CN1429547A - Coronary artery skeleton medicinal coating for preventing restenosis of blood vessel - Google Patents
Coronary artery skeleton medicinal coating for preventing restenosis of blood vessel Download PDFInfo
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- CN1429547A CN1429547A CN02100011A CN02100011A CN1429547A CN 1429547 A CN1429547 A CN 1429547A CN 02100011 A CN02100011 A CN 02100011A CN 02100011 A CN02100011 A CN 02100011A CN 1429547 A CN1429547 A CN 1429547A
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Abstract
A coated medicine layer on the scaffold in arteria coronaria for preventing angiostenosis is prepared through dissolving the aliphatic polylactone and its copolymer is solvent, adding taxusol, stirring while dissolving, filtering, coating on the scaffold, evaporating the solvent, removing the solvent for 48 hr under vacuum, and disinfecting by epoxy ethane.
Description
Technical field
The present invention relates to a kind of be the preventing restenosis of blood vessel medicine with the paclitaxel, be the coronary artery skeleton medicinal coating of the preventing restenosis of blood vessel of pharmaceutical carrier with the biodegradable fatty polylactone.
Background technology
The coronary artery balloon expandable forms applying once of art and once brought glad tidings for numerous patients with coronary heart disease, but the greatest drawback of this iatrotechnics--the vascular restenosis problem has limited its curative effect to a great extent.The mechanism of vascular restenosis is at present illustrated, shows the generation and early stage elastical retraction, the thrombosis in treatment operation back of vascular restenosis, the smooth muscle migration in mid-term, hypertrophy, and the blood vessel in late period is reinvented etc., and factor is relevant in many ways.At the generation of prevention of restenosis, for many years carried out a large amount of research, Therapeutic Method such as endovascular stent, rotary-cut art have successively appearred; Existing simultaneously multinomial method of preventing with medicine is for example used platelet GB IIb/IIIa receptor antagonist etc., but the effective ways of unrestraint restenosis still so far.
In recent years, the clinicist has also tried out the method for multiple pre-preventing restenosis of blood vessel, but it is still high that the coronary artery balloon expandable forms the restenosis rate of postoperative, all the time maintain between the 20-30%, under the situation of vessel diameter less than 3mm, the incidence rate of restenosis is then higher, and the incidence rate of patient's restenosis of part subgroup becomes very big restriction and obstacle with intervention property means treatment coronary heart disease then up to 50%.
Carry out with the intravascular stent that contains radioactive substance that radiation treatment had once brought a line dawn for pre-preventing restenosis of blood vessel in the blood vessel, but must carry out protection, make operating performance very complicated lonizing radiation because preparation and use contains the radioactive substance intravascular stent, simultaneously because therefore the problem that also exists the Excreta that must prevent to contain radioactive substance that environment is polluted makes it be restricted in clinical using and promote also.
Coating bracket is the new development of intravascular stent, the support with nonmetalloid coatings such as carbon, silicon successively occurs, and has carried out clinical trial, but studies show that its effect is still not good most, and the vascular restenosis rate in the clinical use does not almost reduce.In addition, the vascular restenosis rate of the phosphocholine coating bracket of new development in recent years in the time of six months also reaches about 18%, and curative effect is still undesirable.
Cardiovascular pharmacology discovers that multiple medicine can produce the obvious suppression effect to tunica intima and smooth muscle cell external, but the systemic administration poor effect, and its reason may be crossed low relevant with the body blood drug level that circulates.In addition because this special position of coronary artery is unsuitable for settling the drug disposition delayed release device, therefore how local application and use which kind of medicine to become the key point of research medicine slow release stent.
