CN1751667A - Blood stent covered with arsenic oxide(s) film and preparing method thereof - Google Patents
Blood stent covered with arsenic oxide(s) film and preparing method thereof Download PDFInfo
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- CN1751667A CN1751667A CN 200510010462 CN200510010462A CN1751667A CN 1751667 A CN1751667 A CN 1751667A CN 200510010462 CN200510010462 CN 200510010462 CN 200510010462 A CN200510010462 A CN 200510010462A CN 1751667 A CN1751667 A CN 1751667A
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- arsenic
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Abstract
A vascular scaffold covered by arsenic oxide film is prepared through growing an arsenic film on on the surface of scaffold by molecular beam epitaxy method or vapor deposition method, and natural oxidizing in air. Its advantages are high adhesion and high elasticity.
Description
Technical field
The invention belongs to medical instruments field, relate to a kind of coating stent of medicine and preparation method thereof, particularly a kind of intravascular stent that is coated with the even compact arsenic oxide (s) film and preparation method thereof.
Background technology
Cardiovascular disease is serious threat human life and healthy common disease, and intravascular stent has become cardiovascular and peripheral blood vessel blocks the main means that pathological changes is carried out interventional therapy.Since human body was placed the first routine coronary stent (PTCA support), this technical development was rapid from people such as Sigwart in 1986, had accounted for more than 90% of this type of disease treatment at present.But the greatest drawback of this technology is the generation of support postoperative restenosis, and from present statistics, restenosis rate is about 15%～30% behind the stenting.The reason of support postoperative restenosis is: the support expansion has been brought out vascular smooth muscle cell transition propagation after causing the tunica intima damage, thereby causes vascellum endometrial hyperplasia, and the result causes the restenosis behind the stenting.The propagation of vascular smooth muscle cell (SMC) and migration are the main causes that causes vascellum endometrial hyperplasia and cause restenosis.The method of prevention of restenosis mainly contains: Drug therapy, topical therapeutic, gene therapy, mechanotherapy.In numerous prevention of restenosis methods, coating stent of medicine has become present internationally recognized prefered method, coating stent of medicine slowly discharges at diseased region by the support carrying medicament and prevents and reduce restenosis, restenosis rate can be eased down to below 10%.The selection great majority of bracket coating medicine are to suppress SMC propagation and migration, as paclitaxel and rapamycin FirebirdTM at present.Keeping relative balance between normal vascular SMC propagation and the apoptosis, the apoptosis of therefore controlling the vascular SMC cell can be used as a kind of new way of treatment restenosis.The CN1657023A report is with As
2O
3Prepare bracket for controlling releasing and elution as medication coat.Result of study shows, As
2O
3After coating stent of medicine is implanted healthy hybrid adult dogs coronary artery, observe brace sections blood vessel NIP, no thrombosis forms, no arterial wall attenuation, and no aneurysm forms, film adventitia necrosis in the nothing, the no pathologic infringement of tissue such as conscience spleen lung kidney brain shows As
2O
3Coating stent of medicine has the favorable tissue compatibility and safety; Support is implanted 4 weeks of back, and the purer groups of holders neointimal hyperplasia of coating stent of medicine group degree obviously reduces, and tube chamber enlarges markedly.As seen the apoptosis of controlling the vascular SMC cell can be used as a kind of new method of treatment restenosis, As
2O
3Can be used as the apoptotic medicine of a kind of effective control.But the thin film on the existing intravascular stent is polymer mostly, coating all be two-layer more than, they exist the problem with the matrix bond defective tightness, thereby influence the performance of drug effect.The preparation method of coating stent of medicine commonly used is that polymer and medicine are made mixed liquor at present, is coated to metal support surface, promptly forms the one layer of polymeric medication coat at rack surface after the solvent seasoning.But polymer coating and metal surface can not form chemical bonding, thus can not between coating and support, produce very strong adhesion, and the more stiff elasticity that lacks of coating.Cover the method for medicine also in continuous renewal at rack surface, mainly be by increasing the bond strength that surface activity and roughness improve film and support, but, can not solve in itself because of not forming chemical bonding between polymer and the support causes adhesion less, film easily comes off, the problem that elasticity is relatively poor.
