CN110639056B - Preparation method of medical magnesium alloy surface drug release functional coating - Google Patents
Preparation method of medical magnesium alloy surface drug release functional coating Download PDFInfo
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- CN110639056B CN110639056B CN201910878710.7A CN201910878710A CN110639056B CN 110639056 B CN110639056 B CN 110639056B CN 201910878710 A CN201910878710 A CN 201910878710A CN 110639056 B CN110639056 B CN 110639056B
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 78
- 239000003814 drug Substances 0.000 title claims abstract description 62
- 229940079593 drug Drugs 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 46
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 claims description 9
- 229960003957 dexamethasone Drugs 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052839 forsterite Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229930182555 Penicillin Natural products 0.000 claims description 4
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 229940049954 penicillin Drugs 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- CCESTPXUODXQEN-UHFFFAOYSA-N 1-[diethyl(propyl)silyl]ethanamine Chemical compound NC(C)[Si](CC)(CC)CCC CCESTPXUODXQEN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229930012538 Paclitaxel Natural products 0.000 claims description 3
- OATFZMZHCHJBGR-UHFFFAOYSA-N ethenoxyperoxysilane Chemical compound C(=C)OOO[SiH3] OATFZMZHCHJBGR-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229960004329 metformin hydrochloride Drugs 0.000 claims description 3
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 claims description 3
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin hydrochloride Natural products CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 3
- 229960001592 paclitaxel Drugs 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- ZAHRKKWIAAJSAO-UHFFFAOYSA-N rapamycin Natural products COCC(O)C(=C/C(C)C(=O)CC(OC(=O)C1CCCCN1C(=O)C(=O)C2(O)OC(CC(OC)C(=CC=CC=CC(C)CC(C)C(=O)C)C)CCC2C)C(C)CC3CCC(O)C(C3)OC)C ZAHRKKWIAAJSAO-UHFFFAOYSA-N 0.000 claims description 3
- 229960002930 sirolimus Drugs 0.000 claims description 3
- QFJCIRLUMZQUOT-HPLJOQBZSA-N sirolimus Chemical compound C1C[C@@H](O)[C@H](OC)C[C@@H]1C[C@@H](C)[C@H]1OC(=O)[C@@H]2CCCCN2C(=O)C(=O)[C@](O)(O2)[C@H](C)CC[C@H]2C[C@H](OC)/C(C)=C/C=C/C=C/[C@@H](C)C[C@@H](C)C(=O)[C@H](OC)[C@H](O)/C(C)=C/[C@@H](C)C(=O)C1 QFJCIRLUMZQUOT-HPLJOQBZSA-N 0.000 claims description 3
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 claims description 3
- FJLGEFLZQAZZCD-MCBHFWOFSA-N (3R,5S)-fluvastatin Chemical compound C12=CC=CC=C2N(C(C)C)C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)=C1C1=CC=C(F)C=C1 FJLGEFLZQAZZCD-MCBHFWOFSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229960003765 fluvastatin Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229960003350 isoniazid Drugs 0.000 claims description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- HYIMSNHJOBLJNT-UHFFFAOYSA-N nifedipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC=C1[N+]([O-])=O HYIMSNHJOBLJNT-UHFFFAOYSA-N 0.000 claims description 2
- 229960001597 nifedipine Drugs 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000002444 silanisation Methods 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 206010061218 Inflammation Diseases 0.000 abstract 1
- 229910004283 SiO 4 Inorganic materials 0.000 abstract 1
- 238000005524 ceramic coating Methods 0.000 abstract 1
- 238000002513 implantation Methods 0.000 abstract 1
- 238000001727 in vivo Methods 0.000 abstract 1
- 230000004054 inflammatory process Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 229940126585 therapeutic drug Drugs 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 208000030453 Drug-Related Side Effects and Adverse reaction Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 206010013663 drug dependence Diseases 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940043263 traditional drug Drugs 0.000 description 1
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
