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CN101934091A - Polysaccharide artificial blood vessel and preparation method and application thereof - Google Patents

Polysaccharide artificial blood vessel and preparation method and application thereof Download PDF

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Publication number
CN101934091A
CN101934091A CN2010102739132A CN201010273913A CN101934091A CN 101934091 A CN101934091 A CN 101934091A CN 2010102739132 A CN2010102739132 A CN 2010102739132A CN 201010273913 A CN201010273913 A CN 201010273913A CN 101934091 A CN101934091 A CN 101934091A
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CN
China
Prior art keywords
polysaccharide
blood vessel
artificial blood
chitosan
chitin
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CN2010102739132A
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CN101934091B (en
Inventor
刘万顺
韩宝芹
孔晓颖
潘学理
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QINGDAO BIOTEMED BIOLOGICAL MATERIAL CO., LTD.
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Ocean University of China
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Priority to CN 201010273913 priority Critical patent/CN101934091B/en
Publication of CN101934091A publication Critical patent/CN101934091A/en
Priority to PCT/CN2011/074724 priority patent/WO2012031491A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/20—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Vascular Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

The invention relates to a polysaccharide artificial blood vessel and a preparation method and application thereof. The polysaccharide artificial blood vessel is characterized in that the compact artificial blood vessel is prepared from water-insoluble polysaccharide fibers and colloidal solution which are prepared from polysaccharide; the polysaccharide is one or two of carboxymethylcellulose, hydroxy propyl cellulose, hydroxyethylcellulose, hyaluronic acid, alginate, heparin, chondroitin sulfuric acid, chitin, carboxymethyl chitin, hydroxypropyl chitin, hydroxyethyl chitin, carboxymethyl hydroxypropyl chitin, carboxymethyl hydroxyethyl chitin, hydroxypropyl hydroxyethyl chitin, sulfonated chitin, chitosan, carboxymethyl chitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, carboxymethyl hydroxyethyl chitosan, carboxymethyl hydroxypropyl chitosan, hydroxypropyl hydroxyethyl chitosan, sulfonated chitosan or succinyl chitosan. The polysaccharide artificial blood vessel has the high compactness, stretchability, bendability, mechanical strength and flexibility, can be implanted into bodies during the operation of trauma repair, and is used as artificial blood vessels to replace hurt vessels and improve blood-supply condition.

Description

A kind of polysaccharide artificial blood vessel and its production and application
Technical field
The present invention relates to a kind of medical material, particularly relate to a kind of polysaccharide artificial blood vessel and its production and application.
Background technology
The artificial blood vessel has important effect in treatment vascular conditions and young and middle-aged repair in trauma.The artificial blood vessel succeeds in developing and is used for clinically as far back as the 1950's, has experienced the development experience from simple to complexity, and its performance is constantly improved, more and more near desirable artificial blood vessel's performance requirement.Materials such as terylene, politef, polyurethane heavy caliber (＞6mm) obtain satisfied effect in artificial blood vessel's the manufacturing, patency rate can reach more than 90% in 5 years, therefore was commonly used for artery transplantation big, medium caliber.But above-mentioned material make small-bore (≤6mm) have more problem among the artificial blood vessel, low etc. as easily causing thrombosis, chronic inflammatory reaction, neointimal hyperplasia, long-term patency rate, therefore the application in small-caliber artificial blood vessel is unsatisfactory.
Along with the continuous development of biomaterial science, degradable macromolecular material receives increasing concern as organizational project type artificial blood vessel, is to study focus at present, but not a large amount of clinical use.At present, the artificial blood vessel mainly contains two classes as the organizational project type, one class is artificial polymeric material, as polyglycolic acid (PGA), polylactic acid (PLA), polyglycolic acid (PLLA) etc., the common feature of these materials is: have plasticity and absorbability, but, also produce chronic inflammatory reaction because it progressively is decomposed into micromolecule such as lactic acid, hydroxyacetic acid etc. in vivo.Another kind of is the material that extracts from natural tissues, as fibroin, collagen protein, chitosan, alginic acid etc., these natural materials are widely distributed at occurring in nature, be easy to produce, degradable absorbs, and has excellent biological compatibility, help adhering to and growing of cell, through derivatization modification and special fabrication processes, can obtain ideal small-caliber artificial blood vessel, its key problem in technology is to reduce inflammatory reaction, raising anticoagulant property, raising long-term patency rate, quickening endothelialization process.
