CN102068718B - Preparation technology of nano arsenic trioxide/poly (lactic-co-glycolic acid) coated bracket - Google Patents
Preparation technology of nano arsenic trioxide/poly (lactic-co-glycolic acid) coated bracket Download PDFInfo
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- CN102068718B CN102068718B CN 201010533299 CN201010533299A CN102068718B CN 102068718 B CN102068718 B CN 102068718B CN 201010533299 CN201010533299 CN 201010533299 CN 201010533299 A CN201010533299 A CN 201010533299A CN 102068718 B CN102068718 B CN 102068718B
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Abstract
A nano arsenic trioxide/poly (lactic-co-glycolic acid) coated bracket comprises a bracket body which is coated by a nano arsenic trioxide coating. The preparation method comprises: a certain amount of arsenic trioxide powder is fully dissolved in a sodium hydroxide solution, and the pH value is adjusted to form A solution; a certain amount of poly (lactic-co-glycolic acid) is dissolved in dichloromethane to form B solution; A solution is added to B solution, and the mixed solution is phacoemulsified to form C solution; polyvinyl alcohol is added to C solution to be ultrasonically dispersed in ice water, and D solution forms; D solution is stirred to form nano arsenic trioxide/poly (lactic-co-glycolic acid) colloidal solution, which is E solution; the stainless steel bare metal stent is ultrasonically cleaned, dried, then kept to stand in B solution; after dried the stent is kept to stand in E solution; the stent is kept in an oven to be dried after the E solution is removed, and the nano arsenic trioxide/poly (lactic-co-glycolic acid) coating stent forms at last.
Description
Technical field
The present invention relates to a kind of coating bracket and preparation technology thereof of anti-angiogenic restenosis, relate in particular to a kind of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket and preparation technology thereof.
Background technology
Along with change and the average life-time dilatation of people life style, the sickness rate of cardiovascular and cerebrovascular vessel and Peripheral vascular occlusion disease obviously raises.Since Gruzentig completed first case percutaneous coronary intracavity forming (PTCA) in 1977, percutaneous transluminal angio plasty (PTA) has become the primary method that solves vascular occlusive disease, but restenosis occurs the patient of the postoperative 30-50% of still having of PTA, affected the late result of PTA.People's reinventing of the postoperative blood vessel of PTA retraction and blood vessel that adopted again Endovascular Stent-assisted Angioplasty (Endoluminal stenting) effectively to solve afterwards, restenosis rate has also dropped to 18% left and right.In the stent forming postoperative support mechanism of restenosis (ISR) except blood vessel wall after vasodilation elastical retraction and thrombosis, the hyper-proliferative of the vascular smooth muscle cell (VSMC) that damage is induced has also also played crucial effect to the migration of inner membrance, so the propagation of prevention vascular smooth muscle cell becomes and solves the key that ISR occurs with migration.On this basis, for the propagation of vascular smooth muscle cell, coating stent of medicine (DES) arises at the historic moment, at present, application be paclitaxel and rapamycin coating stent of medicine the most widely.Yet, although angiocarpy bracket can reduce the incidence rate of ISR effectively, but metal rack itself is as foreign body, stimulate the VSMC hypertrophy, can not prevent the generation of ISR fully, therefore select the high molecular polymer that biocompatibility is good to cover rack surface, not only can overcome the bolt that causes that metal rack itself brings, accelerate the process of blood vessel endothelium, and can be used as the carrier of anti-proliferative drugs, directly and concentrated area arrives patient part, thus can avoid the toxic and side effects of whole body administration.