Act on the cell microtubule system according to paclitaxel, can influence cell division, quicken apoptosis, thereby suppress proliferation of cells, divide a word with a hyphen at the end of a line and the performance of signal conduction, become widely used gradually new antitumor drug in recent years, it is again a class fat-soluble medicine simultaneously, permeate through cell membranes enters cell rapidly, has rapid-action advantage; And but its pair cell skeleton produces firm effect, thereby can slow down it in intracellular metabolism, to prolong the characteristics of action time.The factor that influences paclitaxel release behavior in the coronary artery skeleton medicinal coating is a lot of, except the geometry of support, the dissolving of the material category, paclitaxel that in coating, plays the paclitaxel carrier effect in carrier material and the degradation speed of diffusion velocity, carrier material, and the concentration of paclitaxel in coating and the distribution in carrier etc. all have significant effects.Wherein, the character of carrier material has the greatest impact to the release behavior of paclitaxel.Because if when being the carrier of paclitaxel with nondegradable material, the a large amount of initial stage burst releases that discharge of paclitaxel then can when coronary artery bracket is just implanted arteria coronaria, occur, make the paclitaxel blood drug level at initial stage surpass the poisoning limit, and, make the burst size of paclitaxel not reach the valid density that prevents restenosis afterwards along with the minimizing of content of taxol in the coating; In addition, if carrier material is too poor with the compatibility of paclitaxel, then can cause because the release that paclitaxel diffusion velocity in carrier is too slow, the initial stage of implanting arteria coronaria at support does not have paclitaxel, the stage of the easiest generation thrombosis does not reach effective paclitaxel blood drug level so after surgery, causes coronary restenosis easily.Therefore, these two kinds of drug release behaviors that form owing to the pharmaceutical carrier non-degradable all are not meet the clinical practice that prevents restenosis to require.
Ideal pharmaceutical carrier should have " zero level " (i.e. " constant speed ") release behavior, i.e. drug releasing rate time to time change not, thus can make blood drug level continue to maintain the level of optimum curative effect.With biodegradable macromolecular material during as pharmaceutical carrier, though carrier also will slow down along with the reduction of medicament contg to the rate of release of medicine, because along with the progressively structure of degraded, carrier of pharmaceutical carrier becomes loose, drug molecule is increased to body dissolving and diffusion velocity quickening, release amount of medicine from carrier.Therefore, in the biodegradation rate that is adjusted to carrier is a timing, just can make the minimizing that reduces the release amount of medicine cause owing to medicament contg with offseting the constant release of realization medicine because drug molecule dissolving diffusion velocity is accelerated the increase of the release amount of medicine that causes.In addition, since the Biodegradable high molecular pharmaceutical carrier can physiological environment in vivo under, owing to the effect of body fluid and enzyme etc. be degraded into micromolecule or monomer, so that finally absorbed or metabolism by body, therefore also having not to need the advantage of taking out again in body after drug release is finished, be optimal pharmaceutical carrier.
Summary of the invention
The coronary artery skeleton medicinal coating that the purpose of this invention is to provide a kind of preventing restenosis of blood vessel, the present invention can realize the constant release of medicine.
For achieving the above object, the present invention is with aliphatic poly lactone and copolymer dissolution with solvents thereof, and the even back of dissolving adds as the coronary artery skeleton medicinal paclitaxel that prevents vascular restenosis, uses after stirring, dissolving all even filtration.The coronary artery bracket medication coat can adopt the solution of being prepared by paclitaxel and pharmaceutical carrier to process with solution spraying method or solution dipping method coated on the coronary artery bracket surface.Coated evenly the back in air solvent flashing, then under vacuum condition in room temperature desolventizing 48 hours, standby behind the ethane via epoxyethane sterilization.Drug taxol content in the support can be controlled by the concentration of paclitaxel, the concentration of coating solution and the coated number of times of coating.
Wherein, in weight portion, comprising:
10 parts of paclitaxels,
Pharmaceutical carrier 100-10000 part is preferably 200-8000 part.
Described pharmaceutical carrier is biodegradable fatty polylactone and copolymer thereof, and they can be: polylactide (PLA), polycaprolactone (PCL), poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester) (PLG), poly-(lactide-caprolactone) (PLC), poly-(Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) (PGC) or poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) (PGLC) random or block copolymer; The molecular weight of aliphatic poly lactone and copolymer thereof is 8000～500000.