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Abstract
一种医用镁合金表面释药功能涂层的制备方法，特别适用于生物医药材料的表面处理及表面改性领域。本方法通过化学聚合法在镁或镁合金的无机涂层上制备释药涂层，旨在降低镁或镁合金的降解速度，并起到释放药物的作用，从而保证镁或镁合金在实际应用中的力学性能并更好缓解生物体的排异反应。镁或镁合金表面通过微弧氧化制备得到无机涂层，之后无机涂层上制备载药层。无机涂层是由MgO、Mg2SiO4和Mg3(PO4)2所构成的具有极佳耐蚀性的陶瓷涂层，可以有效地降低镁或镁合金的体内降解速度。载药层由载药聚合物与治疗性药物构成，减少植入后炎症反应的发生率和对药物的依赖作用及其副作用，并进一步提高镁或镁合金的耐蚀性。
The invention discloses a preparation method of a drug-releasing functional coating on the surface of a medical magnesium alloy, which is particularly suitable for the fields of surface treatment and surface modification of biomedical materials. The method prepares a drug-releasing coating on the inorganic coating of magnesium or magnesium alloy by chemical polymerization, aiming at reducing the degradation rate of magnesium or magnesium alloy and releasing the drug, thereby ensuring the practical application of magnesium or magnesium alloy The mechanical properties and better alleviation of the organism's rejection response. An inorganic coating is prepared on the surface of magnesium or magnesium alloy by micro-arc oxidation, and then a drug-carrying layer is prepared on the inorganic coating. The inorganic coating is a ceramic coating composed of MgO, Mg 2 SiO 4 and Mg 3 (PO 4 ) 2 with excellent corrosion resistance, which can effectively reduce the degradation rate of magnesium or magnesium alloys in vivo. The drug-loaded layer is composed of a drug-loaded polymer and a therapeutic drug, which reduces the incidence of post-implantation inflammatory reactions, dependence on drugs and their side effects, and further improves the corrosion resistance of magnesium or magnesium alloys.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a method for preparing a coating with a drug release function on the surface of medical magnesium alloy.
Background
Since the 70's of the 19 th century, magnesium alloys having good biocompatibility and magnesium density of 1.74g/cm, as compared with conventional metals, have been used as biomedical materials for over a century3Is mixed with natural bone (1.8-2.1 g/cm)3) Close to each other, the mechanical property is compatible with human skeleton-no stress shielding effect exists, and Mg2+It has also been shown to promote the adsorption and growth of bone cells. Magnesium alloy is considered as a biodegradable material with great development potential, but has limited wide application due to its fast degradation rate in human body.
Research results show that appropriate surface treatment can effectively reduce the corrosion rate of the magnesium alloy, and the current methods for improving the corrosion resistance of the magnesium alloy mainly comprise surface treatment technologies such as electrochemical deposition, chemical conversion coating, biodegradable polymer coating, micro-arc oxidation and the like. With the development of the technology, researchers do not simply satisfy the improvement of the corrosion resistance, and aim to improve the functionality of the coating so that the coating can play a greater role in practical application. The research hotspots mainly include: promoting the growth of coatings on affected parts, antibacterial coatings and drug release coatings on patient parts, wherein the drug release coatings have gradually become the hot spots of research.
Many studies have been made on preparing drug-releasing coatings on the surface of magnesium alloy, mainly focusing on using polymer to load drugs, but the polymer coating coated on the surface of magnesium alloy lacks enough hardness and wear resistance, and there is a risk of coating failure in practical surgical application. The traditional drug release coating has many limitations, the phenomenon of rapid drug release in the initial stage is still a problem, and most of the current researches on polymer drug release coatings mainly focus on the surfaces of inert metals such as titanium and the like, which proves that drugs with different amounts can be released according to the magnitude of current, and the preparation of the degradable metal surface is relatively less.
