CN106236342A - A kind of implanted complete biological absorbable blood vessel polymer support - Google Patents

A kind of implanted complete biological absorbable blood vessel polymer support Download PDF

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Publication number
CN106236342A
CN106236342A CN201610708181.2A CN201610708181A CN106236342A CN 106236342 A CN106236342 A CN 106236342A CN 201610708181 A CN201610708181 A CN 201610708181A CN 106236342 A CN106236342 A CN 106236342A
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class
support
shape
degree
angle
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CN201610708181.2A
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CN106236342B (en
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陈泳
胡晓露
高康荣
申峰
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SHENZHEN XINLITAI BIOLOGICAL MEDICAL ENGINEERING Co Ltd
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SHENZHEN XINLITAI BIOLOGICAL MEDICAL ENGINEERING Co Ltd
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Priority to CN201610708181.2A priority Critical patent/CN106236342B/en
Priority claimed from CN201610708181.2A external-priority patent/CN106236342B/en
Publication of CN106236342A publication Critical patent/CN106236342A/en
Priority to CN201780040433.1A priority patent/CN109640882B/en
Priority to PCT/CN2017/098108 priority patent/WO2018036434A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
    • A61F2/915—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes with bands having a meander structure, adjacent bands being connected to each other
    • 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
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M31/00—Devices for introducing or retaining media, e.g. remedies, in cavities of the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
    • A61F2/915—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes with bands having a meander structure, adjacent bands being connected to each other
    • A61F2002/9155—Adjacent bands being connected to each other
    • A61F2002/91575—Adjacent bands being connected to each other connected peak to trough
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2230/00—Geometry of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2230/0002—Two-dimensional shapes, e.g. cross-sections
    • A61F2230/0028—Shapes in the form of latin or greek characters
    • A61F2230/0045—Omega-shaped
    • 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
    • A61L2300/416—Anti-neoplastic or anti-proliferative or anti-restenosis or anti-angiogenic agents, e.g. paclitaxel, sirolimus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2210/00—Anatomical parts of the body
    • A61M2210/12—Blood circulatory system

Abstract

The present invention relates to a kind of implanted complete biological absorbable blood vessel polymer support, including the ring waveform support bar of more than five, and the connecting rod that interval is connected between this support bar, the support bar of described support is alternately formed by connecting by class " Ω " shape ripple and class " m " shape ripple, wherein, class " Ω " shape ripple and class " m " shape wavelength-division not by two groups just " s " and fall " s " connect and compose, connection between adjacent two support bars is to be coupled together at class " Ω " shape wave crest and class " m " shape wave base by connecting rod, this polymer support reticulation patterns pattern is to be formed through laser engraving by thin-wall pipes.The program be in harmonious proportion polymer support radial direction support force and wall thickness, compliance between contradiction, realize three to take into account, have and good pass through performance, also the mechanical support that lesion is enough can be given in the special time of wound healing, and progressively it is absorbed by organisms after wound healing, endothelialization is good, is effectively reduced stent restenosis rate and the risk of thrombus in stents in late period.

Description

A kind of implanted complete biological absorbable blood vessel polymer support
Technical field
The invention belongs to medical instruments field, particularly to a kind of implanted complete biological absorbable blood vessel Polymer-supported Frame.
Background technology
Since first case metal rack Palmaz-Schatz in 1985 implants human body, support Successful treatment with interventional ground solves The difficult problem that simple balloon expandable epoch restenosis rate of having determined is the highest, becomes the Main Means of clinical treatment, along with more and more After metal rack implants human body, it has been found that due to inflammatory reaction, neointimal hyperplasia, the reconstruct of blood vessel negativity and support endothelialization The reasons such as delay, in-stent restenosis rate is still up to about 20%.
In order to solve this problem, first generation polymer coating bracket for eluting medicament arises at the historic moment.Bracket for eluting medicament Occur postoperative for interventional therapy restenosis by the 30～40% of the simple PTCA epoch, through the 15～25% of the BMS epoch, be reduced to Present less than 10%, it might even be possible to saying, the appearance of bracket for eluting medicament is one of milestone of coronary intervention, has and draws The meaning in epoch.
But, the analysis delivered in JIUYUE, 2006 Barcelona ESC/WCC meeting and research display, non-degradable gathers Permanent stimulation, office is there is to blood vessel wall in rack surface remaining for a long time in compound bracket for eluting medicament due to drug-carrying polymer coating Portion's inflammatory reaction etc., so that the increase of thrombus in stents risk in late period, the hypertrophy etc. of inner membrance.
Research display, late period thrombus in stents generation and stenting after the delay of endothelialization closely related.Endothelialization refers to After stenter to implant blood vessel, cradling piece forms groove in imbedding blood vessel wall, is not embedded into some endotheliocytes of site residues, these endotheliums Cell gradually grows in multicenter, mutually merges, and whole inwall of Landfill covering, this process should complete within several weeks.In Skin degree is the upper important indicator predicting support advanced thrombus probability of happening of histology.
