CN112043876B - Reproducible and repairable vascular stent covering film and preparation method thereof - Google Patents
Reproducible and repairable vascular stent covering film and preparation method thereof Download PDFInfo
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- CN112043876B CN112043876B CN202010781023.6A CN202010781023A CN112043876B CN 112043876 B CN112043876 B CN 112043876B CN 202010781023 A CN202010781023 A CN 202010781023A CN 112043876 B CN112043876 B CN 112043876B
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
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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
- A61L27/54—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
- 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
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—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
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
- C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
- C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/42—Anti-thrombotic agents, anticoagulants, anti-platelet agents
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
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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
- A61L2420/08—Coatings comprising two or more layers
Abstract
The invention discloses a regenerative and repairable vascular stent covering film and a preparation method thereof, silkworm silk is divided into two groups, one group is twisted and doubled and is a silk group, the other group is a monofilament group, the silk group is degummed by sodium carbonate, sodium bicarbonate or biological enzyme, the monofilament group is degummed by boiling water, sodium carbonate, sodium bicarbonate or biological enzyme, the silk fibroin dissolving solution is prepared by dissolving the degummed silk fibroin dissolving solution in a lithium bromide neutral salt solution, the silk fibroin dissolving solution is filled in a dialysis bag for dialysis to obtain a purified silkworm fibroin aqueous solution, and silk fibroin is concentrated to a proper mass fraction by a rotary evaporator. Adding a hydrophilic cross-linking agent of flexible molecules into the silk fibroin aqueous solution, uniformly mixing and de-bubbling to obtain a modified silk fibroin solution, then weaving a tubular structure with single silk, immersing the tubular structure into the modified silk fibroin solution, and air-drying to obtain the renewable and repairable vascular stent coating. The tectorial membrane has excellent toughness, and induces the regeneration of the blood vessel intima for regulating the blood system balance in situ.
Description
Technical Field
The invention relates to the technical field of preparation of vascular stent covering films, in particular to a reproducible and repairable vascular stent covering film and a preparation method thereof.
Background
With the improvement of living standard and the acceleration of aging process, the incidence of cardiovascular and cerebrovascular diseases is obviously increased year by year, and the cardiovascular and cerebrovascular diseases such as embolism, vascular stenosis, vascular aneurysm and the like seriously threaten the health of human beings and become the cause of the highest human mortality. With the development of medical science, minimally invasive endoluminal isolation gradually becomes a main treatment mode of multiple arterial lesions due to small surgical trauma, a blood vessel covered stent is a main body of endoluminal isolation treatment, the performance of the blood vessel covered stent directly influences the clinical treatment effect, but complications such as slippage, internal leakage, new stent-derived lacerations and the like of the blood vessel covered stent still occur in the middle and long periods after surgery, thrombus and restenosis still occur, and the clinical problems are worthy of close attention. The main reasons for inducing postoperative complications are poor biocompatibility (particularly histocompatibility and blood compatibility) of the vascular stent graft, incompatibility of biomechanical properties and long-term wrapping of non-degradable materials by blood components, so that the development of the vascular stent graft matched with the biological properties of host blood vessels is urgently needed.
The key point of the endoluminal repair is the development of a vascular stent system, wherein the vascular stent system comprises a stent, a coating and a conveying system, the research on the aspects of coating and stent design, processing and manufacturing is not deep enough in China at present, and the coated stent for clinical application depends on import and is expensive. The tectorial membrane is an important bearer for the luminal isolation, and the biological performance is extremely important. The current film covering material applied clinically has no excellent tissue compatibility, and is easy to generate restenosis at a long term after operation and generate complications such as slippage and the like. Long term use of drugs to maintain antithrombotic activity is an inappropriate option for the middle and young age groups with increasing incidence. Silkworm silk is natural animal protein, has wide source and high purity, wherein silk fibroin is a silk core, accounts for 70-80% of the mass of the silk, and is simple and convenient to purify. The silk fibroin fiber has excellent mechanical property and biocompatibility, the silk fibroin is composed of 20 amino acids, and the silk fibroin is an absorbable material and can not cause obvious immunoreaction. A great deal of literature research shows that the silk fibroin material can support the growth of various cells, has more research on anticoagulation property, has great attention on tissue engineering materials, and is a preferred material for an absorbable coating.