Disclosure of Invention
The invention aims to solve the problem of preparing a drug release coating on the surface of degradable metal and provides a method for preparing a coating with a drug release function on the surface of medical magnesium alloy. The preparation method provided by the invention has simple and controllable process, and can realize the preparation of the coating with the function of releasing the medicine on the surface of the magnesium alloy. The functional coating for releasing the drugs prepared by the method has good bonding performance with the degradable magnesium alloy matrix, not only improves the corrosion resistance of the magnesium alloy, but also can control the release of the drugs through the transmission of biological signals at focus. In the practical application process, the on-demand administration of organisms is realized, so that the dependence on medicines and the side effect thereof can be reduced, and the recovery period of patients can be effectively shortened.
Technical scheme of the invention
A preparation method of a medical magnesium alloy surface drug release functional coating comprises the following steps:
A. using pure magnesium or magnesium alloy as anode, and carrying out micro-arc oxidation in electrolyte to obtain the product containing MgO and Mg2SiO4And Mg3(PO4)2Micro-arc oxidation film layer; the electrolyte comprises 2-25 g/L of trisodium phosphate, 2-10 g/L of sodium silicate and 2-15 g/L of sodium hydroxide.
B. And B, immersing the magnesium or magnesium alloy obtained in the step A into a silanization solution prepared by a silane coupling agent, and forming a silane layer on the surface of the magnesium or magnesium alloy.
C. Preparing a polymer monomer, a drug and an organic solvent to form an organic solution, and preparing an oxidant to form a solution.
D. And C, immersing the magnesium or magnesium alloy containing the silane layer obtained in the step B into the organic solution obtained in the step C, taking out the magnesium or magnesium alloy, putting the magnesium or magnesium alloy into the oxidant solution obtained in the step C, and repeating the operation for a plurality of times to form a coating with a drug release function on the surface of the magnesium or magnesium alloy.
Wherein, before the micro-arc oxidation in the step A, the method further comprises the following steps: polishing the magnesium alloy, and carrying out ultrasonic cleaning and oil removal by using acetone and ethanol in sequence.
And the pH value of the electrolyte in the step A is 8-12. The parameters of the micro-arc oxidation comprise: the current density is 0.5 to 300mA/cm2The positive voltage is 250-500V, the negative voltage is 5-30V, the current frequency is 200-2000 Hz, the positive-negative frequency ratio is 0.5-2, the positive duty ratio is 10-50%, the negative duty ratio is 10-25%, the reaction time is 5-40 min, and the reaction temperature is 20-50 ℃.
And C, in the step C, the concentration of the polymer monomer in the organic solution is 0.1-1 mol/L, the concentration of the medicine is 1-10 mmol/L, the concentration of the oxidant is 0.1-3 mmol/L, and the organic solvent is one of ethanol, ethylene glycol, propanol, isopropanol and butanol.
The magnesium alloy is one of multi-element alloys such as biomedical binary magnesium alloy, biomedical ternary magnesium alloy, biomedical quaternary magnesium alloy and biomedical quinary magnesium alloy.
And the silane coupling agent in the step B is one of bis- (gamma-triethoxysilylpropane) tetrasulfide, aminopropyl triethyl silane, vinyl trioxysilane, vinyl trimethoxy silane or vinyl tri (beta-methoxyethoxy) silane.
And the polymer monomer in the step C is one of pyrrole, aniline, acetylene or thiophene. The oxidant is one of copper chloride, ferric chloride, ferrous chloride, silver chloride, ammonium persulfate, molybdenum chloride or hydrogen peroxide. The drug is one of dexamethasone, rapamycin, penicillin, isoniazid, paclitaxel, fluvastatin, nifedipine or metformin hydrochloride.
And D, repeating the operation for 1-5 times.
The invention has the advantages and beneficial effects that:
1. the invention realizes the surface modification of magnesium or magnesium alloy, and the prepared drug-releasing coating can be firmly attached to the surface of magnesium or magnesium alloy and is loaded with drugs;
2. the invention provides a novel method for preparing a drug release layer on the surface of magnesium or magnesium alloy, which controls the drug release by controlling the redox property of a polymer through the change of bioelectric current, realizes the drug release at the diseased part and reduces the drug dependence and side effects caused by over-administration.