Permanent drug support causes the chronic injury of blood vessel in Ink vessel transfusing remaining for a long time, and the later stage can cause media The neointimal hyperplasia of atrophy, Aneurysmformation and reactivity, ultimately results in the generation of vascular restenosis.Clinic only need support exist Blood vessel plays in the special time of wound healing the effect of mechanical support, and therefore, best blood vessel polymer support should give Support that lesion is enough and being the most progressively absorbed by organisms.
Occur in that the polymer blood vessel stent of many biodegradable at present, to temporary transient support blood vessels wall, keep Unobstructed blood vessel, progressively can be absorbed by organisms in the later stage again.
But current conventional macromolecule polymer material generally also exists: mechanical strength causes support radially resistance to compression not Poor performance, pressure holds and is easily broken off, and material has mechanical relaxation behavior, causes support unstable properties, radially support force in time under Fall, the problems such as shelf life is short.In order to improve the polylactic acid deficiency in mechanical performance, the most much with provisional capital to polylactic acid blood Pipe polymer support is studied, and Venkatraman etc., by improving technique, makes the support force intensity of PLLA support reach 0.21 ～0.25MPa, and the support strength of common stainless steel stent is 0.20～0.22MPa, in mechanical strength, PLLA up to To metal rack level.Applicant's early-stage Study result applies for a patent CN102499999B, to for preparing polymer support Polylactic acid tubing is modified, and is further used for during support making support strength meet requirement.
Additionally, list or have multiple pattern structure at the support ground, wherein m (or w) shape and n (or Ω) shape are to grind Think in studying carefully preferably can embodiment, main purpose makes support energy radial compression and radial dilatation, and still can keep foot Enough support performances, thus reduce acute resilience and reduce the incidence rate of stent restenosis.Such as, first US5514154A proposes A kind of m (or w) shape and the structure figure support of n (or Ω) shape.
But, the program exists the most clearly disadvantageous in radial direction support force and compliance etc., in follow-up study, for understanding Certainly its problem existed, researcher transforms and optimizes, such as: applicant's early-stage Study scheme CN201431532Y provides A kind of coronary artery bracket, this support includes the support bar of the ring waveform of more than five, and interval is connected between this support bar Connecting rod, wherein, the support bar at described support both ends is " Ω " shape ripple, and two ends support bar is adjacent between support bar Connecting rod is connected between adjacent two " Ω " shape wave crest；The support bar of described support mid portion is by " m " and " Ω " shape ripple Alternately being formed by connecting, the connecting rod between far-end second row support bar and the 3rd row's support bar is connected to adjacent two " m " shape Between wave base, the connecting rod between remainder support bar is connected between adjacent " m " shape wave base and " Ω " shape wave crest.The party Case is more suitable for the application of metal rack, and when for polymer support scheme, its support force and compliance are by the most obvious Restriction.
It addition, as CN1923154A provides the expanding blood vessel of a kind of puncture shaping surgery treatment angiemphraxis Support.This kind of structure stand, in addition to for cardiovascular, applies also for peripheral blood vessel, thin micro tube reticulate knot through laser engraving Structure, its structure is formed by connecting by connecting rod by organizing waveform bracing ring more, and often group waveform bracing ring is by 2-5 group multiple unit ripple Combination constitute, use 2 to 10 connecting rods to connect between adjacent waveform bracing ring.Said structure design ensure that stenter to implant After tissue prolapse little, avoid cradling piece pressure hold and expand time interference, add compliance.But, the program is setting Put less pressure and hold diametrically, and during especially for polymer support, the support of its section and stability there is also bigger Deficiency.
It addition, the tube wall thickness of existing biodegradable stent by the reason of material and manufacturing process all than metal rack Thickness, for 2 times or more of metal rack, so, adds endotheliocyte and climbs up cradling piece fully wrapped around difficulty so that Frame surface is difficult to endothelialization again, has influence on the risk of thrombus in stents.
At present, the various complete biological absorbable support on market still can not realize the perfect unity of each technical specification, The particularly radial direction support force of support, wall thickness and compliance aspect.
Summary of the invention
The problem existed in view of prior art, the invention reside in offer a kind of implanted complete biological absorbable blood vessel polymerization Thing support, has been in harmonious proportion the contradiction between radial direction support force and wall thickness, the compliance of complete biological absorbable support, it is achieved San Zhejian Turn round and look at, meet clinical needs.
The technical scheme that the present invention solves problem is as follows:
A kind of implanted complete biological absorbable blood vessel polymer support, it is characterised in that include more than five ring-type Waveform support bar, and interval is connected to the connecting rod of this support bar support, the support bar of described support by class " Ω " shape ripple and Class " m " shape ripple is alternately formed by connecting, wherein, class " Ω " shape ripple and class " m " shape respectively by two groups just " s " and fall " s " connect and compose, Connection between adjacent two support bars is to be coupled together at class " Ω " shape wave crest and class " m " shape wave base by connecting rod, connecting rod Be shaped as straight-bar.
