CN104860284B - A kind of preparation method of amorphous calcium phosphate nanosphere - Google Patents
A kind of preparation method of amorphous calcium phosphate nanosphere Download PDFInfo
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Abstract
The present invention relates to a kind of amorphous calcium phosphate nanosphere and preparation method thereof.The method comprises the steps：1) calcium salt and phosphate are dissolved in acid solution, are subsequently adding stabilizer and obtain mixed solution；2) mixed solution is sprayed into fine droplet aerosol using Compressed air nebulization device, by aerosol under the nitrogen atmosphere of certain flow rate by being blown into alkaline buffer solution after helix tube, be filtrated to get amorphous calcium phosphate nanosphere precipitation；3) by step 2) washing of the amorphous calcium phosphate nanosphere that obtains, it is dried to obtain amorphous calcium phosphate nanosphere.Obtained amorphous calcium phosphate nanometer below bulb diameter 100nm, section diameter below 40nm of the invention, are more convenient for promoting dentin collagen fiber remineralization, Ca/P is than adjustable, form in relatively regular spherical, can stable existence 200h or so in aqueous, be suitable to load medicine or participate in biomimetic mineralization.Apparatus of the present invention assembling is simple, prepares simple and feasible, is easy to final realize mass producing.
Description
Technical field
The present invention relates to a kind of preparation method of amorphous calcium phosphate nanosphere, more particularly to a kind of size contains particle diameter
The particle of below 40nm is applied to for inducing the amorphous calcium phosphate nanosphere of remineralization inside and outside dentine type i collagen fiber
Preparation method.
Background technology
Amorphous calcium phosphate (amorphous calcium phosphate, ACP) is that a class X-ray diffraction is amorphous state
Calcium phosphate material general name.Research discovery, the osteoblast adhesion of ACP, osteoconductive, biodegradation rate, life in the past
Thing compatibility is superior to other kinds of calcium phosphate.These performances make it be widely used in biomedical sector, as biology
The study hotspot of mineralizing material.Acid etching dentine is bonded in carious tooth stowing operation or involve dentine dental caries it is bad exist it is exposed
The problem that collagenous fibres are destroyed by matrix metalloproteinase, this will cause the destruction of bonding interface and dentine.Researchers are not
It is disconnected to attempt to promote exposed collagenous fibres remineralization by biomimetic mineralization means, sufficiently small hydroxyapatite crystal is replaced glue
Moisture inside and outside fibrillation network fiber, it is to avoid the exposure of collagenous fibres and enzymolysis.Amorphous calcium phosphate is that hydroxyapatite is formed
During a kind of amorphous interphase, be present in the starting stage of dentinal permeability.It is biological by the transformation of this interphase
Body can overcome the energy barrier that classical crystal nucleation needs, so that more efficiently synthesizing hydroxylapatite.Therefore, using amorphous
Calcium phosphate promotes dentine remineralization as study hotspot.But in tooth structure, dentine remineralization is that research is hot at present
Point and difficult point, main cause are that dentine is a kind of organic matter and mineral complex, organic matter based on type i collagen fiber,
Hydroxyapatite crystal is present in fiber and between fiber.Realize being mineralized into difficult point in fiber, main cause is fiber endoporus
Gap is small (about below 40nm), and size is big, the mineralizing material of bad dispersibility, poor fluidity cannot really form the interior ore deposit again of fiber
Change.Therefore dentine remineralization is related in type i collagen fiber the remineralization and between fiber.It is amorphous that research and utilization is had both at home and abroad
This characteristic of calcium phosphate, promotes dentine type i collagen fiber remineralization.But all researchs use amorphous calcium phosphate at present
Solution realizes mineralising, is clinically difficult to add in direct vertex-gluing graph material and applies.
The content of the invention
It is contemplated that research and development good stability, small size, good dispersion, the amorphous phosphoric acid of the solid state of good fluidity
Calcium nanosphere, is easy to add the promotion dentine biomimetic mineralization into direct vertex-gluing graph material.This preparation method is simple and easy to apply,
Than adjustable, ACP stability is controllable, Product size morphology controllable for Ca/P.
Based on this, the present invention provides a kind of preparation method of amorphous calcium phosphate nanosphere, makes amorphous calcium phosphate nanometer
Ball Product size is more uniform, and in below 100nm, partly positioned at below 40nm, profile is the spheric granules of rule, energy to particle size
Enough longer-term stable existences, preparation method is simple and easy to apply, and preparation cost is relatively low, is easy to large-scale production, and be easy to negative in the future
Carry medicine.