Summary of the invention
Medication coat at existing intravascular stent is a multilamellar, exist medicine to combine the problem of defective tightness with support, and the thin film for preparing of existing method exists and easily comes off and problem that elasticity is relatively poor, the invention provides a kind of thin film difficult drop-off and elasticity and is coated with intravascular stent of arsenic oxide (s) film and preparation method thereof preferably.A kind of intravascular stent that is coated with arsenic oxide (s) film, it comprises support and medication coat, described medication coat has only the oxide film layer of arsenic.Be coated with the preparation method of the intravascular stent of arsenic oxide (s) film, it may further comprise the steps successively: a. with molecular beam epitaxy at growth arsenic film on the support: in the growth room of molecular beam epitaxial growth device, be placed with solid arsenic; Support is put into this growth room, at As
4580～610 ℃ of the underlayer temperatures of control support under the atmosphere, growth room's vacuum≤5 * 10
-11T, growth time 0.2～8h promptly finishes the growth of arsenic film on support; B. propping up behind the plated film is placed on autoxidation in the air, promptly obtains the purpose product.The another kind of preparation method that is coated with the intravascular stent of arsenic oxide (s) film may further comprise the steps successively: a. plates arsenic with the method for evaporation coating at rack surface: at first bare bracket is hung on and put into quartz ampoule on the carriage, evacuation is also put into arsenic granule, sealed silica envelope under vacuum state; Then sealed silica envelope is put into heating furnace and heat, heating-up temperature is 700～800 ℃, and be 1～20min heat time heating time; B. propping up behind the plated film is placed on autoxidation in the air, promptly obtains the purpose product.The present invention induces smooth muscle cell (SMC) apoptosis to prevent restenosis with the oxide of arsenic as medicine layer.Arsenic is the silver gray semimetal, compares with high molecular polymer, and between the metal better the combination can be arranged.The present invention is directly carrying out oxidation behind the plating arsenic on the support, and its ingredient does not contain polymer, and arsenic oxide is one deck only, through experimental verification, directly is plated in the arsenic film difficult drop-off on the support and toughness and elasticity are preferably arranged.Simultaneously, the inventive method has been utilized the volatility of arsenic, by control arsenic under vacuum state heating and directly solid-state arsenic is plated in rack surface; The present invention plates arsenic with molecular beam epitaxial device and evaporating and coating equipment at rack surface respectively, then propping up behind the plated film is placed on autoxidation in the air, obtain the oxide drugs layer of arsenic, have stronger adhesion between gained medication coat and the support, arsenic film difficult drop-off; Simultaneously, the gained medication coat has better elastic, and the arsenic film also can change thereupon when support occurs bending and deformation, and the phenomenon that medicine layer comes off does not take place; With the arsenic oxide (s) film intravascular stent of gained of the present invention to the rabbit stenting after the neointimal hyperplasia confirmation that experimentizes, the result shows that product of the present invention can well suppress neointimal hyperplasia, prevents restenosis, and preparation method is simply suitable, is beneficial to and applies.
Description of drawings
Fig. 1 is the specific embodiment six equipment therefor structural representations.
The specific embodiment
The specific embodiment one: a kind of intravascular stent that is coated with arsenic oxide (s) film, it comprises support and medication coat, described medication coat has only the oxide film layer of arsenic.The present invention has successfully prepared arsenic oxide (s) film at the support matrix surface, this arsenic oxide (s) film only is one deck structure, though resulting arsenic oxide (s) film combines character also in further studying with matrix, but experimental result confirms this thin film even compact, and the existing thin film of the adhesion of itself and matrix is greatly improved really.
The specific embodiment two: existing with As
2O
3Support material as medication coat is a rustless steel, because rustless steel does not have memory effect, so be unfavorable for fusion in vivo; The support composition that the present invention selects for use is a Nitinol, because Nitinol has memory effect, so can adapt to blood vessel admirably, avoids health to be subjected to undue harm.The medicament contg that support is every square millimeter is 1.6～3.2 μ g, and coating layer thickness is 0.2～3 μ m.Experimental verification, this medicament contg can well play therapeutical effect.