The coating materials of the vascular stent reported in the prior publication are mainly synthetic macromolecules such as polytetrafluoroethylene, polyester, polyamide, polyethylene, polypropylene, polyurethane and the like, and the coating is formed by weaving or alternately weaving polyester yarns and nickel-titanium alloy yarns. The lack of histocompatibility of the synthesized polymer is an important reason for postoperative complications, the inner surface of the coated membrane is difficult to endothelialize, and the coated membrane can generate immunologic rejection after being placed in a body for a period of time, and can induce other more serious diseases by long-term administration. In order to solve the bottleneck problem of the existing clinical application and the morbid phenomenon of the younger and more young (even live baby), the research and development of a regenerative and reparative vascular stent covering film are needed to solve the problems.
Disclosure of Invention
The invention aims to provide a reproducible and repairable vascular stent covering film and a preparation method thereof, which are used for producing a reproducible and repairable vascular stent which can be absorbed, can be quickly endothelialized in situ and can induce the reconstruction of healthy vascular tissues.
The invention has a technical scheme that:
provides a reproducible and repairable vascular stent covering film with axial tensile strength>2MPa, elongation at break>40% tensile strength in circumferential direction>6MPa, elongation at break >140 percent, and the whole water leakage is less than 2ml/min at the water pressure of 120mmHg2Rate of hemolysis<0.1％。
The preparation method of the reproducible and repairable vascular stent covering film comprises the following steps:
(1) preparing degummed silkworm fibroin fibers and cooked silk threads: selecting 40-160D silk yarns and silk monofilaments, twisting and combining the silk yarns by using raw silkworms to obtain the silk monofilaments, degumming the silk monofilaments by using any one of boiling water, sodium carbonate, sodium bicarbonate or biological enzyme to obtain degummed silkworm fibroin fibers, and degumming the silk yarns by using any one of sodium carbonate, sodium bicarbonate or biological enzyme to obtain degummed mature silk yarns;
(2) preparing a silkworm fibroin aqueous solution: dissolving the degummed silkworm fibroin fibers in a 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), processing at 65 +/-10 ℃ until the silkworm fibroin fibers are completely dissolved to obtain a silkworm fibroin solution, filling the silkworm fibroin solution into a dialysis bag, wherein the dialysis bag is made of a semipermeable membrane and has a molecular weight cutoff of 10-50 kDa, placing the dialysis bag filled with the silkworm fibroin solution into a container containing deionized water, replacing the liquid in the container with new deionized water every 2 hours, and continuously dialyzing for 3 days to obtain a purified silkworm fibroin aqueous solution;
(3) Preparing a modified silk fibroin solution: concentrating, adjusting and measuring the purified silk fibroin aqueous solution by using a rotary evaporator to enable the mass fraction of the purified silk fibroin aqueous solution to be 1-10%, adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to silk fibroin, uniformly stirring and removing bubbles to obtain a modified silk fibroin solution;
(4) preparing a silk fibroin tubular film: weaving the boiled silk yarns on a stainless steel bar into a tubular structure which is 30-90 degrees interwoven, has the linear density of 4-10 threads/cm and the inner diameter of 2-20 mm by adopting a weaving technology, putting the tubular structure into the modified silk fibroin solution, soaking for 3-30 seconds, taking out, putting the tubular structure into a hot air drying oven, rotating to form a film along the circumferential direction under the condition that the temperature is lower than 50 ℃, controlling the surface of the film to keep moist, and repeating the step for 2-10 times to obtain the renewable and repairable vascular stent covering film.
Further, the preparation of the degummed bombyx mori silk fibroin fibers and the degummed silk threads in the step (1) comprises the following steps: selecting 40-160D silk yarns and silk yarns, wherein the silk yarns are obtained by twisting and combining raw silks of silkworms, putting the silk yarns and the silk yarns into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, fully cleaning the silk yarns and the silk yarns with deionized water, and then drying the silk yarns and the silk yarns in an oven at the temperature of 60 ℃ to obtain degummed silk fibroin fibers and cooked silk yarns.
