CN109453432A - A kind of surface modifying method of hydroxyapatite, modified hydroxylapatite and its application - Google Patents
A kind of surface modifying method of hydroxyapatite, modified hydroxylapatite and its application Download PDFInfo
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- CN109453432A CN109453432A CN201811356534.2A CN201811356534A CN109453432A CN 109453432 A CN109453432 A CN 109453432A CN 201811356534 A CN201811356534 A CN 201811356534A CN 109453432 A CN109453432 A CN 109453432A
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- hydroxyapatite
- surface modifying
- dopamine
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- modifying method
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The invention discloses a kind of surface modifying methods of hydroxyapatite, comprising steps of the disodium phosphate soln of S1, the configuration calcium nitrate solution of 0.5~1mol/L, the sodium dihydrogen phosphate of 0.2~0.3mol/L, 0.3~0.4mol/L, sodium dihydrogen phosphate and disodium phosphate soln are mixed in equal volume, it is slowly added in the calcium nitrate solution equal with gained mixeding liquid volume, in 120~130 DEG C of water-bath 4h, then it is down to room temperature, it is filtered after standing 10h, washing, obtains hydroxyapatite；The dopamine of 25~40mg/ml is added in S2, the hydroxyapatite suspended dispersed Yu Shuizhong by step S1, and adjusting pH is 9, and 30h is stirred in shading, is then centrifuged for, and washs, obtains the hydroxyapatite of poly-dopamine modified lithium.The present invention is conducive to improve the biocompatibility of hydroxyapatite and to histiocytic adsorptivity, gained modified hydroxylapatite can be used for the surface treatment of medical alloy material.
Description
Technical field
The present invention relates to hydroxyapatite modified technical fields, and in particular to one kind is with the in-situ modified hydroxyl phosphorus of poly-dopamine
The method of lime stone surface characteristic, using modified hydroxylapatite made from this method and its application.
Background technique
Hydroxyapatite is the main constituents of skeleton and tooth, has good osteoconductive and osteoinductive
And biocompatibility, it is good artificial bone substitute materials, but simple hydroxyapatite scaffold brittleness is big, mechanical stability
Difference.To overcome this defect, a kind of method is to load hydroxyapatite films in alloy material surface, to take into account the mechanics of alloy
The biocompatibility of performance and hydroxyapatite.But non-modified hydroxyapatite is easy to reunite, modified hydroxy-apatite
Stone may will affect its biological characteristics or method of modifying is complicated, be not suitable for large-scale application.
Summary of the invention
In view of the above shortcomings of the prior art, an object of the present invention is to provide one kind and is changed in situ with poly-dopamine
Property hydroxyapatite method, gained hydroxyapatite have preferable adhesiveness and histocompatbility.
To achieve the above object, the invention adopts the following technical scheme:
A kind of surface modifying method of hydroxyapatite, comprising steps of
S1, configure the calcium nitrate solution of 0.5~1mol/L, the sodium dihydrogen phosphate of 0.2~0.3mol/L, 0.3~
Sodium dihydrogen phosphate and disodium phosphate soln are mixed in equal volume, are slowly added to by the disodium phosphate soln of 0.4mol/L
In the calcium nitrate solution equal with gained mixeding liquid volume, in 120~130 DEG C of water-bath 4h, it is then down to room temperature, is stood
It is filtered after 10h, washs, obtain hydroxyapatite；
The dopamine of 25~40mg/ml is added in S2, the hydroxyapatite suspended dispersed Yu Shuizhong by step S1, adjusts pH
It is 9,30h is stirred in shading, is then centrifuged for, and is washed, is obtained the hydroxyapatite of poly-dopamine modified lithium.
It further comprises the steps of: to disperse the hydroxyapatite of poly-dopamine modified lithium obtained in solvent and forms dispersion liquid.
Preferably, the solvent is deionized water, tetrahydrofuran, chloroform, dioxane or dehydrated alcohol.
Preferably, in the step S2, the dispersing mode of hydroxyapatite is ultrasonic disperse.
It is a further object of the present invention to provide a kind of using modified hydroxylapatite made from the above method, can be used for curing
With the surface treatment of alloy material.
Beneficial effects of the present invention:
Dopamine autohemagglutination under alkaline condition can coat poly-dopamine in hydroxyapatite surface, be conducive to improve hydroxyl
The biocompatibility of apatite and to histiocytic adsorptivity, gained modified hydroxylapatite can be used for medical alloy material
Surface treatment, the experimental results showed that, the surface that the hydroxyapatite of the modification is used for magnesium alloy is modified, and it is resistance to significantly improve its
Corrosive nature.
Specific embodiment
Below by specific embodiment, the present invention will be described in detail.
