Artificial ligament with development function and preparation method thereof

Abstract

The present application relates to the field of biomedicine technology, and specifically discloses an artificial ligament with a developing function and a preparation method thereof. The artificial yarn with a developing function is composed of a support structure woven by yarn and a coating on the surface of the support structure; the yarn is a core-spun yarn structure, with modified PET fiber as the core yarn and composite fiber as the outer covering yarn; the coating is made from a coating liquid; the above scheme is simple, and the obtained artificial ligament has a developing function and its degradation is controllable; the preparation method of the artificial yarn with a developing function is to first weave the yarn into a supporting structure, then add the coating liquid to the supporting structure, take it out, dry it, and form a coating on the surface of the supporting structure to obtain an artificial ligament with a developing function. The above preparation method is simple, and the obtained artificial ligament can better meet the needs of doctors and patients.

Description

Technical Field

[0001] The present application relates to the field of biomedicine technology, and more specifically, to an artificial ligament with a developing function and a preparation method thereof. Background Art

[0002] With the rapid development of economy and technology, people are increasingly paying attention to exercise. However, if you do not pay attention to protection during exercise, it is easy to cause damage to parts of the body. In particular, anterior cruciate ligament (ACL) rupture is a serious surgical injury. Ligament rupture or poor repair often causes joint instability, further causing articular cartilage damage and leading to osteoarthritis, which seriously affects the patient's daily quality of life. In current cruciate ligament reconstruction treatment, artificial ligaments are increasingly used.

[0003] Artificial ligaments are mainly divided into two categories: one is a permanent artificial ligament made of polymer materials. This type of ligament has mechanical properties similar to those of the human body and can meet the needs of daily life while providing recovery. However, the recovery period of this type of ligament is long and it is easy to cause inflammation after implantation. The other type is based on the former, replacing part of the polymer material with absorbable material woven into the ligament. This type of ligament recovers more quickly after implantation, but in actual use, the degradation rate of the absorbable material is often not perfectly matched with the healing rate of the soft tissue implanted in the body; and the specific situation of artificial ligament degradation cannot be detected, which cannot better meet the needs of doctors and patients, greatly limiting the wider use of artificial ligaments in the medical field.

[0004] Therefore, in order to solve the problem that the degradation rate of existing artificial ligaments does not match the ligament regeneration rate and the degradation of artificial ligaments cannot be detected, it is urgent to propose an artificial ligament with development function and its preparation method, so that the artificial ligament has both development and controllable degradation functions and can be better used in the medical field. Summary of the Invention

[0005] In order to solve the problem that the degradation rate of existing artificial ligaments does not match the ligament regeneration rate and the degradation of artificial ligaments cannot be detected, the present application provides an artificial ligament with a development function and a preparation method thereof.

[0006] In a first aspect, the present application provides an artificial ligament with a developing function, which adopts the following technical solution: an artificial ligament with a developing function, comprising a yarn-woven support structure and a coating on the surface of the support structure;

[0007] The yarn is a core-spun yarn structure, with modified PET fiber as the core yarn and composite fiber as the outer covering yarn;

[0008] The composite fiber comprises the following raw materials in parts by weight: 60-80 parts of polylactic acid, 30-40 parts of gamma-polyglutamic acid, 4-8 parts of sodium alginate, 6-10 parts of mesoporous nano-hydroxyapatite, and 1-5 parts of sodium isoglossate.

[0009] By adopting the above technical solution, the artificial ligament of the present application is composed of a support structure woven from yarn and a coating on the surface of the support structure. The yarn is a core-spun yarn structure, which is conducive to the degradation of the yarn. The yarn uses modified PET fiber as the core yarn and composite fiber as the outer covering yarn. The modified PET fiber has excellent mechanical properties and good biocompatibility. The composite fiber can achieve the purpose of controllable degradation through the mass ratio of polylactic acid and γ-polyglutamic acid, which is conducive to the recovery of the damaged area. At the same time, it has a developing function and can monitor the degradation of the artificial ligament at any time. The artificial ligament of the present application not only has a developing function, but also has a controllable degradation function, which is more conducive to the healing of ligament wounds.

[0010] Preferably, the modified PET fiber is prepared by the following method:

[0011] Step 1: Take PET fibers with a diameter of 10-50 μm, first treat the PET fibers with plasma, and then soak them in a 10-20 wt% sodium gluconate solution for a period of time to obtain pretreated PET fibers;

[0012] Step 2: First, chitosan, nano-hydroxyapatite and citric acid are added to water, and dissolved at 60-80°C and a rotation speed of 600-800 r / min for 10-20 minutes. Then, the pretreated PET fiber obtained in step 1 is added, and the same temperature and rotation speed are maintained. The mixture is fully reacted for 1-2 hours to obtain modified PET fiber.

[0013] Preferably, the modified PET fiber comprises the following raw materials in parts by weight: 30-50 parts of PET fiber, 60-80 parts of sodium gluconate solution, 6-10 parts of chitosan, 2-4 parts of nano-hydroxyapatite, 10-15 parts of citric acid, and 100-200 parts of water.

[0014] By adopting the above-mentioned technical solution, the present application first uses plasma to treat the PET fiber, so that active groups appear on the surface of the PET fiber, and then uses sodium gluconate to treat it, so that a large number of amino groups and hydroxyl groups appear on the surface of the pretreated PET, which can well connect chitosan and nano-hydroxyapatite, so that the modified PET fiber can maintain excellent mechanical properties while also having significant biocompatibility and bone bonding ability; in addition, the present application controls various process parameters, so that the comprehensive performance of the modified PET fiber of the present application is even better.

