CN104860284A - Preparation method for amorphous calcium phosphate nanospheres - Google Patents
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Abstract
The invention relates to a preparation method for amorphous calcium phosphate nanospheres. The method comprises the following steps: first, calcium salt and phosphate are dissolved in an acidic solution, then stabilizing agents are added and a mixed solution is obtained; second, the mixed solution is sprayed into minimal liquid drop aerial fog by utilization of an air compression atomizer, the aerial fog goes through a spiral pipe in a nitrogen atmosphere with a certain flow velocity and then is blown into an alkaline buffer solution, and amorphous calcium phosphate nanosphere precipitate is obtained after filtering; third, the amorphous calcium phosphate nanosphere precipitate obtained from the second step is washed and dried, and amorphous calcium phosphate nanospheres are obtained. The diameters of the obtained amorphous calcium phosphate nanospheres are less 100nm, the diameters of part nanospheres are less than 40nm, which is convenient for promotion of remineralization of dentin collagen fibers. The Ca/p ratio is adjustable, the forms of the amorphous calcium phosphate nanospheres are regular spheres, and the amorphous calcium phosphate nanospheres can exist stably for about 200h in an aqueous solution and is suitable for medicine loading and participation in bionic mineralization. The devices are simple to assemble, preparation is simple and practical, and the preparation method facilitates final achievement of large scale production.
Description
Technical field
The present invention relates to a kind of preparation method of amorphous calcium phosphate nanometer ball, the particle that particularly a kind of size contains below particle diameter 40nm is applicable to the preparation method of the amorphous calcium phosphate nanometer ball for inducing remineralization inside and outside dentine type i collagen fiber.
Background technology
The general name of amorphous calcium phosphate (amorphous calcium phosphate, ACP) to be a class X-ray diffraction be amorphous calcium phosphate material.Studied discovery, the osteoblast adhesion of ACP, osteoconductive, biodegradation rate, biocompatibility are all better than the calcium phosphate of other types in the past.These performances all make it be widely used in biomedical sector, become the study hotspot of biomineralization material.Bonding acid etching dentine or involve the problem that the bad collegen filament that all there is exposure of Dentinal dental caries are destroyed by matrix metalloproteinase in carious tooth stowing operation, this will cause bonding interface and Dentinal destruction.Investigators constantly attempt the collegen filament remineralization being promoted exposure by biomimetic mineralization means, make the moisture inside and outside enough little hydroxyapatite crystal replacement collegen filament network fiber, avoid exposure and the enzymolysis of collegen filament.Amorphous calcium phosphate is the amorphous mesophase spherule of one in hydroxyapatite forming process, is present in the starting stage of dentinal permeability.By the transformation of this mesophase spherule, organism can overcome the energy barrier that classical crystal nucleation needs, thus synthesizing hydroxylapatite more efficiently.Therefore, dentine remineralization becomes study hotspot to utilize amorphous calcium phosphate to promote.But in tooth structure, dentine remineralization is current study hotspot and difficult point, major cause is dentine is a kind of organism and mineral complex, and organism is based on type i collagen fiber, and hydroxyapatite crystal is present in fiber and between fiber.Realize being mineralized into difficult point in fiber, major cause is fiber inner pore little (being about below 40nm), and size is large, the mineralizing material of bad dispersibility, poor fluidity cannot really form remineralization in fiber.Therefore dentine remineralization relates in type i collagen fiber and remineralization between fiber.Existing this characteristic of research and utilization amorphous calcium phosphate both at home and abroad, promotes dentine type i collagen fiber remineralization.But current all research all uses amorphous calcium phosphate solution to realize mineralising, not easily add clinically in direct vertex-gluing graph material and apply.
Summary of the invention
The present invention is intended to research and develop that good stability, size are little, the amorphous calcium phosphate nanometer ball of the solid state of good dispersity, good fluidity, is convenient to be added in direct vertex-gluing graph material promote dentine biomimetic mineralization.This preparation method is simple, and Ca/P is than adjustable, and ACP stability is controlled, Product size morphology controllable.
Based on this, the invention provides a kind of preparation method of amorphous calcium phosphate nanometer ball, make amorphous calcium phosphate nanometer ball Product size more homogeneous, size is at below 100nm, and part is positioned at below 40nm, profile is the spheroidal particle of rule, can longer-term stable existence, preparation method is simple, and preparation cost is lower, be convenient to scale operation, and be convenient to carrying medicament in the future.
