CN101161295A - Method for modifying medical metallic grafting body surface collagen by galvano-chemistry method - Google Patents
Method for modifying medical metallic grafting body surface collagen by galvano-chemistry method Download PDFInfo
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- CN101161295A CN101161295A CNA2007101565517A CN200710156551A CN101161295A CN 101161295 A CN101161295 A CN 101161295A CN A2007101565517 A CNA2007101565517 A CN A2007101565517A CN 200710156551 A CN200710156551 A CN 200710156551A CN 101161295 A CN101161295 A CN 101161295A
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Abstract
The present invention discloses a method for modifying the surface collagen of the medical metal graft with electrochemical method. The method uses the medical metal graft as a working electrode, platinum as a reference electrode, and the collagen molecules are self-assembled to collagen fiber with the electrode reaction and adhered to the surface of the medical metal graft to form the collagen fiber layer in the electrolyte solution dissolved with collagen molecules. The collagen which works as the essential component of the cell epimatrix can effectively increase the bioavailability and bioactivity on the surface of the medical metal. The collagen modifying medical metal graft obtained by the method of the invention settles the disadvantages of limited surface bioactivity of the commercial medical metal biological graft, not facilitating the restoring of the tissue and long curing time, etc. The invention has the advantages of simple preparing technique, highly effective and easy industrialization.
Description
Technical field
The present invention relates to a kind of as hard tissue repair or alternate a kind of electrochemical process method to collagen modification of medical metal implant surface.
Background technology
Medical metal material, has been widely used in clinical treatment orthopaedics, dentistry etc. and has answered tissue injury or disease owing to have excellent biological compatibility and excellent mechanical property as titanium and alloy, vitallium and medical stainless steel etc.Adopt plasma spray coating process to prepare hydroxyapatite coating layer in tooth section metal surface as Chinese patent CN1064610, Chinese patent CN1316274 adopts strike to prepare hydroxyapatite coating layer etc.But simple hydroxyapatite coating layer biological activity is limited, and this makes implant combine slowly with osseous tissue in vivo, and healing period is long, poor effect.Utilize electrochemical reaction to produce the pH gradient by the electrolyte solution around metallic matrix, for the tropocollagen molecule self assembly provides reaction power and microenvironment, obtaining the surface of collagen modification, is to strengthen medical transplant material biological activity, accelerates the Perfected process of early stage healing speed.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts electrochemical method to collagen modification of medical metal implant surface,, optimize its clinical practice usefulness, shorten healing time to improve the medical metal surface bioactive.
With the method for electrochemical process, may further comprise the steps collagen modification of medical metal implant surface:
1) collagen being added pH value is in 1～4 the acid solution, stirring and dissolving, and the preparation collagen concentration is the A solution of 0.05g/L～5.0g/L and places under 4 ℃;
2) add soluble-salt in A solution, form B solution, the concentration that makes soluble-salt in the B solution is 0.05M～0.3M;
3) pH value of adjusting B solution is 3.5～5.0, as electrolyte solution;
4) in electrochemical depositer, as negative electrode, platinum is anode with medical metal implant, and saturated calomel electrode or silver chloride electrode are that reference electrode immerses above-mentioned electrolyte solution, the electrolyte solution temperature is 18 ℃～50 ℃, and operating distance is 1cm～20cm between negative electrode and anode;
5) adopt constant current or constant voltage mode to deposit in the medical transplant surface electrical, the size of current of constant current mode is 0.5mA～100mA, the voltage of constant voltage mode is 1V～30V, sedimentation time is 0.25h～24h, reaction finishes the back and takes out the medical metal implant cleaning, and dry back obtains the medical metal implant of surface collagen modification.
Among the present invention, said acid solution can be hydrochloric acid or acetum.Said soluble-salt can be sodium chloride, Chile saltpeter, potassium chloride or potassium nitrate.Said medical metal implant can be titanium, titanium alloy, vitallium, cochrome, medical stainless steel or medical metal implant with coating.Said coating can be hydroxyapatite coating layer, fluoridated hydroxyapatite coating or coating of titanium dioxide.
