CN109650364A - A kind of micron of hexagonal prism strontium-incorporated hydroxyapatite and its synthesis technology - Google Patents
A kind of micron of hexagonal prism strontium-incorporated hydroxyapatite and its synthesis technology Download PDFInfo
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- CN109650364A CN109650364A CN201811622641.5A CN201811622641A CN109650364A CN 109650364 A CN109650364 A CN 109650364A CN 201811622641 A CN201811622641 A CN 201811622641A CN 109650364 A CN109650364 A CN 109650364A
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- strontium
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- hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/40—Particle morphology extending in three dimensions prism-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses the synthesis technology of a kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, includes the following steps: 1) to prepare strontium salt solution and phosphoric acid solution respectively, the two is uniformly mixed, mixed solution is obtained；2) urea is added into gained mixed solution, carries out water-bath under agitation, then static ageing at room temperature, then gained reaction solution is filtered, washs, it is dry, obtain a micron hexagonal prism strontium-incorporated hydroxyapatite.Present invention firstly provides using strontium salt and phosphate as primary raw material, under urea effect, it is aided with low temperature water bath condition, prepare rice hexagonal prism strontium-incorporated hydroxyapatite, the preparation method being related to is simple, and reaction condition is mild, and gained hydroxyapatite product can express better biomaterial toughness and mechanical mechanics property, with good biological safety and compatibility, it is suitble to promote and apply.
Description
Technical field
The invention belongs to chemistry, technical field of biological materials, and in particular to a kind of micron of hexagonal prism strontium-incorporated hydroxyapatite and
Its synthesis technology.
Background technique
Strontium is one of essential trace element in human body, and the content in bone is about 0.01%, calcium content is far below, in human body
Bioprocess mineralization process identical with calcium ion is follow in liquid or simulated body fluid (SBF), strontium is introduced into hydroxyapatite
For calcium constituent, it is contemplated that obtain the more superior strontium-incorporated hydroxyapatite of performance.Patent CN1762897A discloses a kind of phosphorus containing strontium
The preparation method of lime stone mainly prepares strontium containing hydroxyapatite by mixing the phosphate of the phosphate of various calcium and strontium,
It is needed in preparation process by techniques such as solidification, baking and sintering；A kind of strontium-incorporated hydroxyapatite is disclosed in patent CN1673177A
Preparation method, using ammonium dihydrogen phosphate and strontium carbonate as primary raw material, it is agitated under the conditions of heating and seal isolation, filtering,
Calcining etc. is prepared.However, these methods all use the process of high temperature and pressure, it be easy to cause the drop of material in vivo
Solve rate decline.
At present about the report of nanometer strontium hydroxyapatite, such as Chinese publication number CN103086337A and CN103086337B
In the preparation method about nanometer strontium hydroxyapatite mentioned, using diammonium hydrogen phosphate and strontium nitrate as primary raw material, and utilize
Concentrated ammonia liquor and freeze-drying method, products therefrom are the aggregation of nano whiskers strontium-incorporated hydroxyapatite crystal.However, nanoscale
There is the problems such as being easy to reunite, solubility is lower in strontium-incorporated hydroxyapatite, be unfavorable for guaranteeing its bioactivity and biocompatibility, and
Limit its application in the fields such as Medical Biology；And the preparation process being related to need to introduce concentrated ammonia liquor or other highly basic items
Part, and there are energy consumption height, the problems such as environmental pollution need to be easy to cause in conjunction with high-temperature and high-pressure conditions.Therefore, it further explores specific
The strontium-incorporated hydroxyapatite of form and structure simultaneously optimizes its preparation process, has important research and application value.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of micron of hexagonal prism strontium hydroxyl phosphorus
Lime stone and its synthesis technology, the synthesis cost being related to is low, and simple process, reaction condition are mild, environmental-friendly, gained strontium hydroxyl phosphorus
Lime stone is in micron order hexagonal prism shape, and crystallization shape is complete, can express excellent bioactivity and biocompatibility.
To achieve the above object, the technical solution adopted by the present invention are as follows:
The synthesis technology of a kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, specifically comprises the following steps:
1) strontium salt solution and phosphate solution are prepared respectively, and the two is uniformly mixed, mixed solution is obtained；
2) urea is added into gained mixed solution, carries out water-bath under agitation, then at room temperature
It is still aging, then gained reaction solution is filtered, it washs, it is dry to get micron hexagonal prism strontium-incorporated hydroxyapatite.