Wherein, use class " Ω " shape ripple and class " m " shape respectively by two groups just " s " and fall " s " connect and compose, if using directly Bar or have straight-bar transition similar structures and be formed by connecting, its stress of straight-bar that either crest still connects is concentrated the brightest Aobvious, easily make stent fatigue, produce fracture, and use two groups of just " s " and " s " connections of falling by core design of the present invention, permissible The stress greatly reducing crest and connecting rod position is concentrated, and not only increases the support performance of support, moreover it is possible to keep support performance Stability.
Further one of preferred version is 5～45 degree for the angle of aforementioned just " s " and " s " linkage section, preferably 10～ 30 degree, strengthen support performance as far as possible, improve stability.This special design on the one hand hold based on pressure after by external diameter Size considers, is found by great many of experiments, beyond this scope not only have influence on after pressure is held by external diameter, on the other hand also can make Becoming support bar and the extruding of connecting rod, so that damaging medicine film, affecting the release of medicine.
Angle [alpha] 1 scope that further one of preferred version is aforementioned class " Ω " shape wave crest is 130～180 degree；Class " Ω " Angle [alpha] 2 scope of shape wave base is 130～180 degree.
The above-mentioned angular range of employing of class " Ω " shape wave crest and wave base, with just " s " or fall " s " be connected the angle of arc-shaped transition section Degree scope is sufficiently large so that class " Ω " shape ripple can't be the biggest in the amplitude opened or shrink, it is provided that during support, needs open Amplitude need not very big, and the amplitude of contraction is also little, not only provides good support performance, moreover it is possible to keep the stability of performance.
Further one of preferred version is 90～130 degree for angle beta 1 scope of aforementioned class " m " shape left (or right) wave crest； Angle beta 2 scope of class " m " shape left (or right) wave base is 130～180 degree.
Class " m " shape left (or right) wave crest uses above-mentioned angular range, with just " s " or fall " s " be connected the angle of arc-shaped transition section Degree scope is sufficiently large so that class " m " shape ripple can't be the biggest in the amplitude opened or shrink, it is provided that need the width opened during support Degree need not very big, and the amplitude of contraction is also little, not only provides good support performance, moreover it is possible to keep the stability of performance.Class The above-mentioned angular range of employing of " m " shape left (or right) wave base, be conducive to controlling with the angular range being connected straight-bar thus to this portion The stress and the width that divide are any limitation as.
Further one of preferred version is the angle γ 1 of " s " junction point tangent line and class " Ω " shape wave crest circular arc tangential line Scope is 5～30 degree；The angle γ 2 of " s " junction point tangent line and class " Ω " shape wave base circular arc tangential line is in the range of 5～30 degree；“s” The angle δ 1 of junction point tangent line and class " m " shape wave crest circular arc tangential line is in the range of 5～30 degree；" s " junction point tangent line and class " m " shape The angle δ 2 of wave base circular arc tangential line is in the range of 5～30 degree.
" s " junction point tangent line uses above-mentioned scope with the angle of class " Ω " or class " m " shape wave crest (end) circular arc tangential line, connects Point is the roundest and the most smooth, and stress transmission and dispersion evenly, are not easily formed serious stress and concentrate and affect support performance and stability thereof.
The angle η 1 that one of further preferred version is class " m " shape wave base and connecting rod is in the range of 0～30 degree；Class The angle η 2 of " Ω " shape wave crest and connecting rod is in the range of 0～30 degree.
Class " m " shape wave base (or class " Ω " shape wave crest) uses above-mentioned scope with the angular range of connecting rod, the most favourable In the width of control connecting rod, and then control the external diameter after pressure is held；On the other hand class " m " shape wave base (class " Ω " shape is suitably increased Wave crest) angle, its angular range with class " m " shape wave crest based on as, in the case, its stress concentration degree is the least, The serious stress of class " m " shape ripple can be effectively reduced concentrate.
Furthermore, on the basis of the preferred version of aforementioned structure design, further preferred class " Ω " shape wave-wave top and wave base The proportion 0.5～2 of the length of line and connecting rod, preferably 0.8～1.5；Class " m " shape wave-wave top and the line of wave base and company The proportion 0.5～2 of the length of extension bar, preferably 0.8～1.5.
The line of class " Ω " shape or class " m " shape wave crest and wave base is too short relative to connecting rod, is not only easily caused connecting rod Concentrating substantially with the junction stress at the bottom of class " Ω " shape wave-wave top and class " m " shape wave-wave, the stress that also can increase connecting rod is concentrated, Fatigue strength is exceedingly added while adding compliance；The line of class " Ω " shape wave-wave top and wave base is relative to connecting rod mistake Long, it is easily caused when pressure is held and supports in the support waveform that waveform embeds adjacent ring, cause support bar to extrude, so that damaging medicine Film, affects the release of medicine.
As can be seen here, designed by aforementioned structure, add that class " Ω " shape, class " m " shape length are preferred with connecting rod length Proportion, serves synergy in performance.Coordinated by foregoing aspects, thus solve radially support force and wall Contradiction between thickness, compliance, it is achieved three takes into account.Relatively thin support wall thickness, in good support pattern structure design Under, still keep the best radial direction support performance, and the excellent in stability of performance；Meanwhile, relatively thin propping up is had benefited from Frame wall thickness and good support pattern structure, it is less that the pressure of support holds external diameter, and compliance is good, can reach lesion smoothly, reduces The wound of implantation process and the damage of support.
