CN110624130A - High-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold and preparation method thereof - Google Patents
High-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold and preparation method thereof Download PDFInfo
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- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/10—Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
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Abstract
The invention discloses a preparation method of a high-elasticity water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold, which is characterized by preparing a spinning solution, wherein the components of the spinning solution comprise protein, epoxy compound and a dispersing agent, and further comprise a chain extender according to requirements; and (3) performing electrostatic spinning on the spinning solution to form a bracket, and then performing stable reinforcing post-treatment and end-sealing post-treatment on the bracket in sequence to obtain the high-elasticity water-stability protein-based/epoxy composite superfine fiber tissue engineering bracket. The support comprises micro-nano fibers and a pore structure formed by randomly stacking the micro-nano fibers, the porosity is 50-70%, and the average pore diameter is 1-5 microns. The invention endows the liquid phase of the protein superfine fiber with form stability, elasticity and elastic resilience, and effectively improves the mechanical property of the protein superfine fiber. The invention widens the application field of the protein-based material superfine fiber material, promotes the development of the composite functional tissue repair material, and can realize continuous production.
Description
Technical Field
The invention belongs to the field of biomedical textile materials and preparation, and particularly relates to a tissue engineering biomaterial and preparation thereof, in particular to a high-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold and a preparation method thereof.
Background
The electrostatic spinning technology can rapidly and stably prepare superfine fibers with the size ranging from tens of nanometers to several micrometers, and the raw materials are wide in selection range. The prepared superfine fiber system has ultrahigh specific surface area and porosity, the structure is similar to a three-dimensional (3D) fiber network in natural extracellular matrices (ECMs), the cell behaviors such as cell attachment, migration, proliferation, differentiation and the like can be promoted, and the superfine fiber system also has efficient drug adsorption and carrying functions. The interconnected pore structure in the structure is helpful for the transportation of oxygen, nutrient substances and cell metabolites. Therefore, the electrostatic spinning superfine fiber material is favored in the biomedical field.
The protein-based biomaterial has a macromolecular structure similar to natural protein components in ECMs, has good biocompatibility, is biodegradable, and can be metabolized. The protein has a complex multilevel structure, can adjust charge under different pH value environments, has hydrophilic and hydrophobic two-phase properties, shows wide adsorbability and can be used as a carrier of various materials. However, the hydrophilic property of protein materials makes the protein materials have low morphological stability in water phase, and the protein materials are easy to swell, shrink or even dissolve. The protein superfine fiber system prepared by electrostatic spinning has higher sensitivity in a water phase, and compared with the shapes of fibers in a shape of a body, a sheet, a sponge, a gel, a conventional scale and the like, the shape deformation degree of the superfine fiber structure bracket is higher, the shape stability of the superfine fiber structure bracket is difficult to maintain by conventional stability treatment, and the application of the superfine fiber structure bracket in the biomedical field is greatly limited.
Epoxy compounds have been reported to be used for fixation of biological valves, preparation of porous fibroin scaffold materials and the like, and are acceptable polarization and ring materials with biological modified charges. The epoxy compound is a compound containing single, double or multiple epoxy groups in the molecule, the epoxy group has extremely high reactivity due to the existence of oxygen ring tension in the epoxy group, and the epoxy compound can be combined with amino groups, carboxyl groups and the like in protein in a single-point, double-point or multi-point manner to generate chemical modification and crosslinking effects.
