CN110203900A - A kind of preparation method of the good porous flake apatite of biocompatibility - Google Patents
A kind of preparation method of the good porous flake apatite of biocompatibility Download PDFInfo
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- CN110203900A CN110203900A CN201910476274.0A CN201910476274A CN110203900A CN 110203900 A CN110203900 A CN 110203900A CN 201910476274 A CN201910476274 A CN 201910476274A CN 110203900 A CN110203900 A CN 110203900A
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a kind of preparation methods of the good porous flake apatite of biocompatibility in biological medicine Material Field, first polyvinyl alcohol is added in calcium salt soln for it, phosphate solution is added dropwise again, it will obtain mixed liquor and be transferred to closed reactor, heating reaction 20-24h in an oven, by product first with Muffle furnace is put into after ethyl alcohol and water washing, 1.5-2.5h is kept the temperature after being heated to 850-950 DEG C, porous flake apatite is obtained after its natural cooling.The present invention, by adjusting the dosage of polyvinyl alcohol, regulates and controls the pattern of the apatite of synthesis, template is nontoxic, and dosage is few and easily removes using polyvinyl alcohol as template.The hydroxyapatite of the method for the present invention synthesis is sheet porous structural and biocompatibility is good, can be used for adsorbing, and carries the purposes such as medicine.
Description
Technical field
Biological medicine material preparation technology technical field of the present invention, is related to a kind of preparation method of apatite, and in particular to
A kind of preparation method of the good porous flake apatite of biocompatibility.
Background technique
It is existing studies have shown that the apatite with hole configurations correspond to the structure of cancellous bone, hole provides cell and adheres to
Surface and bone uptake space (Prakasam et al.. Properties and Applications of Dense
Hydroxyapatite: A Review[J]. Journal of Functional Biomaterials.2015;6: 1099-
1140.), while conducive to ingrowing (Son et al. of surrounding tissue. Preparation and Characterization
of Porous Hydroxyapatite Block Using a HHP Method[J]. Key Engineering
Materials, 2006,309-311:1067-1070.), and then there is higher biocompatibility, in addition, hole configurations is also
Be conducive to (the Xia et al. such as absorption property and drug loading, the sustained release in later period. A facile synthesis of
hydroxyapatite for effective removal strontium ion[J]. Journal of Hazardous
Materials, 2019,368:326-335.).But the ability that hydroxyapatite itself forms porous structure is limited, institute
Method to need to develop the hydroxyapatite that synthesis has hole configurations.
The method of currently used synthesizing hydroxylapatite has a precipitation method, hydro-thermal method, sol-gel method, ultrasonic,
(research [J] of the bioactivity of Pang Xiaofeng, Zeng Hongjuan nano hydroxyapatite powder such as microemulsion method and ultrasonic
Material engineering, 2009,2009 (4): 14-17.).If it is the hydroxyapatite of certain specific morphologies and structure is obtained, usually
It will use a large amount of toxic templates, lead to the material residual harmful substance of production or the post-processing approach of high cost.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the good porous flake apatite of biocompatibility.The party
Method can obtain sheet, porous, the good hydroxyapatite of biocompatibility.
Realize that the technical solution of the object of the invention is as follows:
A kind of preparation method of the good porous flake apatite of biocompatibility, comprises the following steps that
Polyvinyl alcohol (PVA) is added in solubility calcium salting liquid, phosphate solution is then added dropwise, obtained mixed liquor is shifted
Enter closed reactor, be heated to 140-180 DEG C in an oven, reacts 20-24h, first tentatively washed with second alcohol and water after reaction
The soluble salts substances of removal are washed, then solid matter is put into Muffle furnace, are heated to 3-5 DEG C/min of heating rate
Porous flake apatite is obtained after keeping the temperature 1.5-2.5h, then natural cooling after 850-950 DEG C.
In the mixed solution, the molar ratio of calcium ion and phosphate anion is (1.5-2): 1, phosphate anion rubs
Your concentration is 0.01-0.5mol/L.
In the mixed solution, the mass concentration of polyvinyl alcohol is 0.04%-1.2%.
In the present invention, soluble calcium salt is preferably calcium chloride or calcium nitrate.
The phosphate is preferably ten phosphate dihydrate trisodiums.