On the basis of aforesaid scheme, the width of further preferred support bar and connecting rod is identical or different；And/or The width of the width of the support bar at support two ends and the support bar of support mid portion is identical or different；And/or support two ends The width of connecting rod and the width of connecting rod of support mid portion identical or different.
By the identical or different design of width, technically, identical scheme is easier to realize and processing, but In order to meet support or the needs of intensity, through the scheme that a step is the most different, in particular it is preferred that near a ring at support two ends Or the thickness of the waveform support bar of two rings is more than the width of the support bar near mid portion.Support bar and the width of connecting rod Preferably scope is 0.10～0.30mm.
The design focusing on pattern structure of the present invention, its structure can be by prior art or the side suitably adjusted Case is prepared, and the reticulation patterns pattern of usual support is to be formed through laser engraving by thin-wall pipes.
By aforesaid conceptual design, the present invention is found by numerous studies, and the polymer support prepared is controlling Internal diameter is 1.50～5.00mm, in the case of wall thickness is 0.05～0.2mm so that radial strength is 240kpa～280kpa, fills Divide the support strength meeting support.
Further preferably scope be internal diameter be 2.50～4.00mm, wall thickness is 0.08～0.18mm, and radial strength is 250kpa～270kpa, farthest controls wall thickness in the case of meeting radial strength sufficiently thin.
Further, described polymer support is 0.5-2.0N/mm, preferably 1.0～2.0N/ in per unit axial length load Mm, meets the serviceability that various vascular lesion is implanted.
Per unit axial length load refers to the load (pressure or pressure) of each per unit axial length, i.e. support is totally subject to Load/total stent length, represent with N/mm.
Being found by animal experiment study method, the polymer support that the present invention provides both can be when wound healing specific In give the mechanical support that lesion is enough, and be progressively absorbed by organisms after wound healing, endothelialization is good, effectively Reduce stent restenosis rate and the risk of thrombus in stents in late period.
In the present invention, the material composition of described polymer support is preferably one or both of following polymers, or Its mixture, including: polylactic acid, PLLA, DL-polylactic acid, polyglycolic acid, polycaprolactone etc..
In order to meet the Clinical practice needs of support, rack surface (including inner side or outside) is coated with suppression blood vessel and exists The coating of the medicine repelled is implanted in narrow or suppression, and coated carrier can be the various carriers with good biocompatibility.
Coated carrier material preferably includes Poly-L-lactic acid (PLLA), polylactic-co-glycolic acid (PLGA), raceme Polylactic acid (PDLLA), Polyethylene Glycol, PEG-PCL, polysorbate, PVP, xylan alcohol, polyglycerin ester, sea Sodium alginate, chitosan, chitin, glucosan, poly-hard acid esters, poly-citrate etc.；Above-mentioned coating is loaded with the medicine of therapeutic dose Thing, preferably includes anti-oxidation medicine, anticoagulants, anticancer class medicine, suppression vascular smooth muscle cell curing class medicine, resists One or more in scorching class medicine or immune suppressant drug.
Above-mentioned anti-oxidation medicine includes superoxide dismutase, catalase, coenzyme Q10, glutathione peroxidase Enzyme；Anticoagulants includes aspirin, heparin, clopidogrel etc.；Anticancer class medicine includes colchicine, paclitaxel；Press down Vascular smooth muscle cell curing class medicine processed includes angiogenic peptide, 17-hydroxy-11-dehydrocorticosterone, calcium ion antagonist；Anti-inflammatory drug includes more giving birth to Mycin, Depsidomycin, KanglemycinC, Spergualin, Mytiocin, Gllooxin；Immune suppressant drug bag Include rapamycin, Ciclosporin A, ciclosporin C, brefeldin A.Said medicine and coated carrier mass ratio be 1: 10～ 2: 1, preferably 1: 3～1: 1.
The present invention includes relative to the beneficial effect of prior art:
(1) the invention provides a kind of implanted complete biological absorbable blood vessel polymer support, this support has excellence Pattern structure design, under relatively thin support wall thickness, still keep the best radial direction support performance, and stability All good.
(2) the invention provides a kind of implanted complete biological absorbable blood vessel polymer support, this support has relatively Relatively thin support wall thickness and good support pattern structure, it is less that the pressure of support holds external diameter, and compliance is good, has stronger passing through Ability and operability, can reach lesion smoothly, reduces wound and the damage of support of implantation process.
(3) a kind of implanted complete biological absorbable blood vessel polymer support of offer is provided, has been in harmonious proportion the most raw Contradiction between the radial direction support force of thing bioabsorbable stent and wall thickness, compliance, it is achieved three takes into account, meets clinical needs.
(4) the invention reside in a kind of implanted complete biological absorbable blood vessel polymer support of offer, with rack surface (bag Include inner side or outside) it is coated with the coating that suppression blood vessel implants the medicine of repulsion in narrow or suppression, coated carrier has Good biocompatibility, meets the Clinical practice needs of support.