The present invention adopts electrochemical method, in the tart electrolyte solution that is dissolved with collagen protein, can make medical metal material by electrode reaction around the topical solutions pH value raise, and it is whole acid not influence electrolyte solution.The solution pH value raises and makes dissolved collagen gelation around the medical metal material, and promptly tropocollagen molecule is self-assembled into and is collagen fiber.The local pH value variation that the present invention forms by electrode reaction helps collagen fiber and is attached to the medical metal material surface, forms collagen fiber layer.Collagen fiber are main components of extracellular matrix, and the present invention has improved the medical metal surface bioactive to the surface collagen modification of medical metal, help adhesion and the tissue repair and the growth of cell.Medical metal material surface collagen method of modifying provided by the invention is simple, and is efficient, is easy to industrialization.
Description of drawings
Accompanying drawing be the present invention adopt electrochemical process to titanium alloy biomaterial surface collagen modification the SEM photo.
The specific embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
Collagen is added in the hydrochloric acid solution, and the hydrochloric acid solution pH value is 1, stirring and dissolving, and the preparation collagen concentration is the A solution of 5.0g/L and places 4 ℃.In A solution, add sodium chloride, form B solution, make that sodium chloride concentration is 0.3M in the B solution.The pH value of regulating B solution with ammonia spirit is 3.5, as electrolyte solution.In electrochemical depositer, be negative electrode with the medical titanium alloy transplant, platinum is anode, and saturated calomel electrode is that reference electrode immerses electrolyte solution, and the electrolyte solution temperature is 18 ℃, and operating distance is 2cm between negative electrode and anode.Adopt constant current mode in medical transplant surface electrical deposition, size of current is 0.5mA, and sedimentation time is 1h.Reaction finishes the back and takes out the cleaning of medical titanium alloy transplant, and dry back obtains the medical titanium alloy transplant of surface collagen modification.See accompanying drawing, adhere to collagen fiber layer at the titanium alloy biomaterial surface.
Embodiment 2
Collagen is added in the acetum, and the acetum pH value is 2, stirring and dissolving, and the preparation collagen concentration is the A solution of 1g/L and places 4 ℃.In A solution, add Chile saltpeter, form B solution, make that sodium nitrate concentration is 0.05M in the B solution.The pH value of regulating B solution with sodium hydroxide solution is 4, as electrolyte solution.In electrochemical depositer, be negative electrode with the medical stainless steel transplant, platinum is anode, and silver chloride electrode is that reference electrode immerses electrolyte solution, and the electrolyte solution temperature is 18 ℃, and operating distance is 20cm between negative electrode and anode.Adopt constant voltage mode in medical transplant surface electrical deposition, voltage swing is 30V, and sedimentation time is 24h.Reaction finishes the back and takes out the medical stainless steel cleaning, and dry back obtains the medical stainless steel transplant of surface collagen modification.
Embodiment 3
Collagen is added in the hydrochloric acid solution, and the hydrochloric acid solution pH value is 4, stirring and dissolving, and the preparation collagen concentration is the A solution of 0.3g/L and places 4 ℃.In A solution, add potassium chloride, form B solution, make that potassium chloride concentration is 0.1M in the B solution.The pH value of regulating B solution with Tris buffer solution is 5, as electrolyte solution.In electrochemical depositer, be negative electrode with medical vitallium transplant, platinum is anode, and silver chloride electrode is that reference electrode immerses electrolyte solution, and the electrolyte solution temperature is 50 ℃, and operating distance is 1cm between negative electrode and anode.Adopt constant voltage mode in medical transplant surface electrical deposition, voltage swing is 3V, and sedimentation time is 2h.Reaction finishes the back and takes out medical vitallium transplant cleaning, and dry back obtains the medical vitallium transplant of surface collagen modification.
Embodiment 4
Collagen is added in the acetum, and the acetum pH value is 2, stirring and dissolving, and the preparation collagen concentration is the A solution of 0.5g/L and places 4 ℃.In A solution, add potassium nitrate, form B solution, make that potassium nitrate concentration is 0.2M in the B solution.The pH value of regulating B solution with potassium hydroxide solution is 4.5, as electrolyte solution.In electrochemical depositer, to have fluoridated hydroxyapatite coating metal transplant be negative electrode with medical, and platinum is anode, and saturated calomel electrode is that reference electrode immerses electrolyte solution, the electrolyte solution temperature is 40 ℃, and operating distance is 2.5cm between negative electrode and anode.Adopt constant current mode in medical transplant surface electrical deposition, size of current is 10mA, and sedimentation time is 4h.Reaction finishes the back and takes out the medical transplant cleaning, and dry back obtains the medical metal implant of surface collagen modification.