[0015] Preferably, the composite fiber is prepared by the following method:

[0016] Polylactic acid, gamma-polyglutamic acid, sodium alginate, mesoporous nano-hydroxyapatite and sodium isoglossate are fully mixed at a rotation speed of 1000-1500 r / min for 6-10 minutes to obtain a mixture; after twin-screw extrusion, the mixture is melt-spun at 170-190° C. to obtain composite fibers with a diameter of 10-50 μm.

[0017] By adopting the above-mentioned technical scheme, the present application uses polylactic acid and γ-polyglutamic acid as the main materials of the composite fiber, controls the mass ratio of the two, and can control the degradation rate of the composite fiber. At the same time, mesoporous nanohydroxyapatite is added, which can be beneficial to the growth of bone cells on the one hand, and on the other hand, the mesoporous structure can effectively regulate the degradation rate of the composite fiber; sodium alginate has good biocompatibility and degradability, and contains a large number of hydroxyl and carboxyl groups in its structure, which can combine with calcium ions; therefore, sodium alginate and mesoporous nanohydroxyapatite can work synergistically to effectively promote bone formation; at the same time, the developer sodium isoglossate is added to give the prepared composite fiber the functions of development and controllable degradation.

[0018] Preferably, the yarn is made by the following method:

[0019] 16-20 composite fibers are twisted together to form outer covering yarn, and 20-30 modified PET fibers are twisted together to form core yarn; compact sirofil spinning technology is used to control the drafting ratio of the core yarn to 2.5-3.5 times to obtain yarn.

[0020] Preferably, the twist of the composite fiber is 300-500 twists / m, and the twist of the modified PET fiber is 450-700 twists / m.

[0021] By adopting the above technical solution, the present application controls various process parameters during the preparation of the yarn, so that the yarn has excellent mechanical properties, good biocompatibility, and controllable degradation.

[0022] Preferably, the coating liquid comprises the following raw materials in parts by weight: 40-60 parts of silk fibroin, 10-20 parts of hyaluronic acid, 1-2 parts of silver acetate, 2-6 parts of strontium chloride, 6-10 parts of mesoporous nano-β-tricalcium phosphate, and 80-120 parts of water.

[0023] Preferably, the coating liquid is prepared by the following method:

[0024] First, silver acetate, silk fibroin and hyaluronic acid are added into water, the pH value is adjusted to 7.5-8.5, and then strontium chloride and mesoporous nano-β-tricalcium phosphate are added and stirred evenly to obtain a coating liquid.

[0025] By adopting the above-mentioned technical scheme, the coating liquid of the present application contains silk fibroin, hyaluronic acid, silver acetate, strontium chloride, and mesoporous nano-β-tricalcium phosphate. Silk fibroin has a good promoting effect on cell adhesion, proliferation and migration, and is more conducive to the rapid growth of host cells over the ligament, thereby achieving rapid regeneration; hyaluronic acid can cooperate with silk fibroin to promote the degradation of the coating; silver acetate has antibacterial and anti-inflammatory effects and development functions, and strontium can significantly promote the growth and replication of osteoblasts, stimulate new bone formation, and inhibit osteoclast activity, reducing the resorption of newly formed bone; the coating formed by the coating liquid of the present application can provide a good environment for cell growth, and has the effect of degradation and slow release, which is more conducive to wound healing in the ligament area.

[0026] In a second aspect, a method for preparing an artificial ligament with a developing function is provided, which adopts the following technical solution:

[0027] A method for preparing an artificial ligament with a developing function comprises the following steps:

[0028] First, the yarn is woven into a support structure, and then the support structure is added with the coating liquid, taken out, and dried to form a coating on the surface of the support structure to obtain an artificial ligament with a developing function.

[0029] Preferably, the method for preparing the artificial ligament with development function comprises the following specific steps:

[0030] S1. Weaving the yarn into a tubular textile fabric and placing it in a mold. Heat-setting the entire mold at 66-75° C. for 30-60 minutes is performed, and then the mold is removed to obtain a support structure.

[0031] S2. First, add the support structure obtained in step S1 to the coating liquid with a mass ratio of the support structure to the coating liquid of 1:10-20. After fully stirring for 10-30 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 30-40wt% for 5-10 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with a developing function.

[0032] By adopting the above-mentioned technology, the artificial ligament of the present application is composed of a yarn woven support structure and a coating on the surface of the support structure, and various process parameters are controlled so that the artificial ligament of the present application has excellent mechanical properties, controllable degradation, and good development function, and can monitor the degradation of the artificial ligament at any time. The preparation method of the artificial ligament with development function of the present application is simple to operate, mild conditions, and environmentally friendly, and can be widely used in the medical field.

[0033] In summary, this application has the following beneficial effects:

[0034] 1. The artificial ligament of the present application is composed of a support structure woven from yarns and a coating on the surface of the support structure; the yarn is a core-spun yarn structure, with modified PET fiber as the core yarn and composite fiber as the outer covering yarn; the composite fiber is made of polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nano-hydroxyapatite, and sodium isodiatrizoate as raw materials; the coating contains silk fibroin, hyaluronic acid, silver acetate, strontium chloride, and mesoporous nano-β-tricalcium phosphate; this makes the artificial ligament of the present application have good development function and controllable degradation function, as well as significant biocompatibility and bone bonding ability.