In above scheme, the strontium compound that strontium nitrate, strontium chloride or strontium bromide etc. are dissolved in water is can be selected in the strontium salt.
In above scheme, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid hydrogen two is can be selected in the phosphate
Sodium, diammonium hydrogen phosphate or ammonium dihydrogen phosphate etc..
In above scheme, the strontium salt and phosphatic molar ratio are 1.66~1.8:1.
In above scheme, the urea and phosphatic molar ratio are 190~240:1.
In above scheme, phosphatic concentration is 0.023~0.0035mol/L in the mixed solution.
In above scheme, the water-bath temperature be 90~100 DEG C, the time be 20~for 24 hours.
In above scheme, the static digestion time be 20~for 24 hours.
In above scheme, the washing step is alternately to be washed with dehydrated alcohol and deionized water.
In above scheme, the drying condition is 100~120 DEG C of constant temperature forced air dryings 12~for 24 hours.
In above scheme, the stirring condition is water-bath magnetic agitation.
According to micron hexagonal prism strontium-incorporated hydroxyapatite prepared by above scheme, it has micron hexagonal prism structure, compared to biography
Hydroxyapatite of uniting can express better bioactivity and biocompatibility, can promote osteoblast in conjunction with natural bone
Growth inhibits damaged bone cell growth, achievees the purpose that treat osteoporosis.
Compared with prior art, the invention has the benefit that
1) preparation method of the present invention is simple, and reaction condition is mild, high temperature and pressure and closed reactor is not necessarily to, normal
Pressure carries out, easily controllable and implementation；
2) present invention need not introduce concentrated ammonia liquor or the highly basic of other high concentrations, and water is carried out under the conditions of urea and relative low temperature
Bath reaction, advantageously ensures that the purity and uniformity of products therefrom, obtains pattern and the pure micron hexagonal prism strontium hydroxyl of uniform particle sizes
Base apatite；
3) micron hexagonal prism strontium-incorporated hydroxyapatite stable yield of the present invention can express compared to traditional hydroxyapatite
Better biomaterial toughness and mechanical mechanics property, have good biological safety and compatibility.
Detailed description of the invention
Fig. 1 is the XRD spectrum of 1 gained micron hexagonal prism strontium-incorporated hydroxyapatite of embodiment.
Fig. 2 is that the SEM of 1 gained micron hexagonal prism strontium-incorporated hydroxyapatite of embodiment schemes.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, synthesis technology include the following steps:
1) 0.0058mol strontium nitrate and 0.0035mol biphosphate are sequentially added in the beaker equipped with 100ml distilled water
Sodium stirs evenly to obtain mixed solution；
2) 0.6667mol urea is added into mixed solution, under agitation, under conditions of bath temperature is 95 DEG C,
20h is reacted, then at room temperature, still aging solution generates layering for 24 hours, and upper layer is clear liquid, and lower layer is micron hexagonal prism strontium hydroxyl
Base apatite precipitating；
3) cooled to room temperature after reaction, products therefrom precipitating is placed in a beaker, by sediment dehydrated alcohol
It is alternately washed with deionized water, until object bubble generates when filtering；Gained powder filter cake will be filtered again, in 100 DEG C of constant temperature drums
It air-dries dry for 24 hours to get micron hexagonal prism strontium-incorporated hydroxyapatite.
The present embodiment products therefrom is subjected to X-ray diffraction analysis, the results showed that products therefrom is pure strontium hydroxy-apatite
Stone (see Fig. 1).
Fig. 2 is that the SEM of the present embodiment products therefrom schemes, and crystal morphology is micron order hexagonal prism.
Embodiment 2
A kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, synthesis technology include the following steps:
1) 0.0058mol strontium nitrate and 0.0035mol biphosphate are sequentially added in the beaker equipped with 125ml distilled water
Sodium stirs evenly to obtain mixed solution；
2) 0.75mol urea is added into mixed solution, under agitation, under conditions of bath temperature is 95 DEG C, instead
20h is answered, then at room temperature, still aging solution generates layering for 24 hours, and upper layer is clear liquid, and lower layer is micron hexagonal prism strontium hydroxyl
Apatite precipitating；
3) cooled to room temperature after reaction, products therefrom precipitating is placed in a beaker, by sediment dehydrated alcohol
It is alternately washed with deionized water, until object bubble generates when filtering；Gained powder filter cake will be filtered again, in 100 DEG C of constant temperature drums
It air-dries dry for 24 hours to get micron hexagonal prism strontium-incorporated hydroxyapatite.