Described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester) (PLG) in, the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester can be from 1-60mol%, optimal proportion is 15-50mol%;
Described poly-(lactide-caprolactone) (PLC) in, the content of polylactide can be from 1-99mol%, optimal proportion is 10 to 90mol%;
Described poly-(Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) (PGC) in, the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester can be from 1 to 30mol%, optimal proportion is 3 to 20mol%;
Described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) (PGLC) in, the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester can be from 1 to 30mol%, optimal proportion is 3 to 20mol%; The content optimal proportion of polycaprolactone is 3 to 75mol%.
Described coronary artery bracket material can be rustless steel, Ni-Ti memorial alloy, or the high molecule plastic of biocompatibility.
The solvent of the medication coat solution of being prepared by paclitaxel and pharmaceutical carrier can be oxolane, acetone, dichloromethane, or chloroform.
The concentration of the medication coat solution that is mixed with by aliphatic poly lactone and copolymer solution and paclitaxel can be in 0.5～5% scope.
The cycle of the paclitaxel release of the coronary artery skeleton medicinal coating of preventing restenosis of blood vessel of the present invention is that a week is to January.
Characteristics of the present invention be the key that will prevent vascular restenosis be conceived to suppress in the smooth muscle cell of rete under cytokine and cell growth factor effect, cause abnormality proliferation to the theca interna migration.Therefore enter the DNA synthesis stage from the beginning trophophase and set about the restenosis of anti-hemostatic tube to suppress smooth muscle cell.
Consider that intracoronary stent is one of means the most frequently used in the coronary heart disease interventional therapy, the coronary heart disease patient of the 40-70% that the has an appointment implant frame of need performing the operation.Therefore with the medium of support,, can make medicine directly act on the local lesion position by with being close to vascular inner surface behind the coronary stent implantable intravascular, the drug slow that is covered on the support being discharged as the release medicine.Simultaneously, owing to have only trace drug to enter in the body, can also avoid because the general untoward reaction that medicine produced.
The aliphatic poly lactone all is to have gone through to be used for intravital Biodegradable high molecular as polylactide (PLA), poly-Acetic acid, hydroxy-, bimol. cyclic ester (PGA), polycaprolactone (PCL).They are nontoxic, have excellent biological compatibility and good physicochemical performance, they can also carry out copolymerization, by regulating the component of copolymer, form, molecular weight and molecular weight distribution etc. are regulated the degradation speed of copolymer on a large scale, physicochemical property, thereby regulate their drug releasing rate, make to the drug release life-span and can between a couple of days to several months, regulate, thereby as the treatment cancer, detoxifcation, infect and the pharmaceutical carrier of medicine such as contraception clinical be applied and commercialization (as Decapeptyl , LupronDepot , Zoladex , Adriamycin and Capronor etc.).
The specific embodiment
Embodiment one: 0.1g gathers (lactide-Acetic acid, hydroxy-, bimol. cyclic ester) random copolymer (PLGA, lactide/glycolides=50/50 (mol/mol)) be dissolved in the 5ml chloroform after, add the 2mg paclitaxel, after stirring, all even filtration of dissolving, spray to 316L stainless steel stent surface, solvent flashing in air then repeats spraying once, in air behind the solvent flashing again under vacuum condition in room temperature desolventizing 48 hours, the content of taxol in the support is 50 μ g.Implant the arteria coronaria of dog behind the ethane via epoxyethane sterilization, do not see after two weeks that thrombosis generates.
