CN110203900B - Preparation method of porous flaky apatite with good biocompatibility - Google Patents
Preparation method of porous flaky apatite with good biocompatibility Download PDFInfo
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- CN110203900B CN110203900B CN201910476274.0A CN201910476274A CN110203900B CN 110203900 B CN110203900 B CN 110203900B CN 201910476274 A CN201910476274 A CN 201910476274A CN 110203900 B CN110203900 B CN 110203900B
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- 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
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- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a preparation method of porous flaky apatite with good biocompatibility, which belongs to the field of biomedical materials. The invention takes polyvinyl alcohol as a template agent, regulates and controls the appearance of the synthesized apatite by adjusting the dosage of the polyvinyl alcohol, and the template agent is non-toxic, has small dosage and is easy to remove. The hydroxyapatite synthesized by the method is of a sheet porous structure and has good biocompatibility, and can be used for adsorption, drug loading and other purposes.
Description
Technical Field
The invention belongs to the technical field of preparation of biomedical materials, and relates to a preparation method of apatite, in particular to a preparation method of porous flaky apatite with good biocompatibility.
Background
It has been shown in the prior art that apatite having a pore structure corresponds to the structure of cancellous bone, and pores provide a surface for cell attachment and a space for bone growth (Prakasam et al: Properties and Applications of Dense Hydroxypatite: A Review [ J ]. Journal of Functional biomaterials.2015;6: 1099-; 1140.), and facilitates the ingrowth of surrounding tissues (Son et al: Preparation and Characterization of pore Hydroxypatite Block Using a HHP Method [ J ]. Key Engineering Materials,2006, 309: 1067-), thereby having higher biocompatibility, and further, the pore structure facilitates later adsorption and drug loading, release [ 326 ] of Porous hydrogel for bone growth [ J.: 2019,368. ]. However, the hydroxyapatite itself has a limited ability to form a porous structure, so that it is required to develop a method for synthesizing the hydroxyapatite having a porous structure.
The currently common methods for synthesizing hydroxyapatite include precipitation, hydrothermal, sol-gel, ultrasonic synthesis, microemulsion, and ultrasonic synthesis (dawn, Zeanxuan, study of biological activity of nano hydroxyapatite powder [ J ] material engineering, 2009, 2009(4): 14-17.). If hydroxyapatite with certain specific morphology and structure is obtained, a large amount of toxic template agent is generally used, and the produced material has harmful substances or expensive post-treatment methods.
Disclosure of Invention
The invention aims to provide a preparation method of porous flaky apatite with good biocompatibility. The method can obtain hydroxyapatite with good sheet shape, porosity and biocompatibility.
The technical scheme for realizing the purpose of the invention is as follows:
a method for preparing porous flaky apatite with good biocompatibility comprises the following steps:
adding polyvinyl alcohol (PVA) into a soluble calcium salt solution, then dropwise adding a phosphate solution, transferring the obtained mixed solution into a closed reaction kettle, heating the mixed solution to 140 ℃ and 180 ℃ in an oven, reacting for 20-24h, firstly, preliminarily washing the mixed solution with ethanol and water to remove soluble salt substances after the reaction is finished, then, putting the solid substance into a muffle furnace, heating the mixed solution to 850 ℃ and 950 ℃ at the heating rate of 3-5 ℃/min, then, preserving the heat for 1.5-2.5h, and naturally cooling to obtain the porous flaky apatite.
In the mixed solution, the molar ratio of calcium ions to phosphate ions is (1.5-2): 1, the molar concentration of phosphate ions is 0.01-0.5 mol/L.
In the mixed solution, the mass concentration of the polyvinyl alcohol is 0.04-1.2%.
In the present invention, the soluble calcium salt is preferably calcium chloride or calcium nitrate.
The phosphate is preferably trisodium phosphate dodecahydrate.