The characteristic of 1 lactic-co-glycolic acid (PLGA)
The polylactic acid (PLA) that lactic-co-glycolic acid (PLGA) is synthetic and the copolymer of polyglycolic acid (PGA), a large amount of experimentatioies has proved that PLGA is a kind of important biological medical polymer material with good biodegradability properties and biocompatibility, can not cause obvious inflammatory reaction, immunoreation and cell-cytotoxic reaction, and ratify the material as preparations such as injectable drug, nanoparticle, implants through FDA (FDA), be widely used in the research of drug delivery system.Lactic-co-glycolic acid is passed through the catabolism of enzyme in vivo, final formation carbon dioxide and water are excreted, can not cause the pollution to the human internal environment, thereby be considered to the most rising Biodegradable polymer material, enjoy domestic and international concern.Lactic-co-glycolic acid, as the carrier with medicine, can, by regulating lactic acid (LA) and the ratio of hydroxyacetic acid (GA) and the size of molecular weight in the lactic-co-glycolic acid molecule, be obtained to the carrier material of different degradation rates.Lactic-co-glycolic acid ratio commonly used has 80: 20,75: 25,50: 50 etc., be divided into again different specifications by the size of molecular weight.The PLGA that ratio is 50: 50 is due to good hydrophilic property, and has suspendible dispersive property preferably, thereby is lactic-co-glycolic acid specification the most commonly used at present.
The antiproliferative effect of 2 arsenic trioxide
Arsenic trioxide (arsenic trioxide, As
2o
3) be commonly called as arsenicum, arsenious acid etc., be a kind of hypertoxic medicine, be again a kind of effect medicine widely, as the medicinal application history of existing more than 2400 year.1865, Lessauer once used oral FowlerShi liquid (also claiming Fowler's soln) treatment leukemia, and this is considered to use for the first time the cancer drug therapy malignant tumor.First Hospital report application arsenic trioxide injection treatment acute promyelocytic leukemia (the acute promyelocytic leukaemia of Harbin Medical University in 1996, APL), the clinical good efficacy that obtains, cause domestic and international colleague re-recognizing arsenic.After this have again many pieces of articles further report take injection that arsenic trioxide is main component and there is the effect of obvious anti-acute promyelocytic leukemia.The old Guoqiang of Ruijin Hospital Attached to Shanghai Medical Univ No.2 etc. has illustrated its mechanism of action from cell and molecular biology angle, and U.S. food and drug administration be the scheme of arsenicum treatment acute promyelocytic leukemia for official approval also.Therefore, people have therefrom obtained inspiration, start the curative effect of further exploratory development arsenic trioxide to other Several Kinds of Malignancies.At present existing lot of experiments the effect of acute promyelocytic leukemia to solid tumor and tumor cell, as liver HepG2 and SMMC-7721 cell, gastric cancer cell line MGC-803, neuroblastoma, squamous cell carcinoma, pulmonary carcinoma NCI-H69 cell, esophageal carcinoma EC8712 cell, pancreatic cancer cell, Human Bladder Cancer Cell Line BIU etc. have all proved that arsenic has certain broad spectrum anticancer, its mechanism is mainly the effect of inhibition tumor cell growth and inducing apoptosis of tumour cell, and multipath suppresses tumor proliferation to be shifted.
The application of 3 nanotechnologys in field of medicaments
Nanotechnology (Nano technology) refers to handling atom and molecule in 0.1～100nm space scale, material is processed, manufacture has the product of specific function, or something is studied, and grasps the characteristics of motion of its atom and molecule and the new and high technology of characteristic.And many high-tech areas and even entire society have all been produced to tremendous influence.After the concept of nanotechnology in last century is suggested, in each fields such as material, metallurgy, chemical, medical science, environment, food, all show huge application prospect.Along with continuous infiltration and the impact of nanosecond science and technology on the medical research field, this new term of Nano medication that has been born, thus caused the revolution far away of field of medicaments one field depth.Nano medication refers to nanoscale high molecular nanometer grain (nano-particles, NP) or nanosphere (nano-spheres, NS), nanocapsule (nano-capsules, NC) etc. be carrier, the medicine of making after combining in a certain way with medicine, its particle diameter may surpass 100nm, but usually should be less than 500nm, and Nano medication can be also the nanoparticle of directly material medicine being processed into.