Further, the preparation of the degummed bombyx mori silk fibroin fibers and the matured silk threads in the step (1) comprises the following steps: selecting 40-160D silk yarns and silk monofilaments, wherein the silk yarns are obtained by twisting and combining raw silks of silkworms, putting the silk yarns into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, fully cleaning the silk yarns with deionized water, and then drying the silk yarns in an oven with the temperature of 60 ℃ to obtain degummed mature silk yarns; and (2) putting the silk monofilament into deionized water according to a bath ratio of 1:50(g/mL), boiling for 7 hours at the temperature of 98-100 ℃, replacing the deionized water for many times, then fully cleaning the silk monofilament with the deionized water, and drying in an oven at the temperature of 60 ℃ to obtain the degummed silkworm fibroin fiber.
Further, the silk thread in the step (1) is 60D-120D.
Further, the molecular weight cut-off of the dialysis bag in the step (2) is 50 kDa.
Further, the mass fraction of the purified bombyx mori silk fibroin aqueous solution in the step (3) is 3%.
Further, in the step (4), the boiled silk threads are woven on the stainless steel bar by adopting a weaving technology to form a tubular structure which is interwoven at an angle of 60-90 degrees, has a linear density of 4-12 threads/cm and has an inner diameter of 2-20 mm.
Further, the dipping time in the step (4) is 5-15 seconds, and the number of times of repeating the step is 3-5 times.
The invention provides a reproducible and repairable vascular stent covering film and a preparation method thereof. Can be prepared into in-vivo grafts with various shapes applied to the treatment of cardiovascular diseases (such as heart repair patches, vascular stent tectorial membranes and artificial heart valves), and can also be expanded to be used for other medical instruments such as tissue engineering stents and the like.
Detailed Description
The invention aims to develop a preparation technology of a blood vessel stent coating of a natural high molecular silk fibroin protein material (the molecular weight is more than or equal to 50kDa) to promote tissue regeneration and function recovery of diseased and defective blood vessels aiming at the complications of blood vessel stent coating transplantation, internal leakage, stent-derived new laceration and the like after the existing cardiovascular and cerebrovascular disease endoluminal exclusion treatment and the severe clinical problems of device failure, restenosis and the like caused by long-term fatigue damage. Axial tensile strength of the film >2MPa, elongation at break>40% tensile strength in circumferential direction>6MPa, elongation at break>140% of the total water leakage is 120Less than 2ml/min.cm under mmHg water pressure2Rate of hemolysis<0.1 percent. The film has excellent tensile property, bursting strength, compliance and fatigue resistance, and the film layer of the film is completely welded with the silk thread and does not slide even when the film is in tensile fracture. The nanoscale layer-by-layer self-assembly is controlled, so that the film has excellent flexibility, the film does not leak inwards, and the film is tightly combined with lesion tissues after being implanted and does not slide. The molecular weight of the silk fibroin is controlled, and excellent mechanical properties can be obtained by adopting low-concentration and low-level coating. The vascular stent covering membrane with different parts of the organism required by physical dimensions and physical properties is obtained by adjusting preparation parameters such as silk fibroin concentration, geometric parameters of tubular texture, the number of self-assembly layers and the like. On the other hand, the stent covering membrane provided by the invention has excellent cell compatibility, histocompatibility and rapid endothelialization capability, and meanwhile, the covering membrane is degraded and absorbed in a gradient manner, so that the endovascular tissue of the blood vessel is repaired in situ, and the failure of the device caused by long-term fatigue damage after the covering membrane is implanted into a human body can be avoided. Moreover, rapid endothelialization is the fundamental factor for inhibiting thrombosis and restenosis, and the rapid formation of intimal tissue will completely restore the regulatory function of the blood coagulation system equilibrium of the blood vessel.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The embodiment shows a preparation method of a reproducible and repairable vascular stent covering film, which comprises the following steps:
1. twisting and combining raw silks of silkworms to obtain a 120D silk thread group, wherein the other silk thread group is a silk monofilament group, putting the silk monofilaments and silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silks with deionized water, and drying in an oven at the temperature of 60 ℃ to obtain degummed silk fibroin fibers and mature silk threads of the silkworms.