The preparation method of the amorphous calcium phosphate nanosphere that the present invention is provided, is made with soluble calcium salt and soluble phosphate
It is calcium phosphorus source, using polyacrylic acid as stabilizer, above-mentioned solution is sprayed to form aerosol by Compressed air nebulization device, using nitrogen
Be collected in fine droplet aerosol in alkaline buffer as carrier gas by gas, and washing precipitation is dried to obtain product.The inventive method
Feature is more easy and effective preparation method, suitable high-volume controllable preparation.The nanosphere size of preparation is homogeneous, form is in regular ball
Shape, Ca/P than it is adjustable, can longer-term keep amorphous state.Specifically, the method for the present invention comprises the steps：
1) soluble calcium salt and phosphate are dissolved in acid solution, are subsequently adding stabilizer, stirring mixing is equal at room temperature
It is even, obtain mixed solution；
2) using Compressed air nebulization device by step 1) mixed solution that obtains is sprayed into fine droplet, uses nitrogen as load
Gas, atomization gas are blown into the helix tube for being heated to uniform temperature, and buffer solution (buffering range is pH7-9) is used as reception liquid, mistake
Filter, obtains amorphous calcium phosphate nanosphere precipitation；
3) by step 2) the amorphous calcium phosphate nanosphere washing of precipitate that obtains, it is dried to obtain amorphous calcium phosphate nanometer
Ball.
The principle of the invention is the droplet using multicomponent self assembling process and combination spray process generation, realizes water
The preparation of amorphous calcium phosphate nanosphere in solution, breaks through traditional template method, using aerosol droplets or single bubble as
Template and reactor react in gas phase media, and without template, process is simple, and further improve production efficiency is easy to implement work
Industry.
The step 1) in, the acid solution pH scopes are 2.5-3.5.The acid solution can for acetic acid solution or
Hydrochloric acid solution.
The step 1) in, concentration range is 0.5-40mmol/L after soluble calcium salt is dissolved in acid solution, and phosphate is molten
In concentration range after acid solution be 0.5-20mmol/L.
The step 1) in, the calcium salt and phosphatic addition, calcium, P elements mol ratio are (1-2)：1.
The step 1) in, the calcium salt is soluble calcium salt, such as calcium chloride, calcium bicarbonate；The phosphate is solvable
Acid phosphate is preferably disodium hydrogen phosphate.
The step 1) in, the stabilizer is polyacrylic acid or magnesium ion, preferably polyacrylic acid, addition be more than
Equal to 500 μ g/ml, preferably 500 μ g/ml.
The step 2) in, atomization rates are more than 0.1mL/min.
The step 2) in, nitrogen flow rate is 10-50L/min.
The step 2) in, the temperature in helix tube is in the range of 100 DEG C -170 DEG C.
The step 2) in, the cushioning liquid is preferably the Tris-HCI buffer solutions that pH is 8.0,0.5mol/L.
The step 3) in, the washing can be washed with ethanol, acetone or deionized water, and it is freeze-drying or vacuum to dry
Dry.
The present invention has following positive effect：
(1) product constituent is amorphous calcium phosphate, can be maintained for a long time without hydroxyapatite crystal, and product
Amorphous state is without to crystal transformation, Ca/P is conducive to the application in terms of biomedical biomimetic mineralization than adjustable.
(2) preparation method is simple and easy to apply, without template, is easy to follow-up coating medicine, beneficial to the further aspect such as drug release
Using.
(3) Product size is small, less than 100nm, and is adjustable to less than 40nm, and the size is particularly easy to dentin collagen fiber
Remineralization.Product size is homogeneous, in typical sphere, there is specific surface area and permeability higher, beneficial to release calcium phosphorus particle.
(4) preparation time is short, and production efficiency is high, is not required to large-scale instrument and equipment, and reaction condition is gentle, convenient to carry out.
The invention belongs to national natural science fund subsidy project (51103001) and Municipal Commission of Science and Technology's fund
(Z141100000514016) part in, the result for being obtained will be applied to oral cavity innovation kind preclinical study and be particularly
The production and clinical practice of novel mouth vertex-gluing graph material.
Brief description of the drawings
Fig. 1 represents pattern under amorphous calcium phosphate nanosphere ESEM；Amorphous calcium phosphate nanosphere is regular spherical
Pattern, size, in below 100nm, is partly below 40nm.
Fig. 2 represents structure under amorphous calcium phosphate nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
Amorphous calcium phosphate nanosphere prepares X-ray diffraction analysis after 200h during Fig. 3 represents embodiment 1；There is not diffraction maximum,
It is still amorphous state to illustrate product, stable performance.