Claims (5)
1. electrochemical process is characterized in that the method for collagen modification of medical metal implant surface: may further comprise the steps:
1) collagen being added pH value is in 1～4 the acid solution, stirring and dissolving, and the preparation collagen concentration is the A solution of 0.05g/L～5.0g/L and places under 4 ℃;
2) add soluble-salt in A solution, form B solution, the concentration that makes soluble-salt in the B solution is 0.05 M～0.3M;
3) pH value of adjusting B solution is 3.5～5.0, as electrolyte solution;
4) in electrochemical depositer, as negative electrode, platinum is anode with medical metal implant, and saturated calomel electrode or silver chloride electrode are that reference electrode immerses above-mentioned electrolyte solution, the electrolyte solution temperature is 18 ℃～50 ℃, and operating distance is 1cm～20cm between negative electrode and anode;
5) adopt constant current or constant voltage mode to deposit in the medical transplant surface electrical, the size of current of constant current mode is 0.5mA～100mA, the voltage of constant voltage mode is 1V～30V, sedimentation time is 0.25h～24h, reaction finishes the back and takes out the medical metal implant cleaning, and dry back obtains the medical metal implant of surface collagen modification.
2. electrochemical process according to claim 1 is characterized in that to the method for collagen modification of medical metal implant surface said acid solution is hydrochloric acid or acetum.
3. electrochemical process according to claim 1 is characterized in that to the method for collagen modification of medical metal implant surface said soluble-salt is sodium chloride, Chile saltpeter, potassium chloride or potassium nitrate.
4. electrochemical process according to claim 1 is characterized in that to the method for collagen modification of medical metal implant surface said medical metal implant is the medical metal implant of titanium, titanium alloy, vitallium, cochrome, medical stainless steel or biologically active coating.
5. electrochemical process according to claim 4 is characterized in that to the method for collagen modification of medical metal implant surface said bioactivity coatings is hydroxyapatite coating layer, fluoridated hydroxyapatite coating or coating of titanium dioxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101565517A CN101161295A (en) | 2007-11-08 | 2007-11-08 | Method for modifying medical metallic grafting body surface collagen by galvano-chemistry method |
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| CNA2007101565517A CN101161295A (en) | 2007-11-08 | 2007-11-08 | Method for modifying medical metallic grafting body surface collagen by galvano-chemistry method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041976A (en) * | 2012-12-25 | 2013-04-17 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
| CN110331124A (en) * | 2019-06-14 | 2019-10-15 | 浙江大学 | A kind of electric polypyrrole/extracellular matrix laminated film and preparation method thereof |
| CN114808081A (en) * | 2022-01-27 | 2022-07-29 | 华东理工大学 | Short-distance oriented amorphous collagen material capable of being stripped from electrode and electrochemical preparation method thereof |
| CN115518206A (en) * | 2022-10-18 | 2022-12-27 | 华中科技大学同济医学院附属协和医院 | Self-mineralized GBR film and preparation method thereof |
| WO2023142599A1 (en) * | 2022-01-27 | 2023-08-03 | 华东理工大学 | Preparation method for collagen material stripped from electrode, and use of collagen material |
-
2007
- 2007-11-08 CN CNA2007101565517A patent/CN101161295A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041976A (en) * | 2012-12-25 | 2013-04-17 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
| CN103041976B (en) * | 2012-12-25 | 2014-04-30 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
| CN110331124A (en) * | 2019-06-14 | 2019-10-15 | 浙江大学 | A kind of electric polypyrrole/extracellular matrix laminated film and preparation method thereof |
| CN110331124B (en) * | 2019-06-14 | 2022-03-22 | 浙江大学 | Conductive polypyrrole/extracellular matrix composite film and preparation method thereof |
| CN114808081A (en) * | 2022-01-27 | 2022-07-29 | 华东理工大学 | Short-distance oriented amorphous collagen material capable of being stripped from electrode and electrochemical preparation method thereof |
| WO2023142599A1 (en) * | 2022-01-27 | 2023-08-03 | 华东理工大学 | Preparation method for collagen material stripped from electrode, and use of collagen material |
| CN115518206A (en) * | 2022-10-18 | 2022-12-27 | 华中科技大学同济医学院附属协和医院 | Self-mineralized GBR film and preparation method thereof |
| CN115518206B (en) * | 2022-10-18 | 2024-01-23 | 华中科技大学同济医学院附属协和医院 | Self-mineralizing GBR membrane and preparation method thereof |
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