CN108815589A - 一种医用可降解锌基合金血管支架制品 - Google Patents
一种医用可降解锌基合金血管支架制品 Download PDFInfo
- Publication number
- CN108815589A CN108815589A CN201810255109.8A CN201810255109A CN108815589A CN 108815589 A CN108815589 A CN 108815589A CN 201810255109 A CN201810255109 A CN 201810255109A CN 108815589 A CN108815589 A CN 108815589A
- Authority
- CN
- China
- Prior art keywords
- zinc
- degradable
- alloy
- intravascular stent
- containing alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 40
- 239000011701 zinc Substances 0.000 title claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 229940021171 curative drug Drugs 0.000 claims abstract description 21
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000007888 film coating Substances 0.000 claims abstract description 13
- 238000009501 film coating Methods 0.000 claims abstract description 13
- 239000010953 base metal Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 7
- 239000004626 polylactic acid Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- ZAHRKKWIAAJSAO-UHFFFAOYSA-N rapamycin Natural products COCC(O)C(=C/C(C)C(=O)CC(OC(=O)C1CCCCN1C(=O)C(=O)C2(O)OC(CC(OC)C(=CC=CC=CC(C)CC(C)C(=O)C)C)CCC2C)C(C)CC3CCC(O)C(C3)OC)C ZAHRKKWIAAJSAO-UHFFFAOYSA-N 0.000 claims description 6
- QFJCIRLUMZQUOT-HPLJOQBZSA-N sirolimus Chemical compound C1C[C@@H](O)[C@H](OC)C[C@@H]1C[C@@H](C)[C@H]1OC(=O)[C@@H]2CCCCN2C(=O)C(=O)[C@](O)(O2)[C@H](C)CC[C@H]2C[C@H](OC)/C(C)=C/C=C/C=C/[C@@H](C)C[C@@H](C)C(=O)[C@H](OC)[C@H](O)/C(C)=C/[C@@H](C)C(=O)C1 QFJCIRLUMZQUOT-HPLJOQBZSA-N 0.000 claims description 6
- 229960002930 sirolimus Drugs 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 19
- 208000007536 Thrombosis Diseases 0.000 abstract description 7
- 206010061218 Inflammation Diseases 0.000 abstract description 6
- 238000001727 in vivo Methods 0.000 abstract description 6
- 230000004054 inflammatory process Effects 0.000 abstract description 6
- 239000012567 medical material Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 208000037803 restenosis Diseases 0.000 abstract description 3
- 239000007943 implant Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 14
- 239000003814 drug Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 11