3. The preparation method can be used for coating magnesium alloy with any shape, can be used for surface modification of magnesium alloy with complex structure, can control the thickness and the drug loading of the coating by controlling different preparation processes, and can be widely applied to actual production.
Drawings
FIG. 1 is a schematic scanning electron microscope of the micro-arc oxidation coating on the surface of the magnesium alloy in step A of the preparation method.
FIG. 2 is a schematic scanning electron microscope of a surface silane layer formed on the surface of a magnesium alloy in step B of the preparation method of the present invention.
Fig. 3 is a schematic scanning electron microscope of the drug release coating formed on the surface of the magnesium alloy in step D of the preparation method of the present invention.
FIG. 4 is a representation of the drug release amount of the drug release coating of example 1, example 2 and example 4 with different drug addition amounts in the preparation method of the present invention.
Detailed Description
The invention is described in detail below with reference to the attached drawing figures:
example 1:
a method for preparing a coating with a drug release function on the surface of medical magnesium alloy comprises the following steps:
A. after the pure magnesium is polished and cleaned, the pure magnesium is taken as an anode, and the current density is 0.5mA/cm2The micro-arc oxidation treatment is carried out in the electrolyte under the conditions that the positive voltage is 250V, the negative voltage is 5V, the current frequency is 200Hz, the positive-negative frequency ratio is 0.5, the positive duty ratio is 10 percent, the negative duty ratio is 20 percent, the reaction time is 5min and the reaction temperature is 20 ℃, so as to obtain the catalyst containing MgO and Mg2SiO4And Mg3(PO4)2Micro-arc oxidation film layer, scanning electrodeMirror see fig. 1; the electrolyte comprises 2g/L of trisodium phosphate, 2g/L of sodium silicate and 2g/L of sodium hydroxide.
B. And C, preparing 5% by volume of vinyltrioxysilane into silanized ethanol solution, immersing the pure magnesium obtained in the step A into the solution, and forming a silane layer on the surface of the magnesium, wherein a scanning electron microscope is shown in figure 2.
C. Pyrrole monomer and dexamethasone are prepared to form ethanol organic solutions with the concentrations of 1mol/L and 2mg/mL respectively, and copper chloride is prepared to form an oxidant solution with the concentration of 2 mol/L.
D. And D, immersing the pure magnesium containing the silane layer obtained in the step B into the organic solution obtained in the step C for 10 minutes, then taking out, putting into the oxidant solution obtained in the step C for 10 minutes, repeating the operation for 3 times, and forming a coating with a drug release function on the surface of the magnesium alloy, wherein a scanning electron microscope is shown in figure 3. Characterization of drug release is shown in figure 4.
Example 2:
a method for preparing a coating with a drug release function on the surface of medical magnesium alloy comprises the following steps:
A. after the pure magnesium is polished and cleaned, the pure magnesium is taken as an anode, and the current density is 300mA/cm2Micro-arc oxidation treatment is carried out in the electrolyte under the conditions that the positive voltage is 350V, the negative voltage is 20V, the current frequency is 950Hz, the positive-negative frequency ratio is 1, the positive duty ratio is 30 percent, the negative duty ratio is 10 percent, the reaction time is 23min and the reaction temperature is 35 ℃ to obtain the product containing MgO and Mg2SiO4And Mg3(PO4)2Micro-arc oxidation film layer; the electrolyte comprises 13g/L of trisodium phosphate, 6g/L of sodium silicate and 8g/L of sodium hydroxide.
B. And B, preparing 10% by volume of vinyl trimethoxy silane to form a silanized ethanol solution, and immersing the pure magnesium obtained in the step A into the silanized ethanol solution to form a surface silane layer.
C. Thiophene monomer and dexamethasone are prepared to form glycol organic solution with the concentration of 0.5mol/L and 1mg/mL respectively, and ammonium persulfate is prepared to form oxidant solution with the concentration of 1 mol/L.