The Nano medication granule is little, surface reaction activity is high, active center is many, catalytic efficiency is high, high adsorption capacity.Nano medication is compared and had following characteristics with conventional medicine: (1) can increase drug solubility and degree of absorbing, and reduces drug dose, alleviates or eliminates toxic and side effects and save drug resource; (2) nano-particle, as the carrier of biomacromolecule, can improve absorption and the bioavailability of the oral drugs such as protein, polypeptide class macromole; (3) Nano medication can be realized slow release, controlled release and targeted therapy.Medicament slow release refers to after medication that the sustained release medicine is to reach long-acting in a long time; Medicine controlled releasing refers to that medicine can be in the given time initiatively in effect organ or particular target tissue, and maintains in valid density the drug level long period by a certain speed constant release from preparation.At present, existing many pieces of articles report, by after the conventional medicament nanorize, drug effect improves greatly, particularly in antitumor research, has shown sufficient superiority.
Summary of the invention
Body of the present invention provides a kind of and can extend arsenic trioxide to the effective acting time of vascular smooth muscle cell and have the preparation technology of the nanometer arsenic trioxide that slow release revises/lactic-co-glycolic acid coating bracket.
The present invention adopts following technical scheme to solve its technical problem:
The preparation method of a kind of nanometer arsenic trioxide of the present invention/lactic-co-glycolic acid coating bracket is characterized in that:
The preparation of step 1 nanometer arsenic trioxide/lactic-co-glycolic acid:
Get in the sodium hydroxide solution that 0.01-0.03g arsenic trioxide powder is 1mmol/L in molar concentration and fully dissolve, and with the hydrochloric acid of 1mmol/L, pH value is adjusted to 7.2-7.4, form A liquid;
The 100mg lactic-co-glycolic acid is dissolved in the dichloromethane of 2ml, forms B liquid;
A liquid is added to B liquid, and (volume ratio of A liquid and B liquid is 6-10: 1), ultrasonic emulsification 1min, form C liquid;
The polyvinyl alcohol that is 2.25% by the mass percent concentration of 12ml adds in the C liquid of 60-100ml, uses supersonic generator to carry out ultrasonic 90 seconds C liquid, in frozen water, disperses, and forms D liquid;
D liquid is risen to room temperature and stirs 3h with the 300r/min rotating speed, form nanometer arsenic trioxide/lactic-co-glycolic acid colloid solution, obtain E liquid, by arsenic trioxide/lactic-co-glycolic acid nanoparticle colloid solution in 4 ℃, 15000rpm, centrifugal 30min, abandoning supernatant, distillation washing 3 times for precipitation, remove the not free drug of parcel, vacuum freeze-drying obtains lyophilized powder, and sealing is placed on 4 ℃ of preservations;
The preparation of step 2 nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket:
The stainless steel metal bare bracket is cleaned 3 minutes in the CQ50 supersonic generator, be statically placed in 24h in above-mentioned B liquid after oven dry, form the support of lactic-co-glycolic acid parcel, after drying, the support of lactic-co-glycolic acid parcel is statically placed in to 48h in E liquid, after removal in 37 ℃ of baking boxs dry 30min, finally form nanometer lactic-co-glycolic acid coating bracket.
Compared with prior art, the present invention has obtained following beneficial effect:
Employ new technology and prepared the novel form that lactic-co-glycolic acid is carried arsenic trioxide, nanometer arsenic trioxide/lactic-co-glycolic acid is a kind of comparatively ideal slow delivery formulations, can extend the effective acting time of arsenic trioxide to vascular smooth muscle cell, external have certain cell growth inhibiting and an apoptosis-induced effect.Preliminary experimentation confirms that its propagation to vascular smooth muscle cell and migration have certain inhibitory action, and this novel pharmaceutical formulation will be expected to become the medication coat on coating stent of medicine surface from now on, for the clinical prevention in-stent restenosis provides new thinking and method.