- 229940079593 drug Drugs 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000007769 metal material Substances 0.000 description 10
- 238000002513 implantation Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000004663 cell proliferation Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910007565 Zn—Cu Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012620 biological material Substances 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 210000002889 endothelial cell Anatomy 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 201000006828 endometrial hyperplasia Diseases 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 208000020925 Bipolar disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 210000000702 aorta abdominal Anatomy 0.000 description 1
- 230000003143 atherosclerotic effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 210000000887 face Anatomy 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- -1 meanwhile Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940126585 therapeutic drug Drugs 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 231100000216 vascular lesion Toxicity 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- 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
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- 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
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
-
- 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
- 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
- A61L31/10—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
- 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
-
- 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
- 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
- A61L31/18—Materials at least partially X-ray or laser opaque
-
- 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
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
-
- 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
- A61L2300/40—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
-
- 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
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Heart & Thoracic Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明涉及医用材料及其器械领域,是一种在体内可降解的植入性血管支架制品。本发明公开的内容包括:1)一种在体内可降解的植入性锌基金属材料。2)由1)所述的锌基合金材料制作而成的血管支架制品为管网式结构。3)由2)所述的管网式支架制品表面沉积有均匀分布的金属镁薄膜涂层。4)在镁薄膜涂层外设置有均匀涂覆的可降解聚合物涂层,该聚合物涂层可含有治疗性药物。本发明提供的锌基合金,力学性能优良,腐蚀可控性强,卓越的相容性。同时,本发明提供的血管支架制品,表面特殊设置利于保持初期结构完整,利于支架内皮化,减少炎性反应,以降低支架植入后局部炎症、再狭窄及支架内血栓风险。
