CN102764171B - A kind of electrostatic spinning composite vascular stent and preparation method thereof - Google Patents
A kind of electrostatic spinning composite vascular stent and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of electrostatic spinning composite vascular stent and preparation method thereof, and described composite vascular stent is made up of annular basal membrane layer and shelf layer two parts, wherein: described annular basal membrane layer is annular tube shaped membrane structure, has good mechanical performance; Described shelf layer is the nanofiber of one deck uniform diameter adopting electrospinning process to spray on this annular basal membrane layer, has typical three-D space structure, is beneficial to adhesion and the propagation of cell; Described annular basal membrane layer and electrospun scaffolds layer all adopt degradable macromolecular material to make.The present invention has good mechanical performance, not yielding in liquid environment, has better regulation form; Preparation technology is simple, and equipment requirements is low, and preparation cost is cheap, and preparation efficiency is high, with low cost, is easy to promote.
Description
Technical field
The present invention relates to a kind of novel electrostatic spinning composite vascular stent and preparation method thereof, be applicable to blood vessel and manually repair or intravascular tissue engineering field.
Background technology
Support plays an important role in Tissue Engineering Study, and it is the key that organizational project realizes industrialization.Along with the arrival of aging society and the change of people's dietary structure, the sickness rate of cardiovascular disease and periphery obstructive pulmonary disease thereof rises year by year.The replacement vessels of the various diameter of urgent clinical needs repairs injured blood vessel.Desirable intravascular stent should possess following characteristics:
(1) nontoxic and there is good biocompatibility;
(2) there is certain mechanical strength and compliance;
(3) there is biodegradability and degraded controllability;
(4) there is 3 D stereo loose structure, be beneficial to cell adhesion, growth and propagation;
(5) there is good blood compatibility.
Material at present for the preparation of intravascular stent mainly contains metal rack and the large class of high molecular polymer support two.Metal rack has good mechanical performance, clinically existing certain application, but due to not enough curative effects limiting Stent such as its material surface anticoagulation function are poor, there is thrombogenicity, metal surface is difficult to carrying medicament.And degradable metal support, the mechanical property as magnesium alloy is not good enough, and its Sensitivity of Stress Corrosion is higher, cause support not all degraded time just premature failure (as patent publication No.: CN 1887360A).Biology explanation polymeric material for the preparation of support has polyglycolic acid (polyglycolic acid, PGA), the poly-pungent fat (polyhydroxoctanoate of hydroxyl usually, PHO), polylactic acid (polylactic acid, PLA), polycaprolactone (PCL) and copolymer etc. thereof.The macromolecular material of this kind of degradable or absorbable material synthesis, play after machinery makes, provides the effect of Growth of Cells microenvironment in the early stage, later stage along with degraded produce space again for tissue growth provides space, make artificial blood vessel substitute by new article blood vessel.With novel biodegradable macromolecular material polylactic acid for representative, be the lactic acid of body institute energy metabolism after its degraded, final formation carbon dioxide and water is decomposed through body endoenzyme, nontoxic nonirritant, and there is good mechanical strength, absorbability, chemical stability, degradability and biocompatibility and receive much concern.But polylactic acid bracket self fragility is comparatively large, and cellular affinity is not good enough.(as patent publication No. CN1410132A; CN101703808A)
The method preparing intravascular stent mainly contains granule deposition method, gas foaming method, freeze-drying, speed forming method, method of electrostatic spinning etc., wherein electrostatic spinning forms the method that injection stream prepares nanofiber under utilizing high voltage electric field effect, the high molecular polymer nanofiber obtained has typical tridimensional network, there is fabulous toughness and cellular affinity, its porosity and specific surface area high, be conducive to sticking of cell, growth and propagation, and can by change diameter control aperture and pore structure and by regulating relevant parameter to change fibre morphology and then improve the physical and mechanical property of timbering material, coordinate the gathering-device of definite shape, the timbering material with given configuration can be obtained: adopt the bar-shaped gathering-device rotated can collect the artificial blood vessel's material with certain internal diameter and control the thickness of spinning layer by liquid inlet volume.In addition, it is simple that this method also has equipment, easy to operate, the advantages such as cost is low.Weak point is, the intravascular stent mechanical strength of acquisition is not good enough and cannot stable existence in vivo.（Vaz et.al,2005;Xu et.al,2004）
Based on above-mentioned background, consider to adopt electrostatic spinning technique to obtain composite vascular stent on the counterdie that polylactic acid is raw material, make it the advantage of both, biological activity demand can be met and do not lose mechanical property again, thus make the intravascular stent obtained more meet clinical demand.
Summary of the invention
An object of the present invention is to provide a kind of new electrostatic spinning composite vascular stent, biology can be degradable, can be applicable to field of tissue engineering technology.
