CN102028569A - Degradable bracket with radiotherapy and chemotherapy synergistic effect and preparation method thereof - Google Patents
Degradable bracket with radiotherapy and chemotherapy synergistic effect and preparation method thereof Download PDFInfo
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- CN102028569A CN102028569A CN2010105968754A CN201010596875A CN102028569A CN 102028569 A CN102028569 A CN 102028569A CN 2010105968754 A CN2010105968754 A CN 2010105968754A CN 201010596875 A CN201010596875 A CN 201010596875A CN 102028569 A CN102028569 A CN 102028569A
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Abstract
The invention relates to the technical field of medical instruments, and in particular discloses a degradable bracket with radiotherapy and chemotherapy synergistic effect and a preparation method thereof. The degradable bracket with the radiotherapy and chemotherapy synergistic effect is characterized in that: the bracket is a meshy bracket formed by weaving degradable thin threads or a hollow tubular bracket prepared by a degradable mixture; both the degradable thin threads and the degradable mixture consist of degradable polymers and a certain content of auxiliary agents; the bracket is grafted with a substance which contains non-radioactive elements after surface modification of hydroammonolysis, coupling and the like; and a non-radioactive iodine element is replaced by radioactive 125I by isotopic replacement technology, and covered by a degradable polymer film which contains a medicine and/or an X-ray developing agent. In the invention, partial radiotherapy and partial chemotherapy are performed on canceration cavities by loading a 125I radioactive iodine source and an anti-cancer medicine, and the material degrading speed of a bracket main body and the degradable polymer film can be adjusted and controlled according to treatment to adjust and control the degrading speed and the medicine releasing speed of the bracket.
Description
Technical field
The invention belongs to technical field of medical instruments, be specifically related to biodegradable stent that has the chemicotherapy synergistic function and preparation method thereof.
Background technology
Interventional therapy is the emerging Therapeutic Method between surgery, medical treatment, comprises in the blood vessel getting involved and non-vascular interventional treatment, wherein is used for bile duct, and the interventional therapy support of official jargons such as trachea and esophagus belongs to non-vascular interventional treatment.At bile duct, what practical application was maximum in the interventional therapy of official jargon such as trachea and esophagus is metal rack, at present, the domestic medical support that is used for the narrow interventional therapy of official jargon of China substantially all is the recalled nitinol alloy stent after establishment, and it can prevent effectively that official jargon is inaccessible or narrow.But the application of metal rack also exists some obviously not enough: the metal rack that 1. forever the retains reaction that causes inflammation easily, and metal rack can discharge the toxic metals ion, as metals such as Ni; 2. whether support can still require study in fatigue fracture; In case 3. the support accidental just can only adopt the method for operation to take out, and brings extra misery to patient.
Further investigation along with Biodegradable polymer material, the homopolymer and the random copolymer of aliphatic cyclic ester (CL, LA, GA, EO) are the absorbable biological medicinal material that is most widely used in the world, and pass through the permission of the United States Federal's health and food control office (FDA), so the aliphatic cyclic ester can be used as the material of preparation biodegradable stent in interventional therapy.The polymer biodegradable stent that is made of Biodegradable material is considered to the direction of following support development fully, external a lot of medical apparatus corporation, Ltds such as Boston technology Corp, and Johnson ﹠ Johnson, Medtronic being is all is being researched and developed the biodegradable stent product and is being applied for all kinds of patents.This is because the compatibility of biodegradable stent and official jargon wall is better than metal rack, can avoid the intimal proliferation in later stage.After biodegradable stent is inserted human body, can after being set in certain hour, degrade, being converted into harmless micromolecule gets rid of external, even the support accidental takes place, also can be by disappearing after the human body degraded and absorbed, need not operation and take out, thereby this support has the incomparable advantage of metal rack.