In application number is 200910264239.9 Chinese invention patent, a kind of non-vessel stent with the chitin fiber braiding is disclosed, the length of support is 100 ± 3mm, diameter is 18 ± 2mm, and illustrates the network structure of this non-vessel stent for braiding; In application number is 200910264238.4 Chinese invention patent, a kind of intravascular stent with the chitin fiber braiding is disclosed, the length of support is 28-32mm, diameter is 16-20mm, and illustrates the network structure of this intravascular stent for braiding.Above-mentioned two patents of invention because it is woven into network structure, can make liquid such as blood by mesh, anti-side leakage effect, and the tube chamber postoperative control that therefore can only be used for blood vessel is narrow, can not be as artificial blood vessel's succedaneum.
Summary of the invention
The purpose of this invention is to provide a kind of polysaccharide artificial blood vessel and its production and application, to overcome the above-mentioned shortcoming of prior art.
A kind of polysaccharide artificial blood vessel is characterized in that the water-insoluble polysaccharide fiber made by polysaccharide and the artificial blood vessel of the densification of being made jointly by the colloid solution that polysaccharide is made; Described polysaccharide is a carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl-cellulose, hyaluronic acid, alginate, heparin, chondroitin sulfate, chitin, carboxymethyl chitin, Chitofilmer, ethoxyl chitin, the carboxy-methyl hydroxy propyl chitin, the carboxymethyl ethoxyl chitin, the hydroxypropyl ethoxyl chitin, sulfonated chitin, chitosan, carboxymethyl chitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, the carboxymethyl hydroxyethyl chitosan, the carboxy-methyl hydroxy propyl chitosan, the hydroxypropyl hydroxyethyl chitosan, in sulfonated chitosan or the succinyl-chitosan a kind or 2 kinds.
Above-mentioned polysaccharide artificial blood vessel's preparation method, it is characterized in that at cross-sectional diameter be 1-10mm, length is on artificial blood vessel's mould of 2-50cm, evenly be coated with polysaccharide colloid solution, with ground winding of water-insoluble polysaccharide fibre compact or braiding or woven on artificial blood vessel's mould, form fine and close polysaccharide fiber layer, on the polysaccharide fiber layer, be coated with polysaccharide colloid solution again, through natural drying/heat drying, or carry out crosslinkedly with cross-linking agent, again through natural drying/heat drying, form fine and close rete, polysaccharide fiber and polysaccharide membrane form fine and close tubular structure jointly, take off from mould, through cutting, packing, sterilization makes the polysaccharide artificial blood vessel.
Above-mentioned polysaccharide artificial blood vessel in the implant into body, substitutes damage or damaged blood vessel as the artificial blood vessel in clinical operation, improve the application of blood supply situation.
Polysaccharide artificial blood vessel of the present invention has compactness, tensility, flexible, mechanical strength and compliance preferably, in implanting animal body or after in the human body, can be by the slow degraded and absorbed of body, non-immunogenicity, have better biocompatibility, and can promote the growth of vascular endothelial cell, can be implanted in the body in the repair in trauma operation, substitute damage or damaged blood vessel as the artificial blood vessel, improve the blood supply situation.
Macromolecule polysaccharide is biodegradable, have no side effect, also have good one-tenth colloidality, film property, spinnability, part polysaccharide such as chitosan, hyaluronic acid etc. also have good biological function, have effects such as promoting wound healing, suppress scar hyperplasia, be antibiotic, all these characteristics are all given the premium properties of macromolecule polysaccharide as bio-medical material.