(5) support preparation method of the present invention is simple, it is easy to reappear, and is suitable for industrialization and produces.
Accompanying drawing explanation
Fig. 1 is the flat deployable structure schematic diagram of a kind of implanted complete biological absorbable blood vessel polymer support, wherein, Support bar 1, connecting rod 2, class " Ω " shape ripple 3, class " m " shape ripple 4.
Fig. 2 is waveform by just " s " and the schematic diagram that " s " connect that falls, wherein, with determining of class " Ω " shape ripple or class " m " shape ripple Circle of position arc datum line makees the tangent line L2 (or L2 ＇) of the camber line of tangent line L1 (or L1 ＇), circular arc and " s " phase contact, and L3 (or L3 ＇) is The intermediate bar tangent line of " s ", just " s " and fall " s " linkage section angle refer to L1 (or L1 ＇) and the angle of L2 (or L2 ＇), L3 The angle of (or L3 ＇) and L2 (or L2 ＇) with and the angle of L1 (or L1 ＇) and L2 (or L2 ＇) basically identical, the most tangent camber line enters The angle of mouth and outlet is basically identical, it is ensured that the symmetry of transition arc, thus ensures the uniformity of its stress.Wherein, L1, L2 and L3, L1 ＇, L2 ＇ and L3 ＇ is respectively one group, and angle is corresponding.
In Fig. 3, Fig. 3 A 3G is class " m " shape ripple and class " Ω " shape involves the schematic diagram with connecting rod, wherein, class " Ω " shape The angle [alpha] 1 of wave crest, the angle [alpha] 2 of class " Ω " shape wave base；The angle beta 1 of class " m " shape left (or right) wave crest；Class " m " shape left (or right) The angle beta 2 of wave base；" s " junction point tangent line and the angle γ 1 of class " Ω " shape wave crest circular arc tangential line, " s " junction point tangent line and class The angle γ 2 of " Ω " shape wave base circular arc tangential line；" s " junction point tangent line is with the angle δ 1 of class " m " shape wave crest circular arc tangential line, " s " even Contact tangent line and the angle δ 2 of class " m " shape wave base circular arc tangential line；Class " m " shape wave base and the angle η 1 of connecting rod, class " Ω " shape ripple Top and the angle η 2 of connecting rod.
In Fig. 4, Fig. 4 B is the partial enlarged drawing of class " Ω " the shape ripple of Fig. 4 A, and wherein, L4 is class " Ω " shape wave-wave top and ripple The line at the end.
In Fig. 5, Fig. 5 B is the partial enlarged drawing of class " m " the shape ripple of Fig. 5 A, and wherein, L5 is class " m " shape wave-wave top and wave base Line.
In Fig. 6, Fig. 6 A is the planar development of another kind implanted of the present invention complete biological absorbable blood vessel polymer support Structural representation, stent ends bar is wider than center-pole width, and Fig. 6 B, 6D are the enlarged diagrams of Fig. 6 A connecting rod, and L6 is to connect The length of bar, Fig. 6 C is the partial enlarged drawing of class " Ω " the shape ripple of Fig. 6 A, and Fig. 6 E is the partial enlargement of class " m " the shape ripple of Fig. 6 A Figure, the line of class " Ω " shape wave-wave top and wave base is L4:L6 with the length ratio of connecting rod, class " m " shape wave-wave top and the company of wave base The length of line and connecting rod is than for L5:L6.
Fig. 7 is the flat deployable structure signal of another implanted of the present invention complete biological absorbable blood vessel polymer support Figure.
The SEM result of 30 days after Fig. 8 stenter to implant of the present invention animal.
The OCT result of at once with 90 days after Fig. 9 stenter to implant of the present invention animal.
Detailed description of the invention
Below in conjunction with preferred embodiments and drawings, the present invention is described in further detail, but the embodiment of invention is not It is limited to this.
1 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, material is gathered Lactic acid, including the ring waveform support bar 1 of more than five, and interval is connected to the connecting rod 2 of this support bar 1 support, described The support bar 1 of support is alternately formed by connecting by class " Ω " shape ripple 3 and class " m " shape ripple 4, and the connection between adjacent two support bars is Coupled together at class " Ω " shape wave crest and class " m " shape wave base by connecting rod 2.
Described class " m " shape ripple 4, as shown in Figure 3A, and class " Ω " shape ripple 3, as shown in Figure 3 B, respectively by two groups just " s " and " s " connects and composes, the most as shown in Figure 2.
The shape of the connecting rod between described adjacent two support bars is straight-bar.
This implanted complete biological absorbable blood vessel polymer support, is formed through laser engraving by thin-wall pipes.
2 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, including five Individual or above ring waveform support bar 1, and it is spaced the connecting rod 2 being connected to this support bar 1 support, different from embodiment 1 Part is in this specific embodiment, and the width of described support bar and connecting rod is variant, propping up of described support two end portions The width of strut is the thickest, and the width of the connecting rod of support two end portions takes second place, then the width to remaining support bar, remaining connecting rod Width the thinnest.Wherein, just " s " and fall " s " linkage section angle be 5-10 degree.
