrogel ink was prepared from 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g ureido crosslinker, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 7:3).
And 3, soaking the covalent cross-linked hydrogel metamaterial in a zinc nitrate solution with the concentration of 0.1mol/L for carrying out solvent replacement and metal coordination reaction for 5 days.
And 4, finally, carrying out slow water dialysis balancing on the hydrogel metamaterial structure subjected to solvent replacement and metal coordination for 5 days to obtain the photocuring 3D printing double-network hydrogel metamaterial.
Example 4
Step 1 photosensitive 3D printing hydrogel ink was prepared from 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g n, n-methylenebisacrylamide, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 6:4).
And 3, soaking the covalent cross-linked hydrogel metamaterial in a zinc nitrate solution with the concentration of 0.1mol/L for carrying out solvent replacement and metal coordination reaction for 5 days.
And 4, finally, carrying out slow water dialysis balancing on the hydrogel metamaterial structure subjected to solvent replacement and metal coordination for 5 days to obtain the photocuring 3D printing double-network hydrogel metamaterial.
Example 5
Step 1 photosensitive 3D printing hydrogel ink was prepared from 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g n, n-methylenebisacrylamide, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 5:5).
And 3, soaking the covalent cross-linked hydrogel metamaterial in a zinc nitrate solution with the concentration of 0.1mol/L for carrying out solvent replacement and metal coordination reaction for 10 days.
And 4, finally, balancing the hydrogel metamaterial structure subjected to solvent replacement and metal coordination through slow water dialysis for 10 days to obtain the photo-curing 3D printing double-network hydrogel metamaterial.
Example 6
Step 1, a photosensitive 3D printing hydrogel ink was prepared from 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g polyethylene glycol dimethacrylate, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 4:6).
And 3, soaking the covalent cross-linked hydrogel metamaterial in a zinc nitrate solution with the concentration of 0.1mol/L for carrying out solvent replacement and metal coordination reaction for 12 days.
And 4, finally, carrying out slow water dialysis balancing on the hydrogel metamaterial structure subjected to solvent replacement and metal coordination for 12 days to obtain the photocuring 3D printing double-network hydrogel metamaterial.
Example 7
Step 1 photosensitive 3D printing hydrogel ink was prepared from 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g ureido crosslinker, 0.006g lemon Huang Rongjie in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 3:7).
And 3, soaking the covalent cross-linked hydrogel metamaterial in 0.1mol/L zinc nitrate solution for solvent replacement and metal coordination reaction for 7 days.
And 4, finally, carrying out slow water dialysis balancing on the hydrogel metamaterial structure subjected to solvent replacement and metal coordination for 7 days to obtain the photocuring 3D printing double-network hydrogel metamaterial.
Example 8
Step 1 photosensitive 3D printing hydrogel ink was prepared by dissolving 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.34g ureido crosslinker, 0.006g riboflavin in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 7:3).
And 3, soaking the covalent cross-linked hydrogel metamaterial in 0.1mol/L zinc nitrate solution for solvent replacement and metal coordination reaction for 7 days.
And 4, finally, carrying out slow water dialysis balancing on the hydrogel metamaterial structure subjected to solvent replacement and metal coordination for 7 days to obtain the photocuring 3D printing double-network hydrogel metamaterial.
Example 9
Step 1 photosensitive 3D printing hydrogel ink was prepared by dissolving 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.57g ureido crosslinker, 0.006g sodium 2,2' -dihydroxy-4, 4' -dimethoxybenzophenone-5, 5' -disulfonate in a mixed solvent of 100mL water and dimethylsulfoxide (mass ratio 7:3).
And 3, soaking the covalent cross-linked hydrogel metamaterial in 0.1mol/L zinc nitrate solution for solvent replacement and metal coordination reaction for 7 days.
And 4, balancing the hydrogel metamaterial structure subjected to solvent replacement and metal coordination through slow water dialysis for 7 days to obtain the photo-curing 3D printing double-network hydrogel metamaterial.
Comparative example 1
Step 1 photosensitive 3D printing hydrogel ink was prepared by combining 32.69g acrylamide, 13.18g vinylimidazole, 0.23g water-soluble photoinitiator LAP,0.57g ureido crosslinker, 0.006g lemon Huang Rongjie in 100mL water.
Experimental results:
fig. 2 to 9 are photo-curing 3D printing double-network hydrogel metamaterial structure diagrams in examples 1 to 8, and it can be seen from fig. 2 to 9 that the hydrogel metamaterial structure has good shape fidelity.
FIG. 12 is a block diagram of a photo-cured 3D printed dual network hydrogel metamaterial according to comparative example 1, and as can be seen from FIG. 12, the hydrogel metamaterial structure has obvious adhesion and swelling.
Fig. 10 is a photo-cured 3D printed hydrogel metamaterial antimicrobial scaffold of example 9, and as can be seen from fig. 10, the hydrogel metamaterial antimicrobial scaffold has good shape fidelity.
Fig. 11 (a) and 11 (b) show the antibacterial performance of the photo-cured 3D printing hydrogel metamaterial biological antibacterial scaffold of example 9 against staphylococcus aureus (s. Aureus), after the hydrogel is immersed in the culture medium, the growth of staphylococcus aureus strains is inhibited after 24 hours of co-culture, and the hydrogel metamaterial biological antibacterial scaffold has good antibacterial performance against staphylococcus aureus in terms of the number of agar plates before and after culture.