[0035] 2. The preparation method of the artificial ligament of the present application has simple steps and mild conditions, so that the artificial ligament prepared has excellent mechanical properties, controllable degradation, and good development function. It can monitor the degradation of the artificial ligament at any time, facilitates the understanding of the tendon-bone healing condition, and has broad application prospects. DETAILED DESCRIPTION

[0036] The present application is further described in detail below with reference to the embodiments.

[0037] Preparation Examples 1-5 and Comparative Preparation Examples 1 and 2 provide modified PET fibers and preparation methods thereof.

[0038] Preparation Example 1

[0039] Modified PET fiber, including the following raw materials: 300g PET fiber, 600g sodium gluconate solution, 60g chitosan, 20g nanohydroxyapatite, 100g citric acid, 1000g water;

[0040] Modified PET fiber is prepared by the following method:

[0041] Step 1: Take a PET fiber with a diameter of 10 μm, first treat the surface of the PET fiber with Ar plasma under the conditions of a background vacuum of 0.05 Pa and a power of 200 W for 8 minutes, then add it to a 10wt% sodium gluconate solution and soak it at 40°C for 60 minutes to obtain a pretreated PET fiber;

[0042] Step 2: First, chitosan, nano-hydroxyapatite and citric acid were added into water, dissolved at 60°C and 600 r / min for 20 min, and then the pretreated PET fiber obtained in step 1 was added, and the same temperature and rotation speed were maintained, and the reaction was fully carried out for 1 h to obtain modified PET fiber.

[0043] Preparation Example 2

[0044] Modified PET fiber, including the following raw materials: 350g PET fiber, 650g sodium gluconate solution, 70g chitosan, 25g nanohydroxyapatite, 110g citric acid, 1200g water;

[0045] Modified PET fiber is prepared by the following method:

[0046] Step 1: PET fiber with a diameter of 20 μm was first treated with Ar plasma for 10 minutes under the conditions of a background vacuum of 0.06 Pa and a power of 250 W. The surface of the PET fiber was then added to a 12 wt% sodium gluconate solution and soaked at 45° C. for 55 minutes to obtain pretreated PET fiber.

[0047] Step 2: First, chitosan, nano-hydroxyapatite and citric acid were added to water, dissolved at 65°C and a speed of 650 r / min for 18 minutes, and then the pretreated PET fiber obtained in step 1 was added, and the same temperature and speed were maintained. The reaction was fully reacted for 1.2 hours to obtain modified PET fiber.

[0048] Preparation Example 3

[0049] Modified PET fiber, including the following raw materials: 400g PET fiber, 700g sodium gluconate solution, 80g chitosan, 30g nanohydroxyapatite, 130g citric acid, 1500g water;

[0050] Modified PET fiber is prepared by the following method:

[0051] Step 1: PET fiber with a diameter of 30 μm was first treated with Ar plasma for 15 minutes under the conditions of a background vacuum of 0.07 Pa and a power of 300 W. The surface of the PET fiber was then added to a 15 wt% sodium gluconate solution and soaked at 50° C. for 40 minutes to obtain pretreated PET fiber.

[0052] Step 2: First, chitosan, nano-hydroxyapatite and citric acid were added to water, dissolved at 70°C and 700 r / min for 15 minutes, and then the pretreated PET fiber obtained in step 1 was added, and the same temperature and rotation speed were maintained, and the reaction was fully reacted for 1.5 hours to obtain modified PET fiber.

[0053] Preparation Example 4

[0054] Modified PET fiber, including the following raw materials: 450g PET fiber, 750g sodium gluconate solution, 90g chitosan, 35g nanohydroxyapatite, 140g citric acid, 1800g water;

[0055] Modified PET fiber is prepared by the following method:

[0056] Step 1: PET fiber with a diameter of 40 μm was first treated with Ar plasma for 18 minutes under the conditions of a background vacuum of 0.07 Pa and a power of 350 W. The surface of the PET fiber was then added to a sodium gluconate solution with a concentration of 18 wt% and immersed at 55° C. for 35 minutes to obtain a pretreated PET fiber.

[0057] Step 2: First, chitosan, nano-hydroxyapatite and citric acid were added to water, dissolved at 75°C and a speed of 750 r / min for 12 minutes, and then the pretreated PET fiber obtained in step 1 was added, and the same temperature and speed were maintained. The reaction was fully reacted for 1.8 hours to obtain modified PET fiber.

[0058] Preparation Example 5

[0059] Modified PET fiber, including the following raw materials: 500g PET fiber, 800g sodium gluconate solution, 100g chitosan, 40g nanohydroxyapatite, 150g citric acid, 2000g water;

[0060] Modified PET fiber is prepared by the following method:

[0061] Step 1: Take a PET fiber with a diameter of 50 μm, first treat the surface of the PET fiber with Ar plasma under the conditions of a background vacuum of 0.08 Pa and a power of 400 W for 20 minutes, then add it to a 20wt% sodium gluconate solution and soak it at 60°C for 30 minutes to obtain a pretreated PET fiber;

[0062] Step 2: First, chitosan, nano-hydroxyapatite and citric acid were added to water, dissolved at 80°C and 800 r / min for 10 min, and then the pretreated PET fiber obtained in step 1 was added, and the same temperature and rotation speed were maintained, and the reaction was fully carried out for 2 h to obtain modified PET fiber.

