CN113663128B - High-strength composite coating artificial ligament and preparation method and application thereof - Google Patents
High-strength composite coating artificial ligament and preparation method and application thereof Download PDFInfo
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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
- 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
- A61L27/58—Materials at least partially resorbable by the body
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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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
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
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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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
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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
- A61L2430/10—Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments
Abstract
The invention belongs to the technical field of artificial ligaments. The invention provides a high-strength composite coating artificial ligament, which comprises a composite coating and a shell-core structure artificial ligament; the composite coating comprises a calcium phosphate compound, polyurethane and an antibacterial agent; the shell-core structure artificial ligament comprises silk fibroin fibers and degradable fibers; the degradable fiber comprises one or more of polycaprolactone fiber, alginate fiber and polylactic acid fiber. The invention also provides a preparation method and application of the high-strength composite coating artificial ligament. The composite coating and the shell core structure effectively delay the degradation rate of the artificial ligament, improve the mechanical property of the artificial ligament, achieve the breaking strength of 60-80 MPa, and prolong the complete degradation time to 26 months. The composite coating artificial ligament has no cytotoxicity, no sensitization and irritation and excellent biocompatibility.
Description
Technical Field
The invention relates to the technical field of artificial ligaments, in particular to a high-strength composite coating artificial ligament and a preparation method and application thereof.
Background
An ideal artificial ligament product should have the following properties: excellent biocompatibility; adequate mechanical properties; good physical and chemical properties; high wear resistance; high corrosion resistance; sixthly, certain bone healing performance. The performance requires that the artificial ligament material and the degradation products thereof have good biocompatibility, have no toxic or side effect, are not corroded by tissue fluid after being implanted for a long time, keep stable physicochemical performance, and have certain bone induction performance to promote the healing of the tendon and bone; in terms of structure, the joint has good bending and torsion properties to facilitate joint movement, and has certain mechanical properties and elastic recovery properties to support daily motion requirements. In the artificial ligament product, the most widely used LARS artificial ligament is made of non-degradable materials, so that joint instability can be caused in the middle and later periods after implantation due to fatigue and relaxation of the materials, and meanwhile, the healing effect of the tendon and bone is poor, so that a bone tunnel is enlarged and even the artificial ligament slides out.
In the research of applying the degradable material to the artificial ligament, the degradation rate of the artificial synthetic material is often not perfectly matched with the healing rate of soft tissues implanted into a body, so that the artificial ligament is degraded and damaged too early to provide enough supporting strength in the healing middle period, and meanwhile, degradation products such as lactic acid generated by the degradation of the synthetic material are often easy to cause inflammatory reaction. The incompatibility of the degradation cycle and the regeneration cycle and the excessively fast decay of the mechanics of the material are major problems. The silk fibroin fiber material has good biocompatibility and mechanical property, and the degradation period is longer. However, the mechanical attenuation rate and the degradation rate of the artificial ligament made of 100% degradable fiber materials are still different from the ideal state.
Therefore, the artificial ligament with the composite coating is researched and developed to improve the mechanical property of the artificial ligament, regulate and control the degradation rate and have good biocompatibility, so that the ideal targets of excellent mechanical property, controllable degradation and in-situ regeneration of intermediate and long-term ligament tissues in the early stage of artificial ligament transplantation are realized, and the artificial ligament has very important social and economic benefits.
Disclosure of Invention
The invention aims to provide a high-strength composite coating artificial ligament aiming at the defects in the prior art, and aims to solve the problems of poor mechanical property, high degradation speed and poor biocompatibility of the artificial ligament in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-strength composite coating artificial ligament, which comprises a composite coating and a shell-core structure artificial ligament;
the composite coating comprises a calcium phosphate compound, polyurethane and an antibacterial agent;
the shell-core structure artificial ligament comprises silk fibroin fibers and degradable fibers;
the degradable fiber comprises one or more of polycaprolactone fiber, alginate fiber and polylactic acid fiber.
Preferably, the calcium phosphate compound comprises one or more of hydroxyapatite, tricalcium phosphate and bioactive glass; the antibacterial agent comprises one or more of silver-loaded zirconium phosphate, nano silver particles and silver-loaded hydroxyapatite.
Preferably, the particle size of the calcium phosphate compound and the particle size of the antibacterial agent are 10-60 nm independently.
Preferably, the mass ratio of the composite coating to the shell-core structure artificial ligament is 45-95: 100; in the composite coating, the mass ratio of the calcium phosphate compound to the polyurethane to the antibacterial agent is 20-35: 100: 5-8.