The preparation method of amorphous calcium phosphate nanometer ball provided by the invention, using soluble calcium salt and soluble phosphate as calcium phosphorus source, using polyacrylic acid as stablizer, above-mentioned solution is formed aerosol by the ejection of Compressed air nebulization device, utilize nitrogen as carrier gas, be collected in ealkaline buffer by fine droplet aerosol, washing precipitation drying obtains product.The feature of the inventive method is that preparation method is more effectively simple, suitable controlled synthesis in enormous quantities.Homogeneous, the form of nanosphere size of preparation be regular spherical, Ca/P than adjustable, can longer-term maintenance amorphous state.Concrete, method of the present invention comprises the steps:
1) be dissolved in acidic solution by soluble calcium salt and phosphoric acid salt, then add stablizer, stirred at ambient temperature mixes, and obtains mixing solutions;
2) Compressed air nebulization device is utilized by step 1) mixing solutions that obtains is sprayed into fine droplet, utilize nitrogen as carrier gas, atomization gas being blown into is heated in the spiral tube of certain temperature, damping fluid (buffering range is pH7-9) is as receiving liquid, filter, obtain amorphous calcium phosphate nanometer ball precipitation;
3) by step 2) the amorphous calcium phosphate nanometer ball washing of precipitate that obtains, drying obtain amorphous calcium phosphate nanometer ball.
The principle of the invention is to utilize polycomponent self assembling process and the small droplets generated in conjunction with spray process, achieve the preparation of amorphous calcium phosphate nanometer ball in the aqueous solution, break through traditional template method, react in gas phase media using aerosol droplets or single bubble as template and reactor, without the need to template, process is simple, enhances productivity further, is convenient to realize industrialization.
Described step 1) in, described acidic solution pH scope is 2.5-3.5.Described acidic solution can be acetic acid solution or hydrochloric acid soln.
Described step 1) in, after soluble calcium salt is dissolved in acidic solution, concentration range is 0.5-40mmol/L, and after phosphoric acid salt is dissolved in acidic solution, concentration range is 0.5-20mmol/L.
Described step 1) in, described calcium salt and phosphatic interpolation, calcium, phosphoric mol ratio are (1-2): 1.
Described step 1) in, described calcium salt is soluble calcium salt, as calcium chloride, Calcium hydrogen carbonate; Described phosphoric acid salt is that soluble phosphate is preferably Sodium phosphate dibasic.
Described step 1) in, described stablizer is polyacrylic acid or magnesium ion, be preferably polyacrylic acid, addition for being more than or equal to 500 μ g/ml, preferably 500 μ g/ml.
Described step 2) in, atomization rates is more than 0.1mL/min.
Described step 2) in, nitrogen flow rate is 10-50L/min.
Described step 2) in, the temperature in spiral tube is within the scope of 100 DEG C-170 DEG C.
Described step 2) in, described buffered soln is preferably that pH is 8.0, the Tris-HCI damping fluid of 0.5mol/L.
Described step 3) in, the available ethanol of described washing, acetone or deionized water wash, dry is lyophilize or vacuum-drying.
The present invention has following positive effect:
(1) product moiety is amorphous calcium phosphate, not hydroxyl phosphorite crystal, and product can long term maintenance amorphous state and not to crystal transformation, Ca/P, than adjustable, is conducive to the application in biomedical biomimetic mineralization.
(2) preparation method is simple, without the need to template, is convenient to follow-up coating medicine, is beneficial to the application of the aspects such as further release.
(3) Product size is little, is less than 100nm, and can be adjusted to and be less than 40nm, and this size is convenient to dentin collagen fiber remineralization especially.Product size is homogeneous, in typical sphere, has higher specific surface area and perviousness, is beneficial to release calcium phosphorus particle.
(4) preparation time is short, and production efficiency is high, does not need large-scale instrument and equipment, and reaction conditions is gentle, is convenient to implement.
The invention belongs to the part in national natural science fund subsidy project (51103001) and Municipal Commission of Science and Technology's fund (Z141100000514016), the result obtained will be applied to the particularly production of Novel mouth vertex-gluing graph material and the clinical application of oral cavity innovation kind preclinical study.
Accompanying drawing explanation
Fig. 1 represents pattern under amorphous calcium phosphate nanometer ball scanning electron microscope; Amorphous calcium phosphate nanometer ball is regular spherical pattern, and size is at below 100nm, and part is below 40nm.
Fig. 2 represents structure under amorphous calcium phosphate nanometer ball transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
Fig. 3 to represent in embodiment 1 that amorphous calcium phosphate nanometer ball prepares X-ray diffraction analysis after 200h; There is not diffraction peak, illustrate that product is still amorphous state, stable performance.