Description
技术领域
本发明涉及的是一种医用材料及其医疗器械领域,是一种在人体内可降解的植入性血管支架制品。
背景技术
可降解医疗器械在完成既定的医疗目的后自行降解,不长久存留,可避免永久性植入器械在体长期存在引发的生物学炎性反应及生物力学不适配等问题,且降解产物可代谢、无毒副作用,逐渐成为当前科研工作者和医卫工作人员研究的热点。当前,可降解医疗器械在介入医学领域和骨科修复领域的发展取得了令人振奋的成绩。可降解聚合物医疗器械和可降解金属医疗器械已成为可降解医疗器械开发的两个重要方向。而相较于可降解聚合物材料,可降解金属材料所具有的金属特性,其机械性能、加工性能等都具有较大的医用优势。
可降解镁及镁合金的研究与开发已经有了丰厚的积累,并获得了一定的临床关注(Biomaterials,2017,112:287-302.),但其腐蚀速率的调控仍然是研究者所关注的焦点问题,该类可降解金属一般在数天内就会在人体中完全降解,不能起到治疗、支撑作用,同时降解过程中会产生氢气,在组织间形成气囊,影响组织修复与愈合(Acta biomaterialia,2015,23:S28-S40.)。可降解铁及其合金降解速度过于慢,以之制作医疗器械其医学服役疗效与腐蚀产生的失效过程匹配性较差,甚至引发了类似永久性植入物才有的生物学问题(Biomaterials,2006,27(28):4955-4962.),如何加速铁基合金的降解已是开发铁基医疗器械尚未克服的壁垒(Acta Biomaterialia,2017,54:454-468.)。因此,对于具有合适降解速率和力学稳定性的合金的开发需要一个长期的探索过程。而金属锌的化学活性介于镁和铁之间,腐蚀速率应该略快于铁而慢于镁,从腐蚀速率上讲,锌不失为一个理想的可降解金属材料,同时,锌是人体必需的微量元素,具有较好的生物学效应,开发锌作为新型可降解金属材料为可降解材料的研究与开发提供了一个全新的方向。
PK Bowen(Advanced Materials,2013,25(18):2577-2582)在其研究中报道了纯锌丝材在小鼠腹主动脉血管壁的植入实验,揭示了其在体内的腐蚀特性,植入3个月后仍保持截面完整,可见此时仍能保持有效的力学支撑,构成可降解金属支架时应能保持较长时间的血管畅通,同时,植入物周围组织没有发现明显的坏死或对锌丝的排异反应;PK Bowen(ActaBiomaterialia,2017,58:539-549.)在长期的植入研究中(12-20个月)发现,锌丝的降解产物在附近集聚,却被纤维囊包裹,丝材周围没有明显的慢性炎症反应。因此,从降解速度及安全性来讲,锌是一种制造血管支架的理想的可降解金属材料。同时,国内研究单位也有对此领域进行相关探索研究,如中国专利CN 104212998A公布了一种Zn-Mg系锌合金及其制备方法,不得不指出的是,在其优选的实施方式中可见该系合金的塑性并不理想,延伸率最高仅12%左右,以之制作的血管支架将难以承受该支架结构经压握预装并在血管病变位置处膨胀撑开所致的剧烈变形;中国专利CN 106467942A公布了一种生物可降解的医用锌铜合金(Zn-Cu)及其制备方法,在实施方式中可见Zn-Cu合金表现出较为优越的塑性,延伸率22~50%,但强度却在180~270MPa之间,并不是非常理想,PK Bowen(Advancedhealthcarematerials,2016,5(10):1121-1140.)指出理想的支架用可降解金属材料应该确保抗拉强度(Ultimate tensile strength)大于300MPa,显然Zn-Cu合金用于血管支架在性能上还存在不足。因此,全降解血管支架用高强韧的新型可降解金属材料的开发迫在眉睫。
发明内容
本发明针对现有可降解金属材料存在的性能缺陷,克服镁及镁合金降解速度较快、铁基合金降解速度过慢,以及当前研究的锌基合金面临的强韧性不足的缺陷,本发明旨在开发出一种无毒、可完全降解、高强韧医用锌基合金,并由该系合金制作的血管支架制品。
本发明的目的是这样实现的:
当前,可降解金属材料的开发研究已经获得了一定的临床关注与科学积累,但仍还存在着尚未攻克的壁垒制约其广泛应用。比如,镁基可降解金属材料面临腐蚀速率可控性较差的问题,铁基可降解金属材料面临着腐蚀速率过慢,长久以往会产生类似永久性植入物致使的生物学排异反应,锌基可降解金属面临着强韧性不足难题。本发明在实施提出的一种医用可降解植入性金属材料时,进行了充分实验论证,筛选合金化元素从生物学效应角度出发,选用对人体有益元素如Li、Mg、Mn和无毒的Cu和Ti等元素进行合金化,该类元素的引入无需遗传毒性等生物相容性的担忧。同时从冶金学角度,Li的加入可赋予合金优越的强度及塑性;Cu的加入可赋予合金优越的综合力学性能,同样可减轻锌基合金的晶间腐蚀现象;Mn的加入能够提高合金的耐磨性和抗疲劳性能;Ti的引入可提高锌基合金材料的抗蠕变性能并提高合金的再结晶温度,可提高耐疲劳性能及防止性能老化;Mg的加入可显著提高合金的强度、硬度并减少晶间腐蚀现象,确保支架结构在降解过程中的支撑力稳定性。以之制作而成的具有更好治疗效果的新型可降解金属基药物支架,用以克服传统金属裸支架在体内不可降解,长期作为异物存留体内产生炎性刺激反应,又可以避免可降解聚合物支架在体力学支撑性能不佳和不具备显影效果而带来的医学限制以及可降解铁基支架、镁基支架降解速度与管腔内膜重建不匹配的弊端。同时,该支架制品在实施时,在锌基合金支架制品表面沉积有均匀分布的金属镁薄膜涂层,同时在镁薄膜涂层外设置有均匀涂覆的可降解聚合物涂层,该聚合物涂层可含有治疗性药物。