Preferably, in the artificial ligament with the shell-core structure, the mass ratio of the silk fibroin fibers to the degradable fibers is 65-75: 25-35.
The invention also provides a preparation method of the high-strength composite coating artificial ligament, which comprises the following steps:
1) mixing the calcium phosphate compound dispersion liquid, the antibacterial agent and the polyurethane solution to obtain a mixed solution;
2) and (3) coating the mixed solution on the artificial ligament with the shell-core structure, and then drying to obtain the artificial ligament with the high-strength composite coating.
Preferably, the solvent of the calcium phosphate compound dispersion liquid in the step 1) is polyvinylpyrrolidone, and the volume of the polyvinylpyrrolidone is based on the dispersed calcium phosphate compound; the solvent of the polyurethane solution is polyvinylpyrrolidone, and the mass fraction of polyurethane in the polyurethane solution is 6-10%.
Preferably, the coating times in the step 2) are 1-3 times; the drying temperature is 45-60 ℃, and the drying time is 90-110 min.
Preferably, when the number of times of coating is 2 or more, a drying treatment is performed after each coating.
The invention also provides application of the high-strength composite coating artificial ligament in preparation of knee joint transplantation products.
The beneficial effects of the invention include the following:
1) the composite coating and the shell core structure effectively delay the degradation rate of the artificial ligament, improve the mechanical property of the artificial ligament, have the breaking strength of 60-80 MPa, and can effectively regulate and control the mechanical property and the degradation property of the material.
2) The composite coating artificial ligament of the invention has no cytotoxicity, no sensitization and irritation, has excellent biocompatibility and is a good artificial ligament graft.
Detailed Description
The invention provides a high-strength composite coating artificial ligament, which comprises a composite coating and a shell-core structure artificial ligament;
the composite coating comprises a calcium phosphate compound, polyurethane and an antibacterial agent;
the shell-core structure artificial ligament comprises silk fibroin fibers and degradable fibers;
the degradable fiber comprises one or more of polycaprolactone fiber, alginate fiber and polylactic acid fiber.
The calcium phosphate compound preferably comprises one or more of hydroxyapatite, tricalcium phosphate and bioactive glass; when the calcium phosphate-based compound contains several components at the same time, the components are preferably mixed in an equal mass ratio.
The antibacterial agent preferably comprises one or more of silver-loaded zirconium phosphate, nano silver particles and silver-loaded hydroxyapatite; when the antibacterial agent contains several components at the same time, the components are preferably mixed in an equal mass ratio.
The particle size of the calcium phosphate compound and the particle size of the antibacterial agent are independent, preferably 10-60 nm, more preferably 20-50 nm, and even more preferably 30-40 nm.
The mass ratio of the composite coating to the shell-core structure artificial ligament is preferably 45-95: 100, more preferably 55-85: 100, and even more preferably 65-75: 100; in the composite coating, the mass ratio of the calcium phosphate compound to the polyurethane to the antibacterial agent is preferably 20-35: 100: 5-8, more preferably 25-30: 100: 6-7, and even more preferably 28-32: 100: 6.
In the shell-core structure artificial ligament, the mass ratio of the silk fibroin fibers to the degradable fibers is preferably 65-75: 25-35, more preferably 68-72: 28-32, and even more preferably 70: 30; when the degradable fiber contains several kinds of fibers at the same time, the fibers are preferably mixed in an equal mass ratio.
The shell-core structure artificial ligament is preferably prepared by a knitting machine; the number of the inner cores of the artificial ligament with the shell-core structure is preferably 2-4, the inner cores are preferably of a compact structure, the outer shell is preferably of a loose structure, and the number of yarns of each inner core is preferably the same as that of the yarns of the outer shell; in each inner core and the outer shell of the artificial ligament, the mass ratio of the silk fibroin fibers to the degradable fibers is preferably 65-75: 25-35, more preferably 68-72: 28-32, and more preferably 70:30 independently; the preparation method of the shell-core structure artificial ligament is a conventional method.
The artificial ligament with the shell-core structure has obvious and uniform holes on the surface, is suitable for subsequent coating, and has stable structure and better shape retention.
The invention also provides a preparation method of the high-strength composite coating artificial ligament, which comprises the following steps:
1) mixing the calcium phosphate compound dispersion liquid, the antibacterial agent and the polyurethane solution to obtain a mixed solution;
2) and (3) coating the mixed solution on the artificial ligament with the shell-core structure, and then drying to obtain the artificial ligament with the high-strength composite coating.