The existing patent, a protein cross-linking agent and a cross-linking method thereof (CN1524800), relates to the modification of a medicinal protein by an epoxy compound, and the chemical modification of heterologous protein can avoid causing antigen reaction in vivo, thereby effectively playing a therapeutic role. Compared with the pericardium fixed by glutaraldehyde, the yak pericardium treated by the Liuman and the like by Glycol Diglycidyl Ether (EGDE) has the advantages of more elastic trend of collagen fibers, increased tensile strength and elongation at break, small shedding degree of serosal layer and smoothness. In vivo implantation experiments show that the tearing degree is obviously lower, and the mechanical property is obviously better than that of glutaraldehyde modified pericardium (see Liuman, Leberen, Huangjia, Shiyikang, Chengfeng, Angel epoxy modified and scanning electron microscope morphology comparison of glutaraldehyde treated yak pericardium [ J ] biomedical engineering journal, 1996(03): 200-. Sung et al modified porcine thoracic arteries with EGDE to obtain a modified product having a strength of 393.8 + -61.5 g.mm-2. The modified collagen has improved denaturation temperature, enzyme degradation resistance and mechanical strength (see Sung H-W, Hsu C-S, Wang S-P, et al. degradation potential of biological tissue fixed with variations in properties: An in vitro study [ J ]. Journal of biological Materials Research,1997,35(2): 147-55.). The technology effectively improves the mechanical property of the protein material, but does not relate to the field of superfine fibers, and even does not relate to the form stability of the superfine fibers. Minsika et al found that at 60 ℃, the epoxy compound can undergo a crosslinking reaction with silk fibroin to form a three-dimensional network structure with higher stability (see Minsika, Tianli epoxy compound for the structural performance and cell compatibility research [ D ] of the fibroin porous scaffold material prepared by Minsika; Zhejiang university, 2006). However, the formed gel cross-linked structure is relatively stable, so that the epoxy compound reacted in cell culture is not easy to leach out, and the scaffold material presents certain toxicity.
In order to meet the higher water stability requirement of the protein superfine fiber and simultaneously give consideration to spinnability and biocompatibility, the invention introduces an epoxy compound system with high reaction activity into a protein system rich in active hydrogen groups, uses a dispersant system and a chain extender system in a matching way, and obtains the biocompatible superfine fiber scaffold with high elasticity and high water stability by an electrostatic spinning technology and a blocking technology.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation technology of a biocompatible protein superfine fiber scaffold with high elasticity and high water stability, overcomes the defects of low efficiency and high toxicity of the prior modification technology, and realizes the high elasticity, the water stability, the high mechanical property and the biocompatibility of the scaffold.
In order to solve the problems, the invention provides a preparation method of a high-elasticity water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold, which is characterized by comprising the following steps of:
step 1): preparing a spinning solution, wherein the components of the spinning solution comprise protein, epoxy compound and a dispersing agent, and a chain extender is further included according to the requirement;
step 2): and (3) performing electrostatic spinning on the spinning solution to form a bracket, and then performing stable reinforcing post-treatment and end-sealing post-treatment on the bracket in sequence to obtain the high-elasticity water-stability protein-based/epoxy composite superfine fiber tissue engineering bracket.
Preferably, the protein in the step 1) is any one or more of natural protein materials and synthetic protein materials, and the molecular weight of the protein is higher than 15 kDa; the epoxy compound is mutually soluble with protein in a solvent system; the mass ratio of the epoxy compound to the protein is (1-5) to 10; the addition amount of the dispersing agent is 0.5-5% of the mass of the protein; the addition amount of the chain extender is 0.5-5% of the mass of the protein.
More preferably, the protein is any one or more of zein, soybean protein, wheat protein, collagen, silk fibroin and gelatin; the epoxy compound is any one or more of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether; the dispersant is any one or more of diethanolamine, polyethylene glycol, polyvinylpyrrolidone and sodium dodecyl sulfate; the chain extender is any one or more of glycerol, 1, 6-hexanediol, trimethylolpropane and diethylene glycol.
Preferably, the preparation method in the step 1) adopts a direct mixing method, namely adding the protein, the epoxy compound, the dispersant and the chain extender into the solvent, stirring, shaking and standing for 24-48 h; wherein the total mass concentration of the protein and the epoxy compound in the system is 10-40%, and the addition amount of the dispersing agent and the chain extender is 0.5-5% of the mass of the protein.
Preferably, the electrostatic spinning process parameters in the step 2) are as follows: the electrostatic spinning voltage is 15-20 kV, the humidity is 20-50% RH, the temperature is 15-30 ℃, and the spacing distance between the fiber receiving device and the spinning device is kept 10-20 cm.
Preferably, the temperature of the stable strengthening post-treatment in the step 2) is 30-120 ℃, and the treatment time is 1-6 h.