3 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, including five Individual or above ring waveform support bar 1, and it is spaced the connecting rod 2 being connected to this support bar 1 support, different from embodiment 1 Part is in this specific embodiment, and the width of described support bar and connecting rod is variant, propping up of described support two end portions The width of strut is the thickest, and the width of the connecting rod of support two end portions takes second place, then the width to remaining support bar, remaining connecting rod Width the thinnest.Wherein, just " s " and fall " s " linkage section angle be 40-45 degree.
4 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, including five Individual or above ring waveform support bar 1, and it is spaced the connecting rod 2 being connected to this support bar 1 support, different from embodiment 1 Part is in this specific embodiment, and wherein, just the angle of " s " and " s " linkage section is 10 degree；α 1 and α 2 in class " Ω " shape Angle is 130 degree；In class " m " shape, β 1 angle is 130 degree, and β 2 angle is 180 degree；Angle γ 1 and γ 2 angle is 5 degree, folder Angle δ 1 and δ 2 angle is 5 degree；Angle η 1 scope of class " m " shape wave base and connecting rod is 30 degree, class " Ω " shape wave crest be connected Angle η 2 scope of bar is 30 degree.
5 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, including five Individual or above ring waveform support bar 1, and it is spaced the connecting rod 2 being connected to this support bar 1 support, different from embodiment 1 Part is in this specific embodiment, and wherein, just the angle of " s " and " s " linkage section is 30 degree；α 1 and α 2 in class " Ω " shape Angle is 180 degree, and in class " m " shape, β 1 angle is 90 degree, and β 2 angle is 130 degree；Angle γ 1 and γ 2 angle is 30 degree, folder Angle δ 1 and δ 2 angle is 30 degree；Angle η 1 scope of class " m " shape wave base and connecting rod is 0 degree, class " Ω " shape wave crest be connected Angle η 2 scope of bar is 0 degree.
6 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
Seeing shown in accompanying drawing 1,2 and 3A-3G, a kind of implanted complete biological absorbable blood vessel polymer support, including five Individual or above ring waveform support bar 1, and it is spaced the connecting rod 2 being connected to this support bar 1 support, different from embodiment 1 Part is in this specific embodiment, and wherein, just the angle of " s " and " s " linkage section is 20 degree；α 1 and α 2 in class " Ω " shape Angle is 160 degree, and in class " m " shape, β 1 angle is 100 degree, and β 2 angle is 150 degree；Angle γ 1 and γ 2 angle is 15 degree, Angle δ 1 and δ 2 angle is 15 degree；Class " m " shape wave base is 10 degree with angle η 1 scope of connecting rod, class " Ω " shape wave crest and company Angle η 2 scope of extension bar is 10 degree.
7 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
See accompanying drawing 1,2, shown in 3A-3G, 4A-4B, 5A-5B and 6A-6E, a kind of implanted complete biological absorbable blood vessel Polymer support, including five or above ring waveform support bar 1, and interval is connected to the connection of this support bar 1 support Bar 2, difference from Example 4 is in this specific embodiment, described class " Ω " shape wave-wave top and the line of wave base and company The ratio of the length of extension bar is 1, and the line of class " m " shape wave-wave top and wave base is 1 with the ratio of the length of connecting rod.
8 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
See accompanying drawing 1,2, shown in 3A-3G, 4A-4B, 5A-5B and 6A-6E, a kind of implanted complete biological absorbable blood vessel Polymer support, including five or above ring waveform support bar 1, and interval is connected to the connection of this support bar 1 support Bar 2, difference from Example 5 is in this specific embodiment, described class " Ω " shape wave-wave top and the line of wave base and company The ratio of the length of extension bar is 1.5, and the line of class " m " shape wave-wave top and wave base is 1.5 with the ratio of the length of connecting rod.
9 one kinds of implanted complete biological absorbable blood vessel polymer supports of embodiment
See accompanying drawing 1,2, shown in 3A-3G, 4A-4B, 5A-5B, 6A-6E and 7, a kind of implanted complete biological absorbable blood Pipe polymer support, including five or above ring waveform support bar 1, and interval is connected to the company of this support bar 1 support Extension bar 2, difference from Example 6 is in this specific embodiment, the line of described class " Ω " shape wave-wave top and wave base with The ratio of the length of connecting rod is 1.2, and the line of class " m " shape wave-wave top and wave base is 1.2 with the ratio of the length of connecting rod.And Stent ends bar is wider than center-pole width, stent ends bar width: center-pole width is about 1.1-1.2.
Wherein, the polymer support of previous embodiment 19 control internal diameter be 1.50～5.00mm, wall thickness be 0.05～ In the case of 0.2mm, after testing, its radial strength is 240kpa～280kpa, fully meets the support strength of support.Further Preferably scope be internal diameter be 2.50～4.00mm, wall thickness is 0.08～0.18mm, and radial strength is 250kpa～270kpa, maximum The control wall thickness of degree is sufficiently thin.