本发明具体还应包括:
1.一种医用可降解锌基合金血管支架制品,其特征在于包括:由可降解锌基金属材料支架基体构成的管网状结构,并在所述的管网式支架制品表面沉积有均匀分布的金属镁薄膜涂层,同时在镁薄膜涂层外设置有均匀涂覆的可降解聚合物涂层,该聚合物涂层可含有治疗性药物。
2.所述的一种医用可降解锌基合金血管支架制品,其特征在于所述可降解锌基金属材料是锌基合金,为Zn-(0~0.1wt.%)Li-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu,Zn-(0~0.1wt.%)Li-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu-(0~0.2wt.%)Mn或Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.5wt.%)Mg-(0~0.2wt.%)Mn等合金中的一种;所述锌基合金支架基体表面沉积有均匀分布的金属镁薄膜涂层,其厚度为0~10μm,金属薄膜外设置有含治疗性药物的可降解聚合物洗脱涂层,其厚度为1~30μm,所述的治疗性药物为雷帕霉素,可降解聚合物为聚乳酸或聚乳酸-羟基乙酸共聚物、壳聚糖及衍生物等中的一种或多种共混。
3.所述的一种医用可降解锌基合金血管支架制品,其特征在于所述的可降解锌基材料为Zn-0.09Li-0.05Mg(wt.%)或Zn-0.08Li-0.55Cu(wt.%)或Zn-0.08Li-0.09Mn(wt.%)合金;所述锌基合金支架表面金属镁薄膜涂层的厚度为3μm,经真空磁控溅射或蒸镀等形成镀膜;所述含治疗性药物的可降解聚合物涂层的厚度为10μm,聚合物(聚乳酸)和治疗性药物(雷帕霉素)的质量比为9:1,共混后溶于有机溶剂经喷涂或浸涂等涂覆至支架表面。
所述的锌基合金血管支架制品表面设置有金属镁薄膜,可在植入初期作为牺牲阳极,优先于支架基体与体液发生作用,可保持支架结构完整性,并且镁与体液作用形成具有治疗功能的氢气,可减少血栓作用及排异反应;舍此之外,还有可降解聚合物涂层,并含有治疗性药物,释放给药可在抑制平滑肌细胞增殖的同时,利于内皮细胞在支架内壁生长促进内皮化,减少支架内血栓发生风险。所述的药物层是含治疗性药物的可降解聚合物涂层;所述的治疗性药物是可以抑制平滑肌细胞增生的药物,优选的是雷帕霉素;所述的可降解聚合物涂层是聚乳酸或聚乳酸-羟基乙酸共聚物和壳聚糖及衍生物的一种或多种共混物,且制作时与治疗性药物共混涂覆可以控制药物释放,减少突释并使药物缓慢持续的保持一定浓度,可通过药物的药理学作用抑制内膜增生、增厚,从而减少甚至消灭支架内再狭窄的发生。
本发明提供的医用可降解多元锌基合金材料,选用高纯度的原材料或中间合金经真空熔炼制得,后经压力加工,最终制得多元锌基合金具有良好的综合力学性能,耐腐蚀性能优异,能呈现均匀腐蚀,腐蚀失效可控性强,可以满足医疗器械领域对生物材料的生物安全性和综合力学性能的要求。
还需强调的是,经研究证实,由该体系锌合金制备的可降解支架能独特地赋予其显影性,方便术中支架介入及术后随访,不同于当前研究的可降解镁合金支架,因自身密度较小,无法显影而不得不设置几枚不可降解的重金属标记物,此类镁支架在发生降解后重金属标记物长期在体,将会造成长久的刺激作用甚或引起炎性反应。锌合金的化学活性低于镁合金,而高于铁,经试验验证,其腐蚀速率较为适宜,降解速度慢于镁基合金支架而快于铁基合金支架,避免可降解铁基支架、镁基支架降解速度与管腔重建不匹配的弊端,可以有效保证其力学支撑与管腔重建相匹配。
本发明的有益效果是:
1.从材料基体角度
本案提出的一种由对人体无毒的元素组成的多元锌基合金材料,组分涉及含有Zn、Li、Ti、Mg、Cu、Mn等元素,经熔炼及加工制作而成。
从元素的生物学效应角度出发,本案选用对人体无害,甚或有益的元素进行合金化,避开了具有细胞毒性和遗传毒性的合金化元素的引入,甚至还赋予了材料特殊的生物学作用。例如,Li是人体有益的微量元素,锂的无机离子或简单锂盐能影响人的神经活动,医学上用碳酸锂、硫酸锂、谷氨酸锂等锂盐来控制和治疗神经狂躁症。临床揭示锂的有效剂量在0.6~1.0mM(每天剂量在500~1200mg),而高于1.2mM则会产生毒性。美国EPA早在1985年就对锂的摄入量做了推荐,70kg成人的日摄入量建议在650~3100微克。而对于可降解锌基支架来讲,一个支架质量在20-50mg,1.5年内降解完成,日均降解量远低于摄入量。此外,Li离子对于动脉粥样硬化心脏病的发病率有保护作用。Ti是一种对人体无害的元素,成人日摄入量约0.8mg,且金属钛及其合金作为一种成熟的医用材料在骨修复、心血管介入、普外科等领域获得了广泛应用,已被证实具备生物安全性。Mg是维持人体生命活动必需的常量元素,参与人体所有代谢过程,其生理学意义无需赘言,且Mg基合金材料已获临床证实是一种理想的可降解骨科用材料,而被CE和KFDA批准制作固定螺钉用于非承力位置的骨修复;