Composite vascular stent of the present invention is made up of annular basal membrane layer and shelf layer two parts.Annular basal membrane layer is annular tube shaped membrane structure, has better mechanical performance.Shelf layer utilizes electrospinning process to spray the nanofiber of one deck uniform diameter on this basal membrane layer basis, has typical three-D space structure, be beneficial to adhesion and the propagation of cell.
The annular basal membrane layer of described composite vascular stent and shelf layer part, by biological absorbable polymer preparation, as polylactic acid, the blend of lactic acid and caprolactone, lactic acid-caprol acton copolymer or other degradable high polymer material, but prioritizing selection lactic acid-caprol acton copolymer.
Described shelf layer is the three-dimensional rack with loose structure of electrostatic spinning composition, and the diameter of its electrostatic spinning is 200-1000nm.
Another object of the present invention is to provide the preparation method of above-mentioned composite vascular stent, specifically comprises the steps:
1) macromolecular material is dissolved in dichloromethane solvent, is at room temperature positioned on magnetic stirring apparatus and stirs until dissolve completely, form organic facies (I).
2) metal bar is inserted in organic facies (I), rotate several times gently and make it be attached on metal bar.Metal bar is inverted and vertically places, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
3) macromolecular material is dissolved in dichloromethane and N-dimethylformamide mixed solvent, is at room temperature positioned on magnetic stirring apparatus and stirs until copolymer dissolves completely, form organic facies (II);
4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Organic facies (II) is encased in the syringe in sprayer unit, utilizes electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
In described organic facies (I), the concentration range of macromolecular material is 2.5-15%(g/100ml), in organic facies (II), the concentration of macromolecular material is 3-8% (g/10mL).
In described spinning process, needle point and receiving system distance are 15-20cm, and injection rate is at 0.3-1mL/h, and push-in stroke scope is 0.5-2mL.
Described metal bar diameter is 2-8mm, and material is rustless steel.
Technique scheme of the present invention, tool has the following advantages:
(1) Polymer materialspreparation that composite vascular stent can be degradable by biology, has good biocompatibility.
(2) electricity spinning fibre diameter is ultra-fine, and the non-woven fabrics obtained has high porosity and specific surface area.
(3) compared with traditional electrospun scaffolds, composite vascular stent of the present invention has good mechanical performance, not yielding in liquid environment, has better regulation form.
(4) preparation technology of the present invention is simple, and equipment requirements is low, and preparation cost is cheap, and preparation efficiency is high.
Accompanying drawing explanation
Fig. 1 is composite vascular stent structural representation prepared by the present invention, and wherein 1 is annular basal membrane layer, and 2 is electrospun scaffolds layer.
The surface texture enlarged diagram of the electrospun scaffolds layer that Fig. 2 identifies for 3 in 1 figure.
The surface texture enlarged diagram of the annular basal membrane layer that Fig. 3 identifies for 4 in 1 figure.
Fig. 4 is preparation facilities schematic diagram.
Fig. 5 is schematic diagram in kind.
Fig. 6 is the scanning electron microscope shape appearance figure on composite vascular stent surface.
Fig. 7 is the scanning electron microscope shape appearance figure of composite vascular stent cross section.
Detailed description of the invention
Elaborate to embodiments of the invention below, the present embodiment is implemented premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, be electrostatic spinning composite vascular stent schematic diagram, be made up of annular basal membrane layer 1 and electrospun scaffolds layer two parts, wherein: described annular basal membrane layer 1 is annular tube shaped membrane structure, has good mechanical performance; Described shelf layer 2 is the nanofibers of one deck uniform diameter adopting electrospinning process to spray on this annular basal membrane layer, has typical three-D space structure, is beneficial to adhesion and the propagation of cell; Described annular basal membrane layer and electrospun scaffolds layer all adopt degradable macromolecular material to make.
As the surface texture schematic diagram of Fig. 2 electrospun scaffolds layer, Fig. 3 is the surface texture schematic diagram of annular basal membrane layer.
As shown in Figure 4, be the electrostatic spinning apparatus schematic diagram adopted in following examples, in figure: 1-high voltage power supply 2-electrostatic spinning pump 3-syringe 4-syringe needle 5-constant speed stirrer 6-stainless steel metal rod 7-ring-type counterdie.
Embodiment 1
Specific operation process is as follows:
(1) take 1g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 4mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PLLA-co-PCL) 0.15g of Poly-L-lactic acid and caprolactone and copolymer (PDLLA-co-PCL) 0.45g of polycaprolactone-poly-dl-lactide and caprolactone is taken respectively, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 15cm, and injection rate is 0.3mL/h, injection volume 1mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent, pictorial diagram as shown in Figure 5.
