CN107313092A - It is a kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface - Google Patents

It is a kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface Download PDF

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CN107313092A
CN107313092A CN201610270581.XA CN201610270581A CN107313092A CN 107313092 A CN107313092 A CN 107313092A CN 201610270581 A CN201610270581 A CN 201610270581A CN 107313092 A CN107313092 A CN 107313092A
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medical metal
electro
metal material
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medicine
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CN107313092B (en
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鲁雄
谢超鸣
王振铭
韩璐
胥杰龙
甘东林
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Southwest Jiaotong University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/02Electrolytic coating other than with metals with organic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/34Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dermatology (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biomedical Technology (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention discloses a kind of method for being prepared on medical metal surface and having Electro-stimulate response composite microcapsule, the invention belongs to technical field of biological materials.The electrolyte that DOPA amine monomers, conductive high polymer monomer and electronegative medicine are made into by the present invention is accessed in three-electrode electro Chemical system, using the medical metal material with microsphere template array as working electrode, the microsphere template for obtaining the compound parcel of dopamine, conducting polymer and medicine is deposited on medical metal surface, finally the coated medical metal material of surface recombination micro-capsule will be made after the microballoon all dissolving.The present invention realizes that medical metal material surface is modified, and prepares the conductive composite microcapsule of a layer function on its surface, the composite microcapsule can not only by electric signal Drug controlled release and by electric signal can direct regulation and control stem cell break up;Medicine irritation is mutually cooperateed with physical stimulation, the dependence and its side effect to medicine has both been reduced, the self-bone grafting ability of medical metal is also improved.

Description

It is a kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface
Technical field
It is combined the invention belongs to technical field of biological materials, more particularly to a kind of prepared on medical metal surface with Electro-stimulate response The method of micro-capsule.
Background technology
Because the Cranial defect that many reasons are caused is clinically very common, and the Bone Defect Repari of large area and heavy burden Bone Defect Repari are clinical The problem for the treatment of is often faced.Medical metal material is main heavy burden bone renovating material, and it is the gold that a class is used as biomaterial Category or alloy, medical metal material is a class bio-inert material, with higher mechanical strength and anti-fatigue performance, with good Good biomechanical property and the physical property of correlation, but the bioactivity of medical metal material is its in needs The performance indications of raising.
The mankind have been enter into the epoch with high demand to organism, it would be highly desirable to develop more active biomaterials suitable for implant site. Current bio-medical material is combined to multiple material, the direction of performance complement is developed.Process for modifying surface is in biomaterial Using the surface quality for effectively increasing medical metal material, the implantation effect of implant is improved.Therefore, it is modified using surface To improve the development trend that the performance of medical metal material would is that medical metal material from now on.
All the time, the self-bone grafting scarce capacity of medical metal implantation support is one of clinical urgent problem to be solved at this stage.Mesh Before, the research for solving this problem is concentrated mainly on imparting implantation one layer of medicament controlled-release coating with self-bone grafting ability of rack surface, Drug degradation polysaccharide coatings are such as loaded with, its medicine is discharged as polysaccharide is degraded.But, this traditional insoluble drug release body There are many limitations, such as can not accurately control to release drug dose, and medicine easily loses activity in vivo in system.
Compared with conventional medicament delivery systme, respond (such as light, electricity, magnetic) by outside stimulus to control medicine when specific Between, ad-hoc location discharge the given dose drug molecule pre-set, using the timing of medicine, fixed point, quantitative control release, Have become the new trend of organizational project and insoluble drug release development.Current most of medicine-releasing systems can only realize steady release, strictly Saying is a kind of drug sustained release system and is not controlled drug delivery system truly, and drug sustained release system can not typically realize agent The change of amount, therefore real control can not be realized.
It is furthermore pointed out that although drug therapy is an indispensable part in tissue repair, but side effects of pharmaceutical drugs The problem of being also a worth worry.Such as cancer therapy drug can not only kill cancer cell, while may also be to tumour surrounding normal Cell damage, and the resistance to the action of a drug.Single physical treatment (such as electricity treatment) can avoid the influence of drug side-effect, but It is that its therapeutic effect is slower.