Most of medical official jargon support only plays dilating effect both at home and abroad, only removes the narrow of tube chamber and hard resistance, and tumor be there is no therapeutic effect, but more existing patents have been mentioned support to the tumor treatment effect.Such as application number is that 200410062260.8 Chinese patent discloses the preparation method with antitumor action multilayer medicine composite high-molecular material cholangio-stent, and this drug stent can play the effect of local chemotherapy, but has not mentioned local radiotherapeutic effect; Application number is the degradable trachea bracket that 201010103004.4 Chinese patent discloses the degradable membrane that is covered with treatment tracheocarcinoma medicine, though this rack body material is the degradable metal material not, but be not the degradable polymer material, do not mentioned local radiotherapeutic effect simultaneously; Application number is that 03279776.1 Chinese patent discloses the band film netted memory alloy stent of rack body outer wall with the radioactive source medicated bag, this support can play the effect of local radiotherapy, but this rack body is not a degradation material, and has not mentioned the local chemotherapy effect; Application number is that 200620113520.4 Chinese patent discloses the radioactivity biliary tract prosthesis that the treatment tumor that is covered with the degradation material film is used, but this rack body is a Ultimum Ti, is not degradation material, and has not mentioned the local chemotherapy effect; Application number is that 200620113520.4 Chinese patent discloses the novel radioactive biliary stent that support is covered with the radioactivity film outward, but this rack body is a Ultimum Ti, is not degradation material, and has not mentioned the local chemotherapy effect; Application number is that 200910233484.3 Chinese patent discloses the bile duct radiation treatment stent that support is equipped with radioactive particle filling capsule outward, but this rack body also is a Ultimum Ti, is not degradation material, and has not also mentioned the local chemotherapy effect.In sum, the biodegradable stent with radiation and chemotherapy synergistic function has very strong novelty.
Summary of the invention
The object of the present invention is to provide biodegradable stent with chemicotherapy synergistic function and preparation method thereof, solve the limitation of present interventional therapy support in the treatment of cancer of human body official jargon, and strengthened the treatment and the diagnosis of official jargon cancer and restenosis by coated medicament and/or X-ray developing agent.
Biodegradable stent with chemicotherapy synergistic function, it is characterized in that described support is the network or the direct hollow tubular support that is prepared by the degradable mixture of being worked out by the degradable filament, wherein degradable filament and degradable mixture are formed by the auxiliary agent of degradable polymer and certain content, support is through aminolysis, the material that contains the on-radiation I after the surface modifications such as coupling in the grafting is replaced into radioactivity by the isotopic technology with the on-radiation I subsequently
125I, and be covered with the degradable polymer film that contains medicine and/or X-ray developing agent.
Preferably, described degradable polymer is selected from the copolymer or the blend of one or several polymer in the degradable polymer materials such as polylactic acid, polycaprolactone, polyglycolic acid, polycaprolactone, polyhydroxybutyrate valerate, Polyethylene Glycol, degradable polyurethane, and the molecular weight control of polymer is 0.1～800,000.
Preferably, described auxiliary agent is selected from one or more in nucleator, plasticizer, the flexibilizer etc.
Preferably, it is characterized in that described medicine is selected from paclitaxel, amycin, ibuprofen, daunorubicin, norcantharidin, mitoxantrone etc. and has the medicine of treatment official jargon cancer and paclitaxel, rapamycin, dactinomycin etc. and have in the anti-narrow medicine one or more.
Preferably, the diameter of described degradable filament is 0.1～3mm.
Preferably, the diameter of described network and tubular bracket is 1～50mm, and length is 10～200mm.
The present invention also provides a kind of method for preparing biodegradable stent, it is characterized in that said method comprising the steps of:
(1) raw material mix stages: get the degradable polymer of gross mass 60～98% and the polymer builder of gross mass 1～30%, behind vacuum drying, the raw material mix homogeneously is promptly got mixed material;
(2) support preparatory phase: make by former at the mixed material that under the 100-200 ℃ of temperature conditions step (1) is obtained and to be compiled into network on degradable filament and the mould or directly to make the hollow tubular support by former in definite shape;
(3) surface treatment and propiodal load stage: with step (2) gained support is respectively the surface modification solution of 0.01～0.4mol/L successively in concentration, 0.01 the coupling agent solution of～0.5mol/L, 0.1 soak 1～24h in the substance solution that contains the on-radiation I of～5mol/L (solution temperature is 30-80 ℃), wherein putting into another kind of solution from a kind of solution before must be with purified rinse water to remove free functional group.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I.