Fig. 6 is the scanning electron microscope shape appearance figure on composite vascular stent surface.Fig. 7 is the scanning electron microscope shape appearance figure of composite vascular stent cross section.By sem observation composite vascular stent, can observe two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 245nm ± 30nm.By the composite vascular stent prepared by people's blood vessel arterial smooth muscle cell cell detection, there is good biocompatibility.
Embodiment 2
Specific operation process is as follows:
(1) take 0.25g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 2mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PLLA-co-PCL) 0.15g of Poly-L-lactic acid and caprolactone and copolymer (PDLLA-co-PCL) 0.45g of polycaprolactone-poly-dl-lactide and caprolactone is taken respectively, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 15cm, and injection rate is 0.3mL/h, injection volume 1mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
By sem observation composite vascular stent, be two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 280 ± 30nm.By there is good biocompatibility between the compound prepared by people's blood vessel arterial smooth muscle cell cell detection.
Embodiment 3
Specific operation process is as follows:
(1) take 1.5g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 8mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PLLA-co-PCL) 0.3g of Poly-L-lactic acid and caprolactone and copolymer (PDLLA-co-PCL) 0.3g of polycaprolactone-poly-dl-lactide and caprolactone is taken respectively, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 15cm, and injection rate is 0.3mL/h, injection volume 1mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
By sem observation composite vascular stent, be two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 457 ± 20nm.By the composite vascular stent prepared by people's blood vessel arterial smooth muscle cell cell detection, there is good biocompatibility.
Embodiment 4
Specific operation process is as follows:
(1) take 1g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 4mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PLLA-co-PCL) 0.3g of Poly-L-lactic acid and caprolactone and copolymer (PDLLA-co-PCL) 0.3g of polycaprolactone-poly-dl-lactide and caprolactone is taken respectively, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 15cm, and injection rate is 0.3mL/h, injection volume 1mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
By sem observation composite vascular stent, be two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 360 ± 30nm.By the composite vascular stent prepared by people's blood vessel arterial smooth muscle cell cell detection, there is good biocompatibility.
Embodiment 5
Specific operation process is as follows:
(1) take 1g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 4mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PDLLA-co-PCL) 0.6g of polycaprolactone-poly-dl-lactide and caprolactone is taken, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 15cm, and injection rate is 0.3mL/h, injection volume 1mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
By sem observation composite vascular stent, be two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 430 ± 30nm.By the composite vascular stent prepared by people's blood vessel arterial smooth muscle cell cell detection, there is good biocompatibility.
Embodiment 6
Specific operation process is as follows:
(1) take 1g polylactic acid-caprolactone copolymer (PLLA-co-PCL), be placed in 10mL dichloromethane solvent, be at room temperature positioned on magnetic stirring apparatus and stir until dissolve completely, form organic facies (I).
(2) be the metal bar of 4mm by diameter, insert in organic facies (I), rotate several times gently and organic facies is attached on metal bar.Metal bar is inverted and vertically places 24 hours, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar.
(3) copolymer (PLLA-co-PCL) 0.15g of Poly-L-lactic acid and caprolactone and copolymer (PDLLA-co-PCL) 0.45g of polycaprolactone-poly-dl-lactide and caprolactone is taken respectively, be placed in 10ml dichloromethane and N-dimethylformamide (volume ratio 7:3) mixed solvent, at room temperature be positioned on magnetic stirring apparatus and stir until copolymer dissolves completely, form organic facies (II).
(4) build jet deck, the metal bar being coated with counterdie obtained in (2) is fixed on constant speed stirrer.Be encased in the syringe in sprayer unit by organic facies (II), needle point and receiving system distance are 20cm, and injection rate is 1mL/h, injection volume 2mL.Utilize electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
By sem observation composite vascular stent, be two-layer different structure, one deck is smooth counterdie, and one deck is the electrostatic spinning structure of shelf-like.The diameter obtaining nanofiber through sem observation is 760 ± 40nm.By the composite vascular stent prepared by people's blood vessel arterial smooth muscle cell cell detection, there is good biocompatibility.