2. Weighing degummed bombyx mori silk fibroin fibers, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), and treating at 65 ℃ until the bombyx mori silk fibroin fibers are completely dissolved to obtain bombyx mori silk fibroin dissolving solution. And (2) filling the bombyx mori silk fibroin solution into a dialysis bag, wherein the wall of the dialysis bag is a semipermeable membrane, the molecular weight cut-off is within the range of 50kDa, placing the dialysis bag filled with the bombyx mori silk fibroin solution into a container filled with deionized water, replacing the water in the container with new deionized water or pure water every 2 hours, and continuously dialyzing for 3 days to obtain the purified bombyx mori silk fibroin aqueous solution.
3. Concentrating by using a rotary evaporator, adjusting the mass fraction of the purified bombyx mori silk fibroin aqueous solution to be 3%, then adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to the silk fibroin (the mass ratio of the silk fibroin to the polyethylene glycol diglycidyl ether in the purified bombyx mori silk fibroin aqueous solution is 10: 6), stirring uniformly and removing bubbles to obtain the modified silk fibroin solution.
4. Weaving the 120D boiled silk yarns into a tubular fabric which is interwoven at 90 degrees, has the linear density of 10 +/-2 and the inner diameter of 2-20 mm on a stainless steel bar by adopting a weaving technology, soaking the tubular fabric in the modified silk fibroin solution obtained in the step 3 for about 10 seconds, taking out the tubular fabric, placing the tubular fabric in a hot air drying oven at the temperature of below 50 ℃ to form a film in a rotating mode in the inner circumferential direction, and controlling the surface of the film to be kept wet. And repeating the dipping coating for 4 times to obtain the silk fibroin composite vascular stent coating, namely the regenerative and repairable vascular stent coating.
Through detection, the reproducible and repairable vascular stent covering film has excellent mechanical property, and the axial tensile strength is measured according to the national standard detection method>2.5MPa, elongation at break>45% tensile strength in circumferential direction>8MPa, elongation at break>140 percent. The whole water leakage is less than 12ml/min at 120mmHg water pressure2。
The hemolytic rate of the reproducible and repairable vascular stent covering membrane is less than 0.1 percent according to a hemolytic rate test method, and the reproducible and repairable vascular stent covering membrane completely meets the standard (0-2 percent) of a non-hemolytic material. The reproducible and repairable vascular stent covering membrane has no sensitization through animal experiments, and the prepared stent covering membrane has cytotoxicity less than or equal to 1.5 according to national standard detection.
Example 2
The embodiment shows a preparation method of a reproducible and repairable vascular stent covering film, which comprises the following steps:
1. twisting and combining raw silks of silkworms to obtain a 120D silk thread group, wherein the other silk thread group is a silk monofilament group, putting the silk monofilaments and silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silks with deionized water, and drying in an oven at the temperature of 60 ℃ to obtain degummed silk fibroin fibers and mature silk threads of the silkworms.
2. Weighing degummed bombyx mori silk fibroin fibers, dissolving the degummed bombyx mori silk fibroin fibers in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), and treating at 65 ℃ until the degummed bombyx mori silk fibroin fibers are completely dissolved to obtain bombyx mori silk fibroin dissolving solution. And (2) filling the bombyx mori silk fibroin solution into a dialysis bag, wherein the wall of the dialysis bag is a semipermeable membrane, the molecular weight cut-off is within the range of 50kDa, placing the dialysis bag filled with the bombyx mori silk fibroin solution into a container filled with deionized water, replacing the water in the container with new deionized water or pure water every 2 hours, and continuously dialyzing for 3 days to obtain the purified bombyx mori silk fibroin aqueous solution.
3. Concentrating by using a rotary evaporator, adjusting the mass fraction of the purified silkworm silk fibroin aqueous solution to be 3%, then adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to the silk fibroin, uniformly stirring and removing bubbles to obtain the modified silk fibroin solution.
4. Weaving the 120D boiled silk yarns into a tubular fabric which is interwoven at 90 degrees, has the linear density of 6 +/-1 and the inner diameter of 2-20 mm on a stainless steel bar by adopting a weaving technology, soaking the tubular fabric in the modified silk fibroin solution obtained in the step 3 for about 15 seconds, taking out the tubular fabric, placing the tubular fabric in a hot air drying oven at the temperature of below 50 ℃ to form a film in a rotating mode in the inner circumferential direction, and controlling the surface of the film to be kept wet. And repeating the dipping coating for 4 times to obtain the silk fibroin composite vascular stent coating, namely the regenerative and repairable vascular stent coating.