Implanting, in order to meet, the requirement used, this implanted complete biological absorbable blood vessel polymer support surface (includes Inner side or outside) it is coated with the coating that suppression blood vessel implants the medicine of repulsion in narrow or suppression, coated carrier has good Good biocompatibility, can effectively treat angiostenosis pathological changes.
Embodiment 10 performance test experience scheme
Support strength is tested:
Polymer support to embodiment 19 imposes the compression ratio extruding of equilibrium, when significantly reducing or diameter of power occur When reducing at least 50%, record load and relevant diameter, the load of respective diameters per unit axial length meets the requirement of table 1.
Table 1 support radially support strength
The radial direction support strength per unit axial length load of the support of result display test all meets 0.5～2.0N/mm, from And embody polymer support and there is good support force performance；Wherein, embodiment 4-9 has more excellent support force performance, unit Axial length load 1.0～2.0N/mm；Especially more excellent with embodiment 6 and 9, respectively 1.5N/mm and 1.8N/mm.
Stability experiment
A kind of implanted complete biological absorbable blood vessel polymer support of the present invention, it is respectively stored in 40 DEG C ± 2 DEG C, 75%RH ± 5%RH and 25 DEG C ± 2 DEG C, be accelerated in the environment of 60%RH ± 5%RH and real-time stability test.Current Research shows that blood vessel only need to be played the effect of mechanical support in the special time of wound healing by preferable biodegradable stent, is giving Progressively absorbed by body after giving the enough mechanical support of lesion and wound healing.This special time period of coronary artery bracket is generally acknowledged General about half a year.Evaluate a kind of implanted complete biological absorbable blood vessel polymer support of the present invention within the time period Support performance stability, Acceleration study and real-time stabilization result are respectively as shown in table 2 and table 3.
Table 2 accelerated stability test result
Table 3 real-time stability result of the test
Time (moon) Per unit axial length load (N/mm)
1 0.5～2.0
2 0.5～2.0
3 0.5～2.0
4 0.5～2.0
5 0.5～2.0
6 0.5～2.0
7 0.5～2.0
8 0.5～2.0
9 0.5～2.0
The radial direction support strength per unit axial length of the support of result display test is still maintained in being supported on 9 months 0.5～2.0N/mm, thus embody polymer support and there is good support performance stability；Embodiment 4-9 different time records Support force deviation less, there is more excellent stability of strutting system, per unit axial length load is still maintained at 1.0～2.0N/mm, And after 6th month, just start that hydraulic performance decline occurs, especially more excellent with embodiment 6 and 9, be respectively maintained at 1.5～1.8N/mm and 1.8～2.0N/mm, and after 7th month, just start that hydraulic performance decline occurs.
Embodiment 10 animal protocols
Experimental technique: choosing weight 30～40Kg, 6～the healthy white pig in August, healthy miniature pig, respectively at left crown dynamic Arteries and veins anterior descending branch, Circumflex branch and (or) right coronary artery respectively implant the polymer support described in 1 piece of embodiment 3, implant 2～3 pieces altogether Polymer support.Endothelialization degree, thrombosis etc. it are primarily upon in special time period.
Such as Fig. 8, result is that the SEM result of 30 days shows, polymer support substantially completely endothelialization；Such as Fig. 9,0 day and 90 It OCT result shows, polymer support surface is without adhering to any thrombosis, and cradling piece keeps complete, and endothelium covers good, without disconnected Split generation, the most high-visible, thus embody polymer support and there is good support performance and stability is all good.Meanwhile, There is after embodiment 4-9 stenter to implant basically identical effect, especially more excellent with embodiment 6 and 9.
Conclusion: found by animal experiment study method, the polymer support that the present invention provides both can be at wound healing Giving the mechanical support that lesion is enough in special time, and be progressively absorbed by organisms after wound healing, endothelialization is good, It is effectively reduced stent restenosis rate and the risk of thrombus in stents in late period.
Above content is to combine the further details of explanation that the present invention is done by concrete preferred implementation, but not Represent the present invention be embodied as be limited to these explanations.For those skilled in the art, On the premise of present inventive concept, it is also possible to make some simple deductions or replacement, be regarded as belonging to the present invention's Protection domain.

Claims (13)

1. an implanted complete biological absorbable blood vessel polymer support, it is characterised in that include the ring-type ripple of more than five Shape support bar, and the connecting rod that interval is connected between this support bar, the support bar of described support is by class " Ω " shape ripple and class " m " shape ripple is alternately formed by connecting, wherein, class " Ω " shape ripple and class " m " shape wavelength-division not by two groups just " s " and fall " s " connect and compose, Connection between adjacent two support bars is to be coupled together at class " Ω " shape wave crest and class " m " shape wave base by connecting rod, connecting rod For straight-bar.
2. a kind of implanted complete biological absorbable blood vessel polymer support as claimed in claim 1, it is characterised in that just The angle of " s " and " s " linkage section is 5～45 degree, preferably 10～30 degree.