D. And D, immersing the pure magnesium obtained in the step B into the organic solution obtained in the step C for 5 minutes, taking out the pure magnesium, putting the pure magnesium into the oxidant solution obtained in the step C for 5 minutes, and repeating the operation for 2 times to form a coating with a drug release function on the surface of the pure magnesium. Characterization of drug release is shown in figure 4.
Example 3:
a method for preparing a coating with a drug release function on the surface of medical magnesium alloy comprises the following steps:
A. after being polished and cleaned, the biomedical binary magnesium alloy is used as an anode, and the current density is 150mA/cm2Micro-arc oxidation treatment is carried out in the electrolyte under the conditions that the positive voltage is 500V, the negative voltage is 30V, the current frequency is 2000Hz, the positive-negative frequency ratio is 2, the positive duty ratio is 50 percent, the negative duty ratio is 15 percent, the reaction time is 40min and the reaction temperature is 50 ℃, so as to obtain the product containing MgO and Mg2SiO4And Mg3(PO4)2Micro-arc oxidation film layer; the electrolyte comprises 25g/L of trisodium phosphate, 10g/L of sodium silicate and 15g/L of sodium hydroxide.
B. And B, preparing 25% by volume of aminopropyltriethyl silane to form a silanized ethanol solution, and immersing the biomedical binary magnesium alloy obtained in the step A into the silanized ethanol solution to form a silane layer on the surface.
C. Acetylene monomer and penicillin are prepared into butanol organic solutions with the concentrations of 0.5mol/L and 4mg/mL respectively, and ammonium persulfate is prepared into oxidant solutions with the concentration of 1.5 mol/L.
D. And D, immersing the biomedical binary magnesium alloy obtained in the step B into the organic solution obtained in the step C for 3 minutes, taking out, putting into the oxidant solution obtained in the step C for 3 minutes, and repeating the operation for 4 times to form a coating with a drug release function on the surface of the magnesium alloy.
Example 4:
the procedure of this example was substantially the same as example 1 except that the concentration of dexamethasone used in example 1 was changed from 2mg/mL to 4 mg/mL.
Example 5:
the procedure of this example is essentially the same as in example 1, except that the polymer monomer used in example 1 is changed from pyrrole to aniline.
Example 6:
the procedure of this example is essentially the same as example 1, except that the polymer monomer used in example 1 is changed from pyrrole to thiophene.
Example 7:
the operation of this example is essentially the same as example 1 except that the polymer monomer used in example 1 is changed from pyrrole to acetylene.
Example 8:
the operation of this example is basically the same as that of example 1 except that the magnesium alloy used in example 1 is replaced with a biomedical ternary magnesium alloy from pure magnesium.
Example 9:
the operation of this example is basically the same as that of example 1 except that the magnesium alloy used in example 1 is replaced with a biomedical quaternary magnesium alloy from pure magnesium.
Example 10:
the operation of this example is basically the same as that of example 1 except that the magnesium alloy used in example 1 is replaced with a biomedical five-element magnesium alloy from pure magnesium.
Example 11:
the procedure of this example is essentially the same as example 1 except that the drug used in example 1 is changed from dexamethasone to penicillin.
Example 12:
the procedure of this example is essentially the same as example 1 except that the drug used in example 1 is replaced by dexamethasone to rapamycin.
Example 13:
the procedure of this example is essentially the same as example 1 except that the drug used in example 1 is replaced by dexamethasone for paclitaxel.
Example 14:
the procedure of this example is essentially the same as example 1 except that the drug used in example 1 is replaced by dexamethasone to metformin hydrochloride.
Example 15:
the operation of this example is essentially the same as example 1 except that the oxidizing agent used in example 1 is changed from cupric chloride to ferric chloride.
Example 16:
the operation of this example is essentially the same as example 1 except that the oxidizing agent used in example 1 is replaced by copper chloride to ammonium persulfate.
Example 17:
the operation of this example is essentially the same as example 1 except that the oxidizing agent used in example 1 is changed from copper chloride to hydrogen peroxide.