Embodiment 1
1, the phosphoric acid hydrogen of the calcium nitrate solution of 0.5mol/L, the sodium dihydrogen phosphate of 0.2mol/L, 0.3mol/L are configured
Two sodium solutions mix sodium dihydrogen phosphate and disodium phosphate soln in equal volume, are slowly added to and gained mixeding liquid volume
In equal calcium nitrate solution, in 120 DEG C of water-bath 4h, it is then down to room temperature, is filtered after standing 10h, washs, obtains hydroxyl
Apatite；
2, by the hydroxyapatite suspended dispersed Yu Shuizhong of step 1, the dopamine of 25mg/ml is added, adjusting pH is 9, is hidden
Light stirs 30h, is then centrifuged for, is washed with deionized water, be scattered in deionized water under ultrasonication, obtains poly-dopamine and change
The hydroxyapatite dispersion liquid of property.
It carries out surface to magnesium alloy using the hydroxyapatite dispersion liquid of above-mentioned poly-dopamine modified lithium to be modified, steps are as follows:
Magnesium alloy is successively used the sand paper of 200 mesh, 360 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh and 1500 mesh polish
Afterwards, electrobrightening is carried out, polishing fluid is phosphoric acid/ethanol solution that volume ratio is 5:1, and polishing voltage is 5V, polish temperature
It is -10 DEG C, after polishing, cleans surface with alcohol, is electricity with 13g/L potassium hydroxide, 15g/L sodium metasilicate, 5g/L potassium fluoride
Liquid is solved, the differential arc oxidation 30min under 350V pulse voltage is then immersed in the hydroxyapatite dispersion liquid of above-mentioned poly-dopamine modified lithium
In, in 100 DEG C of heat preservation 1h, then takes out, clean surface and drying with distilled water, be again dipped into the hydroxyl of above-mentioned poly-dopamine modified lithium
It in base apatite dispersion liquid, is so repeated 3 times, forms carboxy apatite composite coating in Mg alloy surface.
It is compound using area load hydroxyapatite made from CHI660E electrochemical workstation testing example and comparative example
Corrosion resistance of the magnesium alloy (i.e. sample) of coating in Hank ' s simulated body fluid.Test method are as follows: using sample as work electricity
Pole, platinum electrode are auxiliary electrode, and saturated calomel electrode is reference electrode, and the open circuit corrosion potential testing time is 30min；Electrokinetic potential
Polarization scan range is lower than open circuit corrosion potential 500mV to being higher than between open circuit corrosion potential 800mV, sweep speed 1mV/
s。
The result shows that surface impedance is 23820 Ω cm2, corrosion electric current density is 1.85 × 10-6A·cm-2。
Embodiment 2
1, the phosphoric acid hydrogen two of the calcium nitrate solution of 1mol/L, the sodium dihydrogen phosphate of 0.3mol/L, 0.3mol/L are configured
Sodium solution mixes sodium dihydrogen phosphate and disodium phosphate soln in equal volume, is slowly added to and gained mixeding liquid volume phase
Deng calcium nitrate solution in, in 130 DEG C of water-bath 4h, be then down to room temperature, filtered after standing 10h, washed, obtain hydroxyl phosphorus
Lime stone；
2, by the hydroxyapatite suspended dispersed Yu Shuizhong of step 1, the dopamine of 40mg/ml is added, adjusting pH is 9, is hidden
Light stirs 30h, is then centrifuged for, is washed with deionized water, be scattered in deionized water under ultrasonication, obtains poly-dopamine and change
The hydroxyapatite dispersion liquid of property.
It carries out surface to magnesium alloy using the hydroxyapatite dispersion liquid of above-mentioned poly-dopamine modified lithium to be modified, steps are as follows:
Magnesium alloy is successively used the sand paper of 200 mesh, 360 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh and 1500 mesh polish
Afterwards, electrobrightening is carried out, polishing fluid is phosphoric acid/ethanol solution that volume ratio is 5:1, and polishing voltage is 5V, polish temperature
It is -10 DEG C, after polishing, cleans surface with alcohol, is electricity with 13g/L potassium hydroxide, 15g/L sodium metasilicate, 5g/L potassium fluoride
Liquid is solved, the differential arc oxidation 30min under 350V pulse voltage is then immersed in the hydroxyapatite dispersion liquid of above-mentioned poly-dopamine modified lithium
In, in 120 DEG C of heat preservation 0.5h, then takes out, clean surface and drying with distilled water, be again dipped into above-mentioned poly-dopamine modified lithium
It in hydroxyapatite dispersion liquid, is so repeated 4 times, forms carboxy apatite composite coating in Mg alloy surface.
Corrosion resistance test is carried out using method same as Example 1, the results showed that, surface impedance 27950
Ω·cm2, corrosion electric current density is 1.67 × 10-6A·cm-2。
It is tested using non-modified magnesium alloy as reference examples, the results showed that, surface impedance is 778 Ω cm2, corrosion
Current density is 5.52 × 10-5A·cm-2。
It can be seen from the above result that the table of magnesium alloy can be significantly improved using hydroxyapatite made from method of modifying of the present invention
Face corrosion resisting property.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
Claims (6)
1. a kind of surface modifying method of hydroxyapatite, which is characterized in that comprising steps of
S1, the configuration calcium nitrate solution of 0.5~1mol/L, the sodium dihydrogen phosphate of 0.2~0.3mol/L, 0.3~0.4mol/
The disodium phosphate soln of L mixes sodium dihydrogen phosphate and disodium phosphate soln in equal volume, is slowly added to mixed with gained
It closes in the equal calcium nitrate solution of liquid product, in 120~130 DEG C of water-bath 4h, is then down to room temperature, is filtered after standing 10h,
Washing, obtains hydroxyapatite；
The dopamine of 25~40mg/ml is added in S2, the hydroxyapatite suspended dispersed Yu Shuizhong by step S1, and adjusting pH is 9,
30h is stirred in shading, is then centrifuged for, and is washed, is obtained the hydroxyapatite of poly-dopamine modified lithium.