Compared with the prior art, the invention has the following advantages:
the added polyvinyl alcohol is a template agent, the template agent is low in dosage and non-toxic, the morphology of the synthesized apatite can be regulated and controlled by regulating the dosage of the polyvinyl alcohol, the trend of the template agent is that the pore structure is gradually increased along with the increase of the dosage of the polyvinyl alcohol, the function principle is that when the hydroxyapatite is generated in the initial reaction, the hydroxyapatite grows around the periphery of the template agent and is gradually gathered and enlarged, the hydroxyapatite is heated to 850 ℃ plus 950 ℃ and then is kept for 1.5 to 2.5 hours, the polyvinyl alcohol can be oxidized, decomposed and removed, and the polyvinyl alcohol is easy to remove without residues. The apatite synthesized by the method has a flaky porous structure and good biocompatibility, and can be applied to the fields of adsorption, medicine carrying and the like.
Drawings
FIG. 1 is a transmission electron micrograph of apatite prepared in example 1 without adding polyvinyl alcohol.
FIG. 2 is a transmission electron micrograph of apatite prepared in example 1, in which the polyvinyl alcohol is added in an amount of 0.04%.
FIG. 3 is a transmission electron micrograph of apatite prepared in example 1, in which the content of polyvinyl alcohol is 0.2%.
FIG. 4 is a transmission electron micrograph of apatite prepared in example 1 in which the polyvinyl alcohol is added in an amount of 0.4%.
FIG. 5 is a transmission electron micrograph of apatite prepared in example 1, in which the polyvinyl alcohol is added in an amount of 1.2%.
FIG. 6 is a scanning electron micrograph of apatite obtained in example 1 in which polyvinyl alcohol was not added.
FIG. 7 is a scanning electron micrograph of apatite prepared in example 1, in which the polyvinyl alcohol content is 0.04%.
FIG. 8 is a scanning electron micrograph of apatite prepared in example 1, in which the polyvinyl alcohol is added in an amount of 0.2%.
FIG. 9 is a scanning electron micrograph of apatite prepared in example 1, in which the polyvinyl alcohol is added in an amount of 0.4%.
FIG. 10 is a scanning electron micrograph of apatite prepared in example 1 in which polyvinyl alcohol is added in an amount of 1.2%.
FIG. 11 is an infrared characterization chart of apatite prepared in example 1.
FIG. 12 is a graph showing cell proliferation of MG-63 cells tested using cck8 kit when cultured with apatite prepared in example 1 for 1, 3 and 5 days, in which columns corresponding to days correspond to DMEM, S1, S2, S3, S4 and S5 from left to right, respectively.
FIG. 13 is a photograph of live and dead staining of MG-63 cells cultured with apatite prepared in example 2 for 1 and 3 days. Wherein a-e are photographs of the S1-S5 sample after 1 day of co-culture with the cells, and f is a control group without material; g-k are photographs of the S1-S5 samples after 3 days of co-culture with the cells, l is a control group without material.
FIG. 14 is an X-ray diffraction pattern of a polycrystalline apatite powder prepared in example 3.
FIG. 15 is a scanning electron microscope photograph of apatite prepared in the comparative example in which the polyvinyl alcohol addition amount is 0.04%.
FIG. 16 is a scanning electron microscope photograph of apatite prepared in the comparative example in which the polyvinyl alcohol is added in an amount of 0.2%.
FIG. 17 is a scanning electron microscope photograph of apatite prepared in the comparative example in which the polyvinyl alcohol is added in an amount of 0.4%.