[0063] Comparative Preparation Example 1

[0064] Comparative Preparation Example 1 is the same as Preparation Example 1, except that the PET fiber is not subjected to the pretreatment operation of step 1, and step 2 is directly performed.

[0065] Comparative Preparation Example 2

[0066] Comparative Preparation Example 2 is the same as Preparation Example 1, except that nano-hydroxyapatite is not added in step 2.

[0067] Preparation Examples 6-10 and Comparative Preparations 3-7 provide composite fibers and preparation methods thereof.

[0068] Preparation Example 6

[0069] The composite fiber comprises the following raw materials: 600g of polylactic acid, 300g of gamma-polyglutamic acid, 40g of sodium alginate, 60g of mesoporous nano-hydroxyapatite, and 10g of sodium isoglossate.

[0070] Composite fibers, prepared by the following method:

[0071] Polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nanohydroxyapatite and sodium isoglossate were fully mixed at a rotation speed of 1000 r / min for 10 minutes to obtain a mixture; after twin-screw extrusion, the mixture was melt-spun at 170°C at a spinning speed of 1300 m / min to obtain a composite fiber with a diameter of 10 μm.

[0072] Preparation Example 7

[0073] The composite fiber comprises the following raw materials: 650g of polylactic acid, 350g of gamma-polyglutamic acid, 50g of sodium alginate, 70g of mesoporous nano-hydroxyapatite, and 20g of sodium isoglossate.

[0074] Composite fibers, prepared by the following method:

[0075] Polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nanohydroxyapatite and sodium isoglossate were fully mixed at a rotation speed of 1100 r / min for 7 minutes to obtain a mixture; after twin-screw extrusion, the mixture was melt-spun at 175°C at a spinning speed of 1320 m / min to obtain a composite fiber with a diameter of 20 μm.

[0076] Preparation Example 8

[0077] The composite fiber comprises the following raw materials: 700g of polylactic acid, 380g of gamma-polyglutamic acid, 60g of sodium alginate, 80g of mesoporous nano-hydroxyapatite, and 40g of sodium isoglossate.

[0078] Composite fibers, prepared by the following method:

[0079] Polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nanohydroxyapatite and sodium isoglossate were fully mixed at a rotation speed of 1300 r / min for 8 minutes to obtain a mixture; after twin-screw extrusion, the mixture was melt-spun at 180°C at a spinning speed of 1350 m / min to obtain a composite fiber with a diameter of 30 μm.

[0080] Preparation Example 9

[0081] The composite fiber comprises the following raw materials: 750g of polylactic acid, 380g of gamma-polyglutamic acid, 70g of sodium alginate, 90g of mesoporous nano-hydroxyapatite, and 50g of sodium isoglossate.

[0082] Composite fibers, prepared by the following method:

[0083] Polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nanohydroxyapatite and sodium isoglossate were fully mixed at a rotation speed of 1400 r / min for 6 minutes to obtain a mixture; after twin-screw extrusion, the mixture was melt-spun at 185°C at a spinning speed of 1380 m / min to obtain a composite fiber with a diameter of 40 μm.

[0084] Preparation Example 10

[0085] The composite fiber comprises the following raw materials: 800g of polylactic acid, 400g of gamma-polyglutamic acid, 80g of sodium alginate, 100g of mesoporous nano-hydroxyapatite, and 50g of sodium isoglossate.

[0086] Composite fibers, prepared by the following method:

[0087] Polylactic acid, γ-polyglutamic acid, sodium alginate, mesoporous nanohydroxyapatite and sodium isoglossate were fully mixed at a speed of 1500 r / min for 6 minutes to obtain a mixture; after twin-screw extrusion, the mixture was melt-spun at 190°C at a spinning speed of 1400 m / min to obtain a composite fiber with a diameter of 50 μm.

[0088] Comparative Preparation Example 3

[0089] Comparative Preparation Example 3 is the same as Preparation Example 6, except that no sodium alginate is added.

[0090] Comparative Preparation Example 4

[0091] Comparative Preparation Example 4 is the same as Preparation Example 6, except that no mesoporous nano-hydroxyapatite is added.

[0092] Comparative Preparation Example 5

[0093] Comparative Preparation Example 5 is the same as Preparation Example 6, except that an equal amount of polylactic acid is used to replace γ-polyglutamic acid.

[0094] Comparative Preparation Example 6

[0095] Comparative Preparation Example 6 is the same as Preparation Example 6, except that an equal amount of γ-polyglutamic acid is used to replace polylactic acid.

[0096] Comparative Preparation Example 7

[0097] Comparative Preparation Example 7 is the same as Preparation Example 6, except that sodium isoglossate is not added.

[0098] Preparation Examples 11-15 and Comparative Preparation Examples 8-14 provide methods for preparing yarns.

[0099] Preparation Example 11

[0100] Yarn, produced by:

[0101] Sixteen composite fibers were twisted together to form an outer covering yarn with a twist of 300 twists / m; 20 modified PET fibers were twisted together to form a core yarn with a twist of 450 twists / m. The compact sirofil spinning technology was used to control the draft ratio of the core yarn to 2.5 times to obtain the yarn;

[0102] Among them, the modified PET fiber is prepared by Preparation Example 1; and the composite fiber is prepared by Preparation Example 6.