Compared with prior art, the invention has the following advantages that
In the present invention, the polyvinyl alcohol of addition is template, and template dosage is few and nontoxic, by the use for adjusting polyvinyl alcohol
Amount, the pattern of the apatite of controllable synthesis, trend are to increase hole configurations with the dosage of polyvinyl alcohol to gradually increase, and are acted as
It is that when initial reaction generates hydroxyapatite, hydroxyapatite is grown around template periphery, and gradually aggregation increases with principle
Greatly, 1.5-2.5h is kept the temperature after being heated to 850-950 DEG C, by polyvinyl alcohol oxygenolysis and can be removed, polyvinyl alcohol easily removes,
Noresidue.The method of the present invention synthesis apatite be sheet porous structural and biocompatibility it is good, can meet applied to absorption,
Carry the fields such as medicine.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture that apatite obtained when polyvinyl alcohol is added without in embodiment 1.
Fig. 2 is the transmission electron microscope picture of apatite obtained when polyvinyl alcohol additional amount is 0.04% in embodiment 1.
Fig. 3 is the transmission electron microscope picture of apatite obtained when polyvinyl alcohol additional amount is 0.2% in embodiment 1.
Fig. 4 is the transmission electron microscope picture of apatite obtained when polyvinyl alcohol additional amount is 0.4% in embodiment 1.
Fig. 5 is the transmission electron microscope picture of apatite obtained when polyvinyl alcohol additional amount is 1.2% in embodiment 1.
Fig. 6 is the scanning electron microscope (SEM) photograph that apatite obtained when polyvinyl alcohol is added without in embodiment 1.
Fig. 7 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.04% in embodiment 1.
Fig. 8 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.2% in embodiment 1.
Fig. 9 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.4% in embodiment 1.
Figure 10 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 1.2% in embodiment 1.
Figure 11 is the infrared characterization chart of apatite made from embodiment 1.
Figure 12 is to be surveyed when cultivating 1,3 and 5 day in apatite made from MG-63 cell and embodiment 1 using cck8 kit
The cell Proliferation figure of examination, in figure, the corresponding cylindricality of number of days respectively corresponds DMEM, S1, S2, S3, S4 and S5 from left to right.
Figure 13 is the dead stained photographs of work cultivated in apatite made from MG-63 cell and embodiment 21,3 days.Wherein a-e
Photo after co-culturing 1 day for S1-S5 sample and cell, f are the control group without material；G-k is that S1-S5 sample and cell are total
Photo after culture 3 days, l are the control group without material.
Figure 14 is that apatite polycrystal X-ray diffraction made from embodiment 3 characterizes map.
Figure 15 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.04% in comparative example.
Figure 16 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.2% in comparative example.
Figure 17 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 0.4% in comparative example.
Figure 18 is the scanning electron microscope (SEM) photograph of apatite obtained when polyvinyl alcohol additional amount is 1.2% in comparative example.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
It takes 1.84g anhydrous calcium chloride and appropriate PVA to be dissolved in 30mL deionized water, obtains calcium source solution；Separately take 3.80g 12
Hypophosphite monohydrate trisodium is dissolved in 20mL deionized water, obtains phosphorus source solution.Calcium source solution and phosphorus source solution are sequentially added closed
In inner liner of reaction kettle, and stirred with glass bar.Because sodium phosphate itself hydrolysis causes pH value of solution to increase, so there is no need to ammonium hydroxide is additionally added
Equal substances adjust acid-base property.After stirring the mixture for uniformly, reaction kettle is put into baking oven, heats for 24 hours, has reacted at 160 DEG C
Cheng Hou, it is cooling to reaction kettle, the solids of taking-up water, ethyl alcohol are washed 3 times respectively to remove soluble inorganic salt and a small amount of organic
Obtained solid is respectively put into Muffle furnace after drying by object, is heated in air atmosphere with 4 DEG C of heating rates per minute
900 DEG C, to remove extra PVA, keep the temperature natural cooling after 2h, obtain final product.Wherein, the dosage of PVA is respectively 0g,
0.022g, 0.111g, 0.223g and 0.668g, corresponding products nr are S1, S2, S3, S4 and S5.
