CN102691083B - Electrochemical method for improving blood compatibility of surface of metal material - Google Patents
Electrochemical method for improving blood compatibility of surface of metal material Download PDFInfo
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- CN102691083B CN102691083B CN201210169199.1A CN201210169199A CN102691083B CN 102691083 B CN102691083 B CN 102691083B CN 201210169199 A CN201210169199 A CN 201210169199A CN 102691083 B CN102691083 B CN 102691083B
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Abstract
The invention relates to an electrochemical method for improving the blood compatibility of the surface of a metal material. The electromechanical method comprises the following steps: connecting a metal material to be modified onto a positive electrode of a direct current power supply; immersing the metal material in an aqueous solution containing phenol; and modifying by electrifying; soaking the modified metal material in aqueous solution containing heparin to obtain the metal material with blood compatibility. Compared with a traditional standing coating modification process which has the defects of long modification time, poor attaching power of a coating, non-uniformity in surface and the like, the electromechanical method disclosed by the invention has the advantages that the modification time is greatly shortened and the obtained coating is strong in attaching power and more uniform in surface.
Description
Technical field
The present invention relates to a kind of electrochemical method that improves the blood compatibility of metal material surface.
Background technology
Electrochemical method is to take initiation power and the motivating force that electropotential is polyreaction, makes monomer in electrode surface direct polymerization film forming.Electrochemical method is fairly simple, and it has advantages of that some are unique: (1) polymerization and doping are carried out simultaneously; (2) can generate in electrode previous step the conducting film of self-supporting; (3) by changing polymerization potential, can distinguish easily the redox state of controlling diaphragm; (4) thickness of film can be controlled by electric current and voltage; (5) product is without separating step; (6) on electrode, generating the process of polymkeric substance and the polymkeric substance of generation can study by electrochemistry or spectral method easily, without catalyzer etc., has therefore obtained broad research.Electrochemical method comprises cyclic voltammetry, potentiostatic method, galvanostatic method etc.In electrochemical method, cathode reduction method is because the conductivity of the conducting polymer film obtaining at electrode surface is poor, and film thickness is difficult to surpass 100nm; So study fewerly.Therefore electrochemical method generally refers to anonizing.
Heparin is a kind of acidic mucopolysaccharide, is mainly to be produced by mastocyte and basophilic granulocyte.There is in vivo and in vitro very strong blood coagulation resisting function, therefore clinical, it is widely used as antithrombotics.Heparin is widely used in preventing and treating early treatment and the external anti-freezing of thrombotic disease, disseminated intravascular coagulation clinically.Clinical application and studies show that: heparin, except having anticoagulation, also has multiple biological activity and clinical application.Along with pharmacology and clinical medical progress, the application of heparin constantly expands.
Summary of the invention
The defect existing for prior art, the present invention aims to provide a kind of electrochemical method that improves the blood compatibility of metal material surface, is to material surface, and particularly metallic surface applies phenols and grafting heparin carries out twice-modified method fast.Formerly in electrolyzer, material is immersed in the aqueous solution of phenol, electric polymerization reaction occurs in metallic surface.Its feature is mainly greatly to shorten coating time, and the coating obtaining is more even, fine and close, and sticking power is stronger.Again the material having applied is immersed in heparin solution, obtains the metallic substance of excellent blood compatibility.
For achieving the above object, the present invention adopts following technical scheme:
Improve an electrochemical method for metal material surface blood compatibility, in electrolyzer, metallic substance is immersed containing in the aqueous solution of phenol, at metal material surface generation electric polymerization reaction, then the metallic substance having applied is immersed in heparin solution; Specific embodiment is:
1) adopt 1%Na
2sO
4the aqueous solution, as solvent, takes 0.2 ~ 0.6g phenol under room temperature, be dissolved in solution, and the concentration of solution is 2 ~ 6mg/ml;
2) metallic substance to be coated is immersed in the phenol aqueous solution, at electrolyzer Anodic generation electropolymerization, the required reaction times is 10 ~ 30min;
3) coated metallic substance is immersed in heparin solution, the concentration of heparin solution is 10mg/mL, and the reaction times is 24h, takes out the unnecessary heparin of washing.