Preferably, the blocking post-treatment in step 2) is a step of combining an unreacted epoxy group with a blocking agent to remove the reactivity, so as to improve the biocompatibility of the composite scaffold, wherein the blocking agent contains an active hydrogen group molecule, and specifically comprises: preparing an end capping agent into a coagulating bath with the concentration of 25-100 mg/mL, placing the stably enhanced bracket into the coagulating bath with the bath ratio of 1:40 and the pH value of 6.5-11, placing the coagulating bath into a constant-temperature water bath shaking table to oscillate at the speed of 100r/min, and treating for 1-4 h at the temperature of 20-75 ℃; and then, putting the bracket into distilled water for immersion washing for 1-3 times, and finally, freeze-drying the bracket.
More preferably, the end capping agent is any one or more of amino acids, polypeptides, proteins, monosaccharides, polysaccharides, glycoproteins, and steroids.
The invention also provides a high-elasticity water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold prepared by the preparation method, which is characterized by comprising the micro-nanofibers and a pore structure formed by randomly stacking the micro-nanofibers, wherein the porosity is 50-70%, and the average pore diameter is 1-5 microns.
Preferably, the wet elongation at break of the stent is 100-300%, the elastic recovery rate is 70-100%, and the shrinkage/swelling rate is lower than 2%.
The preparation method can be applied to a high-elastic water-stable protein-based/epoxy composite superfine fiber system.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, an epoxy system is introduced into a protein superfine fiber system, and the composite system combines the active hydrogen excitation reaction characteristic of epoxy and the structural characteristic that a protein-based material is rich in active hydrogen, so that a protein/epoxy composite three-dimensional network cross-linked structure is easily realized, and a protein superfine fiber structure with water stability and ultrahigh elastic resilience is constructed;
(2) the protein-based/epoxy composite superfine fiber system obtained by the invention has high water stability and mechanical properties. The obtained superfine fiber membrane has the wet-state elongation at break of 100-300%, the elastic recovery rate of 70-100%, and the shrinkage/swelling rate of only about 1-2%, which is about 1/3 of the citric acid crosslinking treatment with the best treatment effect in the prior art;
(3) the protein-based/epoxy composite superfine fiber tissue engineering scaffold obtained by the invention has good biocompatibility and can be biodegraded and absorbed; cell toxicity tests show that cells grow well in the scaffold, no toxic or side effect exists, and cell proliferation is about 1-2 times of that of citric acid crosslinking treatment with the best treatment effect;
(4) the post-treatment process related by the invention is simple and efficient;
(5) the tissue engineering scaffold prepared by the invention can be used for constructing artificial tissues such as joints, tendons, rotator cuff, cartilage and the like, and has the advantages of low cost, simple and convenient method, easy repetition and wider clinical application prospect.
Drawings
FIG. 1 is a flow chart of a preparation method provided by the present invention.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of a protein-based/epoxy composite superfine fiber tissue engineering scaffold comprises the following steps:
adding zein and ethylene glycol diglycidyl ether into 75% ethanol at a ratio of 10:3 while stirring, wherein the total mass concentration of the zein and the ethylene glycol diglycidyl ether is 30%. And adding polyvinylpyrrolidone into the spinning solution in a proportion of 5% of the mass of the zein, then stirring at 500rpm at room temperature for 30min until the zein is completely dissolved, and standing at room temperature for 24h to obtain a zein/ethylene glycol diglycidyl ether solution.
And placing the spinning solution in a solution cavity of a single-needle electrostatic spinning device, controlling the spinning environment at 25 ℃ and 40% RH, and controlling the fiber receiving device to be a roller type receiver at the rotating speed of 300 r/min. The distance from a spinning nozzle is 18cm, the solution injection speed is determined to be 3.0mL/h in the spinning process, and the voltage is kept at 15 kV. After the fibers are collected, the fibers are treated for 1h at 120 ℃ to form a stable three-dimensional network crosslinking structure. And then carrying out end capping treatment, immersing the superfine fiber membrane in an aqueous solution of lysine with the concentration of 50mg/mL, adjusting the pH value to 10 at a bath ratio of 1:40, and then placing the superfine fiber membrane in a water bath shaker at 60 ℃ and shaking the superfine fiber membrane for 1h at the speed of 100r/min to obtain the zein/ethylene glycol diglycidyl ether composite superfine fiber tissue engineering scaffold with the wet-state elongation at break of 260%, the elastic recovery of 100% and the swelling rate of 1.3%.
