CN100450557C - Medication eluting type blood vessel bracket - Google Patents
Medication eluting type blood vessel bracket Download PDFInfo
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- CN100450557C CN100450557C CNB2006101594159A CN200610159415A CN100450557C CN 100450557 C CN100450557 C CN 100450557C CN B2006101594159 A CNB2006101594159 A CN B2006101594159A CN 200610159415 A CN200610159415 A CN 200610159415A CN 100450557 C CN100450557 C CN 100450557C
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Abstract
A medicine eluted scaffold of blood vessel is composed of a scaffold body, a TiO2 layer and a surficial medicine-polymer layer. Its preparing process includes such steps as roughening the surface of scaffold body, preparing a TiO2 layer on the roughened surface, coating a polymer layer, and combing medicine with said polymer layer.
Description
The application divides an application, and the applying date of original application is on August 13rd, 2004, and application number is 200410040450X, and denomination of invention is: the preparation method of medication eluting type blood vessel bracket and medication eluting type blood vessel bracket
Technical field
The present invention relates to intravascular stent, particularly a kind of medication eluting type blood vessel bracket that can discharge curative drug.This medication eluting type blood vessel bracket can effectively be prevented and treated restenosis and thrombosis behind the Stent.
Background technology
Dotter was placed on the close screw thread intravascular stent of homemade rustless steel in the peripheral vessels of dog under perspective in 1969, this support is kept vascular patency for 2 years half, he has proved rustless steel intravascular stent [the DotlerCT.Transluminally placed coil springs and arterial tube graffs.Long-tern patency in the carinepopliteal artery.Invest Radiol that can be integrated with blood vessel wall first, 1969,4:329-332].Sigwart in 1987 etc. have reported and laid intravascular stent in coronary artery, be mainly used in percutaneous coronary acute vascular obturation and PTCA postoperative restenosis [the Sigwart U that the dissatisfied or concurrent inner membrance avulsion of postoperative of (PTCA) art curative effect, interlayer cause that be shaped, et al.Intravascular stents to prevent occlusion andrestenosis after tranaluminal angioplasty.N Engl J Med, 1987; 316:701].
At present, there is nearly 90% coronary artery interventional therapy all to comprise the implantable intravascular support.Lay intravascular stent in the coronary artery and have characteristics such as success rate height, curative effect is obvious, adaptability is strong, but because intravascular stent itself is as a kind of metallic foreign body, have the hyperamization bolt to form and foreign body reaction, the postoperative subacute stent thrombosis forms and restenosis is still two big major complications.For solving an above-mentioned difficult problem, people constantly design novel intravascular stent, and medication eluting type blood vessel bracket is exactly wherein a kind of.Medication eluting type blood vessel bracket (drug-eluting stent) directly is coated in certain medicine on the metallic blood vessel bracket, perhaps certain polymer is coated in the metallic blood vessel bracket surface, and on this basis in conjunction with one or more medicative medicine or antibody, medicine is transported to diseased region improves local drug concentration, reach therapeutic purposes.According to measuring and calculating, adopt this method can make local drug concentration reach 10 of whole body administration
6Doubly, thus more effectively prevent postoperative restenosis and thrombotic generation.
The drug main that drug-eluting stent is commonly used will be divided into following a few class at present:
1, the medicine that suppresses cell migration
The hypertrophy of tunica intima and vascular smooth muscle cell (SMC) migrated to the inner membrance growth after support was implanted substantial connection.Therefore, the migration that hinders SMC has also just reduced the hypertrophy of tunica intima, has reduced the generation of restenosis.As c-protease inhibitor (C-Proteinase inhibitors), prolyl 3-hydroxylase inhibitors (Prolyl Hydroxylase inhibitors), halofuginone etc.
2, the medicine that suppresses cell proliferation
Such medicine is the support eluting medicine of the present inhibition restenosis that generally adopts.Comprise rapamycin (Rapamycn), paclitaxel (Taxol), vincristine (Vincristine), mitomycin (Mitomycin), Paclitaxel etc.