The renewable and repairable vascular stent covering film has excellent mechanical properties through detection, and the axial tensile strength is measured according to the national standard detection method>2.0MPa, elongation at break>40% tensile strength in circumferential direction>6MPa, elongation at break>140 percent. And the whole water leakage is less than 3ml/min at 120mmHg water pressure2。
The hemolytic rate of the reproducible and repairable vascular stent covering membrane is less than 0.1 percent according to a hemolytic rate test method, and the reproducible and repairable vascular stent covering membrane completely meets the standard (0-2 percent) of a non-hemolytic material. The reproducible and repairable vascular stent covering membrane has no sensitization through animal experiments, and the cytotoxicity is detected to be less than or equal to 1 according to the national standard.
Example 3
The embodiment shows a preparation method of a reproducible and repairable vascular stent covering film, which comprises the following steps:
1. twisting and combining raw silks of silkworms to obtain a 120D silk thread group, wherein the other silk thread group is a silk monofilament group, putting the silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk threads with deionized water, and drying in an oven at the temperature of 60 ℃ to obtain the degummed mature silk threads. Putting silk monofilaments into deionized water according to a bath ratio of 1:50(g/mL), boiling for 7 hours at 98-100 ℃, changing the deionized water for many times, then fully cleaning the silk with the deionized water, and drying in an oven at 60 ℃ to obtain the degummed bombyx mori silk fibroin fiber.
2. Weighing degummed bombyx mori silk fibroin fibers, dissolving the degummed bombyx mori silk fibroin fibers in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), and treating at 65 ℃ until the bombyx mori silk fibroin fibers are completely dissolved to obtain a bombyx mori silk fibroin dissolving solution. And (2) filling the bombyx mori silk fibroin solution into a dialysis bag, wherein the wall of the dialysis bag is a semipermeable membrane, the molecular weight cutoff is within the range of 50kDa, placing the dialysis bag filled with the bombyx mori silk fibroin solution into a container filled with deionized water, replacing the water in the container with new deionized water or pure water every 2 hours, and continuously dialyzing for 3 days to obtain the purified bombyx mori silk fibroin aqueous solution.
3. Concentrating by using a rotary evaporator, adjusting the mass fraction of the purified silkworm silk fibroin aqueous solution to be 3%, then adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to the silk fibroin, uniformly stirring and removing bubbles to obtain the modified silk fibroin solution.
4. Weaving the 120D boiled silk yarns into a tubular fabric which is interwoven at 90 degrees, has the linear density of 10 +/-2 and the inner diameter of 2-20 mm on a stainless steel bar by adopting a weaving technology, soaking the tubular fabric in the modified silk fibroin solution obtained in the step 3 for about 5 seconds, taking out the tubular fabric, placing the tubular fabric in a hot air drying oven at the temperature of below 50 ℃ to form a film in a rotating mode in the inner circumferential direction, and controlling the surface of the film to be kept wet. And repeating the dipping coating for 4 times to obtain the silk fibroin composite vascular stent coating, namely the regenerative and repairable vascular stent coating.
The renewable and repairable vascular stent covering film has excellent mechanical properties through detection, and the axial tensile strength is measured according to the national standard detection method>3.0MPa, elongation at break>70% tensile strength in circumferential direction>12MPa, elongation at break>200 percent. And the overall water leakage is less than 2ml/min at 120mmHg water pressure2。
The hemolytic rate of the reproducible and repairable vascular stent covering membrane is less than 0.1 percent according to a hemolytic rate test method, and the reproducible and repairable vascular stent covering membrane completely meets the standard (0-2 percent) of a non-hemolytic material. The reproducible and repairable vascular stent covering membrane has no sensitization through animal experiments, and the cytotoxicity is detected to be less than or equal to 1 according to the national standard.
Example 4
The embodiment shows a preparation method of a reproducible and repairable vascular stent covering film, which comprises the following steps:
1. the method comprises the steps of twisting and combining silkworm raw silks to obtain a 60D silk thread group, enabling the other silk thread group to be a silk monofilament group, putting the silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk threads with deionized water, and drying in a 60 ℃ oven to obtain the degummed mature silk threads. Putting silk monofilaments into deionized water according to a bath ratio of 1:50(g/mL), boiling for 7 hours at 98-100 ℃, changing the deionized water for many times, then fully cleaning the silk with the deionized water, and drying in an oven at 60 ℃ to obtain the degummed bombyx mori silk fibroin fiber.