The specific embodiment
Embodiment 1
Getting length is 30cm, diameter is the bar-shaped artificial blood vessel's mould of the ganoid rustless steel of 2mm, the chitin polysaccharide fiber is twined the tubular structure that forms densification equably on the bar-shaped artificial blood vessel's mould of above-mentioned rustless steel, the coating quality percentage concentration is the acetic acid hydrocolloid solution (mass percentage concentration of acetic acid is 1% in the acetic acid hydrocolloid solution) of the chitosan of 2% (together following) on chitin polysaccharide fiber tubular structure again, natural drying becomes fine and close chitosan polysaccharide membrane, carefully take off the tubular structure of above-mentioned densification of making by chitin polysaccharide fiber and chitosan polysaccharide membrane, through cutting from stainless steel bar shape artificial blood vessel mould, packing; 60Co sterilizes, and makes the polysaccharide artificial blood vessel of cross sectional inner diameter 2mm.
Embodiment 2
Getting length is 30cm, diameter is the bar-shaped artificial blood vessel's mould of the ganoid rustless steel of 4mm, the carboxymethyl cellulose polysaccharide fiber is twined the tubular structure that forms densification equably on the bar-shaped artificial blood vessel's mould of above-mentioned rustless steel, the coating quality percentage concentration is the acetic acid hydrocolloid solution (mass percentage concentration of acetic acid is 1% in the acetic acid hydrocolloid solution) of the chitosan of 2% (together following) on carboxymethyl cellulose polysaccharide fiber tubular structure again, natural drying becomes fine and close chitosan polysaccharide membrane, carefully take off the tubular structure of above-mentioned densification of making by carboxymethyl cellulose polysaccharide fiber and chitosan polysaccharide membrane, through cutting from stainless steel bar shape artificial blood vessel mould, packing; 60Co sterilizes, and makes the polysaccharide artificial blood vessel of cross sectional inner diameter 4mm.
Embodiment 3
Getting length is 20cm, diameter is the bar-shaped artificial blood vessel's mould of the ganoid glass of 6mm, to by mass ratio the line that is spun into after mixing at 3: 7 by chitosan polysaccharide fiber and chitin polysaccharide fiber, form fine and close tubular structure along the bar-shaped artificial blood vessel's mould braiding of rustless steel, the hydrocolloid solution of the carboxymethyl chitin of coating above-mentioned 2% on tubulose, natural drying becomes fine and close carboxymethyl chitin polysaccharide membrane, carefully take off above-mentioned by the chitin polysaccharide fiber from the bar-shaped artificial blood vessel's mould of glass, the fine and close tubular structure that chitosan polysaccharide fiber and carboxymethyl chitin polysaccharide membrane are made is through cutting, packing; 60The Co sterilization, making cross sectional inner diameter is the polysaccharide artificial blood vessel of 6mm.
Embodiment 4
Getting length is 50cm, diameter is the ganoid rustless steel tubulose artificial blood vessel mould of 8mm, the coating quality percentage concentration is carboxymethyl chitin-hyaluronic polysaccharide colloid aqueous solution (carboxymethyl chitin and hyaluronic mass ratio are 9: 1) of 2% equably on the surface of tubular artificial blood vessel mould mould, be wrapped on the above-mentioned rustless steel tubulose mould that scribbles carboxymethyl chitin-hyaluronic polysaccharide colloid solution with getting alginic acid polysaccharide fiber even compact, coating carboxymethyl chitin-hyaluronic polysaccharide colloid solution of above-mentioned 2% on the alginic acid polysaccharide fiber again, natural drying becomes fine and close polysaccharide membrane, tubular structure is immersed in the aqueous solution contain 1% glutaraldehyde cross-linking agent, crosslinked 60min, immerse again after the taking-up and contain reductase 12 h in 2% the sodium borohydride aqueous solution, take out the water of putting into cleaning again and soak 12h, taking out the back dries naturally, carefully take off the tubular structure of above-mentioned densification, through cutting from stainless steel tubular artificial blood vessel's mould, packing; 60The Co sterilization, making cross sectional inner diameter is the polysaccharide artificial blood vessel of 8mm.