3, promote the medicine of healing and endothelialization
Can select for use BCP671, estrogen (Estrogen) and VEGF somatomedin to wait and promote blood vessel endotheliumization, prevent thrombosis and reduce restenosis rate.
4, the medicine of inflammation-inhibiting reaction
Glucocorticoid commonly used is as dexamethasone (Dexamethasone), radiosone (Methyl-prednisolone) etc.
Comprehensive said medicine can find that the medicine that medication eluting type blood vessel bracket discharges can go to prevent restenosis and thrombosis from a plurality of angles.However, thrombosis and restenosis still fail to be effectively controlled behind the Stent.For this reason, the present invention is different from above-mentioned approach, from antiplatelet and anticoagulant angle, selects suitable drug to make a kind of medication eluting type blood vessel bracket, thereby realizes reducing even eliminate thrombosis and restenosis behind the Stent.
The preparation method of existing medication eluting type blood vessel bracket all is that polymer, medicine, solvent are total to molten formation coating solution, again this solution is applied to the intravascular stent surface, form the polymeric layer that contains medicine on the intravascular stent surface behind the evaporating solvent, but it is still have defectives such as polymeric layer easily comes off, and unworkable at all for protein drug the method.
Medication eluting type blood vessel bracket research, report abroad is more, but only has minority mechanism to carry out this research at home, and relevant patent seldom.
Summary of the invention
The objective of the invention is to disclose a kind of medication eluting type blood vessel bracket.After this medication eluting type blood vessel bracket was implanted, function medicament discharged, and brings into play antiplatelet and anticoagulation efficiently at implant site, with problem such as overcome the restenosis that prior art exists and subacute stent thrombosis forms and polymeric layer easily comes off.
The structure of newtype drug eluting type blood vessel bracket of the present invention is made up of the titanium dioxide layer and the lip-deep pharmaceutical polymer layer of titanium dioxide layer on intravascular stent and surface thereof in this way, the roughness of titanium dioxide layer is 0.1～0.5 μ m, the gross thickness of pharmaceutical polymer layer is 15～110 μ m, and medicine accounts for 1～45% of coating gross weight.
Described titanium dioxide layer is to place butyl titanate solution to handle intravascular stent to obtain, butyl titanate solution is by following material and molar concentration rate preparation, butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=(0.5～5): (10～30): (0.5～5): (1～10), earlier in ethylene glycol monomethyl ether, add butyl titanate, add ethyl acetoacetate and water behind the mixing again; Processing method is: place butyl titanate solution to soak 5～30 minutes intravascular stent, take out the back drying at room temperature, place heating furnace to be heated to 450～600 ℃ again, programming rate is 4～8 ℃/min, is incubated 0.5～5 hour, takes out and cools off this intravascular stent;
Described pharmaceutical polymer layer is to have the intravascular stent of titanium dioxide layer to be soaked in earlier in the polymer solution 1～30 minute on the surface, take out and dry this intravascular stent, be soaked in then in the hirudin or antiplatelet monoclonal antibody or any one pharmaceutical aqueous solution of protamine that concentration is 0.1～10.0mg/ml, soak time 10～50 hours finally obtains; The concentration of polymer solution is 1～20%, and it is to be dissolved in chloroform, oxolane, dimethylbenzene, the acetone in any one solvent and to be obtained by any one polymer in polylactic acid, polycaprolactone, poly-anhydride, the polyglycolic acid.
The present invention compared with prior art has following technique effect:
Medication eluting type blood vessel bracket of the present invention carries out surface roughening to intravascular stent before coating the polymeric medicine layer handles, form the titanium dioxide layer of an even compact on the intravascular stent surface, not only increased the blood compatibility of intravascular stent but make polymer and the intravascular stent surface combination firm, difficult drop-off.