Than prior art, the inventive method advantage and effect can be concluded and be described below:
1) electrochemical method rapid and convenient, compares the general moving chemical reaction of several hours, within tens minutes, just can complete.
2) directly there is redox reaction in electrochemical method on electrode, do not need to use extra chemical reagent, the cheap environmental protection of reaction cost.
3) heparin can direct-coupling in coating, without coupling agent, clean environment firendly.Resulting coating adhesion is strong, and surface is more even.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
Fig. 2 is reforming apparatus schematic diagram of the present invention.
Embodiment
As shown in Figure 2, material of the present invention shows the device schematic diagram of modification.Comprise and treat substrate modified 1, containing the aqueous solution 2 and the direct supply 3 of phenols.
As shown in Figure 1, a kind of electrochemical method that improves metal material surface blood compatibility immerses metallic substance in the aqueous solution of phenol in electrolyzer, at metal material surface generation electric polymerization reaction, then the metallic substance having applied is immersed in heparin solution; Specific embodiment is:
1) adopt 1%Na
2sO
4the aqueous solution, as solvent, takes 0.2 ~ 0.6g phenol under room temperature, be dissolved in solution, and the concentration of solution is 2 ~ 6mg/ml;
2) metallic substance to be coated is immersed in the phenol aqueous solution, at electrolyzer Anodic generation electropolymerization, the required reaction times is 10 ~ 30min;
3) coated metallic substance is immersed in heparin solution, the concentration of heparin solution is 10mg/mL, and the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 1
1) adopt 100mL1%Na
2sO
4the aqueous solution, as solvent, is got 0.6g pyrocatechol and is dissolved in wherein, is made into the solution of 6mg/mL;
2) stainless steel substrates is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 10 minutes;
3) the better stainless steel of modification is soaked to sheet not in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 2
1) adopt 100mL1%Na
2sO
4the aqueous solution, as solvent, is got 0.2g pyrocatechol and is dissolved in wherein, is made into the solution of 2mg/mL;
2) stainless steel substrates is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 30 minutes;
3) the better stainless steel substrates of modification is immersed in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 3
1) adopt 100mL1%Na
2sO
4the aqueous solution, as solvent, is got 0.2g pyrocatechol and is dissolved in wherein, is made into the solution of 2mg/mL;
2) titanium sheet is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 30 minutes;
3) the better titanium sheet of modification is immersed in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 4
1) adopt 100mL1%Na
2sO
4the aqueous solution, as solvent, is got 0.4g pyrocatechol and is dissolved in wherein, is made into the solution of 4mg/mL;
2) titanium sheet is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 20 minutes;
3) the better titanium sheet of modification is immersed in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 5
1) adopt the 100mL1%Na2SO4 aqueous solution as solvent, get 0.2g Dopamine HCL and be dissolved in wherein, be made into the solution of 2mg/mL;
2) titanium sheet is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 30 minutes;
3) the better titanium sheet of modification is immersed in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
embodiment 6
1) adopt the 100mL1%Na2SO4 aqueous solution as solvent, get 0.6g Dopamine HCL and be dissolved in wherein, be made into the solution of 6mg/mL;
2) stainless steel substrates is connected on DC power anode, Pt electrode is negative pole, and voltage is 2V, is immersed in the phenol aqueous solution electrochemical coating 10 minutes;
3) the better stainless steel of modification is soaked to sheet not in 10mg/mL heparin solution, the reaction times is 24h, takes out the unnecessary heparin of washing.