[0103] Preparation Example 12

[0104] Yarn, produced by:

[0105] 17 composite fibers were twisted together to form an outer covering yarn with a twist of 350 twists / m; 22 modified PET fibers were twisted together to form a core yarn with a twist of 500 twists / m. The compact sirofil spinning technology was used to control the draft ratio of the core yarn to 2.8 times to obtain the yarn;

[0106] Among them, the modified PET fiber is prepared by Preparation Example 2; and the composite fiber is prepared by Preparation Example 7.

[0107] Preparation Example 13

[0108] Yarn, produced by:

[0109] 18 composite fibers were twisted together to form an outer covering yarn with a twist of 400 twists / m; 25 modified PET fibers were twisted together to form a core yarn with a twist of 550 twists / m. The compact sirofil spinning technology was used to control the draft of the core yarn to 3 times to obtain the yarn;

[0110] Among them, the modified PET fiber is prepared by Preparation Example 3; and the composite fiber is prepared by Preparation Example 8.

[0111] Preparation Example 14

[0112] Yarn, produced by:

[0113] 18 composite fibers were twisted together to form an outer covering yarn with a twist of 450 twists / m; 28 modified PET fibers were twisted together to form a core yarn; and the compact sirofil spinning technology was used to control the draft ratio of the core yarn to 3.2 times to obtain the yarn.

[0114] Among them, the modified PET fiber is prepared by Preparation Example 4; and the composite fiber is prepared by Preparation Example 9.

[0115] Preparation Example 15

[0116] Yarn, produced by:

[0117] 20 composite fibers were twisted together to form an outer covering yarn with a twist of 500 twists / m; 30 modified PET fibers were twisted together to form a core yarn with a twist of 700 twists / m; the compact sirofil spinning technology was used to control the draft ratio of the core yarn to 3.5 times to obtain the yarn;

[0118] Among them, the modified PET fiber is prepared by Preparation Example 5; and the composite fiber is prepared by Preparation Example 10.

[0119] Comparative Preparation Example 8

[0120] Comparative Preparation Example 8 is the same as Preparation Example 11, except that the modified PET fiber is prepared by Comparative Preparation Example 1.

[0121] Comparative Preparation Example 9

[0122] Comparative Preparation Example 9 is the same as Preparation Example 11, except that the modified PET fiber is prepared by Comparative Preparation Example 2.

[0123] Comparative Preparation Example 10

[0124] Comparative Preparation Example 10 is the same as Preparation Example 11, except that the composite fiber is prepared by Comparative Preparation Example 3.

[0125] Comparative Preparation Example 11

[0126] Comparative Preparation Example 11 is the same as Preparation Example 11, except that the composite fiber is prepared by Comparative Preparation Example 4.

[0127] Comparative Preparation Example 12

[0128] Comparative Preparation Example 12 is the same as Preparation Example 11, except that the composite fiber is prepared by Comparative Preparation Example 5.

[0129] Comparative Preparation Example 13

[0130] Comparative Preparation Example 13 is the same as Preparation Example 11, except that the composite fiber is prepared by Comparative Preparation Example 6.

[0131] Comparative Preparation Example 14

[0132] Comparative Preparation Example 14 is the same as Preparation Example 11, except that the composite fiber is prepared by Comparative Preparation Example 7.

[0133] Preparation Examples 16-20 and Comparative Preparation Examples 15-17 provide coating liquids and preparation methods.

[0134] Preparation Example 16

[0135] The coating solution includes the following raw materials: 400 g silk fibroin, 100 g hyaluronic acid, 10 g silver acetate, 20 g strontium chloride, 60 g mesoporous nano-β-tricalcium phosphate, and 800 g water;

[0136] The coating liquid is prepared by the following method:

[0137] First, silver acetate, silk fibroin, and hyaluronic acid were added to water, and the pH value was adjusted to 7.5. Then, strontium chloride and mesoporous nano-β-tricalcium phosphate were added. The mixture was stirred at 60° C. and a speed of 600 r / min for 60 minutes to obtain a coating liquid.

[0138] Preparation Example 17

[0139] The coating solution includes the following raw materials: 450g silk fibroin, 120g hyaluronic acid, 12g silver acetate, 30g strontium chloride, 70g mesoporous nano-β-tricalcium phosphate, and 900g water;

[0140] The coating liquid is prepared by the following method:

[0141] First, silver acetate, silk fibroin, and hyaluronic acid were added to water, and the pH value was adjusted to 7.8. Then, strontium chloride and mesoporous nano-β-tricalcium phosphate were added. The mixture was stirred at 60° C. and a speed of 650 r / min for 55 minutes to obtain a coating liquid.

[0142] Preparation Example 18

[0143] The coating solution includes the following raw materials: 500 g silk fibroin, 150 g hyaluronic acid, 15 g silver acetate, 40 g strontium chloride, 80 g mesoporous nano-β-tricalcium phosphate, and 1000 g water;

[0144] The coating liquid is prepared by the following method:

[0145] First, silver acetate, silk fibroin, and hyaluronic acid were added to water, and the pH value was adjusted to 8. Then, strontium chloride and mesoporous nano-β-tricalcium phosphate were added. The mixture was stirred at 70° C. and a speed of 700 r / min for 50 minutes to obtain a coating liquid.