Medication eluting type blood vessel bracket of the present invention is earlier polymer solution to be coated on the titanium dioxide layer on intravascular stent surface, and dry back forms polymeric layer, this intravascular stent is soaked in the drug solution again, and medicine is attached in the polymer in the mode of passive absorption.This is different from the past to be applied to the intravascular stent surface with this solution again with polymer, medicine, solvent molten formation coating solution altogether, forms the medication eluting type blood vessel bracket of the polymeric layer that contains medicine behind the evaporating solvent on the intravascular stent surface.Because protein drug is dissolved in volatile organic solvent hardly, therefore this with polymer, medicine, solvent altogether the defective of the method maximum of molten formation coating solution be the preparation that can not be used for the protein drug eluting type blood vessel bracket.And the present invention is coated to polymer and medicine on the intravascular stent in two steps, has overcome the defective that polymer and medicine can not be dissolved in same volatile organic solvent altogether, thereby has opened up new world for the preparation method of protein drug eluting type blood vessel bracket.
The present invention adopts antiplatelet substance and the anticoagulant substances eluting medicine as intravascular stent, eluting medicine different from the past, as immunosuppressant rapamycin (Rapamycin) pair cell damaging action is arranged, influence the healing of endothelium, cause the formation of thrombosis.Platelet is particularly being played the part of important role in the artery thrombosis in thrombosis, and the main cause acute and that subacute stent thrombosis form of intravascular stent after implanting is blood coagulation system and the thrombogenicity of intravascular stent itself and the damage of implant site tunica intima that interventional procedure has activated blood, while thrombosis and restenosis substantial connection arranged.Therefore the present invention adopts antiplatelet substance and the anticoagulant substances eluting medicine as support, can reach efficient, the purpose of safety of local application, reduced the danger of hemorrhage complication again, also reach simultaneously the dual function of formation of anti-(Asia) acute thrombus and restenosis, improved patient's survival rate and quality of life greatly.
Description of drawings
Fig. 1: the structural profile sketch map of medication eluting type blood vessel bracket
Fig. 2: medication eluting type blood vessel bracket pictorial diagram
Fig. 3: the intravascular stent of roughening (contrast) not under the inverted microscope
Fig. 4: the intravascular stent of roughening under the inverted microscope
Fig. 5: the sem photograph (contrast) that does not contain the intravascular stent of antiplatelet monoclonal antibody
Fig. 6: the sem photograph of antiplatelet monoclonal antibody eluting type blood vessel bracket
1 is intravascular stent among Fig. 1; The 2nd, titanium dioxide layer; The 3rd, the pharmaceutical polymer layer
The specific embodiment
A kind of preparation process of hirudin eluting type blood vessel bracket is as follows:
(1) preparation butyl titanate solution
The butyl titanate lipoprotein solution is prepared butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=0.5: 10: 0.5 by following material and molar concentration rate: 1, in ethylene glycol monomethyl ether, add butyl titanate earlier, and add ethyl acetoacetate and water behind the mixing again;
(2) intravascular stent is placed butyl titanate solution handle
Place butyl titanate solution to soak 5 minutes intravascular stent, take out the back drying at room temperature, place Muffle furnace to heat-treat again in 600 ℃, programming rate is 8 ℃/min, be incubated 5 hours, take out also and at room temperature cool off this intravascular stent, making the intravascular stent surface form the layer of surface roughness is the titanium dioxide layer of 0.5 μ m;
(3) prepared polymer solution
The 1g polylactic acid is dissolved in the 5ml chloroform, is mixed with concentration and is 20% polylactic acid solution;
(4) surface is had the intravascular stent of titanium dioxide layer be soaked in the polylactic acid solution, soak time is 30 minutes, takes out this intravascular stent, drying at room temperature, and making the titanium dioxide laminar surface formation thickness of intravascular stent is the polylactic acid layers of 100 μ m;
(5) intravascular stent after the above-mentioned processing is soaked in the hirudin aqueous solution that sub-concentration is 0.1mg/ml, soak time is 50 hours, and medicine accounts for 1% of coating gross weight.