The content of the invention
The present invention is answered in order to overcome the shortcomings of the prior art, providing a kind of prepared on medical metal surface with Electro-stimulate response The method for closing micro-capsule.The present invention is realized to be modified to medical metal material surface, the conductive medicine of a layer function is prepared on its surface micro- Capsule, the composite microcapsule can not only by electric signal Drug controlled release and by electric signal can direct regulation and control stem cell break up. Under the conditions of same treatment, medicine irritation is mutually cooperateed with physical stimulation, the dependence and its side effect to medicine has both been reduced, Also Bone Defect Repari is effectively accelerated.
The present invention is to be achieved through the following technical solutions:
It is a kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface, comprise the following steps:
A, medical metal material surface formed microsphere template array it is standby;
B, DOPA amine monomers, conductive high polymer monomer and electronegative medicine prepared to form electrolyte, the dopamine list The concentration of body is 1~20mmol/L, and the conductive high polymer monomer concentration is 0.1~0.5mol/L, the electronegative medicine Concentration is 1~10mmol/L;
C, by step B electrolyte access three-electrode electro Chemical system in, the working electrode, reference electrode with to electrode Current loop is constituted, wherein, using the medical metal material with microsphere template as working electrode, deposited on medical metal material Obtain the microsphere template of the compound parcel of dopamine, conducting polymer and medicine;
D, the obtained medical metal materials of step C are soaked in organic solvent, treat that the microballoon on medical metal material surface is whole After dissolving, the coated medical metal material of surface micro-capsule is made, the micro-capsule is combined by dopamine, conducting polymer and medicine Formed.
In the preparation method of composite microcapsule coating medical metal material of the present invention, the step A is specially:By medical metal After material is cleaned by ultrasonic with acetone and distilled water successively, microspheres solution is added dropwise on medical metal material surface, surface is made after drying Form the medical metal material of microsphere template array.
In the preparation method of composite microcapsule coating medical metal material of the present invention, with microsphere template in the step C Medical metal material is working electrode, and working electrode is connected with electrochemical workstation, in the oxidation that voltage range is 0.8~2V Under the conditions of deposit 0.5~2 hour, be made dopamine, conducting polymer and medicine composite coating parcel microsphere template.
In the preparation method of composite microcapsule coating medical metal material of the present invention, described microballoon is polystyrene microsphere or two Silicon oxide microsphere.
In the preparation method of composite microcapsule of the present invention coating medical metal material, described conductive high polymer monomer is pyrroles, Any of aniline, acetylene and thiophene.
In the preparation method of composite microcapsule coating medical metal material of the present invention, the described medicine with negative electricity is mould Any of element, nifedipine, dexamethasone, N'-Dimethylguanylguanidine hydrochloride and isoniazid.
In the preparation method of composite microcapsule coating medical metal material of the present invention, described medical metal material is titanium, titanium is closed Any of gold, cobalt alloy, nickel alloy, stainless steel and magnesium alloy.
In the preparation method of composite microcapsule coating medical metal material of the present invention, described is titanium, titanium alloy, cobalt to electrode Any of alloy, nickel alloy, stainless steel and platinum.
In the preparation method of composite microcapsule coating medical metal material of the present invention, described reference electrode is saturation calomel electricity It is any in pole, hydrogen electrode, Ag/AgCl electrodes and Hg/HgO electrodes.
In the preparation method of composite microcapsule coating medical metal material of the present invention, described organic solvent is tetrahydrofuran, first It is any in benzene, chloroform, dichloromethane, vinegar butyl ester and ethylbenzene.
The innovative point of the present invention is:
1. the composite microcapsule that the present invention is prepared on medical metal surface has um porous structure in configuration aspects, it can not only carry The load capacity of high medicine and the microenvironment that extracellular matrix can be similar to for the raising of internal cell, are conducive to cell to breed and break up.