In the foregoing description 1 to embodiment 4, chitin polysaccharide fiber, carboxymethyl cellulose polysaccharide fiber, chitosan polysaccharide fiber and alginic acid polysaccharide fiber are the water-insoluble polysaccharide fiber; With the chitin polysaccharide fiber, the carboxymethyl cellulose polysaccharide fiber, it is hydroxypropyl cellulose that chitosan polysaccharide fiber or alginic acid polysaccharide fiber change polysaccharide into, hydroxyethyl-cellulose, hyaluronic acid, heparin, chondroitin sulfate, carboxymethyl chitin, Chitofilmer, ethoxyl chitin, the carboxy-methyl hydroxy propyl chitin, the carboxymethyl ethoxyl chitin, the hydroxypropyl ethoxyl chitin, sulfonated chitin, carboxymethyl chitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, the carboxymethyl hydroxyethyl chitosan, the carboxy-methyl hydroxy propyl chitosan, the hydroxypropyl hydroxyethyl chitosan, the water-insoluble fiber of sulfonated chitosan or succinyl-chitosan all can reach same effect.
In the foregoing description 1 to embodiment 4, described polysaccharide artificial blood vessel is the artificial blood vessel of the water-insoluble polysaccharide fiber made by polysaccharide and the densification of being made jointly by the colloid solution that polysaccharide is made; Described polysaccharide is a carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl-cellulose, hyaluronic acid, alginate, heparin, chondroitin sulfate, chitin, carboxymethyl chitin, Chitofilmer, ethoxyl chitin, the carboxy-methyl hydroxy propyl chitin, the carboxymethyl ethoxyl chitin, the hydroxypropyl ethoxyl chitin, sulfonated chitin, chitosan, carboxymethyl chitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, the carboxymethyl hydroxyethyl chitosan, the carboxy-methyl hydroxy propyl chitosan, the hydroxypropyl hydroxyethyl chitosan, in sulfonated chitosan or the succinyl-chitosan a kind or 2 kinds; The mass percentage concentration of described polysaccharide colloid solution is 0.5-20%.
In the foregoing description 1 to embodiment 4, when preparing described polysaccharide artificial blood vessel, be 1-10mm at cross-sectional diameter earlier, length is on artificial blood vessel's mould of 2-50cm, evenly be coated with polysaccharide colloid solution, with ground winding of water-insoluble polysaccharide fibre compact or braiding or woven on artificial blood vessel's mould, form fine and close polysaccharide fiber layer, on the polysaccharide fiber layer, be coated with polysaccharide colloid solution again, through natural drying/heat drying, or carry out crosslinked with cross-linking agent, again through natural drying/heat drying, form fine and close rete, polysaccharide fiber and polysaccharide membrane form fine and close tubular structure jointly, take off from mould, through cutting, packing, sterilization, making cross sectional inner diameter is 1-10mm, length is the polysaccharide artificial blood vessel of 2-50cm; Described cross-linking agent is a kind or 2 kinds in Biformyl, malonaldehyde, glutaraldehyde, ethylene glycol bis glycidyl ether, butanediol bisglycidyl ether or the epoxychloropropane; The aqueous solution of cross-linking agent or the mass percentage concentration of alcoholic solution are 0.05-10%.
In polysaccharide artificial blood vessel of the present invention, the water-insoluble polysaccharide fiber forms fine and close tubular structure with compact winding, closely braiding, tight woven mode on artificial blood vessel's mould; The water-insoluble polysaccharide fiber has played skeleton support effect, has increased artificial blood vessel's tensility, flexible, mechanical strength and compliance; Described polysaccharide colloid solution has increased artificial blood vessel's compactness, tensility, flexible, mechanical strength and compliance at the internal layer or the outer rete that is dried to densification of polysaccharide fiber layer, has played the effect that prevents side leakage.