Resulting hirudin eluting type blood vessel bracket, by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.5 μ m, and the gross thickness of pharmaceutical polymer layer is 100 μ m, and medicine accounts for 1% of coating gross weight.This hirudin eluting type blood vessel bracket has the dual function of formation of anti-(Asia) acute thrombus and restenosis, can reach simultaneously that local application is efficient, purpose of safety, reduce the danger of hemorrhage complication again, improved patient's survival rate and quality of life greatly.
A kind of preparation process of antiplatelet monoclonal antibody eluting type blood vessel bracket is as follows:
(1) preparation butyl titanate solution
Butyl titanate solution is prepared butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=3: 30: 3 by following material and molar concentration rate: 10, in ethylene glycol monomethyl ether, add butyl titanate earlier, and add acetoacetic acid second fat and water behind the mixing again;
(2) intravascular stent is placed butyl titanate solution handle
Place butyl titanate solution to soak 5 minutes intravascular stent, take out the back drying at room temperature, place Muffle furnace to heat-treat again in 450 ℃, programming rate is 4 ℃/min, be incubated 0.5 hour, take out this intravascular stent, making the intravascular stent surface form the layer of surface roughness is the titanium dioxide layer of 0.1 μ m;
(3) prepared polymer solution
0.05 poly-anhydride is dissolved in the 5ml oxolane, and being mixed with concentration is 1% poly-anhydride solution;
(4) surface is had the intravascular stent of titanium dioxide layer be soaked in the poly-anhydride solution, soak time is 1 minute, takes out this intravascular stent, drying at room temperature, and making the titanium dioxide laminar surface formation thickness of intravascular stent is the poly-anhydride layer of 10 μ m;
(5) intravascular stent after the above-mentioned processing is soaked in the antiplatelet monoclonal anti liquid solution that concentration is 1mg/ml, soak time is 28 hours, and medicine accounts for 20% of coating gross weight.This intravascular stent with after citric acid anticoagulant fresh whole blood contacts 30 minutes, is observed under scanning electron microscope, and observed result is seen accompanying drawing 3,4.
Resulting antiplatelet monoclonal antibody eluting type blood vessel bracket, by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.1 μ m, the gross thickness of pharmaceutical polymer layer is 10 μ m, and medicine accounts for 20% of coating gross weight.This antiplatelet monoclonal antibody eluting type blood vessel bracket has the dual function of formation of anti-(Asia) acute thrombus and restenosis, can reach simultaneously that local application is efficient, purpose of safety, reduce the danger of hemorrhage complication again, improved patient's survival rate and quality of life greatly.
A kind of preparation process of protamine eluting type blood vessel bracket is as follows:
(1) preparation butyl titanate solution
Butyl titanate solution is prepared butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=2: 20: 2 by following material and molar concentration rate: 5, in ethylene glycol monomethyl ether, add butyl titanate earlier, and add acetoacetic acid second fat and water behind the mixing again;
(2) intravascular stent is placed butyl titanate solution handle
Place butyl titanate solution to soak 20 minutes intravascular stent, take out the back drying at room temperature, place Muffle furnace to heat-treat again in 550 ℃, programming rate is 6 ℃/min, be incubated 3 hours, take out also and at room temperature cool off this intravascular stent, making the intravascular stent surface form the layer of surface roughness is the titanium dioxide layer of 0.3 μ m;
(3) prepared polymer solution
The 0.5g polycaprolactone is dissolved in the 5ml acetone, and being mixed with concentration is 10% polycaprolactone solution;
(4) surface is had the intravascular stent of titanium dioxide layer be soaked in the polycaprolactone solution, soak time is 10 minutes, takes out this intravascular stent, drying at room temperature, and making the titanium dioxide laminar surface formation thickness of intravascular stent is the polycaprolactone layer of 40 μ m;
(5) intravascular stent after the above-mentioned processing is soaked in the protamine aqueous solution that concentration is 10.0mg/ml, soak time is 10 hours, and medicine accounts for 45% of coating gross weight.
