CN102488932A - Magnesium alloy support coated with acylated chitosan and polyester blend medicine coating - Google Patents
Magnesium alloy support coated with acylated chitosan and polyester blend medicine coating Download PDFInfo
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- CN102488932A CN102488932A CN2011104356134A CN201110435613A CN102488932A CN 102488932 A CN102488932 A CN 102488932A CN 2011104356134 A CN2011104356134 A CN 2011104356134A CN 201110435613 A CN201110435613 A CN 201110435613A CN 102488932 A CN102488932 A CN 102488932A
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Abstract
The invention provides a magnesium alloy support coated with an acylated chitosan and polyester blend medicine coating. The support comprises a magnesium alloy bare support, the magnesium alloy bare support comprises at least two annular units formed by cylindrical rods in a sine 'peak-valley' shape, the annular units are connected on the axial direction through a link round rod to form a net structure, a blend medicine eluting type coating composed of acylated chitosan, polyester and medicine is coated on the surface of the magnesium alloy bare support. According to the invention, biological medical chitosan and polyester blend material are taken as a support surface coating to improve the biological compatibility, and the coating carries a medicine with restenosis resistance function, thereby the release speed of the medicine can be controlled, and the treatment purpose can be achieved. The magnesium alloy support coated with the acylated chitosan and polyester blend medicine coating possesses good collateral passing ability and flexibility, good radial supporting performance, and is capable of keeping perfusion smoothness of blood flow, effectively delaying the degradation time of the magnesium alloy support, controlling the release of the medicines, and reducing the incidence rate of acute and subacute thrombus after the support is implanted.
Description
Technical field
What the present invention relates to is a kind of bio-medical material, a kind of specifically biodegradation type intravascular stent.
Background technology
Begin from the eighties, people have successfully used percutaneous transluminal angioplasty (Percutaneous Transluminal Coronary Angioplasty PTCA) to treat cardiovascular disease, and have obtained certain curative effect.But PTCA also exists the restriction of application facet, can cause new wound to blood vessel in the time of like operation, finally causes the incidence rate of postoperative restenosis and the acute obturation of blood vessel.Based on this kind situation, cardiovascular diseases's brainstrust has studied again that the implanted metal bare bracket remedies the undesirable problem that exists through the PTCA treatment in PTCA operation.So far, intracoronary stent (stent) implantation has been ripe and common technology has reduced restenosis rate significantly in the field of treatment cardiovascular disease.Yet the intravascular stent of extensive use is metal material mostly, for the Human Physiology environment of complicacy; Metal material implants as foreign body, itself just exists and causes bolt property, further causes the restenosis of blood vessel; Therefore, research and the clinical experiment result along with nearly decades shows that it is a kind of efficient ways that metal support surface is carried out modification; Wherein preparing polymeric coating layer at metal support surface is that research is more a kind of; And obtained comparatively considerable achievement, and be mainly reflected in the bracket for eluting medicament of heat of present research, promptly carry curative drug as supporter, high molecular polymer as pharmaceutical carrier and be coated in metal support surface with metal rack; Improve the metal support surface biocompatibility on the one hand, on the other hand medicine is carried out slow release control.This research makes the treatment to cardiovascular disease get into new milestone.
Because being coated in the nondegradable macromolecular material of rack surface can for good and all residue in the blood vessel wall; As a kind of foreign body; Effect must cause in the blood vessel wall part and continue inflammatory reaction or anaphylaxis for a long time; Cause the endothelium healing delay, this has just created probability for the formation of the stent thrombosis in late period.Show that according to relevant research it is one of possible cause that takes place the stent thrombosis in late period.Therefore, for fear of this severe bad influence, nondegradable coating is substituted gradually, and the bracket for eluting medicament (DES) that part has adopted Biodegradable polymeric to carry a new generation of medication coat becomes the focus of research.The constantly degraded of these degradable polymers a period of time after implanting, final whole the disappearance, and along with the physiology circulation is got rid of external.And magnesium is the interior cation of cell that is only second to potassium in the human body, in metabolic processes, plays an important role, and has anticoagulant property and histocompatibility.The advantages such as minimal side effect of magnesium alloy good mechanical performance, controlled etching performance and catabolite are called the selection of material of support.Magnesium alloy bracket is used in serious anemia of human body or coronary artery patient, can avoid the specified defect of permanent metal rack, because its degradability, the implantation of magnesium alloy bracket has been exempted healing back second operation and removed the misery that support brings.Therefore; People are carried medicine with the magnesium alloy bracket matrix that can absorb fully; Make the magnesium alloy FirebirdTM; Like the scientific research person's research situation in this regard in recent years that is to put down in writing in the lower integral patent document: publication number is that the patent document of CN101708140A discloses a kind of biologic degradable magnesium alloy medicine supporter for reconstructing blood circulation; This conceptual design the hollow pipe of magnesium or magnesium alloy, aperture that it is 0.2-1mm that hollow tube wall is provided with 0～50 diameter or RF or helix structure, and be provided with at its support surfaces externally and internally and contain cell growth factor or/and the biodegradable polymer layer of heparin; Publication number is to disclose the support that is made up of the wave-like cylinder in the patent document of CN201263728Y, and rack surface scribbles medication coat; Publication number is to disclose a kind of band medicine degradable magnesium alloy angiocarpy bracket and preparation method thereof in the patent document of CN101468216A; Be intended to reduce magnesium alloy initial stage degradation speed in vivo; And carrying curative drug on the magnesium alloy bracket surface, drug-loaded layer is made up of pharmaceutical carrier polymer or albumen and curative drug.