Fig. 1 to Fig. 5 and Fig. 6 to Figure 10 is respectively product S1 in case study on implementation 1, S2, S3, the transmission electron microscope picture of S4 and S5 and
Scanning electron microscope (SEM) photograph.These charts are bright when being free of PVA, and the product that synthesizes is nutty structure, and be not added with that PVA is prepared is nothing
The hydroxyapatite of pore structure, and adding PVA is the hydroxyapatite that the apatite that synthesizes is sheet porous structural after template,
And as the concentration of polyvinyl alcohol increases, the hole configurations of apatite is gradually increased.
Figure 11 is the IR Characterization map that product is made in embodiment 1, phosphate group (473,564,599,960,1021
With 1085 cm-1Place) and hydroxyl (632 and 3567 cm-1Place) absorption peak clearly, and illustrate this without other miscellaneous peaks substantially
A little samples have the features of hydroxyapatite, and have removed the organic matters such as remaining PVA, but cannot exclude and may contain other phosphorus
Hydrochlorate substance.
Figure 12 is that MG-63 cell is surveyed when cultivating 1,3 and 5 day in the apatite made from embodiment 1 using cck8 kit
The cell Proliferation figure of examination.It can be seen from the figure that the material of synthesis plays facilitation for MG-63 cell proliferation, say
Bright material obtained has good biocompatibility and bioactivity.
Embodiment 2
It takes 3.91g four water-calcium nitrate and appropriate PVA to be dissolved in 30mL deionized water, obtains calcium source solution；Separately take 3.80g 12
Hypophosphite monohydrate trisodium is dissolved in 20mL deionized water, obtains phosphorus source solution.Calcium source solution and phosphorus source solution are sequentially added closed
In inner liner of reaction kettle, and stirred with glass bar.After stirring the mixture for uniformly, reaction kettle is put into baking oven, is heated at 140 DEG C
For 24 hours, after the reaction was completed, cooling to reaction kettle, the solids of taking-up water, ethyl alcohol are washed 3 times respectively to remove soluble inorganic salt
And a small amount of organic matter, obtained solid is respectively put into Muffle furnace after drying, with 3 DEG C of heating speed per minute in air atmosphere
Rate is heated to 850 DEG C to remove extra PVA, keeps the temperature natural cooling after 2.5h, obtains final product.Wherein, the dosage of PVA point
Not Wei 0g, 0.023g, 0.115g, 0.231g and 0.693g, corresponding products nr be S1, S2, S3, S4 and S5.
Figure 13 is the dead stained photographs of work that material made from MG-63 cell and embodiment 2 co-cultures 1,3 days.It can be seen by figure
Out, after culture 1 day to 3 days, cellular morphology is normal, and quantity increased and living cells is far more than dead cell, illustrates these materials
Material is to MG-63 cell almost without cytotoxicity.
Embodiment 3
It takes 3.68g anhydrous calcium chloride and appropriate PVA to be dissolved in 30mL deionized water, obtains calcium source solution；Separately take 7.60g 12
Hypophosphite monohydrate trisodium is dissolved in 20mL deionized water, obtains phosphorus source solution.Calcium source solution and phosphorus source solution are sequentially added closed
After stirring the mixture in inner liner of reaction kettle, and after being stirred with glass bar uniformly, reaction kettle is put into baking oven, is added at 180 DEG C
Hot 20h, it is after the reaction was completed, cooling to reaction kettle, the solids of taking-up water, ethyl alcohol are respectively washed 3 times and removed soluble inorganic
Salt and a small amount of organic matter, are respectively put into Muffle furnace for obtained solid after drying, with 5 DEG C of heatings per minute in air atmosphere
Rate is heated to 950 DEG C to remove extra PVA, keeps the temperature natural cooling after 1.5h, obtains final product.Wherein, the dosage of PVA
Respectively 0g, 0.025g, 0.123g, 0.245g and 0.735g, corresponding products nr are S1, S2, S3, S4 and S5.
Figure 14 is that hydroxyl apatite polycrystal X-ray diffraction made from embodiment 3 characterizes map, main peak and hydroxyapatite
Standard card JCPDS No.09-0432 it is consistent, the corresponding crystal face of main diffraction peak has been labeled in figure.But in addition to hydroxyl phosphorus
It is the feature diffraction of bata-tricalcium phosphate (β-TCP) occur at 27.7,31.0 and 34.3 in 2 θ angles outside the diffraction maximum of lime stone
Peak illustrates that during Muffle furnace calcined product, phase transition is had occurred in part of hydroxyl apatite, generates bata-tricalcium phosphate,
But content is less, main body or hydroxyapatite.