Resulting protamine eluting type blood vessel bracket, by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.3 μ m, and the gross thickness of pharmaceutical polymer layer is 40 μ m, and medicine accounts for 45% of coating gross weight.This protamine eluting type blood vessel bracket has the dual function of formation of anti-(Asia) acute thrombus and restenosis, can reach simultaneously that local application is efficient, purpose of safety, reduce the danger of hemorrhage complication again, improved patient's survival rate and quality of life greatly.
Embodiment 4
A kind of preparation process of antiplatelet monoclonal antibody eluting type blood vessel bracket is as follows:
(1) preparation butyl titanate solution
Butyl titanate solution is prepared butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=1: 20: 1 by following material and molar concentration rate: 3, in ethylene glycol monomethyl ether, add butyl titanate earlier, and add acetoacetic acid second fat and water behind the mixing again;
(2) intravascular stent is placed butyl titanate solution handle
Place butyl titanate solution to soak 10 minutes intravascular stent, take out the back drying at room temperature, place Muffle furnace to heat-treat again in 500 ℃, programming rate is 5 ℃/min, be incubated 2 hours, take out also and at room temperature cool off this intravascular stent, making the intravascular stent surface form the layer of surface roughness is the titanium dioxide layer of 0.4 μ m;
(3) prepared polymer solution
The 0.25g polyglycolic acid is dissolved in the 5ml dimethylbenzene, and being mixed with concentration is 5% polyglycolic acid solution;
(4) surface is had the intravascular stent of titanium dioxide layer be soaked in the polyglycolic acid solution, soak time is 10 minutes, takes out this intravascular stent, drying at room temperature, and making the titanium dioxide laminar surface formation thickness of intravascular stent is the polyglycolic acid layer of 20 μ m;
(5) intravascular stent after the above-mentioned processing is soaked in the antiplatelet monoclonal anti liquid solution that concentration is 2mg/ml, soak time is 30 hours, and medicine accounts for 30% of coating gross weight.
Resulting antiplatelet monoclonal antibody eluting type blood vessel bracket, by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.4 μ m, the gross thickness of pharmaceutical polymer layer is 20 μ m, and medicine accounts for 30% of coating gross weight.This antiplatelet monoclonal antibody eluting type blood vessel bracket has the dual function of formation of anti-(Asia) acute thrombus and restenosis, can reach simultaneously that local application is efficient, purpose of safety, reduce the danger of hemorrhage complication again, improved patient's survival rate and quality of life greatly.
Claims (5)
1, a kind of medication eluting type blood vessel bracket, it is characterized in that by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.1～0.5 μ m, the gross thickness of pharmaceutical polymer layer is 15～110 μ m, and medicine accounts for 1～45% of coating gross weight.
2, a kind of medication eluting type blood vessel bracket according to claim 1, it is characterized in that it by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.5 μ m, the gross thickness of pharmaceutical polymer layer is 100 μ m, and medicine accounts for 1% of coating gross weight.
3, a kind of medication eluting type blood vessel bracket according to claim 1, it is characterized in that it by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.3 μ m, the gross thickness of pharmaceutical polymer layer is 40 μ m, and medicine accounts for 45% of coating gross weight.
4, a kind of medication eluting type blood vessel bracket according to claim 1, it is characterized in that it by intravascular stent and the surface titanium dioxide layer and the pharmaceutical polymer layer of titanium dioxide laminar surface form, the roughness of titanium dioxide layer is 0.4 μ m, the gross thickness of pharmaceutical polymer layer is 20 μ m, and medicine accounts for 30% of coating gross weight.