Embodiment 5
Polysaccharide artificial blood vessel's functional evaluation test: the polysaccharide artificial blood vessel who gets the cross sectional inner diameter 2mm that the foregoing description 1 makes, aseptic condition is used the artificial blood vessel of operating scissors clip length 4cm down, with the hybrid dog is experimental animal, adopts the pentobarbital sodium intraperitoneal injection of anesthesia, and dosage is 45mg/Kg.Surgical incision test dog thigh root inboard, the surgical exposure femoral artery is clamped the femoral artery two ends that a segment length is 8cm with hemostatic clamp, block femoral artery 4cm, adopt the end end to sew up, the artificial blood vessel of clip is sewn onto the femoral artery place of blocking, take off hemostatic clamp, layer-by-layer suture muscle, skin.Test Canis familiaris L. postoperative is normally raised, the behavior state of routine observation test Canis familiaris L., and carry out ultrasonic examination femoral artery blood circumstance.Experimental result shows, in 1 week behind the femoral artery prosthetic vessel replacement, the walking of test Canis familiaris L. is basic to recover normal; In the observation period of 3 months after surgery, 6 months and 9 months, animal action and performance are all normal, and the colorful ultrasonic that artificial blood vessel's transplantation site is carried out is observed and shown that artificial blood vessel's blood flow is unobstructed, and port coincide good, does not have significantly narrow and clogging.
Prepared polysaccharide artificial blood vessel in the embodiment of the invention all can obtain similar result in the functional evaluation test research that animal blood vessels is replaced, equal can substituting damaged or damaged blood vessel, improves the application of blood supply situation.
Polysaccharide artificial blood vessel of the present invention has compactness, tensility, flexible, mechanical strength and compliance preferably, in implanting animal body or after in the human body, can be by the slow degraded and absorbed of body, non-immunogenicity has better biocompatibility, and can promote the growth of vascular endothelial cell, can be in clinical repair in trauma operation in the implant into body, as the substitute of injured blood vessel, substitute damage or damaged blood vessel as the artificial blood vessel, improve the blood supply situation.Therefore, polysaccharide artificial blood vessel of the present invention in the implant into body, substitutes damage or damaged blood vessel as the artificial blood vessel in clinical operation, improve the application of blood supply situation.

Claims (6)

1. polysaccharide artificial blood vessel is characterized in that the water-insoluble polysaccharide fiber made by polysaccharide and the artificial blood vessel of the densification of being made jointly by the colloid solution that polysaccharide is made; Described polysaccharide is a carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl-cellulose, hyaluronic acid, alginate, heparin, chondroitin sulfate, chitin, carboxymethyl chitin, Chitofilmer, ethoxyl chitin, the carboxy-methyl hydroxy propyl chitin, the carboxymethyl ethoxyl chitin, the hydroxypropyl ethoxyl chitin, sulfonated chitin, chitosan, carboxymethyl chitosan, hydroxypropyl chitosan, hydroxyethyl chitosan, the carboxymethyl hydroxyethyl chitosan, the carboxy-methyl hydroxy propyl chitosan, the hydroxypropyl hydroxyethyl chitosan, in sulfonated chitosan or the succinyl-chitosan a kind or 2 kinds.
2. polysaccharide artificial blood vessel as claimed in claim 1, the mass percentage concentration that it is characterized in that described polysaccharide colloid solution is 0.5-20%.
3. polysaccharide artificial blood vessel as claimed in claim 1, the cross sectional inner diameter that it is characterized in that described polysaccharide artificial blood vessel is that 1-10mm, length are 2-50cm.
4. the described polysaccharide artificial blood vessel's of claim 1 preparation method, it is characterized in that at cross-sectional diameter be 1-10mm, length is on artificial blood vessel's mould of 2-50cm, evenly be coated with polysaccharide colloid solution, with ground winding of water-insoluble polysaccharide fibre compact or braiding or woven on artificial blood vessel's mould, form fine and close polysaccharide fiber layer, on the polysaccharide fiber layer, be coated with polysaccharide colloid solution again, through natural drying/heat drying, or carry out crosslinkedly with cross-linking agent, again through natural drying/heat drying, form fine and close rete, polysaccharide fiber and polysaccharide membrane form fine and close tubular structure jointly, take off from mould, through cutting, packing, sterilization makes the polysaccharide artificial blood vessel.