Disclosed information is learned from the above-mentioned file relevant with magnesium alloy eluting property drug stent; The public magnesium alloy bracket basal body structure of stating simple and easy; It is less to learn the angle thinking to the complicated bloody path environment liquid of human body; Like the hollow pipe that designs among the CN101708140A, aperture or grid etc. are set on the tube wall, the side shoot trafficability characteristic performance of its support is relatively poor; Mainly there is one deck high-polymer membrane in described drug stent at matrix surface, and carries curative drug, and high-polymer membrane can play the physical barriers effect, to reduce magnesium alloy initial stage degradation speed in vivo.But mostly selected high polymer is polylactic acid etc. and in degradation process, is prone to cause the matrix microenvironment for presenting acidity that sour environment obviously can quicken the initial degradation speed of magnesium alloy substrate.Therefore, take all factors into consideration, to the complicated bloody path environment of human body from the fluidics angle; It is functional to design side shoot trafficability characteristic and pliability etc., and the radial support better performances keeps the unimpeded support matrix of blood perfusion; The local microenvironment shows as neutral or alkalescence around rationally controlling magnesium alloy substrate simultaneously; As starting point protection magnesium alloy substrate, control initial stage degradation speed, and carry curative drug and the magnesium alloy eluting property support prepared when being creation thinking of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of side shoot trafficability characteristic and pliability etc. functional; The radial support better performances; Can keep blood perfusion unimpeded; Can realize that simultaneously medicine evenly discharges slowly, can guarantee that medication coat and metal support surface have strong adhesion, can make the coating acylation chitosan that bracket coating avoids coming off in the body fluid blood flush and the magnesium alloy bracket of polyesters blend medicament coating after sterilization, operation course of conveying and support are implanted.
The objective of the invention is to realize like this:
Comprise bare bracket, said bare bracket is the magnesium alloy bare bracket, and said magnesium alloy bare bracket comprises two annular elements that are made up of the cylindrical bar that is sinusoidal " peak-paddy " at least, and adjacent annular element connects and composes RF through the link round bar in the axial direction; Be covered with the blend medicament eluting coating that is made up of acylation chitosan, polyester and medicine in magnesium alloy bare bracket surfaces coated, said polyester is a kind of among PLLA, PLA, PLGA, PGA or the PCL.
The present invention can also comprise:
1, the matrix length of said magnesium alloy bare bracket is 4～40mm, and diameter is 1mm～7.5mm; The diameter of said cylindrical bar is 0.05mm～0.18mm; Said link round bar length is 0.03～0.3mm.
2, the matrix length of said magnesium alloy bare bracket is 10.24mm, and diameter is 1.5mm; Said cylindrical bar diameter is 0.1mm; Said link cylinder length is 0.21mm.
3, the quality of polyester is than quality=10%～40% of acylation chitosan in the said blend medicament eluting coating, and said acylation chitosan is that lauroyl chloride and chitosan unit are 3 according to mol ratio: 1-7: 1 ratio is carried out the acylation chitosan that modification makes.
4, the matrix of said magnesium alloy bare bracket is that Mg-Sn-Mn is that alloy, Mg-Sn-Mn-Zn are that alloy or Mg-Ca are a kind of in the alloy.
5, said blend medicament eluting coating is the single coating structure, and total coating thickness is 1～100 micron.