2. the present invention is using dopamine as pharmaceutical carrier, conducting polymer master is doped to simultaneously with medicine under the conditions of electrochemical oxidation Composite microcapsule is formed in chain and is attached to medical metal material surface;Dopamine (DA) is main in adhesion protein because its structure has concurrently Composition L-3,4- dihydroxyphenylalanine (DOPA) and a small amount of lysine residue, are proved to superpower Adhesion property, and Dopamine contain a large amount of active function groups can be realized while pharmaceutical carrier is made it is well attached in microsphere template surface.Meanwhile, Dopamine (DA) formation poly-dopamine (PDA) process is simple, dopamine can easily be dissolved in aqueous oxygen aoxidize after And trigger from poly- cross-linking reaction, it can form the poly-dopamine composite bed of close attachment in a kind of substantially any solid material surface; Poly-dopamine (PDA) has good biocompatibility, it is possible to achieve medical metal material surface is modified, and improves material surface Hydrophily, so as to be conducive to sticking for cell, can improve the biocompatibility to osteocyte;Poly-dopamine (PDA) surface Containing a large amount of catechols and amino isoreactivity group, the fixation of medicine is also beneficial to;In addition, poly-dopamine (PDA) is for calcium Ion has stronger active force to realize the calcification of material surface, so as to promote Bone Defect Repari to treat.
3. the composite microcapsule that the present invention is prepared on medical metal surface has Electro-stimulate response ability;Due to being used in the present invention Conducting polymer there is redox characteristic, by taking polypyrrole as an example:Polypyrrole is alternately to be arranged with carbon-carbon single bond and carbon-carbon double bond The five-ring heterocycles molecule of the conjugated structure of row, conjugated polymer has a stronger conductive tendency, thus have to external electric signal compared with Good response;The present invention prepares polypyrrole using pyrrole monomer by electrochemical polymerization mode, can be with by the adjustment of preparation parameter Prepare the different function polypyrrole material of properity.According to the redox characteristic of polypyrrole:In electrochemical oxidation condition Under, it is electrical that polypyrrole main chain positively charged needs electronegative drug molecule doping to neutralize its;And under the conditions of electrochemical reduction, gather Pyrroles's main chain is not charged, so electronegative drug molecule will be discharged.It therefore, it can by controlling the big of recovery voltage The dosage of small next accurate Drug controlled release.
4. the composite microcapsule that the present invention is prepared on medical metal surface is because conductive containing conducting polymer, when to micro- When capsule applies voltage, electric signal can be delivered to the cell sticked on micro-capsule by micro-capsule, finally by electric signal regulating cell Differentiation, reaches and further improves therapeutic effect with drug therapy synergy.
Compared to prior art, the beneficial effects of the present invention are:
Medical metal material surface is modified 1. the present invention is realized, the biocompatibility of medical metal material is improved, especially overcomes The self-bone grafting scarce capacity that existing medical metal implantation support is present, so as to improve the performance of medical metal material.
2. reach that Drug controlled release, raising utilization ratio of drug, reduction body are long-term the invention provides a kind of new medicine-releasing system The drug resistance triggered in high drug concentration;The composite microcapsule coating medical metal material that the present invention is prepared is sharp over the course for the treatment of The purpose that Drug controlled release is reached by adjusting voltage can be realized with the redox characteristic of conducting polymer.
3. the composite microcapsule that the present invention is prepared is coated with medical metal material under the conditions of same treatment by medicine irritation and physical stimulation Mutually collaboration, had both reduced the dependence and its side effect to medicine, and the exclusive advantage of physical treatment had also been played, so that effectively Accelerate Bone Defect Repari.
Brief description of the drawings
Fig. 1 for preparation method of the present invention step A in medical metal material surface microsphere template array scanning Electronic Speculum schematic diagram.
Fig. 2 dopamines made from the step C of preparation method of the present invention, conducting polymer and the composite microcapsule coating of medicine formation Microsphere template ESEM schematic diagram.
Fig. 3 for preparation method of the present invention step D in using organic solvent removing microsphere template after obtain dopamine, conductive polymer The ESEM schematic diagram on the composite microcapsule coating medical metal material surface of son and medicine formation.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings:
Embodiment 1:
A kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface, it is comprised the following steps that:
A, by medical titanium after over cleaning, its surface be added dropwise polystyrene microsphere solution, dry after in medical metal material table Face formed polystyrene microsphere template, will through the above way obtained medical titanium it is standby;
B, DOPA amine monomers, pyrrole monomer and dexamethasone be configured to electrolyte:First by DOPA amine monomers and dexamethasone Mixing, after it fully reacts, adds pyrrole monomer.In the electrolyte, DOPA amine monomers are 1mmol/L, Bi Kadan Body 0.1mol/L, the concentration of dexamethasone is 1mmol/L.