(4) the support overlay film stage: add solvent the degradable polymer of gross mass 0.1～40% and the medicine and/or the X-ray developing agent of gross mass 0.1～10% are made into 0.01～0.2g/ml, adopt methods such as dip-coating and spraying in the rack surface film forming solution for preparing, promptly obtain biodegradable stent after sterilization is handled.
Preferably, described degradable polymer is selected from the copolymer or the blend of one or several polymer in the degradable polymer materials such as polylactic acid, polycaprolactone, polyglycolic acid, polycaprolactone, polyhydroxybutyrate valerate, Polyethylene Glycol, degradable polyurethane, and the molecular weight control of polymer is 0.1～800,000; Described auxiliary agent is selected from one or more in nucleator, plasticizer, the flexibilizer etc.; The described material that contains the on-radiation I is selected from paraiodoaniline or o-iodobenzoic acid; Described surface modification solution is a PEI-normal propyl alcohol solution, in chitosan-acetic acid solution any; Described coupling agent solution is glutaraldehyde-aqueous solution; Described medicine is selected from paclitaxel, amycin, ibuprofen, daunorubicin, norcantharidin, mitoxantrone etc. to have the medicine of treatment official jargon cancer and paclitaxel, rapamycin, dactinomycin etc. and has in the anti-narrow medicine one or more; Described solvent is selected from dichloromethane, chloroform, acetone, methanol, ethanol, oxolane, dioxane, N, dinethylformamide, N, in the volatile solvents such as N-diethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide one or more; The diameter of described degradable filament is 0.1～3mm; The diameter of described network and tubular bracket is 1～50mm, and length is 10～200mm.In addition, the degradation speed of the selected degradable polymer of step (1) will be considerably slower than the degradation speed of the selected degradable polymer of step (4).
In the technical solution of the present invention with behind degradable polymer and the polymer builder mix homogeneously, make the degradable filament and on mould, be wound in network or directly make tubular bracket by former by former, carry out aminated to support, the material that contains the on-radiation I after the surface treatments such as couplingization in the grafting is replaced into radioactivity by the isotopic technology with the on-radiation I subsequently
125I, the polymer solution that will contain medicine and/or X-ray developing agent again handle the biodegradable stent that promptly obtains having the chemicotherapy synergistic function with the ethane peroxide suffocating sterilization at last in the rack surface film forming.This invention adopts degradable polymer to overcome the deficiency of metal rack as timbering material, and by load
125I radiation propiodal and coating cancer therapy drug have reached the synergy to local radiotherapy of canceration official jargon and local chemotherapy, have broad application prospects.
With respect to scheme of the prior art, advantage of the present invention is:
1, in the technical solution of the present invention except that medicine and X-ray developing agent, raw material is Biodegradable material, compares with metal rack with plastic stent, has the favorable tissue compatibility, the reaction that is difficult for causing inflammation does not cause phenomenons such as poisoning, haemolysis blood coagulation and allergy;
2, have the resilience force of enough intensity with opposing official jargon wall, can degrade voluntarily after the mechanical support effect of the official jargon tube wall being finished certain hour, catabolite has no side effect to tissue, need not second operation and takes out conduit;
3, add the degradable polymer auxiliary agent, can obviously improve toughness, plasticity and the processing characteristics of degradation material;
4, by the isotopic technology on-radiation I is replaced into radioactivity
125I, and with degradable membrane it is wrapped up, in the radiotherapy process, can not produce infringement, thereby reach the effect of local radiotherapy other normal cell.
5, load cancer therapy drug and anti-restenosis medicaments in the degradable polymer film both can reach the effect of local chemotherapy, can reduce the restenosis rate of official jargon again.
6, can regulate and control the degradation speed and the drug releasing rate of support by the material degradation speed of regulation and control rack body and degradable polymer film according to the treatment needs.