FIG. 13 is a mechanical property test of the photo-cured 3D printing dual-network hydrogel metamaterials of examples 1-4, and the mechanical property test results show that when the strain of the photo-cured 3D printing dual-network hydrogel metamaterials is 863+ -14%, the tensile strength reaches 5.19+ -0.72 MPa, the elastic modulus is 2.11+ -0.01 MPa, and the toughness is 22.72+ -1.75 MJ/m 3 。
FIG. 14 is a mechanical property test of the photo-cured 3D printing dual-network hydrogel metamaterials of examples 5-8, and the mechanical property test results show that when the strain of the photo-cured 3D printing dual-network hydrogel metamaterials is 552+ -24%, the tensile strength reaches 1.85+ -0.23 MPa, the elastic modulus is 0.41+ -0.01 MPa, and the toughness is 3.63+ -0.41 MJ/m 3 。
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. The preparation method of the photo-curing 3D printing hydrogel metamaterial is characterized by comprising the following steps of:
step 1, dissolving an unsaturated monomer, a water-based photoinitiator, a crosslinking agent and a light absorber in a solvent to prepare photosensitive 3D printing hydrogel ink;
step 2, establishing a three-dimensional metamaterial structure model by using software, and placing the photosensitive 3D printing hydrogel ink in the step 1 into a trough for photo-curing 3D printing to obtain a covalent cross-linked hydrogel metamaterial structure;
step 3, soaking the covalently crosslinked hydrogel metamaterial in the step 2 in a metal salt solution, and performing solvent replacement and metal coordination crosslinking;
and 4, carrying out water dialysis balancing on the covalent cross-linked and metal coordination cross-linked double-network hydrogel metamaterial structure in the step 3 to obtain the high-strength and high-toughness photo-cured 3D printing hydrogel metamaterial.
2. The method for preparing the photocuring 3D printing hydrogel metamaterial according to claim 1, wherein the unsaturated monomer in the step 1 is one or two of acrylamide, hydroxyethyl acrylamide, dimethylacrylamide, N-isopropyl acrylamide, acryloylmorpholine, acrylic acid, vinylimidazole and N-vinylpyrrolidone; the mass ratio of unsaturated monomers in the photosensitive 3D printing hydrogel ink is 30-60%.
3. The method for preparing a photocurable 3D printing hydrogel metamaterial according to claim 1, wherein the aqueous photoinitiator in step 1 is one of phenyl 2,4, 6-trimethylbenzoyl lithium phosphate, azobisisobutylamidine hydrochloride, phenyl bis 2,4, 6-trimethylbenzoyl sodium phosphate, phenyl bis 2,4, 6-trimethylbenzoyl lithium phosphate, polyethylene glycol/phenyl bis 2,4, 6-trimethylbenzoyl phosphine oxide; the mass ratio of the photoinitiator reagent in the unsaturated monomer is 0.1-1%.
4. The method for preparing the photocuring 3D printing hydrogel metamaterial according to claim 1, wherein the cross-linking agent in the step 1 is one of N, N' -methylenebisacrylamide, polyethylene glycol dimethacrylate, zinc acrylate, zinc methacrylate and urea-based cross-linking agent containing double bonds; the mass ratio of the cross-linking agent in the unsaturated monomer is 0.2-2%.
5. The method for preparing a photo-cured 3D printing hydrogel metamaterial according to claim 1, wherein the light absorber in the step 1 is one of lemon yellow, riboflavin, sodium 2,2' -dihydroxy-4, 4' -dimethoxy benzophenone-5, 5' -disulfonate; the mass ratio of the light absorber in the photosensitive 3D printing hydrogel ink is 2-6 per mill.
6. The method for preparing the photo-curing 3D printing hydrogel metamaterial according to claim 1, wherein the solvent in the step 1 is a mixed solvent of water and dimethyl sulfoxide; the mass ratio of the water to the dimethyl sulfoxide is (7-3) and (3-7).
7. The method for preparing the photo-cured 3D printing hydrogel metamaterial according to claim 1, wherein the wavelength of the light source for the photo-cured 3D printing in the step 2 is 385-405 nm; the intensity of the light source is 300-800 mW; the exposure time of the single layer is 5-60 s; the thickness of the single slice is 0.05-0.2 mm.
8. The method for preparing the photocuring 3D printing hydrogel metamaterial according to claim 1, wherein the metal salt solution in the step 3 is one of zinc nitrate, zinc miscut and zinc chloride; the concentration of the metal salt solution is 0.1-1.0 mol/L; the soaking time of the hydrogel metamaterial structure in the metal salt solution is 3-14 days; the time required for the water dialysis balance of the hydrogel metamaterial structure is 3-14 days.
9. A photocurable 3D printing hydrogel metamaterial obtained by the method of any one of claims 1-8.
10. The use of the photo-cured 3D printing hydrogel metamaterial according to claim 9 for manufacturing a biological antibacterial stent, wherein the biological antibacterial stent is any one or more than two of a heart stent, a vascular stent, a tracheal stent and an esophageal stent.
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