从冶金学角度,Li的加入可赋予合金优越的强度及塑性,并通过Li的含量可卓有成效的调节合金材料的强韧性;Cu的加入可赋予合金优越的综合力学性能,同样可减轻锌基合金的晶间腐蚀现象;Mn的加入能够提高合金的耐磨性和抗疲劳性能;Ti的引入可提高锌基合金材料的抗蠕变性能并提高合金的再结晶温度,可提高基体材料的耐疲劳性能并防止性能老化;Mg的加入可显著提高合金的强度、硬度并减少晶间腐蚀现象,确保支架结构在降解过程中的支撑力稳定性。
本案最终制得多元锌基合金具有良好的综合力学性能,耐腐蚀性能优异,能呈现均匀腐蚀,腐蚀失效可控性强,可以满足可降解支架对生物材料的生物安全性和综合力学性能的要求。
2.从支架的实施方案角度来讲
从降解角度讲,由锌合金制备的可降解支架能独特地赋予其显影性,方便术中支架介入及术后随访,不同于当前研究的可降解镁合金支架,因自身密度较小,无法显影而不得不设置几枚不可降解的重金属标记物,此类镁支架在发生降解后重金属标记物长期在体,将会造成长久的刺激作用甚或引起炎性反应。锌合金的化学活性低于镁合金,而高于铁,经试验验证,其腐蚀速率较为适宜,降解速度慢于镁基合金支架而快于铁基合金支架,避免可降解铁基支架、镁基支架降解速度与管腔重建不匹配的弊端,可以有效保证其力学支撑与管腔重建相匹配。
从涂层及载药平台角度讲,所述的锌基合金血管支架制品表面设置有金属镁薄膜,可在植入初期作为牺牲阳极,优先于支架基体与体液发生作用,可保持支架结构完整性,并且镁与体液作用形成具有治疗功能的氢气,可减少血栓作用及排异反应;舍此之外,还有可降解聚合物涂层,并含有治疗性药物,释放给药可在抑制平滑肌细胞增殖的同时,利于内皮细胞在支架内壁生长促进内皮化,减少支架内血栓发生风险。所述的药物层是含治疗性药物的可降解聚合物涂层;所述的治疗性药物是可以抑制平滑肌细胞增生的药物,优选的是雷帕霉素;所述的可降解聚合物涂层是聚乳酸或聚乳酸-羟基乙酸共聚物和壳聚糖及衍生物的一种或多种共混物,且制作时与治疗性药物共混涂覆可以控制药物释放,减少突释并使药物缓慢持续的保持一定浓度,可通过药物的药理学作用抑制内膜增生、增厚,从而减少甚至消灭支架内再狭窄的发生。
附图说明
本发明的具体实施例将结合说明书附图来进行详细说明。
图1是本发明提供的具体实施方式中经加工处理获得的一种可降解植入性金属棒料。
图2是本发明提供的一种医用可降解锌基合金血管支架样品。
图3是本发明提供的血管支架样品连接杆的断面示意图。
具体实施方式
下面给出本发明的实施例对本发明进一步说明,而不是限制本发明的范围。
具体实施如下:
本发明实施时采用纯锌(纯度为99.99%)、纯锂(纯度为99.9%)、纯镁(纯度为99.99%),Zn-Cu和Zn-Ti中间合金为原料进行配备,然后使用真空感应熔炼炉,在6公斤高纯石墨坩埚中熔炼并浇铸,得到12种合金铸锭,其具体化学成分在使用ICP-AES检测后显示如表1所示。
表1本发明实施的医用可降解锌基合金材料的化学成分
熔炼后分别对12种不同实施例所熔炼的锌基合金材料进行车削去除氧化皮及缩口,在210℃充分预热3小时,随后进行压力加工处理,为方便后续加工,本实施例选用挤压处理,并采用正向挤压的方法,在挤压后形成棒材,如图1所示,经退火处理后消除其加工应力,测试获得的力学性能及经浸泡实验获得的腐蚀速率如表2所示。
表2本发明实施的医用可降解锌基合金材料的力学性能及腐蚀速率数据
在后续的加工中,经过挤压-拉拔等深加工后获得了支架用细径薄壁管材,壁厚在0.15mm。随后结合实施方式2所述的锌基合金管材的材料学属性,并通过有限元的方法设计与优化了锌基合金支架结构,依此结构将管材切割与抛光制作了血管支架制品,支架样品如图2所示(优选实施方式1或2或3锌基合金作为支架材料,经切割抛光制得的支架制品最终控制支架壁厚90±5μm,支撑环和连杆宽度100±5μm)。随后在所述锌基合金支架表面进行后处理,示意图如图3所示,连接杆(301)表面沉积了一层3μm厚的金属镁薄膜涂层(302),另在镁薄膜涂层(302)外设置有均匀涂覆的可降解聚合物涂层(303),该聚合物(聚乳酸)涂层厚度为10μm,并可含有治疗性药物(雷帕霉素),聚合物(聚乳酸)和治疗性药物(雷帕霉素)的质量比为9:1,共混后溶于有机溶剂经喷涂或浸涂等涂覆至金属镁涂层(302)表面,支架样品连接杆的断面示意图如图3所示。所述的锌基合金血管支架制品表面设置有金属镁薄膜,可在植入初期作为牺牲阳极,优先于支架基体与体液发生作用,可保持支架结构完整性,并且镁与体液作用形成具有治疗功能的氢气,可减少血栓作用及排异反应;舍此之外,还有可降解聚合物涂层,并含有治疗性药物,释放给药可在抑制平滑肌细胞增殖的同时,利于内皮细胞在支架内壁生长促进内皮化,减少支架内血栓发生风险。
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (4)
1.一种医用可降解锌基合金血管支架制品,其特征在于包括:由可降解锌基金属材料支架基体构成的管网状结构,并在所述的管网式支架制品表面沉积有均匀分布的金属镁薄膜涂层,同时在镁薄膜涂层外设置有均匀涂覆的可降解聚合物涂层,该聚合物涂层可含有治疗性药物。