FIG. 18 is a scanning electron microscope photograph of apatite prepared in the comparative example in which the polyvinyl alcohol addition amount is 1.2%.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
Dissolving 1.84g of anhydrous calcium chloride and a proper amount of PVA in 30mL of deionized water to obtain a calcium source solution; and dissolving 3.80g of trisodium phosphate dodecahydrate in 20mL of deionized water to obtain a phosphorus source solution. And sequentially adding the calcium source solution and the phosphorus source solution into the lining of the closed reaction kettle, and stirring by using a glass rod. As the pH value of the solution is increased due to the self-hydrolysis of the sodium phosphate, the pH value of the solution is not required to be adjusted by adding substances such as ammonia water and the like additionally. And (2) after the mixture is uniformly stirred, putting the reaction kettle into an oven, heating for 24h at 160 ℃, after the reaction is finished, cooling the reaction kettle, washing the taken out solid with water and ethanol for 3 times respectively to remove soluble inorganic salt and a small amount of organic matters, drying, putting the obtained solid into a muffle furnace respectively, heating to 900 ℃ in an air atmosphere at a heating rate of 4 ℃ per minute to remove redundant PVA, preserving heat for 2h, and naturally cooling to obtain a final product. The amounts of PVA used were 0g, 0.022g, 0.111g, 0.223g and 0.668g, respectively, corresponding to product numbers S1, S2, S3, S4 and S5.
Fig. 1 to 5 and 6 to 10 are transmission electron micrographs and scanning electron micrographs of the products S1, S2, S3, S4 and S5 in example 1, respectively. These figures show that the product synthesized without PVA is granular, hydroxyapatite with non-porous structure is prepared without PVA, and apatite synthesized with PVA as template is hydroxyapatite with sheet porous structure and has gradually increased pore structure with the increased concentration of PVA.
FIG. 11 is an infrared characterization spectrum of the product obtained in example 1, phosphate groups (473, 564, 599, 960, 1021, and 1085 cm) -1 Para) and hydroxy (632 and 3567 cm) -1 The absorption peak is very obvious and basically has no other impurity peaks, which indicates that the samples have the characteristics of hydroxyapatite and remove residual organic matters such as PVA, but cannot exclude the substances possibly containing other phosphate substances.
FIG. 12 is a graph showing cell proliferation of MG-63 cells tested using the cck8 kit when cultured in apatite prepared in example 1 for 1, 3, and 5 days. As can be seen from the figure, the synthesized material has the promotion effect on the MG-63 cell proliferation, and the prepared material has good biocompatibility and bioactivity.
Example 2
Dissolving 3.91g of calcium nitrate tetrahydrate and a proper amount of PVA (polyvinyl alcohol) in 30mL of deionized water to obtain a calcium source solution; and dissolving 3.80g of trisodium phosphate dodecahydrate in 20mL of deionized water to obtain a phosphorus source solution. And sequentially adding the calcium source solution and the phosphorus source solution into the lining of the closed reaction kettle, and stirring by using a glass rod. And after the mixture is uniformly stirred, putting the reaction kettle into an oven, heating for 24 hours at the temperature of 140 ℃, after the reaction is finished, cooling the reaction kettle, washing the taken out solid with water and ethanol for 3 times respectively to remove soluble inorganic salt and a small amount of organic matters, drying, putting the obtained solid into a muffle furnace respectively, heating to 850 ℃ in an air atmosphere at the heating rate of 3 ℃ per minute to remove redundant PVA, preserving heat for 2.5 hours, and naturally cooling to obtain a final product. The amounts of PVA used were 0g, 0.023g, 0.115g, 0.231g and 0.693g, respectively, and the corresponding products were numbered S1, S2, S3, S4 and S5.
FIG. 13 is a photograph of live and dead staining of MG-63 cells cultured for 1 and 3 days with the material obtained in example 2. As can be seen, the cell morphology was normal, the number increased and the number of viable cells was much greater than that of dead cells after 1 to 3 days of culture, indicating that these materials were almost non-cytotoxic to MG-63 cells.