Cell experiments show that the composite superfine fiber tissue engineering scaffold has good adhesion, diffusion and proliferation effects on mouse fibroblast (L929) cells, and can be used for constructing artificial tissues such as joints, tendons, rotator cuff, cartilage and the like.
Example 2
A preparation method of a protein-based/epoxy composite superfine fiber tissue engineering scaffold comprises the following steps:
adding wheat protein and diethylene glycol diglycidyl ether into 75% acetic acid at a ratio of 10:3 while stirring, wherein the total mass concentration of the wheat protein and the diethylene glycol diglycidyl ether is 20%. Adding sodium dodecyl sulfate and trimethylolpropane into the spinning solution according to the proportion of 5 percent and 1 percent of the mass of the wheat protein respectively, then stirring for 30min at the room temperature of 500rpm until the wheat protein is completely dissolved, and standing for 24h at the room temperature to obtain the wheat protein/diglycidylether solution.
And placing the spinning solution in a solution cavity of a single-needle electrostatic spinning device, controlling the spinning environment at 25 ℃ and 50% RH, wherein the fiber receiving device is a roller type receiver and the rotating speed is 300 r/min. The distance from a spinning nozzle is 16cm, the solution injection speed is determined to be 3.0mL/h in the spinning process, and the voltage is kept at 15 kV. After the fibers are collected, the fibers are treated for 2 hours at 90 ℃ to form a stable three-dimensional network crosslinking structure. And then carrying out end capping treatment, immersing the superfine fiber membrane in a glucose aqueous solution with the concentration of 75mg/mL, adjusting the pH value to 8.5 at a bath ratio of 1:40, and then placing the superfine fiber membrane in a water bath shaking table at 60 ℃ and shaking the superfine fiber membrane for 1h at the speed of 100r/min to obtain the wheat protein/diethylene glycol diglycidyl ether composite superfine fiber tissue engineering scaffold with the wet-state elongation at break of 200%, the elastic recovery of 80% and the swelling rate of 1.6%.
Cell experiments show that the composite superfine fiber tissue engineering scaffold has good adhesion, diffusion and proliferation effects on mouse fibroblast (L929) cells, and can be used for constructing artificial tissues such as joints, tendons, rotator cuff, cartilage and the like.
Example 3
A preparation method of a protein-based/epoxy composite superfine fiber tissue engineering scaffold comprises the following steps:
adding collagen and 1, 4-butanediol diglycidyl ether into 75% ethanol at a ratio of 10:2 under stirring, wherein the total mass concentration of the collagen and the 1, 4-butanediol diglycidyl ether is 25%. And adding polyvinylpyrrolidone and glycerol into the spinning solution in a ratio of 5% and 1% of the mass of the collagen respectively, stirring at 500rpm at room temperature for 30min until the collagen is completely dissolved, and standing at room temperature for 32h to obtain a collagen/1, 4-butanediol diglycidyl ether solution.
And placing the spinning solution in a solution cavity of a single-needle electrostatic spinning device, controlling the spinning environment at 25 ℃ and 50% RH, wherein the fiber receiving device is a roller type receiver and the rotating speed is 300 r/min. The distance from a spinning nozzle is 16cm, the solution injection speed is determined to be 3.0mL/h in the spinning process, and the voltage is kept at 16 kV. After the fibers are collected, the fibers are treated for 6 hours at the temperature of 30 ℃ to form a stable three-dimensional network crosslinking structure. And then carrying out end capping treatment, immersing the superfine fiber membrane in water-soluble vitamin C with the concentration of 75mg/mL, adjusting the pH value to 6.5 at the bath ratio of 1:40, and then placing the superfine fiber membrane in a water bath shaker at 37 ℃ and shaking the superfine fiber membrane for 2 hours at the speed of 100r/min to obtain the collagen/1, 4-butanediol diglycidyl ether composite superfine fiber tissue engineering scaffold with the wet-state elongation at break of 150%, the elastic recovery of 100% and the shrinkage of 1.2%.
Cell experiments show that the composite superfine fiber tissue engineering scaffold has good adhesion, diffusion and proliferation effects on mouse fibroblast (L929) cells, and can be used for constructing artificial tissues such as joints, tendons, rotator cuff, cartilage and the like.