Embodiment
Below by embodiment, the present invention will be further described, is preference of the present invention, is not used for limiting the present invention, and all within principle of the present invention, any modifications and variations done, all within protection scope of the present invention.Below in conjunction with drawings and Examples, the present invention is set forth further:
The preparation of embodiment 1. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 1mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 0.5mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 10L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 100 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, Fig. 1 represents pattern under amorphous calcium phosphate nanometer ball scanning electron microscope; Amorphous calcium phosphate nanometer ball is regular spherical pattern, and grain size is at below 100nm, and part is below 40nm.Fig. 2 represents structure under amorphous calcium phosphate nanometer ball transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, Fig. 3 to represent in the present embodiment that amorphous calcium phosphate nanometer ball prepares X-ray diffraction analysis after 200h; Result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 2. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 40mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 10L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 100 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 3. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 1mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 1mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 10L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 100 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 4. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 20mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 10L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 100 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 5. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in respectively and are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 1mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 0.5mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 50L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 170 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 6. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 40mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 50L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 170 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 7. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 1mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 1mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 50L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 170 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
The preparation of embodiment 8. amorphous calcium phosphate nanometer ball
The calcium chloride of certain mass and disodium hydrogen phosphate dodecahydrate are dissolved in 500ml respectively, pH is in the acetic acid solution of 2.5, adjustment calcium chloride concentration is 20mmol/L, adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain the mixing solutions of calcium chloride and Sodium phosphate dibasic, add the polyacrylic acid aqueous solution again, adjusting its concentration is 500 μ g/ml, mixes and obtains mixing solutions.By Compressed air nebulization device (atomization rates is 0.2mL/min), solution is sprayed into fine droplet aerosol, utilize flow velocity for 50L/min nitrogen is as carrier gas, aerosol is blown in the spiral tube of 170 DEG C, pH value is 8.0, the Tris-HCl damping fluid of 0.5mol/L as receiving liquid, filter and obtain product precipitation; Undertaken centrifugal by the receiving liquid containing product precipitation obtained, washing with alcohol, vacuum-drying obtain amorphous calcium phosphate nanometer ball.
The amorphous calcium phosphate nanometer ball scanning electron microscope obtained and transmission electron microscope are detected, show that amorphous calcium phosphate nanometer ball is regular spherical pattern, grain size is at below 100nm, and part is below 40nm.Structure under amorphous calcium phosphate nanometer ball transmission electron microscope prepared by the present embodiment, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction analysis after 200h prepared by amorphous calcium phosphate nanometer ball, result shows not occur diffraction peak, illustrates that product is still amorphous state, stable performance.
Claims (11)
1. a preparation method for amorphous calcium phosphate nanometer ball, comprises the steps:
1) soluble calcium salt and phosphoric acid salt are dissolved in acidic solution, then add stablizer, mix, obtain mixing solutions;
2) Compressed air nebulization device is utilized by step 1) mixing solutions that obtains is sprayed into fine droplet, and utilize nitrogen as carrier gas, atomization gas be blown in spiral tube, alkaline buffer solution, as receiving liquid, filters, and obtains amorphous calcium phosphate nanometer ball precipitation;
3) by step 2) the amorphous calcium phosphate nanometer ball washing of precipitate that obtains, drying obtain amorphous calcium phosphate nanometer ball.
2. method according to claim 1, is characterized in that: described step 1) in, described acidic solution pH scope is 2.5-3.5, and described acidic solution is preferably acetic acid solution or hydrochloric acid soln.
3. method according to claim 1, is characterized in that: described step 1) in, after soluble calcium salt is dissolved in acidic solution, concentration range is 0.5-40mmol/L, and after phosphoric acid salt is dissolved in acidic solution, concentration range is 0.5-20mmol/L.
4. method according to claim 1, is characterized in that: described step 1) in, described calcium salt and phosphatic calcium, phosphoric mol ratio are (1-2): 1.
5. method according to claim 1, is characterized in that: described step 1) in, described calcium salt is soluble calcium salt, and described calcium salt is preferably calcium chloride, Calcium hydrogen carbonate; Described phosphoric acid salt is soluble phosphate, is preferably Sodium phosphate dibasic.
6. method according to claim 1, is characterized in that: described step 1) in, described stablizer is polyacrylic acid or magnesium ion, be preferably polyacrylic acid, addition for being more than or equal to 500 μ g/mL, preferably 500 μ g/mL.
7. method according to claim 1, is characterized in that: described step 2) in, atomization rates is more than 0.1mL/min.
8. method according to claim 1, is characterized in that: described step 2) in, nitrogen flow rate is 10-50L/min.
9. method according to claim 1, is characterized in that: described step 2) in, the temperature in spiral tube is within the scope of 100 DEG C-170 DEG C.
10. method according to claim 1, is characterized in that: described step 2) in, to be pH be described buffered soln 8.0, the Tris-HCI damping fluid of 0.5mol/L.
11. methods according to claim 1, is characterized in that: described step 3) in, described washing ethanol, acetone or deionized water wash, dry is lyophilize or vacuum-drying.
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| CN109734066A (en) * | 2019-03-07 | 2019-05-10 | 中山职业技术学院 | A kind of preparation method of high-performance biomedicine amorphous calcium phosphate 3D printing material |
| CN111362661A (en) * | 2020-04-17 | 2020-07-03 | 中山职业技术学院 | High-density amorphous calcium phosphate nano powder and preparation method and application thereof |
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| CN109700666A (en) * | 2019-03-01 | 2019-05-03 | 中国人民解放军联勤保障部队第九四0医院 | A kind of mouth cavity fluid resin material and preparation method thereof |
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| CN109734066B (en) * | 2019-03-07 | 2022-05-20 | 中山职业技术学院 | Preparation method of high-performance amorphous calcium phosphate 3D printing material for biomedicine |
| CN111362661A (en) * | 2020-04-17 | 2020-07-03 | 中山职业技术学院 | High-density amorphous calcium phosphate nano powder and preparation method and application thereof |
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