2. Weighing degummed bombyx mori silk fibroin fibers, dissolving the degummed bombyx mori silk fibroin fibers in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), and treating at 65 ℃ until the bombyx mori silk fibroin fibers are completely dissolved to obtain a bombyx mori silk fibroin dissolving solution. And (2) filling the bombyx mori silk fibroin solution into a dialysis bag, wherein the wall of the dialysis bag is a semipermeable membrane, the molecular weight cutoff is within the range of 50kDa, placing the dialysis bag filled with the bombyx mori silk fibroin solution into a container filled with deionized water, replacing the water in the container with new deionized water or pure water every 2 hours, and continuously dialyzing for 3 days to obtain the purified bombyx mori silk fibroin aqueous solution.
3. Concentrating by using a rotary evaporator, adjusting the mass fraction of the purified silkworm silk fibroin aqueous solution to be 3%, then adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to the silk fibroin, uniformly stirring and removing bubbles to obtain the modified silk fibroin solution.
4. And (3) knitting 60D boiled silk yarns into a tubular fabric which is 90-degree interwoven, has the linear density of 10 +/-2 and the inner diameter of 2-20 mm on a stainless steel bar by adopting a knitting technology, soaking the tubular fabric in the modified silk fibroin solution obtained in the step 3 for about 5 seconds, taking out the tubular fabric, placing the tubular fabric in a hot air drying oven at the temperature of below 50 ℃ to form a film in a rotating mode in the inner circumferential direction, and controlling the surface of the film to be kept wet. And repeating the dipping coating for 4 times to obtain the silk fibroin composite vascular stent coating, namely the regenerative and repairable vascular stent coating.
The renewable and repairable vascular stent covering film has excellent mechanical properties through detection, and the axial tensile strength is measured according to the national standard detection method>2.5MPa, elongation at break>45% tensile strength in circumferential direction>8MPa, elongation at break>150 percent. And the whole water leakage is less than 3ml/min at 120mmHg water pressure2。
The hemolytic rate of the reproducible and repairable vascular stent covering membrane is less than 0.1 percent according to a hemolytic rate test method, and the reproducible and repairable vascular stent covering membrane completely meets the standard (0-2 percent) of a non-hemolytic material. The reproducible and repairable vascular stent covering membrane has no sensitization through animal experiments, and the cytotoxicity is detected to be less than or equal to 1 according to the national standard.
Example 5
1. The method comprises the steps of twisting and combining silkworm raw silks to obtain a 60D silk thread group, enabling the other silk thread group to be a silk monofilament group, putting the silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk threads with deionized water, and drying in a 60 ℃ oven to obtain the degummed mature silk threads. Putting silk monofilaments into deionized water according to a bath ratio of 1:50(g/mL), boiling for 7 hours at 98-100 ℃, replacing the deionized water for many times, fully cleaning the silk monofilaments with the deionized water, and drying in an oven at 60 ℃ to obtain the degummed bombyx mori silk fibroin fibers.
2. Weighing degummed bombyx mori silk fibroin fibers, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:10(g/mL), and treating at 65 ℃ until the bombyx mori silk fibroin fibers are completely dissolved to obtain bombyx mori silk fibroin dissolving solution. And (2) filling the bombyx mori silk fibroin solution into a dialysis bag, wherein the wall of the dialysis bag is a semipermeable membrane, the molecular weight cut-off is within the range of 50kDa, placing the dialysis bag filled with the bombyx mori silk fibroin solution into a container filled with deionized water, replacing the water in the container with new deionized water or pure water every 2 hours, and continuously dialyzing for 3 days to obtain the purified bombyx mori silk fibroin aqueous solution.
3. Concentrating by using a rotary evaporator, adjusting the mass fraction of the purified bombyx mori silk fibroin aqueous solution to be 3%, then adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to the silk fibroin, stirring uniformly, and removing bubbles to obtain the modified silk fibroin solution.