6, said acylation chitosan molecular weight is 200000～1000000.
The main feature that surfaces coated of the present invention is covered with the degradable magnesium alloy support of acylation chitosan and polyesters blend medicament eluting coating is embodied in:
Process bare bracket by magnesium alloy, the magnesium alloy bracket matrix comprises two annular elements that are made up of the cylindrical bar that is sinusoidal " peak-paddy " at least, and adjacent annular element reticulates structure through connecting round bar in the axial direction.The design expression of support goes out good side shoot trafficability characteristic and pliability etc., and the radial support better performances keeps blood perfusion unimpeded.Simultaneously; Be covered with acylation chitosan and polyesters such as blend medicament eluting coatings such as PLLA, PLGA in magnesium alloy bare bracket surfaces coated; When degrading, the blend coating of rack surface design can form a comparatively stable neutral environment in support matrix some areas; Can effectively delay the degradation time of magnesium alloy bracket, reach the progressively purpose of degraded, simultaneously control drug release; Reduced prominent the releasing of medicine and made drug slow continue to keep finite concentration to discharge, implanted to reduce support that the back is acute, the incidence rate of subacute stent thrombosis; The blend of described blend medicament eluting coating is to use lauroyl chloride and bio-medical chitosan to obtain with the acylation chitosan of different mol ratio modification and the biodegradable polyester class mode through physical blending.The annular element that a kind of cylindrical bar that is sinusoidal " peak-paddy " in the bracket for eluting medicament that the present invention designs constitutes; Adjacent annular element is in the axial direction through connecting the magnesium alloy bracket matrix that round bar reticulates structure; Said support matrix length is 10.24mm; Diameter is 1.5mm; The cylindrical bar diameter is 0.1mm, and link cylinder length is 0.21mm, and it is that 5: 1 ratio is carried out biology performance and the mechanical property that eluting property magnesium alloy bracket that acylation chitosan OCS that modification makes and PLLA make with the ratio of PLLA/OCS=10%～40% shows the best that described support matrix surface applies with mol ratio.
Advantage of the present invention is:
1. the biological medical degradable magnesium alloy support has controlled bio-absorbable degradation characteristic, with respect to traditional metal supports such as rustless steel, cobalt chromium, NiTi, the pain of injury that can effectively avoid second operation to bring; The magnesium bracket specific strength is high simultaneously, and elastic modelling quantity is big, and shock absorbing property is compared to the degradable macromolecule support well, the better mechanical property of tool;
2. the magnesium alloy bracket that the present invention designed, its matrix comprise two annular elements that are made up of the cylindrical bar that is sinusoidal " peak-paddy " at least, and adjacent annular element reticulates structure through connecting round bar in the axial direction; Show good side shoot trafficability characteristic and pliability etc., the radial support better performances keeps blood perfusion unimpeded (sacculus struts experimental verification, and pastille polymer coating surfacing, even does not have the cracking obscission);
3. magnesium alloy bracket provided by the invention surface is one deck acylation chitosan and polyesters blend coating, and (this drug stent hemolysis rate is minimum to be 1.36%～3%, but all numerical value is all less than marginal value 5% to show better biocompatibility and the less interior inflammatory reaction of body; Show that these materials do not produce tangible haemolysis when contacting with blood, all meet the requirement of biomaterial hemolysis rate), simultaneously; Can form a comparatively stable neutral environment in some areas during this blend degraded; Can effectively delay the degradation time (degraded 30 days in, polymer degradation microenvironment pH value all about 7, shows near neutral) of magnesium alloy bracket; Reach the progressively purpose of degraded; After the degraded of blend coating finished, magnesium alloy bracket is degraded fully within a certain period of time also, avoids being detained for a long time bring in the body unfavorable;
4. the medicine that has anti-restenosis function in the magnesium alloy bracket face coat disclosed by the invention comprises one or more compound in paclitaxel, rapamycin, dactinomycin, the emodin etc.; Adopt the ultrasonic atomization spraying technology to evenly spread in the polymer coating; Control drug release; Having reduced prominent the releasing of medicine makes drug slow continue to keep finite concentration to discharge; When having kept reducing restenosis and taking place, reduced behind the stenting subacute stent thrombosis again effectively and formed that (when dynamic blood coagulation experimental verification drug stent and blood reached 60min time of contact, its OD value was still greater than 0.1 with angiomatous generation; Show tangible blood coagulation phenomenon does not take place, show that drug stent possesses certain anticoagulation ability).