The specific embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
The preparation of embodiment 1 biodegradable stent
Get the polylactic acid (molecular weight is 150,000) of gross mass 80% and the nucleator of gross mass 1%, behind the vacuum drying raw material mix homogeneously is promptly got mixed material; To make diameter be the degradable filament of 0.3mm and be compiled into network on mould, support external diameter 8mm, long 50mm by former with mixed material under 170 ℃ of temperature conditions; With the gained support is respectively the PEI-normal propyl alcohol solution of 0.2mol/L successively in concentration, 0.15mol/L glutaraldehyde-aqueous solution, 0.5mol/L paraiodoaniline solution (solution temperature is 50 ℃) in soak 12h, must be before wherein putting into another kind of solution with purified rinse water to remove free functional group from a kind of solution.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I; Add dichloromethane polyglycolic acid (molecular weight is 50,000) and the paclitaxel of gross mass 9% of gross mass 10% be made into 0.10g/ml solution, with the solution spraying for preparing at the network surface filming, after the sterilization processing promptly obtains biodegradable stent.
The preparation of embodiment 2 biodegradable stents
Get the polylactic acid (molecular weight is 200,000) of gross mass 50%, the nucleator of polycaprolactone of gross mass 30% (molecular weight is 90,000) and gross mass 1% promptly gets mixed material with the raw material mix homogeneously behind the vacuum drying; Under 160 ℃ of temperature conditions, mixed material is made the hollow tubular support by former, support external diameter 10mm, long 60mm; With the gained support is respectively chitosan-acetic acid solution of 0.3mol/L successively in concentration, 0.10mol/L glutaraldehyde-aqueous solution, 0.5mol/L o-iodobenzoic acid solution (solution temperature is 50 ℃) in soak 10h, must be before wherein putting into another kind of solution with purified rinse water to remove free functional group from a kind of solution.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I; Add the polylactic acid (molecular weight be 8 ten thousand) of dichloromethane with gross mass 10%, the rapamycin of the amycin of gross mass 3% and gross mass 3% is made into 0.10g/ml solution, adopt quick submerged method to make solution, promptly get biodegradable stent after sterilization is handled at the tubular bracket surface filming.
The preparation of embodiment 3 biodegradable stents
Get the polylactic acid (molecular weight is 250,000) of gross mass 50%, the plasticizer of polycaprolactone of gross mass 21% (molecular weight is 50,000) and gross mass 10% promptly gets mixed material with the raw material mix homogeneously behind the vacuum drying; To make diameter be the degradable filament of 0.4mm and be compiled into network on mould, support external diameter 5mm, long 60mm by former with mixed material under 160 ℃ of temperature conditions; With the gained support is respectively the PEI-normal propyl alcohol solution of 0.25mol/L successively in concentration, 0.15mol/L glutaraldehyde-aqueous solution, 0.1mol/L o-iodobenzoic acid solution (solution temperature is 50 ℃) in soak 10h, must be before wherein putting into another kind of solution with purified rinse water to remove free functional group from a kind of solution.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I; Add chloroform the degradable polyurethane (molecular weight is 80,000) of gross mass 10%, the amycin of gross mass 3%, the rapamycin of gross mass 3% and the X-ray developing agent of gross mass 3% are made into 0.15g/ml solution, adopt quick submerged method to make solution, promptly get biodegradable stent after sterilization is handled at the network surface filming.
The preparation of embodiment 4 biodegradable stents
Get the polylactic acid (molecular weight is 200,000) of gross mass 50%, the polycaprolactone of gross mass 21% (molecular weight is 90,000), the plasticizer of gross mass 5% and the nucleator of gross mass 1% promptly get mixed material with the raw material mix homogeneously behind the vacuum drying; Under 180 ℃ of temperature conditions, mixed material is made the hollow tubular support by former, support external diameter 8mm, long 60mm; With the gained support is respectively chitosan-acetic acid solution of 0.3mol/L successively in concentration, 0.10mol/L glutaraldehyde-aqueous solution, 0.80mol/L paraiodoaniline solution (solution temperature is 50 ℃) in soak 8h, must be before wherein putting into another kind of solution with purified rinse water to remove free functional group from a kind of solution.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I; Add chloroform the polylactic acid-glycolic guanidine-acetic acid copolymer (molecular weight is 50,000) of gross mass 10%, the daunorubicin of gross mass 3%, the paclitaxel of gross mass 3% and the X-ray developing agent of gross mass 3% are made into 0.15g/ml solution, adopt the method for spraying to make solution, promptly get biodegradable stent after sterilization is handled at the tubular bracket surface filming.