1. after the ultrasonic dispersion of nanometer arsenic trioxide/lactic-co-glycolic acid that adopts the biphase emulsification evaporation to prepare, use respectively transmission electron microscope (Fig. 1) and scanning electron microscope (Fig. 2) to observe, for sub-circular, and certain electron density is arranged, be the spheroid that is dispersed in distribution.Calculate mean diameter by the CMIAS98A image analysis system, the mean diameter of the nanometer arsenic trioxide/lactic-co-glycolic acid of known experiment preparation is 90nm.Select arbitrarily several visuals field under the scanning electron microscope visual field, with energy disperse spectroscopy, nanometer arsenic trioxide/lactic-co-glycolic acid composition is analyzed to (Fig. 3), the visible composition that wherein contains arsenic, carbon and oxygen, the quality percentage composition (Wt%) of arsenic is 3.25%, atomic percentage conc (At%) is 0.72%, therefore can confirm successfully prepared by nanometer arsenic trioxide/lactic-co-glycolic acid.Adopting the drug loading of the nanometer arsenic trioxide/lactic-co-glycolic acid of atomic fluorescence spectrophotometer mensuration is 1.72%, and average envelop rate is 53.75%.The normal saline of take has been investigated the external dynamic release of nanometer arsenic trioxide/lactic-co-glycolic acid as medium, reaches 96.82% while reaching 72.37%, 15d during the preparation 4d of this medicine as calculated, and progresses into plateau (Figure 13).
2., after the present invention adopts the dip coating preparation to carry nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket, observe bare mental stents surface irregularity (Fig. 4) under scanning electron microscope; The coated metal support surface of lactic-co-glycolic acid obviously covers the membranaceous material of one deck, comparatively smooth (Fig. 7); The surface of nanometer arsenic trioxide/lactic-co-glycolic acid blood vessel coating bracket can be observed the parcel of membranaceous material, and the nano-scale particle (Figure 10) that contains certain electron density on film, the mean diameter of this nano-particle is 92nm, basically identical with our mean diameter of prepared nanometer arsenic trioxide/lactic-co-glycolic acid.Energy disperse spectroscopy has carried out component analysis to bare mental stents (Fig. 6), coated metal rack (Fig. 9) and the coated metal rack (Figure 12) of nanometer arsenic trioxide/lactic-co-glycolic acid of lactic-co-glycolic acid respectively.Energy disperse spectroscopy shows that to the component analysis of nanometer arsenic trioxide/lactic-co-glycolic acid blood vessel coating bracket this support contains outside ferrum, nickel, chromium, carbon and oxygen element, the quality percentage composition (Wt%) of arsenic is 12.57%, atomic percentage conc (At%) is 7.86%, confirmed the existence of arsenic, illustrated that nanometer arsenic trioxide/lactic-co-glycolic acid is coated in rack surface.
3. the arsenic content of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket
The standard working curve of the arsenic of measuring by atomic fluorescence spectrophotometer is: I=3.737+13.097C, r=0.9995, wherein I is the analytic signal peak area, C is arsenic concentration, after measured, the drug loading of nanometer arsenic trioxide/lactic-co-glycolic acid is 1.72%, and average envelop rate is 53.75%.
4. the dynamic measurement result of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket tablets in vitro speed
The normal saline of take has been investigated the external dynamic release of nanometer arsenic trioxide/lactic-co-glycolic acid as medium, reaches 96.82% while reaching 72.37%, 15d during the preparation 4d of this medicine as calculated, and progresses into plateau (Figure 13).
5. the impact of nanometer arsenic trioxide/lactic-co-glycolic acid on vascular endothelial cell proliferation and migration
MTT (methyl thiazolyl tetrazolium) body of laws is measured nanometer arsenic trioxide/lactic-co-glycolic acid outward the inhibitory action of the vascular smooth muscle cell proliferation of former culture is had to time dependence and dose dependent.The time dependence lethal effect of nanometer arsenic trioxide/lactic-co-glycolic acid is always and continues to increase trend.After the flow cytometer result shows drug effect 48h and 72h, the apoptosis-induced effect of higher concentration nanometer arsenic trioxide/lactic-co-glycolic acid (18.71%, 29.9%) obviously is better than low concentration nanometer As2O3/PLGA (10.20%, 18.29%).5. Transwell cell migration experimental result shows that higher concentration nanometer arsenic trioxide/lactic-co-glycolic acid obviously is better than low concentration nanometer arsenic trioxide/lactic-co-glycolic acid (32.5%) to the inhibitory action (77.5%) of vascular smooth muscle cells migration.6. RT-PCR and Western blot show that nanometer arsenic trioxide/lactic-co-glycolic acid has inhibitory action to the expression of the Bcl-2 gene of vascular smooth muscle cell, and the expression of Bax gene is had to facilitation (reduction of Bcl-2/Bax ratio).And along with the increase Bcl-2/Bax ratio of drug level reduces more obviously (seeing Fig. 6,7,8,9).