4. Weaving 60D of the boiled silk yarns into a tubular fabric which is interwoven at 60 degrees, has the linear density of 10 +/-2 and the inner diameter of 2-20 mm on a stainless steel bar by adopting a weaving technology, soaking the tubular fabric in the modified silk fibroin solution obtained in the step 3 for about 5 seconds, taking out the tubular fabric, placing the tubular fabric in a hot air drying box at the temperature of below 50 ℃ to form a film in a rotating manner in the inner circumferential direction, and controlling the surface of the film to keep wet. And repeating the dipping coating for 4 times to obtain the silk fibroin composite vascular stent coating, namely the regenerative and repairable vascular stent coating.
Through detection, the reproducible and repairable vascular stent covering film has excellent mechanical property, and the axial tensile strength is measured according to the national standard detection method>2.0MPa, elongation at break>50% tensile strength in circumferential direction>6MPa, elongation at break>150 percent. And the number of the first and second electrodes,the whole water leakage is less than 3ml/min.cm under the water pressure of 120mmHg2。
The hemolytic rate of the reproducible and repairable vascular stent covering membrane is less than 0.1 percent according to a hemolytic rate test method, and the reproducible and repairable vascular stent covering membrane completely meets the standard (0-2 percent) of a non-hemolytic material. The prepared stent covering film has no sensitization through animal experiments, and the cytotoxicity is detected to be less than or equal to 1 according to the national standard.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (7)
1. A preparation method of a reproducible and repairable vascular stent covering film is characterized by comprising the following steps:
(1) preparing degummed silkworm fibroin fibers and cooked silk threads: selecting 40-160D silk yarns and silk monofilaments, twisting and combining the silk yarns by using raw silkworms to obtain the silk monofilaments, degumming the silk monofilaments by using any one of boiling water, sodium carbonate, sodium bicarbonate or biological enzyme to obtain degummed silkworm fibroin fibers, and degumming the silk yarns by using any one of sodium carbonate, sodium bicarbonate or biological enzyme to obtain degummed mature silk yarns;
(2) preparing a silkworm silk fibroin aqueous solution: dissolving the degummed silkworm fibroin fibers in 9.3M lithium bromide aqueous solution according to a bath ratio of 1g:10mL, processing at the temperature of 65 +/-10 ℃ until the silkworm fibroin fibers are completely dissolved to obtain silkworm fibroin solution, filling the silkworm fibroin solution into a dialysis bag, wherein the dialysis bag is made of a semipermeable membrane and has a molecular weight cutoff of 50kDa, placing the dialysis bag filled with the silkworm fibroin solution into a container containing deionized water, replacing the liquid in the container with new deionized water every 2 hours, and continuously dialyzing for 3 days to obtain purified silkworm fibroin aqueous solution;
(3) Preparing a modified silk fibroin solution: concentrating, adjusting and measuring the purified silk fibroin aqueous solution by using a rotary evaporator to enable the mass fraction of the purified silk fibroin aqueous solution to be 1-10%, adding polyethylene glycol diglycidyl ether with the mass ratio of 0.6 to silk fibroin, uniformly stirring and removing bubbles to obtain a modified silk fibroin solution;
(4) preparing a silk fibroin tubular film: weaving the boiled silk yarns on a stainless steel bar into a tubular structure which is 30-90 degrees interwoven, has the linear density of 4-12 threads/cm and the inner diameter of 2-20 mm by adopting a weaving technology, putting the tubular structure into the modified silk fibroin solution, soaking for 3-30 seconds, taking out, putting the tubular structure into a hot air drying oven, rotating to form a film along the circumferential direction under the condition that the temperature is lower than 50 ℃, controlling the surface of the film to keep moist, and repeating the step for 2-10 times to obtain the renewable and repairable vascular stent coating film.
2. The method for preparing a regenerative and repairable vascular stent graft according to claim 1, wherein the step (1) of preparing the degummed bombyx mori silk fibroin fibers and the ripened silk threads comprises: selecting 40-160D silk yarns and silk yarns, wherein the silk yarns are obtained by twisting and combining raw silks of silkworms, putting the silk yarns and the silk yarns into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1g:50mL, treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, fully cleaning the silk yarns and the silk yarns with deionized water, and then drying the silk yarns and the silk yarns in an oven at the temperature of 60 ℃ to obtain degummed silk fibroin fibers and mature silk yarns.