The preparation of embodiment 5 biodegradable stents
Get the polylactic acid (molecular weight is 250,000) of gross mass 50%, the polyglycolic acid (molecular weight is 90,000) of gross mass 20%, the plasticizer of gross mass 10% and the nucleator of gross mass 1%, behind the vacuum drying raw material mix homogeneously is promptly got mixed material; To make diameter be the degradable filament of 0.3mm and be compiled into network on mould, support external diameter 8mm, long 60mm by former with mixed material under 170 ℃ of temperature conditions; With the gained support is respectively the PEI-normal propyl alcohol solution of 0.25mol/L successively in concentration, 0.15mol/L glutaraldehyde-aqueous solution, 1.0mol/L paraiodoaniline solution (solution temperature is 70 ℃) in soak 6h, must be before wherein putting into another kind of solution with purified rinse water to remove free functional group from a kind of solution.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I; The adding chloroform is made into 0.15g/ml solution with polycaprolactone (molecular weight is 60,000) and the mitoxantrone of gross mass 3%, the rapamycin of gross mass 3% and the X-ray developing agent of gross mass 3% of gross mass 10%, adopt the method for spraying to make solution, promptly get biodegradable stent after sterilization is handled at the network surface filming.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (10)
1. biodegradable stent, it is characterized in that described support is the network or the direct hollow tubular support that is prepared by the degradable mixture of being worked out by the degradable filament, wherein degradable filament and degradable mixture are formed by the auxiliary agent of degradable polymer and certain content, support is through aminolysis, the material that contains the on-radiation I after the surface modifications such as coupling in the grafting is replaced into radioactivity by the isotopic technology with the on-radiation I subsequently
125I, and be covered with the degradable polymer film that contains medicine and/or X-ray developing agent.
2. biodegradable stent according to claim 1, it is characterized in that described degradable polymer is selected from the copolymer or the blend of one or several polymer in the degradable polymer materials such as polylactic acid, polycaprolactone, polyglycolic acid, polycaprolactone, polyhydroxybutyrate valerate, Polyethylene Glycol, degradable polyurethane, the molecular weight control of polymer is 0.1～800,000.
3. biodegradable stent according to claim 1 is characterized in that described auxiliary agent is selected from one or more in nucleator, plasticizer, the flexibilizer etc.
4. biodegradable stent according to claim 1 is characterized in that the described material that contains the on-radiation I is selected from paraiodoaniline or o-iodobenzoic acid.
5. biodegradable stent according to claim 1 is characterized in that described medicine is selected from paclitaxel, amycin, ibuprofen, daunorubicin, norcantharidin, mitoxantrone etc. and has the medicine of treatment official jargon cancer and paclitaxel, rapamycin, dactinomycin etc. and have in the anti-narrow medicine one or more.
6. biodegradable stent according to claim 1, the diameter that it is characterized in that described degradable filament is 0.1～3mm.
7. biodegradable stent according to claim 1, the diameter that it is characterized in that described network and tubular bracket is 1～50mm, length is 10～200mm.
8. method for preparing biodegradable stent is characterized in that described preparation method may further comprise the steps:
(1) raw material mix stages: get the degradable polymer of gross mass 60～98% and the polymer builder of gross mass 1～30%, behind vacuum drying, the raw material mix homogeneously is promptly got mixed material;
(2) support preparatory phase: make by former at the mixed material that under the 100-200 ℃ of temperature conditions step (1) is obtained and to be compiled into network on degradable filament and the mould or directly to make the hollow tubular support by former in definite shape;
(3) surface treatment and propiodal load stage: with step (2) gained support is respectively the surface modification solution of 0.01～0.4mol/L successively in concentration, 0.01 the coupling agent solution of～0.5mol/L, 0.1 soak 1～24h in the substance solution that contains the on-radiation I of～5mol/L (solution temperature is 30-80 ℃), wherein putting into another kind of solution from a kind of solution before must be with purified rinse water to remove free functional group.Support after the flushing is replaced into radioactivity by the isotopic technology with the on-radiation I again
125I.