Specific embodiment
Below by embodiment, the present invention will be further described, is preference of the invention, is not intended to limit this hair
It is bright, all any modifications and variations within principle of the invention, done, within protection scope of the present invention.Tie below
Drawings and Examples are closed the present invention is expanded on further：
The preparation of the amorphous calcium phosphate nanosphere of embodiment 1.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 1mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 0.5mmol/L, obtain calcium chloride and
The mixed solution of disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Close solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using stream
Speed for 10L/min nitrogen as carrier gas, aerosol is blown into 100 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, Fig. 1 represent amorphous calcium phosphate
Pattern under nanosphere ESEM；Amorphous calcium phosphate nanosphere is regular spherical pattern, and grain size is in below 100nm, portion
It is divided into below 40nm.Fig. 2 represents structure under amorphous calcium phosphate nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, and Fig. 3 represents amorphous phosphoric acid in the present embodiment
Calcium nanosphere prepares X-ray diffraction analysis after 200h；Result shows diffraction maximum do not occur, and it is still amorphous state to illustrate product, property
Can stabilization.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 2.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 40mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain calcium chloride and
The mixed solution of disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Close solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using stream
Speed for 10L/min nitrogen as carrier gas, aerosol is blown into 100 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 3.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 1mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 1mmol/L, obtains calcium chloride and phosphorus
The mixed solution of sour disodium hydrogen, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using flow velocity
It is 10L/min nitrogen as carrier gas, aerosol is blown into 100 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 4.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 20mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain calcium chloride and
The mixed solution of disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Close solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using stream
Speed for 10L/min nitrogen as carrier gas, aerosol is blown into 100 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 5.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in respectively and are dissolved in 500ml respectively, pH is 2.5
In acetic acid solution, adjustment calcium chloride concentration is 1mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 0.5mmol/L, is obtained
The mixed solution of calcium chloride and disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, and mixing is equal
It is even to obtain mixed solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet gas
Mist, by the use of flow velocity be 50L/min nitrogen as carrier gas, aerosol is blown into 170 DEG C of helix tube, pH value be 8.0,
The Tris-HCl buffer solutions of 0.5mol/L are filtrated to get product precipitation as reception liquid；The reception containing product precipitation that will be obtained
Liquid is centrifuged, and ethanol washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 6.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 40mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain calcium chloride and
The mixed solution of disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Close solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using stream
Speed for 50L/min nitrogen as carrier gas, aerosol is blown into 170 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 7.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 1mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 1mmol/L, obtains calcium chloride and phosphorus
The mixed solution of sour disodium hydrogen, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using flow velocity
It is 50L/min nitrogen as carrier gas, aerosol is blown into 170 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
The preparation of the amorphous calcium phosphate nanosphere of embodiment 8.
The calcium chloride and disodium hydrogen phosphate dodecahydrate of certain mass are dissolved in 500ml respectively, pH is 2.5 acetic acid solution
In, adjustment calcium chloride concentration is 20mmol/L, and adjustment disodium hydrogen phosphate dodecahydrate concentration is 20mmol/L, obtain calcium chloride and
The mixed solution of disodium hydrogen phosphate, adds the polyacrylic acid aqueous solution, adjusts its concentration for 500 μ g/ml, is mixed
Close solution.By Compressed air nebulization device (atomization rates are 0.2mL/min), solution is sprayed into fine droplet aerosol, using stream
Speed for 50L/min nitrogen as carrier gas, aerosol is blown into 170 DEG C of helix tube, pH value is the Tris- of 8.0,0.5mol/L
HCl buffer solutions are filtrated to get product precipitation as reception liquid；The reception liquid containing product precipitation that will be obtained is centrifuged, ethanol
Washing, vacuum drying obtain amorphous calcium phosphate nanosphere.
Amorphous calcium phosphate nanosphere ESEM and the transmission electron microscope detection that will be obtained, show amorphous calcium phosphate nanometer
Ball is regular spherical pattern, and grain size, in below 100nm, is partly below 40nm.Amorphous phosphoric acid manufactured in the present embodiment
Structure under calcium nanosphere transmission electron microscope, for the homogeneous inorganic structural of sample is penetrated in resistance.
X-ray diffraction is analyzed after prepared by amorphous calcium phosphate nanosphere into 200h, as a result shows diffraction maximum do not occur, illustrates to produce
Thing is still amorphous state, stable performance.