Embodiment two: 0.1g gathers (lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) random copolymer (PGLC, lactide/glycolides/caprolactone=45/45/10 (mol/mol)) be dissolved in the 3ml dichloromethane after, add the 2mg paclitaxel, after stirring, all even filtration of dissolving, dip-coating is to 316L stainless steel stent surface, solvent flashing in air, then again under vacuum condition in room temperature desolventizing 48 hours, the content of taxol in the support is 85 μ g.Implant the arteria coronaria of dog behind the ethane via epoxyethane sterilization, do not see after three weeks that thrombosis generates.
Embodiment three: 0.1g gathers (lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) random copolymer (PGLC, lactide/glycolides/caprolactone=45/45/10 (mol/mol)) be dissolved in the 3ml dichloromethane after, add the 2mg paclitaxel, after stirring, all even filtration of dissolving, dip-coating is to 316L stainless steel stent surface, and solvent flashing in air then repeats dip-coating once again, in air behind the solvent flashing again under vacuum condition in room temperature desolventizing 48 hours, the content of taxol in the support is 250 μ g.Implant the arteria coronaria of dog behind the ethane via epoxyethane sterilization, do not see after February that thrombosis generates.
Embodiment four: 0.2g gathers (lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) block copolymer (PGLC, lactide/glycolides/caprolactone=27/63/10 (mol/mol)) be dissolved in the 6ml dichloromethane after, add the 2mg paclitaxel, after stirring, all even filtration of dissolving, dip-coating is to 316L stainless steel stent surface, in air, repeat dip-coating more once behind the solvent flashing, then again under vacuum condition in room temperature desolventizing 48 hours, use behind the ethane via epoxyethane sterilization.Content of taxol in the support is 200 μ g.
Embodiment five: 0.1g gathers (Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) random copolymer (PGC, Acetic acid, hydroxy-, bimol. cyclic ester/caprolactone=30/70 (mol/mol)) be dissolved in the 10ml dichloromethane after, add the 2mg paclitaxel, after stirring, all even filtration of dissolving, spray to 316L stainless steel stent surface, solvent flashing in air then repeats to spray secondary, in air behind the solvent flashing again under vacuum condition in room temperature desolventizing 48 hours, use behind the ethane via epoxyethane sterilization.Content of taxol in the support is 100 μ g.
Embodiment six: with embodiment four operations, adopt the Ni-Ti memory alloy stent, the content of taxol in the support is 200 μ g.
Embodiment seven: with embodiment five operations, adopt the pla-pcl support, the content of taxol in the support is 100 μ g.
Reference examples one:, but do not have paclitaxel with embodiment one.With poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester) random copolymer (PLGA of 0.1g, lactide/glycolides=50/50 (mol/mol)) is dissolved in 5ml chloroform after-filtration, spray to 316L stainless steel stent surface then, solvent flashing in air, then repeat spraying once, in air behind the solvent flashing again under vacuum condition in room temperature desolventizing 48 hours, implant the dog arteria coronaria behind the ethane via epoxyethane sterilization, contrast examination finds have angiostenosis to sexually revise after two months.
Reference examples two: the 316L stainless steel stent of ethane via epoxyethane sterilization is directly implanted the dog arteria coronaria, check after two months that the narrow property of visible vessels iconography changes.
Zoopery example 1: laboratory animal is the hybrid dog, male, body weight 25kg, row femoral artery otomy behind the general anesthesia, insert the 7F catheter sheath in the femoral artery, send into the guide wire branch ostium place of circling round to a left side, send into guide wire and enter a left side and circle round and prop up along femoral artery, (3.0 * 16mm) are loaded on the foley's tube, send into circle round stage casing, a left side along seal wire will to contain the stainless steel stent of 50 μ g paclitaxels.Operational approach and human body operation process are in full accord.Clinical follow 3 hours is not seen thrombosis.The second, all around polysography inspection does not see that the aberrant angiogenesis iconography changes.