Example 18:
the operation of this example is essentially the same as example 1 except that the organic solvent used in example 1 is changed from ethanol to isopropanol.
Example 19:
the operation of this example is essentially the same as example 2 except that the organic solvent used in example 1 is changed from ethylene glycol to propanol.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. A preparation method of a medical magnesium alloy surface drug release functional coating comprises the following steps:
A. using pure magnesium or magnesium alloy as anode, and carrying out micro-arc oxidation in electrolyte to obtain the product containing MgO and Mg2SiO4And Mg3(PO4)2Micro-arc oxidation film layer; the electrolyte comprises 2-25 g/L of trisodium phosphate, 2-10 g/L of sodium silicate and 2-15 g/L of sodium hydroxide;
B. b, immersing the magnesium or magnesium alloy obtained in the step A into a silanization solution prepared by a silane coupling agent to form a silane layer on the surface of the magnesium or magnesium alloy;
C. preparing a polymer monomer, a drug and an organic solvent to form an organic solution, and preparing an oxidant to form a solution; the polymer monomer is one of pyrrole, aniline, acetylene or thiophene;
D. and C, immersing the magnesium or magnesium alloy containing the silane layer obtained in the step B into the organic solution obtained in the step C, taking out the magnesium or magnesium alloy, putting the magnesium or magnesium alloy into the oxidant solution obtained in the step C, and repeating the operation to form a coating with a drug release function on the surface of the magnesium or magnesium alloy.
2. The method for preparing the medical magnesium alloy surface drug release functional coating according to claim 1, wherein the step A further comprises the following steps before micro-arc oxidation: polishing the magnesium alloy, and carrying out ultrasonic cleaning and oil removal by using acetone and ethanol in sequence, wherein the pH value of the electrolyte is 8-12.
3. The method for preparing the medical magnesium alloy surface drug release functional coating according to claim 1, wherein the parameters of the micro-arc oxidation in the step A comprise: the current density is 0.5 to 300mA/cm2The positive voltage is 250-500V, the negative voltage is 5-30V, the current frequency is 200-2000 Hz, the positive-negative frequency ratio is 0.5-2, the positive duty ratio is 10-50%, the negative duty ratio is 10-25%, the reaction time is 5-40 min, and the reaction temperature is 20-50 ℃.
4. The method for preparing the medical magnesium alloy surface drug release functional coating according to claim 1, wherein the concentration of the polymer monomer in the organic solution in the step C is 0.1-1 mol/L, and the concentration of the drug is 1-10 mmol/L; the concentration of the oxidant is 0.1-3 mmol/L, and the organic solvent is one of ethanol, ethylene glycol, propanol, isopropanol or butanol.
5. The method for preparing the medical magnesium alloy surface drug release functional coating according to any one of claims 1 to 4, wherein the magnesium alloy in the step A is one of biomedical binary magnesium alloy, biomedical ternary magnesium alloy, biomedical quaternary magnesium alloy and biomedical quinary magnesium alloy.
6. The method for preparing the medical magnesium alloy surface drug release functional coating according to any one of claims 1 to 4, wherein the silane coupling agent in the step B is one of bis- (gamma-triethoxysilylpropane) tetrasulfide, aminopropyl triethyl silane, vinyltrioxysilane, vinyltrimethoxysilane or vinyltris (beta-methoxyethoxy) silane.
7. The method for preparing the medical magnesium alloy surface drug release functional coating according to any one of claims 1 to 4, wherein the oxidizing agent in the step C is one of copper chloride, ferric chloride, ferrous chloride, silver chloride, ammonium persulfate, molybdenum chloride, or hydrogen peroxide.
8. The method for preparing a medical magnesium alloy surface drug release functional coating according to any one of claims 1 to 4, wherein the drug in step C is one of dexamethasone, rapamycin, penicillin, isoniazid, paclitaxel, fluvastatin, nifedipine or metformin hydrochloride.