[0146] Preparation Example 19

[0147] The coating solution includes the following raw materials: 550g silk fibroin, 180g hyaluronic acid, 18g silver acetate, 50g strontium chloride, 90g mesoporous nano-β-tricalcium phosphate, and 1100g water;

[0148] The coating liquid is prepared by the following method:

[0149] First, silver acetate, silk fibroin, and hyaluronic acid were added to water, and the pH value was adjusted to 8.3. Then, strontium chloride and mesoporous nano-β-tricalcium phosphate were added. The mixture was stirred at 75° C. and a speed of 750 r / min for 45 minutes to obtain a coating liquid.

[0150] Preparation Example 20

[0151] The coating solution includes the following raw materials: 600g silk fibroin, 200g hyaluronic acid, 20g silver acetate, 60g strontium chloride, 100g mesoporous nano-β-tricalcium phosphate, and 1200g water;

[0152] The coating liquid is prepared by the following method:

[0153] First, silver acetate, silk fibroin, and hyaluronic acid were added to water, and the pH value was adjusted to 8.5. Then, strontium chloride and mesoporous nano-β-tricalcium phosphate were added. The mixture was stirred at 80° C. and a speed of 800 r / min for 40 minutes to obtain a coating liquid.

[0154] Comparative Preparation Example 15

[0155] Comparative Preparation Example 15 is the same as Preparation Example 16, except that no strontium chloride is added.

[0156] Comparative Preparation Example 16

[0157] Comparative Preparation Example 16 is the same as Preparation Example 16, except that no mesoporous nano-β-tricalcium phosphate is added.

[0158] Comparative Preparation Example 17

[0159] Comparative Preparation Example 17 is the same as Preparation Example 16, except that an equal amount of silk fibroin is used to replace hyaluronic acid.

[0160] Comparative Preparation Example 18

[0161] Comparative Preparation Example 18 is the same as Preparation Example 16, except that no silver acetate is added.

[0162] Examples 1-5 provide an artificial ligament with a development function and a preparation method thereof.

[0163] Example 1

[0164] An artificial ligament with a developing function, comprising a yarn-woven support structure and a coating on the surface of the support structure; the coating is made by applying 11 layers of liquid;

[0165] Wherein, the yarn is prepared by Preparation Example 11; the coating liquid is prepared by Preparation Example 16;

[0166] A method for preparing an artificial ligament with a development function, comprising the following specific steps:

[0167] S1. Braid the yarn into a tubular textile and place it in a mold. Heat-set the mold as a whole at 66°C for 60 minutes, then remove the mold to obtain a support structure.

[0168] S2. First, add the support structure obtained in step S1 into a coating liquid with a mass 10 times that of the support structure, stir it thoroughly for 10 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 30wt% for 10 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with development function.

[0169] Example 2

[0170] An artificial ligament with a developing function is composed of a yarn-woven support structure and a coating on the surface of the support structure; the coating is made of a coating liquid;

[0171] Wherein, the yarn is prepared by Preparation Example 12; the coating liquid is prepared by Preparation Example 17;

[0172] A method for preparing an artificial ligament with a development function, comprising the following specific steps:

[0173] S1. Braid the yarn into a tubular textile and place it in a mold. Heat-set the mold as a whole at 68°C for 55 minutes, then remove the mold to obtain a support structure.

[0174] S2. First, add the support structure obtained in step S1 into a coating liquid with a mass 12 times that of the support structure, stir it thoroughly for 15 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 35wt% for 8 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with development function.

[0175] Example 3

[0176] An artificial ligament with a developing function is composed of a yarn-woven support structure and a coating on the surface of the support structure; the coating is made of a coating liquid;

[0177] Wherein, the yarn is prepared by Preparation Example 13; the coating liquid is prepared by Preparation Example 18;

[0178] A method for preparing an artificial ligament with a development function, comprising the following specific steps:

[0179] S1. Braid the yarn into a tubular textile and place it in a mold. Heat-set the mold as a whole at 70°C for 40 minutes, then remove the mold to obtain a support structure.

[0180] S2. First, add the support structure obtained in step S1 into a coating liquid with a mass 15 times that of the support structure, stir it thoroughly for 20 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 35wt% for 6 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with development function.

[0181] Example 4

[0182] An artificial ligament with a developing function is composed of a yarn-woven support structure and a coating on the surface of the support structure; the coating is made of a coating liquid;

[0183] Wherein, the yarn is prepared by Preparation Example 14; the coating liquid is prepared by Preparation Example 19;

[0184] A method for preparing an artificial ligament with a development function, comprising the following specific steps:

[0185] S1. Braid the yarn into a tubular textile and place it in a mold. Heat-set the mold as a whole at 72°C for 35 minutes, then remove the mold to obtain a support structure.

[0186] S2. First, add the support structure obtained in step S1 into a coating liquid with a mass 18 times that of the support structure, stir it thoroughly for 25 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 35wt% for 5 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with development function.

[0187] Example 5

[0188] An artificial ligament with a developing function is composed of a yarn-woven support structure and a coating on the surface of the support structure; the coating is made of a coating liquid;

[0189] Wherein, the yarn is prepared by Preparation Example 15; the coating liquid is prepared by Preparation Example 20;

[0190] A method for preparing an artificial ligament with a development function, comprising the following specific steps:

[0191] S1. Braid the yarn into a tubular textile and place it in a mold. Heat-set the mold as a whole at 75°C for 30 minutes, then remove the mold to obtain a support structure.