The solvent of the calcium phosphate compound dispersion liquid in the step 1) of the invention is preferably polyvinylpyrrolidone, and the volume of the polyvinylpyrrolidone is preferably based on the dispersed calcium phosphate compound; preferably, the calcium phosphate compound is subjected to ultrasonic oscillation treatment in polyvinylpyrrolidone to obtain a mixed solution; the time of the ultrasonic oscillation treatment is preferably 15-20 min, more preferably 17-19 min, and even more preferably 18 min.
The solvent of the polyurethane solution in the step 1) of the invention is preferably polyvinylpyrrolidone, and the mass fraction of polyurethane in the polyurethane solution is preferably 6-10%, more preferably 7-9%, and even more preferably 8%; the polyurethane is preferably stirred in polyvinylpyrrolidone to obtain a polyurethane solution, and the stirring speed is preferably 220-300 r/min, more preferably 240-280 r/min, and even more preferably 250-260 r/min.
The mixing mode in the step 1) of the invention is preferably that the calcium phosphate compound dispersion liquid is dripped into the mixed liquid of the antibacterial agent and the polyurethane solution; the dripping rate is preferably 0.15-0.20 mL/s, more preferably 0.16-0.18 mL/s, and even more preferably 0.17 mL/s; preferably, stirring treatment is carried out in the dripping process; the speed of the stirring treatment is preferably 220 to 300r/min, more preferably 240 to 280r/min, and even more preferably 250 to 260 r/min.
The number of coating times in the step 2) is preferably 1-3, and more preferably 2; the temperature of the drying treatment is preferably 45-60 ℃, more preferably 50-55 ℃, and more preferably 52-54 ℃; the drying time is preferably 90 to 110min, more preferably 95 to 105min, and still more preferably 100 min.
When the number of times of coating is more than or equal to 2, the invention preferably carries out drying treatment once after each coating.
The invention also provides application of the high-strength composite coating artificial ligament in preparation of knee joint transplantation products.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The artificial ligament is characterized in that silk fibroin fibers, polycaprolactone fibers and alginate fibers are used as raw materials to prepare the artificial ligament with the shell-core structure, wherein the artificial ligament comprises two inner cores and a shell, and the two inner cores and the shell respectively comprise 24 fiber yarns. In the two inner cores and the outer shell, the mass ratio of the silk fibroin fibers, the polycaprolactone fibers and the seaweed fibers is 66:20: 14.
100g of polyurethane is evenly stirred in polyvinylpyrrolidone at the speed of 240r/min to obtain a polyurethane solution with the mass fraction of the polyurethane being 7%. 6g of silver-loaded zirconium phosphate (particle size 15nm) was dissolved in the polyurethane solution to obtain an antibacterial agent-containing polyurethane solution. And (3) ultrasonically oscillating 20g of nano hydroxyapatite (the particle size is 20nm) in polyvinylpyrrolidone for 15min, wherein the dosage of the polyvinylpyrrolidone is based on the uniformly dispersed nano hydroxyapatite to obtain nano hydroxyapatite dispersion liquid. And (3) dropwise adding the nano hydroxyapatite dispersion into the polyurethane solution containing the antibacterial agent at the speed of 0.15mL/s, and fully and uniformly stirring at the speed of 240r/min in the dropwise adding process to obtain a mixed solution.
And (3) coating the mixed solution on the artificial ligament with the shell-core structure by using a brush, and drying at 46 ℃ for 110min to obtain the artificial ligament with the composite coating.
Example 2
The artificial ligament is characterized in that silk fibroin fibers, alginate fibers and polylactic acid fibers are used as raw materials to prepare the artificial ligament with the shell-core structure, wherein the artificial ligament comprises two inner cores and a shell, and the two inner cores and the shell respectively contain 24 fiber yarns. In the two inner cores and the outer shell, the mass ratio of the silk fibroin fibers, the seaweed fibers and the polylactic acid fibers is 75:12: 13.
100g of polyurethane is uniformly stirred in polyvinylpyrrolidone at the speed of 280r/min to obtain a polyurethane solution with the polyurethane mass fraction of 10%. 4g of nano-silver particles and 4g of silver-loaded hydroxyapatite (both having a particle size of 55nm) were dissolved in a polyurethane solution to obtain an antibacterial-agent-containing polyurethane solution. And (3) ultrasonically oscillating 17g of tricalcium phosphate and 17g of bioactive glass (the particle size is 60nm) in polyvinylpyrrolidone for 20min, wherein the dosage of the polyvinylpyrrolidone is based on uniformly dispersing the tricalcium phosphate and the bioactive glass to obtain the tricalcium phosphate and bioactive glass dispersion liquid. And (3) dropwise adding the dispersion into the polyurethane solution containing the antibacterial agent at the speed of 0.20mL/s, and fully and uniformly stirring at the speed of 280r/min in the dropwise adding process to obtain a mixed solution.