Zoopery example 2: laboratory animal is the hybrid dog, male, body weight 27kg, row femoral artery otomy behind the general anesthesia is inserted the 7F catheter sheath in the femoral artery, send into the guide wire branch ostium place of circling round to a left side along femoral artery, sending into guide wire enters a left side and circles round, send into circle round to an a left side stage casing of foley's tube and damage in advance, and then (3.0 * 16mm) are loaded on the foley's tube, send into a stage casing of circling round, a left side along seal wire will to contain the stainless steel stent of 85 μ g paclitaxels.Operational approach and human body operation process are in full accord.Clinical follow 4 hours is not seen thrombosis.Polysography is checked during the 3rd week, and no abnormality seen changes.
Zoopery example 3: laboratory animal is the hybrid dog, male, body weight 29kg, row femoral artery otomy behind the general anesthesia is inserted the 7F catheter sheath in the femoral artery, send into the guide wire branch ostium place of circling round to a left side along femoral artery, sending into guide wire enters a left side and circles round, send into circle round to an a left side stage casing of foley's tube and damage in advance, and then (3.0 * 16mm) are loaded on the foley's tube, send into a stage casing of circling round, a left side along seal wire will to contain the stainless steel stent of 250 μ g paclitaxels.Postoperative is the polysography inspection when first month, second month, and no abnormality seen changes.
Control animals experimental example 1: laboratory animal is the hybrid dog, male, body weight 24kg, row femoral artery otomy behind the general anesthesia is inserted the 7F catheter sheath in the femoral artery, send into the guide wire branch ostium place of circling round to a left side along femoral artery, sending into guide wire enters a left side and circles round, send into circle round to an a left side stage casing of foley's tube and damage in advance, and then will not contain paclitaxel and only be coated with the stainless steel stent of polylactone (3.0 * 16mm) are loaded on the foley's tube, send into a stage casing of circling round, a left side along seal wire.Operational approach and human body operation process are in full accord.Clinical follow 4 hours is not seen thrombosis.Polysography is checked in the time of around the, and no abnormality seen changes.
Control animals experimental example 2: 8 of laboratory animal hybrid dogs, male, average weight 26kg, row femoral artery otomy behind the general anesthesia is inserted the 7F catheter sheath in the femoral artery, send into the guide wire branch ostium place of circling round to a left side along femoral artery, sending into guide wire enters a left side and circles round, send into circle round to an a left side stage casing of foley's tube and damage in advance, (3.0 * 15--16mm) are loaded on the foley's tube, send into a stage casing of circling round, a left side along seal wire with the 316L stainless steel stent then.Operational approach and human body operation process are in full accord.First and second, polysography is checked six months the time, 7 animals the angiostenosis iconography successively occurs and change.
Claims (5)
1, a kind of coronary artery skeleton medicinal coating of preventing restenosis of blood vessel, its preparation method is:
Pharmaceutical carrier dissolved in solvent evenly add medicine, the stirring and dissolving after-filtration, again with the even coated of drug solution on the coronary artery bracket surface, solvent flashing in air, room temperature desolventizing 48 hours under vacuum then, ethane via epoxyethane sterilization again is characterized in that:
Described pharmaceutical carrier is aliphatic poly lactone and copolymer thereof;
Described medicine is a paclitaxel;
Wherein, in weight portion, comprising:
10 parts of paclitaxels,
Pharmaceutical carrier 100-10000 part,
The concentration of drug solution is the 0.5-5% scope.
2, coronary artery skeleton medicinal coating as claimed in claim 1, it is characterized in that described biodegradable fatty polylactone and copolymer thereof are polylactide, polycaprolactone, poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester), poly-(lactide-caprolactone), poly-(Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) or poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone) random or block copolymer;
The molecular weight of described aliphatic poly lactone and copolymer thereof is 8000-500000;
In described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 1-60mol%;
In described poly-(lactide-caprolactone), the content of polylactide is 1-99mol%;
In described poly-(Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 1-30mol%;
In described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 1 to 30mol%, and the content of polycaprolactone is 3 to 75mol%;
Described coronary artery bracket material is the high molecule plastic of rustless steel, Ni-Ti memorial alloy or biocompatibility;
Described solvent is oxolane, acetone, dichloromethane or chloroform.