Example 3
Dissolving 3.68g of anhydrous calcium chloride and a proper amount of PVA in 30mL of deionized water to obtain a calcium source solution; another 7.60g of trisodium phosphate dodecahydrate is dissolved in 20mL of deionized water to obtain a phosphorus source solution. Sequentially adding a calcium source solution and a phosphorus source solution into an inner liner of a closed reaction kettle, stirring the mixture uniformly by using a glass rod, putting the reaction kettle into an oven, heating for 20 hours at 180 ℃, after the reaction is finished, cooling the reaction kettle, washing the taken-out solid for 3 times by using water and ethanol respectively to remove soluble inorganic salt and a small amount of organic matters, drying, putting the obtained solid into a muffle furnace respectively, heating to 950 ℃ at a heating rate of 5 ℃ per minute in an air atmosphere to remove redundant PVA, preserving heat for 1.5 hours, and naturally cooling to obtain a final product. The amounts of PVA used were 0g, 0.025g, 0.123g, 0.245g and 0.735g, respectively, corresponding to product numbers S1, S2, S3, S4 and S5.
Fig. 14 is an X-ray diffraction characterization map of the hydroxyapatite polycrystal prepared in example 3, wherein the main peak is consistent with JCPDS No.09-0432 of a standard card of hydroxyapatite, and the crystal face corresponding to the main diffraction peak is marked in the map. However, in addition to the diffraction peaks of hydroxyapatite, characteristic diffraction peaks of β -tricalcium phosphate (β -TCP) appeared at angles of 27.7, 31.0 and 34.3 of 2 θ, indicating that during the muffle furnace calcination of the product, a portion of hydroxyapatite underwent phase transformation to produce β -tricalcium phosphate, but the main body was hydroxyapatite.
Comparative example
This comparative example is substantially the same as S1 in example 1, except that the reaction temperature was set to 80 ℃.
FIGS. 15 to 18 are scanning electron micrographs of the materials prepared in the comparative examples. The pictures show that the apatite obtained in the comparative example has a rod-like morphology, and has no porous sheet-like structure in the examples.
The invention is not limited to the above-mentioned examples, and the parameters in the preparation process can be selected as follows:
heating the mixture in an oven to 140-: 1, the molar concentration of phosphate ions is 0.01-0.5 mol/L. In the mixed solution, the mass concentration of the polyvinyl alcohol is 0.04-1.2%. These parameters may be selected to have any values within a range defined by boundaries, and porous plate-shaped apatite having good biocompatibility can be obtained.
Based on the technical solutions disclosed in the present invention, those skilled in the art can make various alterations and modifications to some technical features without creative efforts based on the disclosed technical contents, and the alterations and modifications are all within the protection scope of the present invention.
Claims (5)
1. A method for preparing porous flaky apatite with good biocompatibility is characterized by comprising the following steps:
adding polyvinyl alcohol into soluble calcium salt solution, then dropwise adding phosphate solution, transferring the obtained mixed solution into a closed reaction kettle, heating the mixed solution to 140-180 ℃ in a drying oven, reacting for 20-24h, firstly, preliminarily washing with ethanol and water to remove soluble salt substances after the reaction is finished, then, putting the solid substance into a muffle furnace, heating the mixed solution to 850-950 ℃ at the heating rate of 3-5 ℃/min, then, preserving heat for 1.5-2.5h, and naturally cooling to obtain the porous flaky apatite.
2. The method of claim 1, wherein the molar ratio of calcium ions to phosphate ions in the mixed solution is (1.5-2): 1, the molar concentration of phosphate ions is 0.01-0.5 mol/L.
3. The method as claimed in claim 1 or 2, wherein the mixed solution contains polyvinyl alcohol in an amount of 0.04 to 1.2% by mass.
4. The method of claim 1 or 2, wherein the calcium salt is calcium chloride or calcium nitrate.
5. The method as claimed in claim 1 or 2, wherein the phosphate is trisodium phosphate dodecahydrate.
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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 |
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| Biomimetically synthesis polymer-hydroxyapatite sheet like nano-composite;Suprablha等;《J Mater Sci:Metar Med》;20070628;第19卷;301-304页 * |
| Hydroxyapatite nanosheet-assembled porous hollow microspheres：DNA-templated hydrothermal synthesis，drug delivery and protein adsorption;Chao Qi等;《Journal of Materials Chemistry》;20120907;第22卷;22642-22650页 * |
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