5. polysaccharide artificial blood vessel's as claimed in claim 4 preparation method is characterized in that described cross-linking agent is a kind or 2 kinds in Biformyl, malonaldehyde, glutaraldehyde, ethylene glycol bis glycidyl ether, butanediol bisglycidyl ether or the epoxychloropropane; The aqueous solution of cross-linking agent or the mass percentage concentration of alcoholic solution are 0.05-10%.
6. the described polysaccharide artificial blood vessel of claim 1 in the implant into body, substitutes damage or damaged blood vessel as the artificial blood vessel in clinical operation, improves the application of blood supply situation.
CN 201010273913 2010-09-07 2010-09-07 Polysaccharide artificial blood vessel and preparation method and application thereof Active CN101934091B (en)

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PCT/CN2011/074724 WO2012031491A1 (en) 2010-09-07 2011-05-26 Artificial vessel of polysaccharide, preparation and use thereof

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WO2012031491A1 (en) * 2010-09-07 2012-03-15 德州海利安生物科技股份有限公司 Artificial vessel of polysaccharide, preparation and use thereof
CN104174065A (en) * 2014-09-02 2014-12-03 青岛博益特生物材料有限公司 Absorbable artificial blood vessel as well as preparation method and application thereof
CN104353128A (en) * 2014-09-02 2015-02-18 青岛博益特生物材料股份有限公司 Degradable intravascular stent and preparation method and application thereof
CN104940999A (en) * 2015-06-29 2015-09-30 苏州佑君环境科技有限公司 Vascular wall elastic basement membrane and preparation method thereof
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WO2012031491A1 (en) * 2010-09-07 2012-03-15 德州海利安生物科技股份有限公司 Artificial vessel of polysaccharide, preparation and use thereof
CN104174065A (en) * 2014-09-02 2014-12-03 青岛博益特生物材料有限公司 Absorbable artificial blood vessel as well as preparation method and application thereof
CN104353128A (en) * 2014-09-02 2015-02-18 青岛博益特生物材料股份有限公司 Degradable intravascular stent and preparation method and application thereof
CN104940999A (en) * 2015-06-29 2015-09-30 苏州佑君环境科技有限公司 Vascular wall elastic basement membrane and preparation method thereof
CN106710406A (en) * 2015-07-21 2017-05-24 上海微创医疗器械（集团）有限公司 Vascular model and manufacturing method thereof, and spraying equipment
CN106710416A (en) * 2015-07-30 2017-05-24 上海微创医疗器械（集团）有限公司 Vessel model, making method thereof, and device for making vessel model
CN106710407A (en) * 2015-07-30 2017-05-24 上海微创医疗器械（集团）有限公司 Blood vessel model, manufacturing method thereof, and device for making blood vessel model
CN105999434A (en) * 2016-05-24 2016-10-12 德州海利安生物科技股份有限公司 Developing type degradable ureter repairing stent
CN106039426A (en) * 2016-05-24 2016-10-26 德州海利安生物科技股份有限公司 Developing type degradable restoration pancreatic duct bracket
CN105999435A (en) * 2016-05-24 2016-10-12 德州海利安生物科技股份有限公司 Developing type degradable urethra repairing stent
CN105944153A (en) * 2016-05-24 2016-09-21 德州海利安生物科技股份有限公司 Development type degradable repair biliary tract stent
CN107049485A (en) * 2017-03-29 2017-08-18 广州迈普再生医学科技有限公司 The preparation method and tissue model of a kind of tissue model with cavity structure
CN107049485B (en) * 2017-03-29 2021-09-17 广州迈普再生医学科技股份有限公司 Preparation method of tissue model with cavity structure and tissue model
CN107469144A (en) * 2017-07-29 2017-12-15 青岛慧生惠众生物科技有限公司 A kind of chitosan-based composite nerve conduit and its preparation method and application
CN112704768A (en) * 2020-11-30 2021-04-27 山东大学 Chondroitin sulfate modified collagen/polycaprolactone vascular repair stent and preparation method and application thereof

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