C, the electrolyte that B is walked is put into three-electrode electro Chemical system electrolytic cell:Medical titanium with polystyrene microsphere template For working electrode, platinum plate is that saturated calomel electrode is reference electrode to electrode.Deposited in the case where voltage is 0.8V oxidizing condition 0.5 hour, obtained on medical titanium surface by the polystyrene microsphere template of the compound parcel of dopamine, polypyrrole and dexamethasone.
D, it will obtain medical titanium after C step depositions and be soaked in tetrahydrofuran, after after its surface polystyrene microsphere all dissolving The medical titanium of composite microcapsule is formed by dopamine, polypyrrole and dexamethasone to surface.
Embodiment 2:
A kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface, it is comprised the following steps that:
A, by medical titanium alloy after over cleaning, its surface be added dropwise polystyrene microsphere solution, dry after in medical metal material Expect surface formed polystyrene microsphere template, will through the above way obtained medical titanium alloy it is standby;
B, DOPA amine monomers, thiophene monomer and chondroitin sulfate be configured to electrolyte:It is first that DOPA amine monomers and sulfuric acid is soft Ossein is mixed, and after it fully reacts, adds thiophene monomer.In the electrolyte, dopamine monomer concentration be 20mmol/L, The concentration of thiophene is 0.5mol/L, and the concentration of dexamethasone is 10mmol/L.
C, the electrolyte that B is walked is put into three-electrode electro Chemical system electrolytic cell:Medical titanium with polystyrene microsphere template Alloy is working electrode, and platinum plate is that saturated calomel electrode is reference electrode to electrode.In voltage under 2V oxidizing condition Deposition 2 hours, obtains micro- by the polystyrene of the compound parcel of dopamine, polythiophene and chondroitin sulfate on medical titanium alloy surface Ball template.
D, it will obtain medical titanium alloy after C step depositions and be soaked in dichloromethane, and treat that its surface polystyrene microsphere will all dissolve The medical titanium alloy that surface is formed composite microcapsule by dopamine, polythiophene and chondroitin sulfate is obtained afterwards.
Embodiment:3:
A kind of to prepare the method with Electro-stimulate response composite microcapsule on medical metal surface, it is comprised the following steps that:
A, by medical stainless steel after over cleaning, its surface be added dropwise polystyrene microsphere solution, dry after in medical stainless steel Surface formed polystyrene microsphere template, will through the above way obtained medical stainless steel it is standby;
B, DOPA amine monomers, ethane monomer and penicillin is configured to electrolyte:First DOPA amine monomers are mixed with penicillin, After it fully reacts, ethane monomer is added.In the electrolyte, dopamine monomer concentration is 10mmol/L, ethane monomer Concentration be 0.3mol/L, the concentration of penicillin is 5mmol/L.
C, the electrolyte that B is walked is put into three-electrode electro Chemical system electrolytic cell:With polystyrene microsphere template it is medical not Rust steel is working electrode, and platinum plate is that saturated calomel electrode is reference electrode to electrode.In voltage under 1.5V oxidizing condition Deposition 1 hour, is obtained on medical stainless steel surface by the polystyrene microsphere mould of the compound parcel of dopamine, polyacetylene and penicillin Plate.
D, it will obtain medical stainless steel after C step depositions and be soaked in toluene, after after its surface polystyrene microsphere all dissolving The medical stainless steel of composite microcapsule is formed by dopamine, polyacetylene and penicillin to surface.
Embodiment 4:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the conductive high polymer monomer used in example 1 by pyrroles Change aniline into.
Embodiment 5:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the conductive high polymer monomer used in example 1 by pyrroles Change acetylene into.
Embodiment 6:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the conductive high polymer monomer used in example 1 by pyrroles Change thiophene into.
Embodiment 7:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the medical metal material used in example 1 by medical titanium Change medical titanium alloy into.
Embodiment 8:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the medical metal material used in example 1 by medical titanium Change medical stainless steel into.