And coating the mixed solution on the artificial ligament with the shell-core structure by using a hairbrush, and drying at 60 ℃ for 90min to obtain the artificial ligament with the composite coating.
Example 3
The artificial ligament is characterized in that silk fibroin fibers, polycaprolactone fibers and polylactic acid fibers are used as raw materials to prepare the artificial ligament with the shell-core structure, wherein the artificial ligament comprises two inner cores and a shell, and the two inner cores and the shell respectively comprise 24 fiber yarns. In the two inner cores and the outer shell, the mass ratio of the silk fibroin fibers, the polycaprolactone fibers and the polylactic acid fibers is 70:15: 15.
100g of polyurethane is uniformly stirred in polyvinylpyrrolidone at a speed of 250r/min to obtain a polyurethane solution with the mass fraction of the polyurethane being 8%. 6g of nano silver particles (particle size 40nm) were dissolved in the polyurethane solution to obtain a polyurethane solution containing nano silver particles. And (3) ultrasonically oscillating 15g of hydroxyapatite and 15g of bioactive glass (the particle size is 40nm) in polyvinylpyrrolidone for 17min, wherein the dosage of the polyvinylpyrrolidone is based on uniformly dispersing the hydroxyapatite and the bioactive glass to obtain the hydroxyapatite and bioactive glass dispersion liquid. And (3) dropwise adding the dispersion into a polyurethane solution containing nano silver particles at the speed of 0.17mL/s, and fully and uniformly stirring at the speed of 250r/min in the dropwise adding process to obtain a mixed solution.
And coating the mixed solution on the artificial ligament with the shell-core structure by using a hairbrush, and drying at 52 ℃ for 100min to obtain the artificial ligament with the composite coating.
Example 4
The number of applications of the mixed solution was two, and drying treatment was performed after each application, and other conditions were the same as in example 3.
Example 5
The number of applications of the mixed solution was three, and drying treatment was performed after each application, and other conditions were the same as in example 3.
Comparative example 1
The mass ratio of the silk fibroin fibers, the polycaprolactone fibers and the polylactic acid fibers in example 5 is changed to be 70:15:15 to be 55:25:20, the mass of the polyurethane, the nano silver particles, the hydroxyapatite and the bioactive glass is respectively changed to be 90g, 10g, 25g and 20g, and other conditions are the same as those in example 5.
Comparative example 2
15g of hydroxyapatite and 15g of bioactive glass in the embodiment 5 are replaced by 10g of nano-silica and 15g of nano-montmorillonite, silk fibroin fibers are not added, the mass ratio of polycaprolactone fibers to polylactic acid fibers is changed to 50:50, the drying temperature is changed to 35 ℃, and other conditions are the same as those in the embodiment 5.
And (3) calculating the load rate of the composite coating:
the mass of the shell-core structure artificial ligament of the embodiments 1-5 and the mass of the prepared composite coating artificial ligament are respectively weighed, 6 samples are weighed for the shell-core structure artificial ligament and the high-strength composite coating artificial ligament of each embodiment, and the average value is calculated to obtain the uploading rate of the composite coating on the artificial ligament. The loading rates of the composite coatings of examples 1 to 5 were 45%, 47%, 50%, 74%, and 95%, respectively.
And (3) testing the mechanical property of the artificial ligament with the composite coating:
the composite-coated artificial ligaments of example 5 and comparative examples 1-2 were subjected to a uniaxial tensile test with reference to YY-T0965-2014, and the rupture strength of the artificial ligament was tested. The rupture strengths of the composite-coated artificial ligaments of example 5 and comparative examples 1 to 2 were 78MPa, 58MPa, and 52MPa, respectively. It can be seen that the change of the components and the proportion thereof of the invention can cause the reduction of the rupture strength of the artificial ligament.