Adopting the polyblend legal system to be equipped with novel composite material is a kind of valid approach, can obtain two kinds of premium properties that material is had separately.The present invention selects the blend of blend medicament eluting coating to be to use lauroyl chloride and bio-medical chitosan to obtain with the acylation chitosan of different mol ratio modification and the biodegradable polyester class mode through physical blending.In biomedical materials field, use chitosan and two kinds of materials of polylactic acid comparatively widely; All have excellent biological compatibility and biodegradability; Yet; They all exist performance deficiency separately, and like the chitosan film poor mechanical property, polylactic acid degraded produces the acid product reaction etc. that is prone to be inflamed.Therefore, polylactic acid and chitosan are carried out the bio-medical material that blend can obtain aspects mutual supplement with each other's advantages such as mechanical property and biocompatibility.This intermingling material is finally become micromolecule through degraded in vivo; By people's institute's metabolism with excrete; Avoided since the drug-loaded layer long-term existence of current bracket for eluting medicament in human body; The generation of associated conditions such as advanced thrombus that possibly cause and restenosis is unfavorable for problems such as the normal endothelialization process of blood vessel.The acylation chitosan of the present invention from using lauroyl chloride and bio-medical chitosan to obtain with the different mol ratio modification; Add a certain proportion of polyester such as PLLA, PLGA etc.; Physical blending obtains specific OCS/PLLA or PLGA blend; Produce acid product be prone to the to be inflamed drawback of reaction to improve the degraded of chitosan film poor mechanical property, polylactic acid; And the interpolation through the blend phase regulates the release behavior of medicine, thereby the drug carrier material that obtains being fit to is finally realized the preparation of acylation chitosan and polyesters blend medicament eluting coating on the magnesium alloy bracket surface through the ultrasonic atomization spraying technology.
Description of drawings
Fig. 1 is a support sketch map of the present invention.
Fig. 2 is a blend coating external degradation local pH change curve.
The specific embodiment
Provide embodiments of the invention below the present invention is further specified, rather than limit scope of the present invention.
The specific embodiment one: in the Loprazolam medium, be that 5: 1 ratio is carried out prepared in reaction and obtained acylation chitosan OCS with mol ratio at first with lauroyl chloride and chitosan unit (molecular weight is 200000); Ratio according to PLLA/OCS=30% is dissolved in two blend constituent elements in the organic solvent, is mixed with homogeneous polymer solution.Again in medicine: the ratio of polymer supported drug material=10%～30% makes an addition to medicine in the polymer solution, adds the organic solvent of certain volume, is mixed with certain density uniform coating solution.Use the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Medicine is that medicine with anti-restenosis function comprises one or more compound in paclitaxel, rapamycin, dactinomycin, the emodin etc.The technological parameter that obtains best coating solution atomizing effect is: solution concentration is 1%, and supersonic generator power is 0.8, and the injection rate of syringe pump floating coat solution is 2psi for the 0.03ml/min compression pressure.The chitin modified back of experiment confirm medicine carrying performance is comparatively good.Coating material is the single coating structure, and promptly medication coat is made up of one deck, and medicine is embedded in the medicine carrying blend uniformly, and total coating thickness is 1～100 micron.Described support, its matrix annular element that the cylindrical bar that is sinusoidal " peak-paddy " constitutes of serving as reasons, adjacent annular element reticulates structure through connecting round bar in the axial direction; Length is 10.24mm; Diameter is 1.5mm, and the cylindrical bar diameter is 0.1mm, and link cylinder length is 0.21mm.
It is still even, smooth that coating bracket struts test experiments later stage coating surfaces at sacculus; The phenomenon that cracking do not occur, comes off; Thereby this coating have certain tension compressive strain ability and with the binding ability of metal rack, can satisfy the mechanical property requirements of coating stent of medicine needs in the clinical operation process.
Simultaneously; The adding of anti-narrow type of medicine increases the hemolysis rate of coating material, and addition many hemolysis rates increase more is big more, when medicament contg is 30%; Its hemolysis rate is 2.97%; But all numerical value shows that all less than marginal value 5% these materials do not produce tangible haemolysis when contacting with blood, all meet the requirement of biomaterial hemolysis rate.