The specific embodiment three: present embodiment is a kind of preparation method that is coated with the intravascular stent of arsenic oxide (s) film, and it may further comprise the steps successively: a with molecular beam epitaxy at growth arsenic film on the support: in the growth room of molecular beam epitaxial growth device, be placed with solid arsenic; Support is put into this growth room, at As
4Under the atmosphere, 580～610 ℃ of the underlayer temperatures of control support, growth room's vacuum≤5 * 10
-11T, by controlling the growth rate that above condition can obtain the arsenic film is 0.51～1.1 μ m/h, can obtain the arsenic film of different-thickness at rack surface by the control growing time, through experimental verification, growth time is controlled at 0.2～8h, needing can obtain the arsenic film of thickness, thereby finish the growth of arsenic film on support; B. propping up behind the plated film is placed on autoxidation in the air, promptly obtains the purpose product.By the growth time difference of control arsenic film, can obtain the coating bracket of different pharmaceutical content, the medicament contg that makes every square millimeter of rack surface is 1.6～3.2 μ g, coating layer thickness is that 0.2～3 μ m gets final product.The described support of present embodiment is a bare bracket, just obtains the support of clean surface after treatment, and its processing method can be present any method in common.Propping up behind the plated film is placed on autoxidation in the air, and its oxidization time is hard-core, and purpose is to make its abundant oxidation, and the longer the better for oxidization time in theory.Underlayer temperature is to utilize lining heat to heat, and lining heat can be a resistance wire, can earlier the support matrix be placed in pallet or the crucible, then pallet or crucible is heated, and measures with thermocouple then to get final product.The gained support is compressed on the sacculus, the plastic bag encapsulation, the ethylene oxide sterilizing sterilization is standby, can make 1.6 μ g/mm
2, 2.4 μ g/mm
2, 3.2 μ g/mm
2The oxide drugs coating bracket of the arsenic of three kinds of concentration uses.
The specific embodiment four: the concrete technological parameter of present embodiment is: 580～610 ℃ of underlayer temperatures, growth room's background vacuum pressure≤5 * 10
-11T, its growth rate 0.51 μ m/h; Other is identical with the specific embodiment three.
The specific embodiment five: present embodiment makes it become a kind of method of bare bracket for support is handled.Before support is put into the growth room, carry out following processing procedure: with support after the degreasing of acetone trichloroethylene, through H in molar ratio
2SO
4: H
2O
2: H
2The corrosive liquid erosion removal surface mechanical damage layer of O=5～6: 0.8～1.2: 0.8～1.2, again through 20M Ω washed with de-ionized water, dry the back at the Sample Room of molecular beam epitaxial growth device through 1～1.5 hour laggard surge chamber of 200～230 ℃ of heat pre-treatment, behind 400～450 ℃ of bake outs, enter the growth room again at surge chamber again.In the growth room, be placed with the arsenic granule, the As that volatilizes at the arsenic granule
4Can remove the oxide-film of rack surface under the atmosphere, thereby obtain the clean surface; Its process can be by the high-energy electron diffiraction in-situ monitoring.
The specific embodiment six: the preparation method of the intravascular stent that is coated with arsenic oxide (s) film of present embodiment, it may further comprise the steps successively: a. plates arsenic with the method for evaporation coating at rack surface: at first bare bracket 3 is hung on and put into quartz ampoule 4 on the carriage 2, concrete structure is with reference to Fig. 1, evacuation is also put into arsenic granule 1, sealed silica envelope 4 under vacuum state; Then sealed silica envelope 4 is put into heating furnace and heat, heating-up temperature is 700～800 ℃, and be 1～20min heat time heating time; Can control the volatilization degree of arsenic granule 1 by controlling heat time heating time and heating-up temperature, thereby be controlled at the arsenic film that support 3 surfaces obtain different-thickness and density.B. the support behind the plated film 3 is placed the air autoxidation, support 3 surfaces become the oxide coating of arsenic, thereby obtain the purpose product.
Drug stent of the present invention can adopt Nitinol as the support matrix, also available other all can be used for intravascular stent that human body is implanted into as the support matrix, all within protection scope of the present invention.
Claims (6)
1. intravascular stent that is coated with arsenic oxide (s) film, it comprises support and medication coat, it is characterized in that described medication coat has only the oxide film layer of arsenic.