3. a kind of implanted complete biological absorbable blood vessel polymer support as claimed in claim 1, it is characterised in that class Angle [alpha] 1 scope of " Ω " shape wave crest is 130～180 degree, and angle [alpha] 2 scope of class " Ω " shape wave base is 130～180 degree；Class " m " Angle beta 1 scope of shape left or right wave crest is 90～130 degree；Angle beta 2 scope of class " m " shape left or right wave base is 130～180 Degree.
4. a kind of implanted complete biological absorbable blood vessel polymer support as claimed in claim 2, it is characterised in that class Angle [alpha] 1 scope of " Ω " shape wave crest is 130～180 degree, and angle [alpha] 2 scope of class " Ω " shape wave base is 130～180 degree；Class " m " Angle beta 1 scope of shape left or right wave crest is 90～130 degree；Angle beta 2 scope of class " m " shape left or right wave base is 130～180 Degree.
5. a kind of implanted complete biological absorbable blood vessel polymer support as described in claim 14 any claim, It is characterized in that, the angle γ 1 of " s " junction point tangent line and class " Ω " shape wave crest circular arc tangential line is in the range of 5～30 degree, and " s " connects The angle γ 2 of contact tangent line and class " Ω " shape wave base circular arc tangential line is in the range of 5～30 degree；" s " junction point tangent line and class " m " shape The angle δ 1 of wave crest circular arc tangential line in the range of 5～30 degree, the angle δ of " s " junction point tangent line and class " m " shape wave base circular arc tangential line 2 in the range of 5～30 degree.
6. a kind of implanted complete biological absorbable blood vessel polymer support as described in claim 14 any claim, It is characterized in that, the angle η 1 of " m " shape wave base and connecting rod is in the range of 0～30 degree；Class " Ω " shape wave crest and the folder of connecting rod Angle η 2 is in the range of 0～30 degree.
7. a kind of implanted complete biological absorbable blood vessel polymer support as claimed in claim 5, it is characterised in that " m " The angle η 1 of shape wave base and connecting rod is in the range of 0～30 degree；The angle η 2 of class " Ω " shape wave crest and connecting rod in the range of 0～ 30 degree.
8. a kind of implanted complete biological absorbable blood vessel polymer support as described in claim 17 any claim, It is characterized in that, the proportion 0.5～2, preferably 0.8 of the line of class " Ω " shape wave-wave top and wave base and the length of connecting rod～ 1.5；The line of class " m " shape wave-wave top and wave base and the proportion 0.5～2 of the length of connecting rod, preferably 0.8～1.5.
9. a kind of implanted complete biological absorbable blood vessel polymer support as described in claim 18 any claim, It is characterized in that, the width of support bar and connecting rod is identical or different；The width of the support bar at support two ends and support pars intermedia The width of the support bar divided is identical or different；The width of the connecting rod at support two ends and the width of the connecting rod of support mid portion Identical or different.
10. a kind of implanted complete biological absorbable blood vessel Polymer-supported as described in claim 19 any claim Frame, it is characterised in that described thin-wall pipes internal diameter is 1.50～5.00mm, wall thickness is 0.05～0.2mm, and radial strength is 240kpa～280kpa；Preferably internal diameter is 2.50～4.00mm, and wall thickness is 0.08～0.18mm, radial strength be 250kpa～ 270kpa。
11. a kind of implanted complete biological absorbable blood vessel polymer supports as claimed in claim 10, it is characterised in that institute Stating polymer support in per unit axial length load is 0.5-2.0N/mm, preferably 1.0～2.0N/mm.
The 12. a kind of implanted complete biological absorbable blood vessel Polymer-supporteds as described in claim 1 11 any claim Frame, it is characterised in that the material composition of described polymer support preferably includes following polymers: polylactic acid, PLLA, DL- Polylactic acid, polyglycolic acid, polycaprolactone one or both, or its mixture.
13. a kind of implanted complete biological absorbable blood vessel polymer supports as claimed in claim 12, it is characterised in that institute Stating polymer support surface-coated has the coating being loaded with medicine, the carrier of described coating to include: Poly-L-lactic acid, polylactic acid-second Alkyd copolymers, poly-dl-lactide, Polyethylene Glycol, PEG-PCL, polysorbate, PVP, xylan alcohol, poly- Glyceride, sodium alginate, chitosan, chitin, glucosan, poly-hard acid esters, poly-citrate etc.；Described medicine includes antioxygen Chemical medicine thing, anticoagulants, anticancer class medicine, suppression vascular smooth muscle cell curing class medicine, anti-inflammatory drug or immunity One or more in inhibitor medicaments.
CN201610708181.2A 2016-08-23 2016-08-23 Implantable complete biological absorbable vascular polymer stent Active CN106236342B (en)

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CN201780040433.1A CN109640882B (en) 2016-08-23 2017-08-18 Implantable completely-bioabsorbable intravascular polymer stent
PCT/CN2017/098108 WO2018036434A1 (en) 2016-08-23 2017-08-18 Implant-type, completely bioabsorbable, vascular polymer stent

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CN112239567B (en) * 2020-08-31 2021-08-31 中国科学院兰州化学物理研究所 Polycaprolactone/sodium alginate composite material and preparation method and application thereof
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