In addition, along with the prolongation of time, the absorbance of coating material all constantly descends, and the degree that descends simultaneously diminishes gradually, and curve tends towards stability, and when material and blood reached 60min time of contact, its OD value showed tangible blood coagulation phenomenon does not take place still greater than 0.1.Show that acylation chitosan and polyesters blend medicament eluting coating possess certain anticoagulation ability.
The specific embodiment two: experiment condition is identical with the specific embodiment one with operating process; Just changing acylation chitosan prepares in the process; Lauroyl chloride and chitosan unit (molecular weight is 200000) are that 5: 1 ratio is reacted with mol ratio; Ratio according to PLLA/OCS=20% is dissolved in two blend constituent elements in the organic solvent, uses the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Finally acylation chitosan and polyesters blend medicament eluting bracket coating are characterized.Experimental result shows that its hemolysis rate is 2.17%; But all numerical value shows that all less than marginal value 5% these materials do not produce tangible haemolysis when contacting with blood, all meet the requirement of biomaterial hemolysis rate; Simultaneously when material and blood reach 60min time of contact; Its OD value is about 0.31, still greater than 0.1, shows tangible blood coagulation phenomenon does not take place.Show that acylation chitosan and polyesters blend medicament eluting coating possess certain anticoagulation ability.
The specific embodiment three: experiment condition is identical with the specific embodiment one with operating process; Just changing acylation chitosan prepares in the process; Lauroyl chloride and chitosan unit (molecular weight is 200000) are that 5: 1 ratio is reacted with mol ratio; Ratio according to PLLA/OCS=10% is dissolved in two blend constituent elements in the organic solvent, uses the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Finally acylation chitosan and polyesters blend medicament eluting bracket coating are characterized.Experimental result shows that its hemolysis rate is 2.46%; But all numerical value shows that all less than marginal value 5% these materials do not produce tangible haemolysis when contacting with blood, all meet the requirement of biomaterial hemolysis rate; Simultaneously when material and blood reach 60min time of contact; Its OD value is about 0.32, still greater than 0.1, shows tangible blood coagulation phenomenon does not take place.Show that acylation chitosan and polyesters blend medicament eluting coating possess certain anticoagulation ability.
The specific embodiment four: experiment condition is identical with the specific embodiment one with operating process; Just changing acylation chitosan prepares in the process; Lauroyl chloride and chitosan unit (molecular weight is 200000) are that 7: 1 ratio is reacted with mol ratio; Ratio according to PLLA/OCS=10%～40% is dissolved in two blend constituent elements in the organic solvent, uses the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Experimental result shows that these materials do not produce tangible haemolysis when contacting with blood, all meets the requirement of biomaterial hemolysis rate, also possesses certain anticoagulation ability simultaneously.
The specific embodiment five: experiment condition is identical with the specific embodiment one with operating process; Just changing acylation chitosan prepares in the process; Lauroyl chloride and chitosan unit (molecular weight is 200000) are that 3: 1 ratio is reacted with mol ratio; Ratio according to PLLA/OCS=10%～40% is dissolved in two blend constituent elements in the organic solvent, uses the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Experimental result shows that these materials do not produce tangible haemolysis when contacting with blood, all meets the requirement of biomaterial hemolysis rate, also possesses certain anticoagulation ability simultaneously.
The specific embodiment six: experiment condition is identical with the specific embodiment one with operating process; Just changing acylation chitosan prepares in the process; Lauroyl chloride and chitosan unit (molecular weight is 1000000) are that different ratios such as 3: 1,5: 1,7: 1 are reacted with mol ratio; Ratio according to PLLA/OCS=10%～40% is dissolved in two blend constituent elements in the organic solvent, uses the method for ultrasonic atomization spraying to be prepared into the monolayer medication coat at last.Experimental result shows that these materials do not produce tangible haemolysis when contacting with blood, all meets the requirement of biomaterial hemolysis rate, also possesses certain anticoagulation ability simultaneously.
Claims (7)
1. magnesium alloy bracket that applies acylation chitosan and polyesters blend medicament coating; Comprise bare bracket; It is characterized in that said bare bracket is the magnesium alloy bare bracket; Said magnesium alloy bare bracket comprises two annular elements that are made up of the cylindrical bar that is sinusoidal " peak-paddy " at least, and adjacent annular element connects and composes RF through the link round bar in the axial direction; Be covered with the blend medicament eluting coating that is made up of acylation chitosan, polyester and medicine in magnesium alloy bare bracket surfaces coated, said polyester is a kind of among PLLA, PLA, PLGA, PGA or the PCL.