2. the surface modifying method of hydroxyapatite according to claim 1, which is characterized in that further comprising the steps of: will make
The hydroxyapatite of the poly-dopamine modified lithium obtained, which is scattered in solvent, forms dispersion liquid.
3. the surface modifying method of hydroxyapatite according to claim 2, which is characterized in that the solvent is deionization
Water, tetrahydrofuran, chloroform, dioxane or dehydrated alcohol.
4. the surface modifying method of hydroxyapatite according to claim 2, which is characterized in that in the step S2, hydroxyl
The dispersing mode of base apatite is ultrasonic disperse.
5. using modified hydroxylapatite made from the described in any item surface modifying methods of claim 1-4.
6. the surface treatment that modified hydroxylapatite described in claim 5 is used for medical alloy material.
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| CN201811356534.2A CN109453432A (en) | 2018-11-15 | 2018-11-15 | A kind of surface modifying method of hydroxyapatite, modified hydroxylapatite and its application |
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| CN201811356534.2A CN109453432A (en) | 2018-11-15 | 2018-11-15 | A kind of surface modifying method of hydroxyapatite, modified hydroxylapatite and its application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128679A (en) * | 2019-06-10 | 2019-08-16 | 西南交通大学 | A kind of preparation method for the integrated regenerated conducting bilayer hydrogel of electro photoluminescence bone cartilage |
| CN111330089A (en) * | 2020-03-04 | 2020-06-26 | 西南交通大学 | Preparation method of fully-degradable magnetic repair hydrogel for bone repair |
| CN111450306A (en) * | 2020-03-06 | 2020-07-28 | 大连理工大学 | External nano hydroxyapatite/polydopamine wet adhesion type styptic powder and preparation method thereof |
| CN114477850A (en) * | 2021-12-21 | 2022-05-13 | 山东大学 | Methacryloylated gelatin/biological ceramic paste and forming and printing method |
| CN114870030A (en) * | 2022-05-13 | 2022-08-09 | 上海摩漾生物科技有限公司 | Hydroxyapatite nano material with high absorptivity and preparation method thereof |
| CN117298348A (en) * | 2023-04-24 | 2023-12-29 | 鹏拓生物科技(杭州)有限公司 | Non-aqueous phase fast-curing biphase calcium phosphate fluid bone cement and preparation method thereof |
| CN117298348B (en) * | 2023-04-24 | 2024-05-17 | 鹏拓生物科技(杭州)有限公司 | Non-aqueous phase fast-curing biphase calcium phosphate fluid bone cement and preparation method thereof |
-
2018
- 2018-11-15 CN CN201811356534.2A patent/CN109453432A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128679A (en) * | 2019-06-10 | 2019-08-16 | 西南交通大学 | A kind of preparation method for the integrated regenerated conducting bilayer hydrogel of electro photoluminescence bone cartilage |
| CN111330089A (en) * | 2020-03-04 | 2020-06-26 | 西南交通大学 | Preparation method of fully-degradable magnetic repair hydrogel for bone repair |
| CN111330089B (en) * | 2020-03-04 | 2021-08-03 | 西南交通大学 | Preparation method of fully-degradable magnetic repair hydrogel for bone repair |
| CN111450306A (en) * | 2020-03-06 | 2020-07-28 | 大连理工大学 | External nano hydroxyapatite/polydopamine wet adhesion type styptic powder and preparation method thereof |
| CN111450306B (en) * | 2020-03-06 | 2021-11-19 | 大连理工大学 | External nano hydroxyapatite/polydopamine wet adhesion type styptic powder and preparation method thereof |
| CN114477850A (en) * | 2021-12-21 | 2022-05-13 | 山东大学 | Methacryloylated gelatin/biological ceramic paste and forming and printing method |
| CN114870030A (en) * | 2022-05-13 | 2022-08-09 | 上海摩漾生物科技有限公司 | Hydroxyapatite nano material with high absorptivity and preparation method thereof |
| CN117298348A (en) * | 2023-04-24 | 2023-12-29 | 鹏拓生物科技(杭州)有限公司 | Non-aqueous phase fast-curing biphase calcium phosphate fluid bone cement and preparation method thereof |
| CN117298348B (en) * | 2023-04-24 | 2024-05-17 | 鹏拓生物科技(杭州)有限公司 | Non-aqueous phase fast-curing biphase calcium phosphate fluid bone cement and preparation method thereof |
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Application publication date: 20190312 |