Embodiment 3
A kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, synthesis technology include the following steps:
1) 0.0058mol strontium nitrate and 0.0035mol biphosphate are sequentially added in the beaker equipped with 150ml distilled water
Sodium stirs evenly to obtain mixed solution；
2) 0.8333mol urea is added into mixed solution, under agitation, under conditions of bath temperature is 95 DEG C,
20h is reacted, then at room temperature, still aging solution generates layering for 24 hours, and upper layer is clear liquid, and lower layer is micron hexagonal prism strontium hydroxyl
Base apatite precipitating；
3) cooled to room temperature, product are deposited in beaker after reaction, by sediment dehydrated alcohol and go from
Sub- water alternately washs, until object bubble generates when filtering；Gained powder filter cake will be filtered again, in 100 DEG C of constant temperature forced air dryings
For 24 hours to get micron hexagonal prism strontium-incorporated hydroxyapatite.
Strontium-incorporated hydroxyapatite powder obtained by Examples 1 to 3 containing different content of strontium is configured to suspension, to people's bone meat
Tumor cell strain Saos-2 is cultivated, as a result, it has been found that cell survival rate tradition hydroxyapatite increases 25-37%；Pass through fluorescence
Staining analysis Apoptosis situation shows not cause Apoptosis using present invention gained strontium-incorporated hydroxyapatite.In addition, passing through
Mtt assay determines proliferative conditions of the Human embryo osteoblast system hFOB 1.19 on strontium-incorporated hydroxyapatite coating, the discovery present invention
Gained strontium-incorporated hydroxyapatite is more preferable than traditional hydroxyapatite group cultivation effect, and scanning electron microscope also shows cell and healthy growth is presented
Morphological feature.Illustrate that strontium-incorporated hydroxyapatite obtained by the present invention has good biological safety and compatibility.
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of technological parameter of the invention, interval value can realize this
Invention, embodiment numerous to list herein.
Claims (9)
1. the synthesis technology of a kind of micron of hexagonal prism strontium-incorporated hydroxyapatite, which comprises the steps of:
1) strontium salt solution and phosphate solution are prepared respectively, and the two is uniformly mixed, mixed solution is obtained；
2) urea is added into gained mixed solution, carries out water-bath under agitation, then stands at room temperature
It is aged, then gained reaction solution is filtered, is washed, it is dry to get micron hexagonal prism strontium-incorporated hydroxyapatite.
2. synthesis technology according to claim 1, which is characterized in that the strontium salt is strontium nitrate, strontium chloride or strontium bromide.
3. synthesis technology according to claim 1, which is characterized in that the phosphate is sodium dihydrogen phosphate, biphosphate
Potassium, sodium dihydrogen phosphate, disodium hydrogen phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
4. synthesis technology according to claim 1, which is characterized in that the strontium salt and phosphatic molar ratio be 1.66~
1.8:1。
5. synthesis technology according to claim 1, which is characterized in that the urea and phosphatic molar ratio be 190~
240:1。
6. synthesis technology according to claim 1, which is characterized in that phosphatic concentration is in the mixed solution
0.023~0.0035mol/L.
7. synthesis technology according to claim 1, which is characterized in that the water-bath temperature is 90~100 DEG C, the time
For 20~for 24 hours.
8. synthesis technology according to claim 1, which is characterized in that the static digestion time be 20~for 24 hours.
9. the micron hexagonal prism strontium-incorporated hydroxyapatite of any one of the claim 1~8 synthesis technology preparation.
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| CN201811622641.5A CN109650364B (en) | 2018-12-28 | 2018-12-28 | Micron hexagonal-column strontium-doped hydroxyapatite and synthesis process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830464A (en) * | 2021-01-20 | 2021-05-25 | 山东大学 | Strontium-doped hydroxyapatite nanotube and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830464A (en) * | 2021-01-20 | 2021-05-25 | 山东大学 | Strontium-doped hydroxyapatite nanotube and preparation method thereof |
| CN112830464B (en) * | 2021-01-20 | 2022-10-04 | 山东大学 | Strontium-doped hydroxyapatite nanotube and preparation method thereof |
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