The accompanying drawing explanation
Fig. 1 is nanometer arsenic trioxide transmission electron microscope photo prepared by the present invention.
Fig. 2 is nanometer arsenic trioxide stereoscan photograph prepared by the present invention.
Fig. 3 is the spectroscopy detection result (annotate: the copper peak is due to copper mesh) of nanometer arsenic trioxide.
Fig. 4 is electromicroscopic photograph of bare mental stents that the present invention makes.
Fig. 5 is another electromicroscopic photograph of the bare mental stents that makes of the present invention.
Fig. 6 be the naked metal that makes of the present invention can spectrogram.
Fig. 7 is coated electromicroscopic photograph of metal rack of lactic-co-glycolic acid prepared by the present invention.
Fig. 8 is coated another stereoscan photograph of metal rack of lactic-co-glycolic acid.
Fig. 9 is the energy spectrogram of the coated metal rack of lactic-co-glycolic acid.
Figure 10 is an electromicroscopic photograph of the coated metal rack of nanometer arsenic trioxide/lactic-co-glycolic acid of preparing of the present invention.
Figure 11 is another electromicroscopic photograph of the coated metal rack of nanometer arsenic trioxide/lactic-co-glycolic acid.
Figure 12 is the coated metal rack EDS figure of nanometer arsenic trioxide/lactic-co-glycolic acid.
Figure 13 is the nanometer arsenic trioxide for preparing of the present invention/lactic-co-glycolic acid coating bracket preparation.
Figure 14 is light microscopic result (* 200 times) after negative control group processing vascular smooth muscle cell 96h.
Figure 15 is light microscopic result (* 200 times) after 2umol/L nanometer arsenic trioxide/lactic-co-glycolic acid group processing vascular smooth muscle cell 96h.
Figure 16 is light microscopic result (* 200 times) after 3 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group processing vascular smooth muscle cell 96h.
Figure 17 is light microscopic result (* 200 times) after 4 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group processing vascular smooth muscle cell 96h.
Figure 18 is light microscopic result (* 200 times) after 5 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group processing vascular smooth muscle cell 96h.
Figure 19 is the impact of negative control group on vascular smooth muscle cells migration.
Figure 20 is the impact of 1 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group on vascular smooth muscle cells migration.
Figure 21 is the impact of 3 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group on vascular smooth muscle cells migration.
Figure 22 is the impact of 6 μ mol/L nanometer arsenic trioxide/lactic-co-glycolic acid group on vascular smooth muscle cells migration.
After Figure 23 is variable concentrations nanometer arsenic trioxide/lactic-co-glycolic acid vasoactive smooth muscle cell 72h, the RT-PCR electrophoresis result.
After Figure 24 is variable concentrations nanometer arsenic trioxide/lactic-co-glycolic acid vasoactive smooth muscle cell 72h, western-blot trace result.
The specific embodiment
A kind of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket comprises: rack body, the outside of rack body is coated with nanometer arsenic trioxide/lactic-co-glycolic acid.