Be more than the preferred embodiment of the present invention, it should be pointed out that the parameter area in conversion above-described embodiment or degradable macromolecular material, the present invention also can realize, and is not limited to the above embodiments.The composite membrane that the present invention mentions has stronger mechanical performance and good biocompatibility, and preparation technology is simple, with low cost, is easy to promote.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (5)
1. the preparation method of an electrostatic spinning composite vascular stent, it is characterized in that, described electrostatic spinning composite vascular stent, be made up of annular basal membrane layer and electrospun scaffolds layer two parts, wherein: described annular basal membrane layer is annular tube shaped membrane structure, has good mechanical performance; Described electrospun scaffolds layer is the nanofiber of one deck uniform diameter adopting electrospinning process to spray on this annular basal membrane layer, has typical three-D space structure, is beneficial to adhesion and the propagation of cell; Described annular basal membrane layer and electrospun scaffolds layer all adopt degradable macromolecular material to make; Described degradable macromolecular material is polylactic acid, the blend of polylactic acid and polycaprolactone or lactic acid-caprol acton copolymer; Described electrospun scaffolds layer is the three-dimensional rack with loose structure of electrostatic spinning composition, and the diameter of silk is 200-1000nm;
Described electrostatic spinning composite vascular stent preparation process comprises the steps:
1) macromolecular material is dissolved in dichloromethane solvent, is at room temperature positioned on magnetic stirring apparatus and stirs until dissolve completely, form organic facies I; In described organic facies I, the concentration range of macromolecular material is 2.5-15%, and concentration refers to g/100mL herein;
2) by metal bar, insert in organic facies I, rotate several times gently and make organic facies be attached on metal bar, metal bar is inverted and vertically places, make organic solvent naturally volatilize, form one deck ring-type counterdie being wrapped in metal bar;
3) macromolecular material is dissolved in dichloromethane and N-dimethylformamide mixed solvent, is at room temperature positioned on magnetic stirring apparatus and stirs until copolymer dissolves completely, form organic facies II; In described organic facies II, the concentration of macromolecular material is 3-8%, and concentration refers to g/100mL herein;
4) jet deck is built, by 2) in the metal bar being coated with counterdie that obtains be fixed on constant speed stirrer, organic facies II is encased in the syringe in sprayer unit, utilizes electrostatic spinning technique to spray electrospun scaffolds layer on ring-type counterdie, finally form composite vascular stent.
2. the preparation method of electrostatic spinning composite vascular stent according to claim 1, is characterized in that, described electrostatic spinning procedure parameter is: needle point and receiving system distance are 15-20cm, and injection rate is at 0.3-1mL/h, and push-in stroke scope is 0.5-2mL.
3. the preparation method of the electrostatic spinning composite vascular stent according to any one of claim 1-2, is characterized in that, the diameter of described metal bar is 2-8mm.
4. the preparation method of the electrostatic spinning composite vascular stent according to any one of claim 1-2, is characterized in that, the material of described metal bar is rustless steel.
5. the preparation method of the electrostatic spinning composite vascular stent according to any one of claim 1-2, is characterized in that, described degradable macromolecular material is lactic acid-caprol acton copolymer.
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| CN103585673B (en) * | 2013-10-16 | 2014-12-10 | 西安交通大学 | Additive manufacturing method for nano fiber bracket with gradient interface |
| CN104998297B (en) * | 2014-04-16 | 2017-10-20 | 山东隽秀生物科技股份有限公司 | One kind is poly-（L lactide co ε caprolactones）Nano-fiber nerve conduit and preparation method |
| CN104815355B (en) * | 2015-04-16 | 2017-08-25 | 四川大学 | Surface has hydroxyapatite/polyamide composite biological material of nanofiber loose structure and preparation method thereof |
| CN104963097A (en) * | 2015-06-17 | 2015-10-07 | 广州迈普再生医学科技有限公司 | Reinforced electrospun mat and preparation method thereof |
| EP3890793A1 (en) * | 2018-12-05 | 2021-10-13 | Xeltis AG | Electrospun suture ring |
| WO2023108469A1 (en) * | 2021-12-15 | 2023-06-22 | 深圳先进技术研究院 | Tubular nanofiber material and preparation method therefor |
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| US4043331A (en) * | 1974-08-05 | 1977-08-23 | Imperial Chemical Industries Limited | Fibrillar product of electrostatically spun organic material |
| CN101543645A (en) * | 2009-05-04 | 2009-09-30 | 东华大学 | Polycaprolactone (PCL) static spinning nerve conduit and preparation and application thereof |
| CN102078643A (en) * | 2010-12-21 | 2011-06-01 | 苏州同科生物材料有限公司 | Film coating method of self-expanding stent |
| CN102470030A (en) * | 2009-08-07 | 2012-05-23 | 宙斯工业产品股份有限公司 | Prosthetic device including electrostatically spun fibrous layer and method for making the same |
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|---|---|---|---|---|
| US4043331A (en) * | 1974-08-05 | 1977-08-23 | Imperial Chemical Industries Limited | Fibrillar product of electrostatically spun organic material |
| CN101543645A (en) * | 2009-05-04 | 2009-09-30 | 东华大学 | Polycaprolactone (PCL) static spinning nerve conduit and preparation and application thereof |
| CN102470030A (en) * | 2009-08-07 | 2012-05-23 | 宙斯工业产品股份有限公司 | Prosthetic device including electrostatically spun fibrous layer and method for making the same |
| CN102078643A (en) * | 2010-12-21 | 2011-06-01 | 苏州同科生物材料有限公司 | Film coating method of self-expanding stent |
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