Claims (10)
1. A preparation method of a high-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold is characterized by comprising the following steps:
step 1): preparing a spinning solution, wherein the components of the spinning solution comprise protein, epoxy compound and a dispersing agent, and a chain extender is further included according to the requirement;
step 2): and (3) performing electrostatic spinning on the spinning solution to form a bracket, and then performing stable reinforcing post-treatment and end-sealing post-treatment on the bracket in sequence to obtain the high-elasticity water-stability protein-based/epoxy composite superfine fiber tissue engineering bracket.
2. The preparation method according to claim 1, wherein the protein in step 1) is any one or more of natural protein material and synthetic protein material, and the molecular weight is higher than 15 kDa; the epoxy compound is mutually soluble with protein in a solvent system; the mass ratio of the epoxy compound to the protein is (1-5) to 10; the addition amount of the dispersing agent is 0.5-5% of the mass of the protein; the addition amount of the chain extender is 0.5-5% of the mass of the protein.
3. The preparation method according to claim 2, wherein the protein is any one or more of zein, soybean protein, wheat protein, collagen, silk fibroin and gelatin; the epoxy compound is any one or more of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether; the dispersant is any one or more of diethanolamine, polyethylene glycol, polyvinylpyrrolidone and sodium dodecyl sulfate; the chain extender is any one or more of glycerol, 1, 6-hexanediol, trimethylolpropane and diethylene glycol.
4. The preparation method of claim 1, wherein the preparation method in step 1) adopts a direct mixing method, that is, adding the protein, the epoxy compound, the dispersant and the chain extender into the solvent, stirring and shaking the mixture, and then standing the mixture for 24 to 48 hours; wherein the total mass concentration of the protein and the epoxy compound in the system is 10-40%, and the addition amount of the dispersing agent and the chain extender is 0.5-5% of the mass of the protein.
5. The preparation method of claim 1, wherein the electrostatic spinning in the step 2) has the following process parameters: the electrostatic spinning voltage is 15-20 kV, the humidity is 20-50% RH, the temperature is 15-30 ℃, and the spacing distance between the fiber receiving device and the spinning device is kept 10-20 cm.
6. The preparation method according to claim 1, wherein the temperature of the stabilization enhancing post-treatment in the step 2) is 30 to 120 ℃ and the treatment time is 1 to 6 hours.
7. The preparation method of claim 1, wherein the blocking post-treatment in step 2) is a step of combining an unreacted epoxy group with a blocking agent to remove the reactivity so as to improve the biocompatibility of the composite scaffold, wherein the blocking agent contains active hydrogen group molecules, and specifically comprises: preparing an end-capping agent into a coagulating bath with the concentration of 25-100 mg/mL, and placing the stably enhanced stent into the coagulating bath with the bath ratio of 1:40, the pH value is 6.5-11, the coagulating bath is put into a constant-temperature water bath shaking table to oscillate at the speed of 100r/min, and the coagulation bath is treated for 1-4 h at the temperature of 20-75 ℃; and then, putting the bracket into distilled water for immersion washing for 1-3 times, and finally, freeze-drying the bracket.
8. The method of claim 7, wherein the capping agent is any one or more of amino acids, polypeptides, proteins, monosaccharides, polysaccharides, glycoproteins, and steroids.
9. The high-elasticity water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising micro-nanofibers and a pore structure formed by randomly stacking the micro-nanofibers, wherein the porosity is 50-70%, and the average pore diameter is 1-5 μm.
10. The high elastic water-stable protein-based/epoxy composite ultrafine fibrous tissue engineering scaffold according to claim 9, wherein the scaffold has a wet elongation at break of 100 to 300%, an elastic recovery of 70 to 100%, and a shrinkage/swelling ratio of less than 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910870205.8A CN110624130B (en) | 2019-09-16 | 2019-09-16 | High-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910870205.8A CN110624130B (en) | 2019-09-16 | 2019-09-16 | High-elastic water-stable protein-based/epoxy composite superfine fiber tissue engineering scaffold and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN1518612A (en) * | 2001-04-02 | 2004-08-04 | ϣ | Silk-based fibre |
| CN103835023A (en) * | 2014-03-25 | 2014-06-04 | 新乡化纤股份有限公司 | Methanol protein modified regenerated cellulose fiber and production process thereof |
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