2.按照权利要求1所述的一种医用可降解锌基合金血管支架制品,其特征在于所述可降解锌基金属材料是锌基合金,为Zn-(0~0.1wt.%)Li-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu,Zn-(0~0.1wt.%)Li-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.2wt.%)Mn,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu-(0~0.5wt.%)Mg,Zn-(0~0.1wt.%)Li-(0~1wt.%)Ti-(0~2wt.%)Cu-(0~0.2wt.%)Mn或Zn-(0~0.1wt.%)Li-(0~2wt.%)Cu-(0~0.5wt.%)Mg-(0~0.2wt.%)Mn等合金中的一种。
3.按照权利要求1所述的一种医用可降解锌基合金血管支架制品,其特征在于所述锌基合金支架基体表面沉积有均匀分布的金属镁薄膜涂层,其厚度为0~10μm,金属薄膜外设置有含治疗性药物的可降解聚合物洗脱涂层,其厚度为1~30μm,所述的治疗性药物为雷帕霉素,可降解聚合物为聚乳酸或聚乳酸-羟基乙酸共聚物、壳聚糖及衍生物等中的一种或多种共混。
4.按照权利要求1所述的一种医用可降解锌基合金血管支架制品,其特征在于所述的医用可降解锌基合金材料优选成分为Zn-0.09Li-0.05Mg(wt.%)或Zn-0.08Li-0.55Cu(wt.%)或Zn-0.08Li-0.09Mn(wt.%)合金;所述锌基合金支架表面金属镁薄膜涂层的厚度为3μm,经真空磁控溅射或蒸镀等形成镀膜;所述含治疗性药物的可降解聚合物涂层的厚度为10μm,聚合物(聚乳酸)和治疗性药物(雷帕霉素)的质量比为9:1,共混后溶于有机溶剂经喷涂或浸涂等涂覆至支架表面。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810255109.8A CN108815589A (zh) | 2018-03-27 | 2018-03-27 | 一种医用可降解锌基合金血管支架制品 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810255109.8A CN108815589A (zh) | 2018-03-27 | 2018-03-27 | 一种医用可降解锌基合金血管支架制品 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108815589A true CN108815589A (zh) | 2018-11-16 |
Family
ID=64154212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810255109.8A Pending CN108815589A (zh) | 2018-03-27 | 2018-03-27 | 一种医用可降解锌基合金血管支架制品 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108815589A (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109939271A (zh) * | 2019-04-11 | 2019-06-28 | 赵亚芳 | 一种医用生物可降解锌合金支架的涂层结构及其制备方法 |
CN111603284A (zh) * | 2020-06-16 | 2020-09-01 | 湖南华耀百奥医疗科技有限公司 | 一种可吸收锌基合金载药支架 |
CN112891640A (zh) * | 2021-01-20 | 2021-06-04 | 湖南华锐科技集团股份有限公司 | 一种Zn-Mg系锌合金血管支架及其制备方法 |
CN113491796A (zh) * | 2020-04-07 | 2021-10-12 | 元心科技(深圳)有限公司 | 含锌医疗器械 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101468216A (zh) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | 一种带药可降解镁合金心血管支架及其制备方法 |
CN104587535A (zh) * | 2014-12-30 | 2015-05-06 | 马艳荣 | 一种生物可降解聚合物涂层载药镁合金洗脱支架 |
CN104857570A (zh) * | 2015-05-05 | 2015-08-26 | 乐普(北京)医疗器械股份有限公司 | 一种可降解锌基合金支架及其制备方法 |
CN107519539A (zh) * | 2017-09-11 | 2017-12-29 | 乐普(北京)医疗器械股份有限公司 | 一种医用可降解锌基合金材料及其血管支架制品 |
-
2018