(4) the support overlay film stage: add solvent the degradable polymer of gross mass 0.1～40% and the medicine and/or the X-ray developing agent of gross mass 0.1～10% are made into 0.01～0.2g/ml, adopt methods such as dip-coating and spraying in the rack surface film forming solution for preparing, promptly obtain biodegradable stent after sterilization is handled.
9. method according to claim 8, it is characterized in that described degradable polymer is selected from the copolymer or the blend of one or several polymer in the degradable polymer materials such as polylactic acid, polycaprolactone, polyglycolic acid, polycaprolactone, polyhydroxybutyrate valerate, Polyethylene Glycol, degradable polyurethane, the molecular weight control of polymer is 0.1～800,000; Described auxiliary agent is selected from one or more in nucleator, plasticizer, the flexibilizer etc.; The described material that contains the on-radiation I is selected from paraiodoaniline or o-iodobenzoic acid; Described surface modification solution is a PEI-normal propyl alcohol solution, in chitosan-acetic acid solution any; Described coupling agent solution is glutaraldehyde-aqueous solution; Described medicine is selected from paclitaxel, amycin, ibuprofen, daunorubicin, norcantharidin, mitoxantrone etc. to have the medicine of treatment official jargon cancer and paclitaxel, rapamycin, dactinomycin etc. and has in the anti-narrow medicine one or more; Described solvent is selected from dichloromethane, chloroform, acetone, methanol, ethanol, oxolane, dioxane, N, dinethylformamide, N, in the volatile solvents such as N-diethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide one or more; The diameter of described degradable filament is 0.1～3mm; The diameter of described network and tubular bracket is 1～50mm, and length is 10～200mm.
10. method according to claim 8 is characterized in that the degradation speed of the selected degradable polymer of described step (1) will be considerably slower than the degradation speed of the selected degradable polymer of step (4).
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| CN2010105968754A CN102028569A (en) | 2010-12-21 | 2010-12-21 | Degradable bracket with radiotherapy and chemotherapy synergistic effect and preparation method thereof |
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| CN2010105968754A CN102028569A (en) | 2010-12-21 | 2010-12-21 | Degradable bracket with radiotherapy and chemotherapy synergistic effect and preparation method thereof |
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| CN103721298A (en) * | 2014-01-07 | 2014-04-16 | 东南大学 | Absorbable orthopedic instrument material with piezoelectric effect and preparation method thereof |
| CN103736155A (en) * | 2014-01-07 | 2014-04-23 | 东南大学 | Cerium-loaded functional absorbable orthopedic instrument material and preparation method thereof |
| CN103767803A (en) * | 2014-01-29 | 2014-05-07 | 胡堃 | Degradable spiral artificial trachea and preparation method thereof |
| CN111544605A (en) * | 2020-05-12 | 2020-08-18 | 太阳雨林（厦门）生物医药有限公司 | Carrier sheet for loading radioactive iodine 125 particles and preparation method thereof |
| CN113908346A (en) * | 2021-11-12 | 2022-01-11 | 上海交通大学 | Radioactive lumen stent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103721298A (en) * | 2014-01-07 | 2014-04-16 | 东南大学 | Absorbable orthopedic instrument material with piezoelectric effect and preparation method thereof |
| CN103736155A (en) * | 2014-01-07 | 2014-04-23 | 东南大学 | Cerium-loaded functional absorbable orthopedic instrument material and preparation method thereof |
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| CN103767803A (en) * | 2014-01-29 | 2014-05-07 | 胡堃 | Degradable spiral artificial trachea and preparation method thereof |
| CN111544605A (en) * | 2020-05-12 | 2020-08-18 | 太阳雨林（厦门）生物医药有限公司 | Carrier sheet for loading radioactive iodine 125 particles and preparation method thereof |
| CN113908346A (en) * | 2021-11-12 | 2022-01-11 | 上海交通大学 | Radioactive lumen stent and preparation method thereof |
| CN113908346B (en) * | 2021-11-12 | 2023-03-07 | 上海交通大学 | Radioactive lumen stent and preparation method thereof |
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