9. The method for preparing the medical magnesium alloy surface drug release functional coating according to any one of claims 1 to 4, wherein the number of times of repeating the above operation in the step D is 1 to 5.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007036682A1 (en) * | 2005-06-17 | 2007-04-05 | Nanosphere Limited | Coated microspheres |
| WO2008071047A1 (en) * | 2006-12-14 | 2008-06-19 | Lepu Medical Technology (Beijing) Co., Ltd | Nanoporous drug release structure for drug elute instruments and the preparation method thereof |
| CN102206342A (en) * | 2011-03-31 | 2011-10-05 | 南京大学 | Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer |
| TWI534299B (en) * | 2014-11-21 | 2016-05-21 | 財團法人金屬工業研究發展中心 | A method for processing the surface of magnesium alloy |
| CN106521603A (en) * | 2016-11-22 | 2017-03-22 | 佳木斯大学 | Preparation method of medical pure magnesium surface coupling load inducing bone growth traditional Chinese medicine coating |
| CN108948379A (en) * | 2018-06-20 | 2018-12-07 | 东莞蚂蚁三维科技有限公司 | A kind of preparation method of 3D printing conductive hydrogel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7780838B2 (en) * | 2004-02-18 | 2010-08-24 | Chemetall Gmbh | Method of anodizing metallic surfaces |
| US20080086195A1 (en) * | 2006-10-05 | 2008-04-10 | Boston Scientific Scimed, Inc. | Polymer-Free Coatings For Medical Devices Formed By Plasma Electrolytic Deposition |
-
2019
- 2019-09-17 CN CN201910878710.7A patent/CN110639056B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007036682A1 (en) * | 2005-06-17 | 2007-04-05 | Nanosphere Limited | Coated microspheres |
| WO2008071047A1 (en) * | 2006-12-14 | 2008-06-19 | Lepu Medical Technology (Beijing) Co., Ltd | Nanoporous drug release structure for drug elute instruments and the preparation method thereof |
| CN102206342A (en) * | 2011-03-31 | 2011-10-05 | 南京大学 | Electric conduction polymer and synthesis method thereof and electroactive electrode with surface covered with electric conduction polymer |
| TWI534299B (en) * | 2014-11-21 | 2016-05-21 | 財團法人金屬工業研究發展中心 | A method for processing the surface of magnesium alloy |
| CN106521603A (en) * | 2016-11-22 | 2017-03-22 | 佳木斯大学 | Preparation method of medical pure magnesium surface coupling load inducing bone growth traditional Chinese medicine coating |
| CN108948379A (en) * | 2018-06-20 | 2018-12-07 | 东莞蚂蚁三维科技有限公司 | A kind of preparation method of 3D printing conductive hydrogel |
Non-Patent Citations (7)
| Title |
|---|
| A conductive nanostructured polymer electrodeposited on titanium as a controllable, local drug delivery platform;Sirivisoot Sirinrath等;《Journal of biomedical materials research. Part A》;20111215;第99卷(第4期);全文 * |
| AZ31镁合金表面聚吡咯的化学氧化合成及其耐蚀性能;黄荣等;《物理化学学报》;20110115;第27卷(第1期);全文 * |
| AZ81镁合金表面微弧氧化改性及涂层的药物释放研究;方铭中;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20110615(第6期);全文 * |
| Corrosion resistant properties of polyaniline-acrylic coating on magnesium alloy;Sathiyanarayanan, S等;《APPLIED SURFACE SCIENCE》;20061215;第253卷(第4期);全文 * |
| In Vitro and in Vivo Degradation Behavior and Biocompatibility Evaluation of Microarc Oxidation-Fluoridated Hydroxyapatite-Coated Mg–Zn–Zr–Sr Alloy for Bone Application;Wang, Yansong;《ACS BIOMATERIALS SCIENCE & ENGINEERING》;20190630;第5卷(第6期);全文 * |
| 可降解生物医用镁合金表面智能释药涂层的制备及表征;王岩松;《天津理工大学硕士论文》;20200301;全文 * |
| 钛金属表面基于金属有机骨架功能化涂层的构建;林沙;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20190415(第4期);全文 * |
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