5, according to claim 1,2,3 or 4 described a kind of medication eluting type blood vessel brackets, it is characterized in that:
Described titanium dioxide layer is to place butyl titanate solution to handle intravascular stent to obtain, butyl titanate solution is by following material and molar concentration rate preparation, butyl titanate: ethylene glycol monomethyl ether: ethyl acetoacetate: water=(0.5～5): (10～30): (0.5～5): (1～10), earlier in ethylene glycol monomethyl ether, add butyl titanate, add ethyl acetoacetate and water behind the mixing again; Processing method is: place butyl titanate solution to soak 5～30 minutes intravascular stent, take out the back drying at room temperature, place heating furnace to be heated to 450～600 ℃ again, programming rate is 4～8 ℃/min, is incubated 0.5～5 hour, takes out and cools off this intravascular stent;
Described pharmaceutical polymer layer is to have the intravascular stent of titanium dioxide layer to be soaked in earlier in the polymer solution 1～30 minute on the surface, take out and dry this intravascular stent, be soaked in then in the hirudin or antiplatelet monoclonal antibody or any one pharmaceutical aqueous solution of protamine that concentration is 0.1～10.0mg/ml, soak time 10～50 hours finally obtains; The concentration of polymer solution is 1～20%, and it is to be dissolved in chloroform, oxolane, dimethylbenzene, the acetone in any one solvent and to be obtained by any one polymer in polylactic acid, polycaprolactone, poly-anhydride, the polyglycolic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101594159A CN100450557C (en) | 2004-08-13 | 2004-08-13 | Medication eluting type blood vessel bracket |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101594159A CN100450557C (en) | 2004-08-13 | 2004-08-13 | Medication eluting type blood vessel bracket |
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| CN 200410040450 Division CN1278743C (en) | 2004-08-13 | 2004-08-13 | Medicine eluent type blood vessel stent, and prepn. method therefor |
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| CN1958083A CN1958083A (en) | 2007-05-09 |
| CN100450557C true CN100450557C (en) | 2009-01-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101496916B (en) * | 2009-02-24 | 2012-11-07 | 重庆大学 | Method for modifying endovascular stent nano coating combined with micropore surface |
| US9254350B2 (en) * | 2009-04-10 | 2016-02-09 | Medtronic Vascular, Inc. | Implantable medical devices having bioabsorbable primer polymer coatings |
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| CN1355005A (en) * | 2001-12-13 | 2002-06-26 | 华东理工大学 | Medicine eluted cardiovascular frame and its preparing process |
| CN1378865A (en) * | 2002-04-26 | 2002-11-13 | 维科医疗器械(苏州)有限公司 | Medicine coated support frame of blood vessel |
| CN1424117A (en) * | 2002-12-30 | 2003-06-18 | 中国中医研究院西苑医院 | Internal cavitary and vessel stent with medicinal coating against spinal canal restenosis and production thereof |
| WO2003099169A1 (en) * | 2002-05-20 | 2003-12-04 | Orbus Medical Technologies Inc. | Drug eluting implantable medical device |
| CN1465410A (en) * | 2002-06-27 | 2004-01-07 | 微创医疗器械(上海)有限公司 | Drug-eluting stent (DES) with multicoating |
| KR20040040834A (en) * | 2002-11-08 | 2004-05-13 | 학교법인 포항공과대학교 | Titanium oxide-coated material for implanting in living body and method for the preparation thereof |
-
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- 2004-08-13 CN CNB2006101594159A patent/CN100450557C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355005A (en) * | 2001-12-13 | 2002-06-26 | 华东理工大学 | Medicine eluted cardiovascular frame and its preparing process |
| CN1378865A (en) * | 2002-04-26 | 2002-11-13 | 维科医疗器械(苏州)有限公司 | Medicine coated support frame of blood vessel |
| WO2003099169A1 (en) * | 2002-05-20 | 2003-12-04 | Orbus Medical Technologies Inc. | Drug eluting implantable medical device |
| CN1465410A (en) * | 2002-06-27 | 2004-01-07 | 微创医疗器械(上海)有限公司 | Drug-eluting stent (DES) with multicoating |
| KR20040040834A (en) * | 2002-11-08 | 2004-05-13 | 학교법인 포항공과대학교 | Titanium oxide-coated material for implanting in living body and method for the preparation thereof |
| CN1424117A (en) * | 2002-12-30 | 2003-06-18 | 中国中医研究院西苑医院 | Internal cavitary and vessel stent with medicinal coating against spinal canal restenosis and production thereof |
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