Claims (1)
1. an electrochemical method that improves metal material surface blood compatibility, it is characterized in that, in electrolyzer, metallic substance is immersed containing in the aqueous solution of phenol, at metal material surface generation electric polymerization reaction, then the metallic substance having applied is immersed in heparin solution; Specific embodiment is:
1) adopt the Na that concentration is 1%
2sO
4the aqueous solution, as solvent, takes 0.2 ~ 0.6g phenol under room temperature, be dissolved in solution, and the concentration of solution is 2 ~ 6mg/ml; Described phenol: pyrocatechol or Dopamine HCL;
2) metallic substance to be coated is immersed in the phenol aqueous solution, at electrolyzer Anodic generation electropolymerization, the required reaction times is 10 ~ 30min;
3) coated metallic substance is immersed in heparin solution, the concentration of heparin solution is 10mg/mL, and the reaction times is 24h, takes out the unnecessary heparin of washing.
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| CN201210169199.1A CN102691083B (en) | 2012-05-29 | 2012-05-29 | Electrochemical method for improving blood compatibility of surface of metal material |
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| CN201210169199.1A CN102691083B (en) | 2012-05-29 | 2012-05-29 | Electrochemical method for improving blood compatibility of surface of metal material |
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| CN102691083B true CN102691083B (en) | 2014-12-03 |
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| CN104060311A (en) * | 2014-06-16 | 2014-09-24 | 浙江大学 | Method for functionally modifying surface of conductive substrate |
| KR102239581B1 (en) | 2015-01-26 | 2021-04-14 | 삼성디스플레이 주식회사 | Display apparatus |
Citations (4)
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| CN1543362A (en) * | 2002-05-09 | 2004-11-03 | ����Ī�����ɷ�����˾ | Medical products comprising a haemocompatible coating, production and use thereof |
| CN101724841A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing polymer/silver composite membrane by depositing dopamine |
| US20100330025A1 (en) * | 2002-07-19 | 2010-12-30 | Northwestern University | Surface Independent, Surface-Modifying, Multifunctional Coatings and Applications Thereof |
| CN102000658A (en) * | 2010-12-15 | 2011-04-06 | 西南交通大学 | Polydopamine-based biofunction modification method |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543362A (en) * | 2002-05-09 | 2004-11-03 | ����Ī�����ɷ�����˾ | Medical products comprising a haemocompatible coating, production and use thereof |
| US20100330025A1 (en) * | 2002-07-19 | 2010-12-30 | Northwestern University | Surface Independent, Surface-Modifying, Multifunctional Coatings and Applications Thereof |
| CN101724841A (en) * | 2008-10-10 | 2010-06-09 | 北京化工大学 | Method for preparing polymer/silver composite membrane by depositing dopamine |
| CN102000658A (en) * | 2010-12-15 | 2011-04-06 | 西南交通大学 | Polydopamine-based biofunction modification method |
Non-Patent Citations (8)
| Title |
|---|
| "Characterization of Dopamine-Melanin Growth on Silicon Oxide";Falk Bernsmann et al.;《J. Phys. Chem. C》;20090414;第113卷(第19期);第8234-8242页 * |
| "Enhancement of Blood Compatibility of Poly(urethane) Substrates by Mussel-Inspired Adhesive Heparin Coating";Inseong You et.al.;《Bioconjugate Chemistry》;20110616;第22卷;第1264-1269 * |
| "Mussel-Inspired Surface Chemistry for Multifunctional Coatings";Haeshin Lee et al.;《Science》;20071019;第318卷;第8234-8242页 * |
| "多巴胺的自聚-附着行为与膜表面功能化";徐又一;《膜科学与技术》;20110630;第31卷(第3期);第32-38页 * |
| Falk Bernsmann et al.."Characterization of Dopamine-Melanin Growth on Silicon Oxide".《J. Phys. Chem. C》.2009,第113卷(第19期),第8234-8242页. * |
| Haeshin Lee et al.."Mussel-Inspired Surface Chemistry for Multifunctional Coatings".《Science》.2007,第318卷第8234-8242页. * |
| Inseong You et.al.."Enhancement of Blood Compatibility of Poly(urethane) Substrates by Mussel-Inspired Adhesive Heparin Coating".《Bioconjugate Chemistry》.2011,第22卷第1264-1269. * |
| 徐又一."多巴胺的自聚-附着行为与膜表面功能化".《膜科学与技术》.2011,第31卷(第3期),第32-38页. * |
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