Comparative example
This comparative example and the S1 in embodiment 1 are essentially identical, unique the difference is that reaction temperature is set as 80 DEG C.
Figure 15-18 is the surface sweeping electromicroscopic photograph of material made from comparative example.Picture shows apatite obtained in comparative example
Pattern be it is rodlike, have no the porous laminated structure in embodiment.
The present invention does not limit to and above-described embodiment, and the parameter in preparation process can select as follows:
It is heated to 140-180 DEG C in baking oven, reacts 20-24h, Muffle furnace can be heated to 3-5 DEG C/min of heating rate
Keep the temperature 1.5-2.5h after 850-950 DEG C, the molar ratio of calcium ion and phosphate anion is (1.5-2): 1, phosphate anion rubs
Your concentration is 0.01-0.5mol/L.In the mixed solution, the mass concentration of polyvinyl alcohol is 0.04%-1.2%.These ginsengs
Number can choose the arbitrary value in boundary value i.e. range, and the good porous flake apatite of biocompatibility can be obtained.
On the basis of technical solution disclosed by the invention, those skilled in the art according to disclosed technology contents,
Some replacements and deformation can be made to some of which technical characteristic by not needing creative labor, these replacements and deformation
It is within the scope of the invention.
Claims (5)
1. a kind of preparation method of the good porous flake apatite of biocompatibility, which is characterized in that comprise the following steps that
Polyvinyl alcohol is added in solubility calcium salting liquid, phosphate solution is then added dropwise, obtained mixed liquor is transferred to close
Reaction kettle is closed, is heated to 140-180 DEG C in an oven, 20-24h is reacted, is first gone after reaction with second alcohol and water primary wash
It is put into Muffle furnace except soluble salts substances, then by solid matter, 850-950 is heated to 3-5 DEG C/min of heating rate
Porous flake apatite is obtained after keeping the temperature 1.5-2.5h, then natural cooling after DEG C.
2. a kind of preparation method of the good porous flake apatite of biocompatibility according to claim 1, feature
It is, in the mixed solution, the molar ratio of calcium ion and phosphate anion is (1.5-2): 1, mole of phosphate anion
Concentration is 0.01-0.5mol/L.
3. a kind of preparation method of the good porous flake apatite of biocompatibility according to claim 1 or 2, special
Sign is, in the mixed solution, the mass concentration of polyvinyl alcohol is 0.04%-1.2%.
4. a kind of preparation method of the good porous flake apatite of biocompatibility according to claim 1 or 2, special
Sign is that calcium salt is calcium chloride or calcium nitrate.
5. a kind of preparation method of the good porous flake apatite of biocompatibility according to claim 1 or 2, special
Sign is that the phosphate is ten phosphate dihydrate trisodiums.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106178127A (en) * | 2016-07-26 | 2016-12-07 | 东华大学 | A kind of original position prepares the method for modified hydroxylapatite/polyvinyl alcohol nano composite membrane |
| CN107376795A (en) * | 2017-07-18 | 2017-11-24 | 中国矿业大学 | A kind of preparation method of polyvinyl alcohol/hydroxyapatite composite microspheres |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106178127A (en) * | 2016-07-26 | 2016-12-07 | 东华大学 | A kind of original position prepares the method for modified hydroxylapatite/polyvinyl alcohol nano composite membrane |
| CN107376795A (en) * | 2017-07-18 | 2017-11-24 | 中国矿业大学 | A kind of preparation method of polyvinyl alcohol/hydroxyapatite composite microspheres |
Non-Patent Citations (5)
| Title |
|---|
| CHAO QI等: "Hydroxyapatite nanosheet-assembled porous hollow microspheres：DNA-templated hydrothermal synthesis，drug delivery and protein adsorption", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| SUPRABLHA等: "Biomimetically synthesis polymer-hydroxyapatite sheet like nano-composite", 《J MATER SCI:METAR MED》 * |
| 李刚等: "非离子表面活性剂改性羟基磷灰石粉体的制备", 《硅酸盐通报》 * |
| 李正茂等: "聚乙烯醇改性纳米羟基磷灰石的制备", 《山东陶瓷》 * |
| 胡路阳等: "羟基磷灰石的形貌控制与表征", 《佳木斯大学学报(自然科学版)》 * |
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