The preparation method of a kind of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket,
The preparation of step 1 nanometer arsenic trioxide/lactic-co-glycolic acid:
Get in the sodium hydroxide solution that 0.01-0.03g arsenic trioxide powder is 1mmol/L in molar concentration and fully dissolve, and with the hydrochloric acid of 1mmol/L, pH value is adjusted to 7.2-7.4, form A liquid;
The 100mg lactic-co-glycolic acid is dissolved in the dichloromethane of 2ml, forms B liquid;
A liquid is added in B liquid, and wherein, the volume ratio of A liquid and B liquid is 6-10: 1, and the present embodiment can be selected 6: 1,7: 1 or 10: 1, and ultrasonic emulsification 1min forms C liquid;
The polyvinyl alcohol that is 2.25% by the mass percent concentration of 12ml adds in the C liquid of 60-100ml, uses supersonic generator to carry out ultrasonic 90 seconds C liquid, in frozen water, disperses, and forms D liquid, and wherein, the model of supersonic generator is CQ50;
D liquid is risen to room temperature and stirs 3h with the 300r/min rotating speed, form nanometer arsenic trioxide/lactic-co-glycolic acid colloid solution, obtain E liquid, by arsenic trioxide/lactic-co-glycolic acid nanoparticle colloid solution in 4 ℃, 15000rpm, centrifugal 30min, abandoning supernatant, distillation washing 3 times for precipitation, remove the not free drug of parcel, vacuum freeze-drying obtains lyophilized powder, and sealing is placed on 4 ℃ of preservations;
The preparation of step 2 nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket:
The stainless steel metal bare bracket is cleaned 3 minutes in the CQ50 supersonic generator, be statically placed in 24h in above-mentioned B liquid after oven dry, form the support of lactic-co-glycolic acid parcel, after drying, the support of lactic-co-glycolic acid parcel is statically placed in to 48h in E liquid, after removal in 37 ℃ of baking boxs dry 30min, finally form nanometer lactic-co-glycolic acid coating bracket.
The present embodiment system nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket, perusal except surface-coated skim sample material, than bare mental stents without significant change.
Claims (1)
1. the preparation technology of nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket, is characterized in that,
The preparation of step 1 nanometer arsenic trioxide/lactic-co-glycolic acid:
Get in the sodium hydroxide solution that 0.01-0.03g arsenic trioxide powder is 1mmol/L in molar concentration and fully dissolve, and with the hydrochloric acid of 1mmol/L, pH value is adjusted to 7.2-7.4, form A liquid;
The 100mg lactic-co-glycolic acid is dissolved in the dichloromethane of 2ml, forms B liquid;
A liquid is added in B liquid, and wherein, the volume ratio of A liquid and B liquid is 6-10:1, and ultrasonic emulsification 1min forms C liquid;
The polyvinyl alcohol that is 2.25% by the mass percent concentration of 12ml adds in the C liquid of 60-100ml, uses supersonic generator to carry out ultrasonic 90 seconds C liquid, in frozen water, disperses, and forms D liquid;
D liquid is risen to room temperature and stirs 3h with the 300r/min rotating speed, form nanometer arsenic trioxide/lactic-co-glycolic acid colloid solution, obtain E liquid, by arsenic trioxide/lactic-co-glycolic acid nanoparticle colloid solution in 4 ℃, 15000rpm, centrifugal 30min, abandoning supernatant, distillation washing 3 times for precipitation, remove the not free drug of parcel, vacuum freeze-drying obtains lyophilized powder, and sealing is placed on 4 ℃ of preservations;
The preparation of step 2 nanometer arsenic trioxide/lactic-co-glycolic acid coating bracket:
The stainless steel metal bare bracket is cleaned 3 minutes in the CQ50 supersonic generator, be statically placed in 24h in above-mentioned B liquid after oven dry, form the support of lactic-co-glycolic acid parcel, after drying, the support of lactic-co-glycolic acid parcel is statically placed in to 48h in E liquid, after removal in 37 ℃ of baking boxs dry 30min, finally form nanometer lactic-co-glycolic acid coating bracket.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0970711A2 (en) * | 1998-06-30 | 2000-01-12 | Ethicon, Inc. | Process for coating stents |
| CN101161300A (en) * | 2007-11-27 | 2008-04-16 | 北京美中双和医疗器械有限公司 | Arsenic trioxide medicament elution bracket |
| CN101214397A (en) * | 2007-12-29 | 2008-07-09 | 杨巍 | Medicament elution bracket for promoting esoderma repair and preventing vascular restenosis |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0970711A2 (en) * | 1998-06-30 | 2000-01-12 | Ethicon, Inc. | Process for coating stents |
| CN101161300A (en) * | 2007-11-27 | 2008-04-16 | 北京美中双和医疗器械有限公司 | Arsenic trioxide medicament elution bracket |
| CN101214397A (en) * | 2007-12-29 | 2008-07-09 | 杨巍 | Medicament elution bracket for promoting esoderma repair and preventing vascular restenosis |
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