- 2018-03-27 CN CN201810255109.8A patent/CN108815589A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101468216A (zh) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | 一种带药可降解镁合金心血管支架及其制备方法 |
CN104587535A (zh) * | 2014-12-30 | 2015-05-06 | 马艳荣 | 一种生物可降解聚合物涂层载药镁合金洗脱支架 |
CN104857570A (zh) * | 2015-05-05 | 2015-08-26 | 乐普(北京)医疗器械股份有限公司 | 一种可降解锌基合金支架及其制备方法 |
CN107519539A (zh) * | 2017-09-11 | 2017-12-29 | 乐普(北京)医疗器械股份有限公司 | 一种医用可降解锌基合金材料及其血管支架制品 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109939271A (zh) * | 2019-04-11 | 2019-06-28 | 赵亚芳 | 一种医用生物可降解锌合金支架的涂层结构及其制备方法 |
CN109939271B (zh) * | 2019-04-11 | 2021-10-15 | 赵亚芳 | 一种医用生物可降解锌合金支架的涂层结构及其制备方法 |
CN113491796A (zh) * | 2020-04-07 | 2021-10-12 | 元心科技(深圳)有限公司 | 含锌医疗器械 |
CN111603284A (zh) * | 2020-06-16 | 2020-09-01 | 湖南华耀百奥医疗科技有限公司 | 一种可吸收锌基合金载药支架 |
CN112891640A (zh) * | 2021-01-20 | 2021-06-04 | 湖南华锐科技集团股份有限公司 | 一种Zn-Mg系锌合金血管支架及其制备方法 |
CN112891640B (zh) * | 2021-01-20 | 2022-06-28 | 湖南华锐科技集团股份有限公司 | 一种Zn-Mg系锌合金血管支架及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106890356B (zh) | 一种可降解的锌基合金植入材料及其制备方法与应用 | |
US11590266B2 (en) | Biodegradable iron-containing compositions, methods of preparing and applications therefor | |
CN106319287A (zh) | 生物可降解医用Zn‑Li‑X系合金材料及制备与应用 | |
CN107519539A (zh) | 一种医用可降解锌基合金材料及其血管支架制品 | |
CN103889474B (zh) | 镁合金和包含该镁合金的可吸收的支架 | |
CN108815589A (zh) | 一种医用可降解锌基合金血管支架制品 | |
CN105671391B (zh) | 一种全降解镁合金及其制备方法 | |
CN104857570B (zh) | 一种可降解锌基合金支架及其制备方法 | |
WO2017028646A1 (zh) | 生物可降解的医用锌铜合金及其制备方法和用途 | |
WO2011160534A1 (zh) | 体内可降解的镁合金血管支架材料及其制造方法 | |
CN107496993B (zh) | 一种医用可降解植入性金属材料 | |
WO2017084363A1 (zh) | 医用可降解Zn-Cu-X合金材料及其制备方法 | |
CN110144503B (zh) | 一种高强韧耐蚀镁合金及其制备方法 | |
CN107541631B (zh) | 一种生物医用可降解耐蚀高强韧镁合金及其制备方法 | |
CN109602960B (zh) | 一种具备超塑性的医用锌合金棒材制备方法 | |
CN106282664A (zh) | 生物可降解医用锌锂二元合金材料及其制备方法与应用 | |
WO2018000219A1 (zh) | 一种生物医用可降解耐蚀高强韧镁合金及其制备方法 | |
CN108277386A (zh) | 一种Zn-Li-Mg系锌合金及其制备方法与应用 | |
WO2016145957A1 (zh) | 一种人体可降解的耐蚀高强韧Zn‐Fe 系锌合金及其应用 | |
CN104888282A (zh) | 一种可降解锌基微孔载药支架及其制备方法 | |
CN108315583A (zh) | 一种Zn-Li-Mn系锌合金及其制备方法与应用 | |
CN108823476A (zh) | 降解速率可控的Mg-Zn-Sn系镁合金及其制备方法和应用 | |
CN108165782B (zh) | 一种医用锌基合金带材及其制备方法 | |
CN106319309A (zh) | 适用于医疗植入物的镁合金及其制造方法 | |
EP3395971B1 (en) | Alloy material and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181116 |