3, coronary artery skeleton medicinal coating as claimed in claim 1 is characterized in that, described pharmaceutical carrier is 200-8000 part by weight.
4, coronary artery skeleton medicinal coating as claimed in claim 1 or 2 is characterized in that:
In described poly-(lactide-caprolactone), the content of polylactide is 10-90mol%;
In described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 15-50mol%;
In described poly-(Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 3-20mol%;
In described poly-(lactide-Acetic acid, hydroxy-, bimol. cyclic ester-caprolactone), the content of poly-Acetic acid, hydroxy-, bimol. cyclic ester is 3-20mol%.
5, coronary artery skeleton medicinal coating as claimed in claim 1 is characterized in that, the cycle of described paclitaxel release is that a week is to January.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021000115A CN1209105C (en) | 2002-01-04 | 2002-01-04 | Coronary artery skeleton medicinal coating for preventing restenosis of blood vessel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021000115A CN1209105C (en) | 2002-01-04 | 2002-01-04 | Coronary artery skeleton medicinal coating for preventing restenosis of blood vessel |
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| Publication Number | Publication Date |
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| CN1429547A true CN1429547A (en) | 2003-07-16 |
| CN1209105C CN1209105C (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021000115A Expired - Fee Related CN1209105C (en) | 2002-01-04 | 2002-01-04 | Coronary artery skeleton medicinal coating for preventing restenosis of blood vessel |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371032C (en) * | 2004-01-16 | 2008-02-27 | 东南大学 | Re-stricture preventing medicinal sustained releasing bracket and its preparation |
| CN100431627C (en) * | 2006-08-18 | 2008-11-12 | 天津百畅医疗器械科技有限公司 | Blood ressel stent medicinal conting layer capable of relieving free radical harmful to cell after blood deficiency refilling |
| CN103992465A (en) * | 2014-05-04 | 2014-08-20 | 电子科技大学 | Biodegradable ternary copolymer |
| CN104174074A (en) * | 2013-11-27 | 2014-12-03 | 浙江归创医疗器械有限公司 | Medicine coating composition as well as preparation method thereof and an implanting or intervention medical apparatus made thereof |
| CN108187151A (en) * | 2018-01-23 | 2018-06-22 | 南京鼓楼医院 | A kind of stent of medication coat |
| CN111035813A (en) * | 2018-10-15 | 2020-04-21 | 复旦大学附属中山医院 | Liquid band-aid type coronary artery membrane stent and manufacturing method thereof |
-
2002
- 2002-01-04 CN CNB021000115A patent/CN1209105C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371032C (en) * | 2004-01-16 | 2008-02-27 | 东南大学 | Re-stricture preventing medicinal sustained releasing bracket and its preparation |
| CN100431627C (en) * | 2006-08-18 | 2008-11-12 | 天津百畅医疗器械科技有限公司 | Blood ressel stent medicinal conting layer capable of relieving free radical harmful to cell after blood deficiency refilling |
| CN104174074A (en) * | 2013-11-27 | 2014-12-03 | 浙江归创医疗器械有限公司 | Medicine coating composition as well as preparation method thereof and an implanting or intervention medical apparatus made thereof |
| CN103992465A (en) * | 2014-05-04 | 2014-08-20 | 电子科技大学 | Biodegradable ternary copolymer |
| CN103992465B (en) * | 2014-05-04 | 2016-02-10 | 电子科技大学 | biodegradable terpolymer |
| CN108187151A (en) * | 2018-01-23 | 2018-06-22 | 南京鼓楼医院 | A kind of stent of medication coat |
| CN111035813A (en) * | 2018-10-15 | 2020-04-21 | 复旦大学附属中山医院 | Liquid band-aid type coronary artery membrane stent and manufacturing method thereof |
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| Publication number | Publication date |
|---|---|
| CN1209105C (en) | 2005-07-06 |
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