[0192] S2. First, add the support structure obtained in step S1 into a coating liquid with a mass 20 times that of the support structure, stir it thoroughly for 30 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 40wt% for 5 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with development function.

[0193] In order to verify the performance of an artificial ligament with a development function provided by the present application, the applicant set up comparative examples 1-10, wherein:

[0194] Comparative Example 1

[0195] Comparative Example 1 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 8.

[0196] Comparative Example 2

[0197] Comparative Example 2 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 9.

[0198] Comparative Example 3

[0199] Comparative Example 3 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 10.

[0200] Comparative Example 4

[0201] Comparative Example 4 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 11.

[0202] Comparative Example 5

[0203] Comparative Example 5 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 12.

[0204] Comparative Example 6

[0205] Comparative Example 6 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 13.

[0206] Comparative Example 7

[0207] Comparative Example 7 is the same as Example 1, except that the coating liquid is prepared by Comparative Preparation Example 15.

[0208] Comparative Example 8

[0209] Comparative Example 8 is the same as Example 1, except that the coating liquid is prepared by Comparative Preparation Example 16.

[0210] Comparative Example 9

[0211] Comparative Example 9 is the same as Example 1, except that the coating liquid is prepared by Comparative Preparation Example 17.

[0212] Comparative Example 10

[0213] Comparative Example 10 is the same as Example 1, except that the yarn is prepared by Comparative Preparation Example 14, and the coating liquid is prepared by Comparative Preparation Example 18.

[0214] The main properties of the artificial ligament with a developing function obtained in Examples 1-5 and Comparative Examples 1-10 were respectively tested, and degradation controllable performance experiments and development tests were carried out.

[0215] 1. Degradation controllable performance experiment

[0216] (1) Preparation of degradation solution: PBS buffer solution was prepared by adding PBS tablets to deionized water at a ratio of 1 tablet: 100 ml solution, and the pH of the buffer solution was adjusted to 7.4. The PBS buffer solution was then placed in a reagent bottle, and a sterilization indicator tape was attached to the bottle mouth and loosened. The bottle was sterilized with high-temperature and high-pressure steam for 1 h. After sterilization, the bottle was placed in a clean bench and naturally cooled to room temperature.

[0217] Protease XIV was added to PBS buffer at a concentration of 1 mg / mL. After stirring until dissolved, the enzyme solution was drawn into a syringe, filtered and sterilized using a 0.22 μm syringe filter, and a penicillin-streptomycin mixture was added at a concentration of 1 ml / L.

[0218] (2) Degradation experiment: According to the standard YY / T 0473-2004, the bath ratio in this experiment was 35:1, and five sampling points were set: 7, 14, 28, 56, and 84 days. Three samples were set at each sampling point. The required volume of enzyme solution was calculated according to the mass of the sample, and the enzyme solution was replaced every 3 days. Samples were taken from each sampling point, rinsed three times with deionized water, and then dried with filter paper. The samples were placed in a sealed bag and frozen at -20°C for more than 24 hours. After freeze-drying in a freeze dryer for 24 hours, they were used for subsequent testing.

[0219] (3) Degradation mass loss rate test: After sample preparation, the initial mass of each sample was weighed on an electronic balance and recorded. The sample taken from each sampling point was placed in a constant temperature and humidity environment for 24 h, and its mass after degradation was weighed on an electronic balance. The mass loss rate was calculated according to the formula: mass loss rate (%) = (M0-M1) / M0×100%; where: M0 is the initial mass of the sample, g; M1 is the mass of the sample after degradation, g. The results are shown in Table 1.

[0220] Table 1:

[0221]

[0222]

[0223] 2. Development test

[0224] The samples were irradiated with CT and the grayscale values ​​of the samples were measured to test the development effect. The results showed that the grayscale values ​​of Examples 1-5 were in the range of 180-190; and the grayscale value of Comparative Example 10 was 123.9.

[0225] The above experimental results show that the artificial ligaments obtained in Examples 1-5 of the present application have excellent development functions and controllable degradation, which can better meet the high performance requirements of artificial ligaments.

[0226] It can be seen from Example 1 and Comparative Examples 1 and 2 that the yarn in Example 1 is prepared by Preparation Example 11, and the modified PET fiber of Preparation Example 1 is used as the core yarn. After pretreatment, the modified PET fiber is modified by adding nano-hydroxyapatite. Compared with Comparative Examples 1 and 2, Example 1 suffers from serious quality loss after 56 days, indicating that the chitosan on the surface of the core yarn begins to degrade around 56 days, and nano-hydroxyapatite contributes to the degradation of chitosan; and the pretreated PET fiber is more conducive to degradation.

[0227] It can be seen from Example 1 and Comparative Examples 3-6 that the yarn in Example 1 is prepared from Preparation Example 11, and the composite fiber of Preparation Example 6 is used as the outer covering yarn. Compared with Comparative Examples 3-6, the quality of Example 1 decreases significantly after 28 days, indicating that the composite fiber supporting the structure begins to degrade around 28 days; and sodium alginate and mesoporous nano-hydroxyapatite are added to the composite fiber of Example 1, which shows that compared with Comparative Examples 3 and 4, sodium alginate and mesoporous nano-hydroxyapatite work synergistically to promote the degradation of the composite fiber; in addition, the main degradation materials of the composite fiber in Example 1 are polylactic acid and γ-polyglutamic acid, which shows that the degradation rate of γ-polyglutamic acid is faster than that of polylactic acid, and the purpose of controllable degradation of the composite fiber can be achieved by controlling the mass ratio of the two.