3. The method for preparing a regenerative and repairable vascular stent graft according to claim 1, wherein the step (1) of preparing the degummed bombyx mori silk fibroin fibers and the ripened silk threads comprises: selecting 40-160D silk threads and silk monofilaments, wherein the silk threads are obtained by twisting and combining raw silks of silkworms, putting the silk threads into a sodium carbonate aqueous solution with the concentration of 0.1-0.6% according to the bath ratio of 1g to 50mL, treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, fully cleaning the silk threads with deionized water, and then drying the silk threads in an oven with the temperature of 60 ℃ to obtain degummed mature silk threads; and (2) putting the silk monofilament into deionized water according to a bath ratio of 1g:50mL, boiling for 7 hours at the temperature of 98-100 ℃, replacing the deionized water for many times, fully cleaning the silk monofilament with the deionized water, and drying in an oven at the temperature of 60 ℃ to obtain the degummed bombyx mori silk fibroin fiber.
4. The preparation method of the regenerative and repairable vascular stent graft according to any one of claims 1 to 3, wherein the preparation method comprises the following steps: the silk thread in the step (1) is 60D-120D.
5. The method for preparing the vascular stent graft capable of being regeneratively repaired according to claim 1, which is characterized in that: and (3) the mass fraction of the purified bombyx mori silk fibroin aqueous solution in the step (3) is 3%.
6. The method for preparing the regenerative and repairable vascular stent graft according to claim 1, wherein: in the step (4), the boiled silk threads are woven into a tubular structure which is interwoven at an angle of 60-90 degrees, has a linear density of 4-12 threads/cm and has an inner diameter of 2-20 mm on a stainless steel bar by adopting a weaving technology.
7. The method for preparing the vascular stent graft capable of being regeneratively repaired according to claim 1, which is characterized in that: the dipping time in the step (4) is 5-10 seconds, and the number of times of repeating the step is 3-5 times.
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| PCT/CN2021/110229 WO2022028397A1 (en) | 2020-08-06 | 2021-08-03 | Regenerative and restorative vascular stent covering membrane and preparation method therefor |
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| CN101703812A (en) * | 2009-11-20 | 2010-05-12 | 东华大学 | Polyamide 66 membrane covered nickel-titanium alloy intravascular scaffold and preparation method thereof |
| CN102274089A (en) * | 2011-05-24 | 2011-12-14 | 苏州大学 | Silk fibroin tubular bracket and preparation method thereof |
| CN102343113A (en) * | 2010-08-02 | 2012-02-08 | 苏州大学 | Preparation method for tubular silk fibroin scaffold for tissue repair |
| CN106310373A (en) * | 2015-07-09 | 2017-01-11 | 陕西佰傲再生医学有限公司 | Biological repair membrane and preparation method thereof |
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| US20010053931A1 (en) * | 1999-11-24 | 2001-12-20 | Salvatore J. Abbruzzese | Thin-layered, endovascular silk-covered stent device and method of manufacture thereof |
| CN104524632B (en) * | 2015-01-21 | 2016-12-07 | 北京航空航天大学 | A kind of preparation method of the anticoagulation composite tube support with good conformability |
| CN104888272B (en) * | 2015-04-27 | 2017-07-21 | 南昌大学第二附属医院 | One kind removes cell aorta petal support and its production and use |
| CN105457092A (en) * | 2015-10-12 | 2016-04-06 | 圆容生物医药无锡有限公司 | Polyurethane (PU) composition with adjustable elasticity modulus and application of PU composition in medical implant materials |
| CN112043876B (en) * | 2020-08-06 | 2022-05-31 | 苏州大学 | Reproducible and repairable vascular stent covering film and preparation method thereof |
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| CN101703812A (en) * | 2009-11-20 | 2010-05-12 | 东华大学 | Polyamide 66 membrane covered nickel-titanium alloy intravascular scaffold and preparation method thereof |
| CN102343113A (en) * | 2010-08-02 | 2012-02-08 | 苏州大学 | Preparation method for tubular silk fibroin scaffold for tissue repair |
| CN102274089A (en) * | 2011-05-24 | 2011-12-14 | 苏州大学 | Silk fibroin tubular bracket and preparation method thereof |
| CN106310373A (en) * | 2015-07-09 | 2017-01-11 | 陕西佰傲再生医学有限公司 | Biological repair membrane and preparation method thereof |
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