Embodiment 9:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the medical metal material used in example 1 by medical titanium Change medical magnesium alloy into.
Embodiment 10:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the electronegative medicine used in example 1 by ground plug rice Pine changes penicillin into.
Embodiment 11:
The operation of the present embodiment is substantially the same manner as Example 1, simply by the electronegative medicine used in example 1 by ground plug rice Pine changes chondroitin sulfate into.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any to be familiar with this skill The personage of art all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Therefore, such as Those of ordinary skill in the art without departing from disclosed spirit with completed under technological thought all etc. Modifications and changes are imitated, should be covered by the claim of the present invention.

Claims (10)

1. a kind of prepare the method with Electro-stimulate response composite microcapsule on medical metal surface, it is characterised in that including following step Suddenly:
A, medical metal material surface formed microsphere template array it is standby;
B, DOPA amine monomers, conductive high polymer monomer and electronegative medicine prepared to form electrolyte, the DOPA amine monomers Concentration be 1~20mmol/L, the conductive high polymer monomer concentration be 0.1~0.5mol/L, the electronegative medicine it is dense Spend for 1~10mmol/L;
C, by step B electrolyte access three-electrode electro Chemical system in, wherein, working electrode with to electrode constitute electric current return Road, working electrode and reference electrode constitute voltage circuit, using the medical metal material with microsphere template as working electrode, in doctor The microsphere template of the compound parcel of dopamine, conducting polymer and medicine is obtained with deposition on metal material;
D, the obtained medical metal materials of step C are soaked in organic solvent, treat that the microballoon on medical metal material surface is all molten Xie Hou, is made the coated medical metal material of surface micro-capsule, the micro-capsule is by dopamine, conducting polymer and medicine complex Into.
2. it is according to claim 1 it is a kind of medical metal surface prepare with Electro-stimulate response composite microcapsule method, its It is characterised by, the step A is specially:After medical metal material is cleaned by ultrasonic with acetone and distilled water successively, in medical gold Belong to material surface and microspheres solution is added dropwise, the medical metal material that surface forms microsphere template array is made after drying.
3. it is according to claim 1 it is a kind of medical metal surface prepare with Electro-stimulate response composite microcapsule method, its It is characterised by, is 0.8~2V in voltage range using the medical metal material with microsphere template as working electrode in the step C Oxidizing condition under deposit 0.5~2 hour, dopamine, the microsphere template of the compound parcel of conducting polymer and medicine is made.
It is micro- that 4. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that described microballoon is polystyrene microsphere or silicon dioxide microsphere.
It is micro- that 5. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that described conductive high polymer monomer is any of pyrroles, aniline, acetylene and thiophene.
It is micro- that 6. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that the described medicine with negative electricity is penicillin, nifedipine, dexamethasone, N'-Dimethylguanylguanidine Any of hydrochloride and isoniazid.
It is micro- that 7. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that described medical metal material is titanium, titanium alloy, cobalt alloy, nickel alloy, stainless steel and magnesium Any of alloy.
It is micro- that 8. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that described is times in titanium, titanium alloy, cobalt alloy, nickel alloy, stainless steel and platinum to electrode It is a kind of.
It is micro- that 9. one kind according to any one of claim 1 to 3 in the preparation of medical metal surface there is Electro-stimulate response to be combined The method of capsule, it is characterised in that described reference electrode is saturated calomel electrode, hydrogen electrode, Ag/AgCl electrodes and Hg/HgO It is any in electrode.
10. a kind of prepared on medical metal surface according to any one of claim 1 to 3 is combined with Electro-stimulate response The method of micro-capsule, it is characterised in that described organic solvent be tetrahydrofuran, toluene, chloroform, dichloromethane, vinegar butyl ester and It is any in ethylbenzene.
CN201610270581.XA 2016-04-27 2016-04-27 A method of on medical metal surface, preparation has Electro-stimulate response composite microcapsule Expired - Fee Related CN107313092B (en)

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CN114250485A (en) * 2021-11-26 2022-03-29 中国华能集团清洁能源技术研究院有限公司 Nickel-molybdenum-iron hydrogen evolution electrode with ordered porous structure, preparation method and application

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