2. the magnesium alloy bracket of coating acylation chitosan according to claim 1 and polyesters blend medicament coating is characterized in that: the matrix length of said magnesium alloy bare bracket is 4～40mm, and diameter is 1mm～7.5mm; The diameter of said cylindrical bar is 0.05mm～0.18mm; Said link round bar length is 0.03～0.3mm.
3. the magnesium alloy bracket of coating acylation chitosan according to claim 1 and polyesters blend medicament coating is characterized in that: the matrix length of said magnesium alloy bare bracket is 10.24mm, and diameter is 1.5mm; Said cylindrical bar diameter is 0.1mm; Said link cylinder length is 0.21mm.
4. according to the magnesium alloy bracket of claim 1,2 or 3 described coating acylation chitosans and polyesters blend medicament coating; It is characterized in that: the quality of polyester is than quality=10%～40% of acylation chitosan in the said blend medicament eluting coating, and said acylation chitosan is that lauroyl chloride and chitosan unit are 3 according to mol ratio: 1-7: 1 ratio is carried out the acylation chitosan that modification makes.
5. the magnesium alloy bracket of coating acylation chitosan according to claim 4 and polyesters blend medicament coating is characterized in that: the matrix of said magnesium alloy bare bracket is that Mg-Sn-Mn is that alloy, Mg-Sn-Mn-Zn are that alloy or Mg-Ca are a kind of in the alloy.
6. the magnesium alloy bracket of coating acylation chitosan according to claim 5 and polyesters blend medicament coating is characterized in that: said blend medicament eluting coating is the single coating structure, and total coating thickness is 1～100 micron.
7. the magnesium alloy bracket of coating acylation chitosan according to claim 6 and polyesters blend medicament coating is characterized in that: said acylation chitosan molecular weight is 200000～1000000.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102805878A (en) * | 2012-08-29 | 2012-12-05 | 哈尔滨工程大学 | Medical degradable magnesium alloy meniscus suture line |
| CN103948453A (en) * | 2014-04-21 | 2014-07-30 | 上海市第六人民医院 | Degradable magnesium alloy membranous stent and membranous stent system |
| CN104491935A (en) * | 2014-12-30 | 2015-04-08 | 马艳荣 | Drug-loading magnesium alloy eluting stent for biodegradable polymer coating |
| CN104524647A (en) * | 2014-12-30 | 2015-04-22 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy-eluting stent |
| CN104587536A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy eluting stent |
| CN104587537A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Magnesium alloy eluting stent with biodegradable polymer coatings carrying drugs |
| CN104587535A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy eluting stent |
| CN104587538A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Magnesium alloy eluting stent with biodegradable polymer coatings carrying drugs |
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| CN201263728Y (en) * | 2008-09-25 | 2009-07-01 | 蔡绪旺 | Vascular medicament stent |
| CN101468216A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | Degradable magnesium alloy angiocarpy bracket with medicine and preparation method thereof |
| CN101704907A (en) * | 2009-12-08 | 2010-05-12 | 广东药学院 | Method for preparing acylation chitosan |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101468216A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | Degradable magnesium alloy angiocarpy bracket with medicine and preparation method thereof |
| CN201263728Y (en) * | 2008-09-25 | 2009-07-01 | 蔡绪旺 | Vascular medicament stent |
| CN101704907A (en) * | 2009-12-08 | 2010-05-12 | 广东药学院 | Method for preparing acylation chitosan |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102805878A (en) * | 2012-08-29 | 2012-12-05 | 哈尔滨工程大学 | Medical degradable magnesium alloy meniscus suture line |
| CN103948453A (en) * | 2014-04-21 | 2014-07-30 | 上海市第六人民医院 | Degradable magnesium alloy membranous stent and membranous stent system |
| CN104491935A (en) * | 2014-12-30 | 2015-04-08 | 马艳荣 | Drug-loading magnesium alloy eluting stent for biodegradable polymer coating |
| CN104524647A (en) * | 2014-12-30 | 2015-04-22 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy-eluting stent |
| CN104587536A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy eluting stent |
| CN104587537A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Magnesium alloy eluting stent with biodegradable polymer coatings carrying drugs |
| CN104587535A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Biodegradable polymer coating drug-loaded magnesium alloy eluting stent |
| CN104587538A (en) * | 2014-12-30 | 2015-05-06 | 马艳荣 | Magnesium alloy eluting stent with biodegradable polymer coatings carrying drugs |
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Application publication date: 20120613 |