[0228] It can be seen from Example 1 and Comparative Examples 7-9 that the coating liquid in Example 1 is prepared by Preparation Example 16. Compared with Comparative Examples 7-9, the quality of Example 1 is significantly reduced on the 7th day, indicating that the coating begins to degrade in about a week; and the coating of Example 1 contains strontium chloride and mesoporous nano-β-tricalcium phosphate, which helps to increase the degradation rate of the coating; in addition, hyaluronic acid is also added to the coating of Example 1. The water absorption property of hyaluronic acid can accelerate the degradation rate of silk fibroin.

[0229] It can be seen from Example 1 and Comparative Example 10 that the addition of sodium isograzioate and silver acetate in Example 1 is superior to that in Comparative Example 10, which shows that sodium isograzioate and silver acetate enable the artificial ligament of the present application to have a developing function, and the addition of sodium isograzioate and silver acetate has almost no effect on the degradation controllable performance of the artificial ligament.

[0230] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An artificial ligament with a development function, characterized in that: It is composed of a yarn-woven support structure and a coating on the surface of the support structure; The yarn is a core-spun yarn structure, with modified PET fiber as the core yarn and composite fiber as the outer covering yarn; The composite fiber comprises the following raw materials in parts by weight: 60-80 parts of polylactic acid, 30-40 parts of gamma-polyglutamic acid, 4-8 parts of sodium alginate, 6-10 parts of mesoporous nano-hydroxyapatite, and 1-5 parts of sodium isoglossate; The coating is prepared from a coating liquid.

2. The artificial ligament with development function according to claim 1, characterized in that: The modified PET fiber is prepared by the following method: Step 1: Take PET fibers with a diameter of 10-50 μm, first treat the PET fibers with plasma, and then soak them in a 10-20 wt% sodium gluconate solution for a period of time to obtain pretreated PET fibers; Step 2: First, chitosan, nano-hydroxyapatite and citric acid are added to water, and dissolved at 60-80°C and a rotation speed of 600-800 r / min for 10-20 minutes. Then, the pretreated PET fiber obtained in step 1 is added, and the same temperature and rotation speed are maintained. The mixture is fully reacted for 1-2 hours to obtain modified PET fiber.

3. The artificial ligament with development function according to claim 2, characterized in that: The modified PET fiber comprises the following raw materials in parts by weight: 30-50 parts of PET fiber, 60-80 parts of sodium gluconate solution, 6-10 parts of chitosan, 2-4 parts of nano-hydroxyapatite, 10-15 parts of citric acid, and 100-200 parts of water.

4. The artificial ligament with development function according to claim 1, characterized in that: The composite fiber is prepared by the following method: Polylactic acid, gamma-polyglutamic acid, sodium alginate, mesoporous nano-hydroxyapatite and sodium isoglossate are fully mixed at a rotation speed of 1000-1500 r / min for 6-10 minutes to obtain a mixture; after twin-screw extrusion, the mixture is melt-spun at 170-190° C. to obtain composite fibers with a diameter of 10-50 μm.

5. The artificial ligament with development function according to claim 1, characterized in that: The yarn is prepared by the following method: 16-20 composite fibers are twisted together to form outer covering yarn; 20-30 modified PET fibers are twisted together to form core yarn; and the compact sirofil spinning technology is used to control the drafting ratio of the core yarn to 2.5-3.5 times to obtain the yarn.

6. The artificial ligament with a development function according to claim 1, characterized in that: The coating liquid comprises the following raw materials in parts by weight: 40-60 parts of silk fibroin, 10-20 parts of hyaluronic acid, 1-2 parts of silver acetate, 2-6 parts of strontium chloride, 6-10 parts of mesoporous nano-β-tricalcium phosphate, and 80-120 parts of water.

7. The artificial ligament with development function according to claim 1, characterized in that: The coating liquid is prepared by the following method: First, silver acetate, silk fibroin and hyaluronic acid are added into water, the pH value is adjusted to 7.5-8.5, and then strontium chloride and mesoporous nano-β-tricalcium phosphate are added and stirred evenly to obtain a coating liquid.

8. A method for preparing an artificial ligament with a developing function according to any one of claims 1 to 7, characterized in that: First, the yarn is woven into a support structure, and then the support structure is added with the coating liquid, taken out, and dried to form a coating on the surface of the support structure to obtain an artificial ligament with a developing function.

9. The method for preparing an artificial ligament with a developing function according to claim 8, characterized in that: The method for preparing the artificial ligament with development function comprises the following specific steps: S1. Weaving the yarn into a tubular textile fabric and placing it in a mold. Heat-setting the entire mold at 66-75° C. for 30-60 minutes is performed, and then the mold is removed to obtain a support structure. S2. First, add the support structure obtained in step S1 to the coating liquid with a mass ratio of the support structure to the coating liquid of 1:10-20. After fully stirring for 10-30 minutes, dry it, and then soak it in a Na2HPO4 solution with a concentration of 30-40wt% for 5-10 minutes. Take it out and dry it to form a coating on the surface of the support structure to obtain an artificial ligament with a developing function.

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