The composite-coated artificial ligaments of examples 1 to 3 were subjected to a uniaxial tensile test with reference to YY-T0965-2014, and the breaking strength of the artificial ligament was tested. The fracture strengths of examples 1 to 3 were 59MPa, 58MPa, and 62MPa, respectively. From the fracture strength of the examples 1 to 3, it can be seen that the content of the calcium phosphate compound has an important influence on the fracture strength of the composite coating artificial ligament. When the content of the calcium phosphate compound is low, the fracture strength of the artificial ligament is remarkably improved along with the increase of the content of the calcium phosphate compound, and when the content of the calcium phosphate compound is too high (more than 30 wt%), an agglomeration phenomenon begins to occur, particularly after the content of the calcium phosphate compound exceeds 35 wt%, the agglomeration phenomenon is serious, the distribution is not uniform, and the fracture strength of the artificial ligament is reduced on the contrary.
And (3) testing the degradation performance of the composite coating artificial ligament:
the artificial ligaments with the composite coatings of examples 1-3 and 5, which are 5cm long, were implanted under the skin of rats, and the degradation conditions were observed periodically for 4 months, 8 months and 12 months.
The composite coating artificial ligament in the example 1 is degraded by 30 percent in 4 months, 48 percent in 8 months and 76 percent in 12 months, and the complete degradation time is 23 months.
The composite coating artificial ligament in the example 2 is degraded by 29 percent in 4 months, 47 percent in 8 months and 78 percent in 12 months, and the complete degradation time is 25 months.
The composite coating artificial ligament in the embodiment 3 is degraded by 27 percent in 4 months, 45 percent in 8 months and 73 percent in 12 months, and the complete degradation time is 26 months.
The composite-coated artificial ligament in the example 5 is degraded by 28 percent in 4 months, 47 percent in 8 months and 75 percent in 12 months, and the complete degradation time is 24 months.
Evaluation of biocompatibility of composite coated artificial ligament
The biocompatibility of the artificial ligaments with the composite coatings of the embodiments 1 to 5 is evaluated according to the GB/T16886 experimental method, and the results show that the artificial ligaments with the composite coatings of the embodiments 1 to 5 have no cytotoxicity, sensitization and irritation to osteoblasts and chondrocytes.
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 (9)
1. A high-strength composite coating artificial ligament is characterized by comprising a composite coating and a shell-core structure artificial ligament;
the composite coating comprises a calcium phosphate compound, polyurethane and an antibacterial agent;
the shell-core structure artificial ligament comprises silk fibroin fibers and degradable fibers;
the degradable fibers comprise alginate fibers and/or polylactic acid fibers;
in the artificial ligament with the shell-core structure, the mass ratio of the silk fibroin fibers to the degradable fibers is 65-75: 25-35.
2. The high strength composite coated artificial ligament of claim 1, wherein the calcium phosphate compound comprises one or more of hydroxyapatite, tricalcium phosphate and bioactive glass; the antibacterial agent comprises one or more of silver-loaded zirconium phosphate, nano silver particles and silver-loaded hydroxyapatite.
3. The high-strength composite coated artificial ligament according to claim 1 or 2, wherein the particle sizes of the calcium phosphate compound and the antibacterial agent are independently 10-60 nm.
4. The high-strength composite coating artificial ligament according to claim 3, wherein the mass ratio of the composite coating to the shell-core structure artificial ligament is 45-95: 100; in the composite coating, the mass ratio of the calcium phosphate compound to the polyurethane to the antibacterial agent is 20-35: 100: 5-8.
5. The method for preparing the artificial ligament with the high-strength composite coating of any one of claims 1 to 4, which is characterized by comprising the following steps:
1) mixing the calcium phosphate compound dispersion liquid, the antibacterial agent and the polyurethane solution to obtain a mixed solution;
2) and (3) coating the mixed solution on the artificial ligament with the shell-core structure, and then drying to obtain the artificial ligament with the high-strength composite coating.
6. The preparation method according to claim 5, wherein the solvent of the calcium phosphate compound dispersion liquid in step 1) is polyvinylpyrrolidone, and the volume of the polyvinylpyrrolidone is based on the volume of the dispersed calcium phosphate compound; the solvent of the polyurethane solution is polyvinylpyrrolidone, and the mass fraction of polyurethane in the polyurethane solution is 6-10%.
7. The method according to claim 5 or 6, wherein the number of the coating in the step 2) is 1 to 3; the drying temperature is 45-60 ℃, and the drying time is 90-110 min.
8. The method according to claim 7, wherein when the number of times of coating is 2 or more, a drying process is performed after each coating.
9. Use of the high strength composite coated artificial ligament according to any one of claims 1 to 4 in the preparation of knee joint transplantation products.
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