Claims (11)
1. a kind of preparation method of amorphous calcium phosphate nanosphere, comprises the steps：
1) soluble calcium salt and phosphate are dissolved in acid solution, are subsequently adding stabilizer, be well mixed, obtain mixing molten
Liquid；
2) using Compressed air nebulization device by step 1) mixed solution that obtains is sprayed into fine droplet, uses nitrogen as carrier gas,
Atomization gas are blown into helix tube, alkaline buffer solution obtains amorphous calcium phosphate nanosphere precipitation as reception liquid, filtering；
Atomization rates are more than 0.1mL/min；Nitrogen flow rate is 10-50L/min；Temperature in helix tube is in 100 DEG C of -170 DEG C of scopes
It is interior；
3) by step 2) the amorphous calcium phosphate nanosphere washing of precipitate that obtains, it is dried to obtain amorphous calcium phosphate nanosphere.
2. method according to claim 1, it is characterised in that：The step 1) in, the acid solution pH scopes are
2.5-3.5。
3. method according to claim 2, it is characterised in that：The step 1) in, the acid solution is acetic acid solution
Or hydrochloric acid solution.
4. method according to claim 1, it is characterised in that：The step 1) in, the soluble calcium salt is dissolved in acidity
Concentration range is 0.5-40mmol/L after solution, and concentration range is 0.5-20mmol/L after phosphate is dissolved in acid solution.
5. method according to claim 1, it is characterised in that：The step 1) in, the soluble calcium salt and phosphate
Calcium, P elements mol ratio be (1-2)：1.
6. method according to claim 1, it is characterised in that：The step 1) in, the phosphate is soluble phosphoric acid
Salt.
7. method according to claim 1, it is characterised in that：The step 1) in, the soluble calcium salt be calcium chloride,
Calcium bicarbonate；The phosphate is disodium hydrogen phosphate.
8. method according to claim 1, it is characterised in that：The step 1) in, the stabilizer is polyacrylic acid, is added
Dosage is more than or equal to 500 μ g/mL.
9. method according to claim 8, it is characterised in that：The step 1) in, the addition of the stabilizer is 500
μg/mL。
10. method according to claim 1, it is characterised in that：The step 2) in, the cushioning liquid be pH be 8.0,
The Tris-HCl buffer solutions of 0.5mol/L.
11. methods according to claim 1, it is characterised in that：The step 3) in, it is described washing with ethanol, acetone or
Deionized water is washed, and it is freeze-drying or vacuum drying to dry.
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| CN107802505B (en) * | 2016-09-09 | 2021-06-01 | 丁观军 | Amorphous calcium phosphate microsphere and application thereof in field of medical daily chemicals |
| CN109401157B (en) * | 2018-11-30 | 2021-02-09 | 中国科学院金属研究所 | Amorphous calcium phosphate-polyacrylic acid hybrid nano material and preparation method and application thereof |
| CN109718249B (en) * | 2019-01-24 | 2020-10-23 | 浙江大学 | Calcium phosphate nanocluster and preparation method and application thereof |
| 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 |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488574A (en) * | 2003-07-28 | 2004-04-14 | 浙江大学 | Method for preparing biomedical amorphous nano calcium phosphate |
| CN1785797A (en) * | 2005-11-15 | 2006-06-14 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
| CN1935636A (en) * | 2006-10-16 | 2007-03-28 | 南京工业大学 | Method for preparing nano amorphous calcium phosphate powder |
| US7517539B1 (en) * | 1996-10-16 | 2009-04-14 | Etex Corporation | Method of preparing a poorly crystalline calcium phosphate and methods of its use |
| CN101518659A (en) * | 2009-03-30 | 2009-09-02 | 浙江大学 | Biological activity bionic calcium phosphate nanometer material as well as preparation method and purpose thereof |
| CN103159198A (en) * | 2013-04-09 | 2013-06-19 | 厦门合众思创生物工程有限公司 | Preparation method of calcium phosphate |
-
2014
- 2014-10-11 CN CN201410535525.5A patent/CN104860284B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7517539B1 (en) * | 1996-10-16 | 2009-04-14 | Etex Corporation | Method of preparing a poorly crystalline calcium phosphate and methods of its use |
| CN1488574A (en) * | 2003-07-28 | 2004-04-14 | 浙江大学 | Method for preparing biomedical amorphous nano calcium phosphate |
| CN1785797A (en) * | 2005-11-15 | 2006-06-14 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
| CN1935636A (en) * | 2006-10-16 | 2007-03-28 | 南京工业大学 | Method for preparing nano amorphous calcium phosphate powder |
| CN101518659A (en) * | 2009-03-30 | 2009-09-02 | 浙江大学 | Biological activity bionic calcium phosphate nanometer material as well as preparation method and purpose thereof |
| CN103159198A (en) * | 2013-04-09 | 2013-06-19 | 厦门合众思创生物工程有限公司 | Preparation method of calcium phosphate |
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