2. a kind of intravascular stent that is coated with arsenic oxide (s) film according to claim 1 is characterized in that described support composition is a Nitinol.
3. a kind of intravascular stent that is coated with arsenic oxide (s) film according to claim 1 and 2 is characterized in that on the support that every square millimeter medicament contg is 1.6～3.2 μ g, and coating layer thickness is 0.2～3 μ m.
4. preparation method that is coated with the intravascular stent of arsenic oxide (s) film is characterized in that it may further comprise the steps successively:
A. with molecular beam epitaxy at growth arsenic film on the support: in the growth room of molecular beam epitaxial growth device, be placed with solid arsenic; Support is put into this growth room, at As
4580～610 ℃ of the underlayer temperatures of control support under the atmosphere, growth room's vacuum≤5 * 10
-11T, growth time 0.2～8h promptly finishes the growth of arsenic film on support;
B. propping up behind the plated film is placed on autoxidation in the air, promptly obtains the purpose product.
5. a kind of preparation method that is coated with the intravascular stent of arsenic oxide (s) film according to claim 4 is characterized in that support puts into before the growth room, with support after the degreasing of acetone trichloroethylene, through H in molar ratio
2SO
4: H
2O
2: H
2The corrosive liquid erosion removal surface mechanical damage layer of O=5～6: 0.8～1.2: 0.8～1.2, again through 20M Ω washed with de-ionized water, dry the back at the Sample Room of molecular beam epitaxial growth device through 1～1.5 hour laggard surge chamber of 200～230 ℃ of heat pre-treatment, behind 400～450 ℃ of bake outs, enter the growth room again at surge chamber again.
6. preparation method that is coated with the intravascular stent of arsenic oxide (s) film is characterized in that it may further comprise the steps successively:
A plates arsenic with the method for evaporation coating at rack surface: at first bare bracket is hung on and put into quartz ampoule on the carriage, evacuation is also put into arsenic granule, sealed silica envelope under vacuum state; Then sealed silica envelope is put into heating furnace and heat, heating-up temperature is 700～800 ℃, and be 1～20min heat time heating time;
B. propping up behind the plated film is placed on autoxidation in the air, promptly obtains the purpose product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100104622A CN100360094C (en) | 2005-10-21 | 2005-10-21 | Blood stent covered with arsenic oxide(s) film and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100104622A CN100360094C (en) | 2005-10-21 | 2005-10-21 | Blood stent covered with arsenic oxide(s) film and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1751667A true CN1751667A (en) | 2006-03-29 |
| CN100360094C CN100360094C (en) | 2008-01-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033669A3 (en) * | 2007-09-06 | 2013-06-05 | Biotronik VI Patent AG | Stent with a base body made of a biocorrodible alloy |
| CN108060394A (en) * | 2017-12-25 | 2018-05-22 | 谢小坚 | The painting method of medication coat on a kind of energy saving and environment friendly implanted medical device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413594A (en) * | 2002-08-07 | 2003-04-30 | 杨巍 | Medicine for prevention and curing reangiostenosis |
| GB2430626B (en) * | 2004-02-09 | 2008-09-24 | Cook Biotech Inc | Stent graft devices having collagen coating |
| US7294145B2 (en) * | 2004-02-26 | 2007-11-13 | Boston Scientific Scimed, Inc. | Stent with differently coated inside and outside surfaces |
| CN1669597A (en) * | 2004-03-16 | 2005-09-21 | 程树军 | Medicine eluted cardiovascular support |
| CN100435756C (en) * | 2005-01-31 | 2008-11-26 | 上海市第一人民医院 | Arsenic trioxide control release elution stent |
-
2005
- 2005-10-21 CN CNB2005100104622A patent/CN100360094C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033669A3 (en) * | 2007-09-06 | 2013-06-05 | Biotronik VI Patent AG | Stent with a base body made of a biocorrodible alloy |
| CN108060394A (en) * | 2017-12-25 | 2018-05-22 | 谢小坚 | The painting method of medication coat on a kind of energy saving and environment friendly implanted medical device |
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| Publication number | Publication date |
|---|---|
| CN100360094C (en) | 2008-01-09 |
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Granted publication date: 20080109 Termination date: 20101021 |