CN110510592B - Method for regulating and preparing hydroxyapatite with excellent cell compatibility - Google Patents
Method for regulating and preparing hydroxyapatite with excellent cell compatibility Download PDFInfo
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- CN110510592B CN110510592B CN201910840823.8A CN201910840823A CN110510592B CN 110510592 B CN110510592 B CN 110510592B CN 201910840823 A CN201910840823 A CN 201910840823A CN 110510592 B CN110510592 B CN 110510592B
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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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention provides a method for regulating and preparing hydroxyapatite with excellent cell compatibility, which is characterized by comprising the following steps: step 1, according to the molar ratio of calcium ions to phosphorus ions of 1.5: 1, respectively preparing Ca (NO)3)2·4H2Aqueous O solution and (NH)4)2HPO4In aqueous solution, and in Ca (NO)3)2·4H2Adding micromolecular amino acid into the O aqueous solution, wherein the concentration ratio of the amino acid to the calcium ion is 4: 1 or 8: 1; step 2, setting parameters during dropwise adding and mixing, and adding (NH)4)2HPO4The mixed aqueous solution of the amino acid and Ca (NO) is slowly dripped into the stirred Ca by a peristaltic pump3)2·4H2O in water solution; step 3, putting the obtained precursor into a microwave digestion instrument, and setting microwave hydrothermal parameters for reaction; and 4, centrifugally washing the solid obtained after the reaction, and then freeze-drying to remove redundant water to obtain the hydroxyapatite.
Description
Technical Field
The invention belongs to the technical field of hydroxyapatite preparation, and particularly relates to a method for preparing hydroxyapatite with excellent cell compatibility by regulation.
Technical Field
Hydroxyapatite (Ca)10(PO4)6(OH)2) The mineral is a main mineral widely existing in bones and teeth of animals, and is the first choice material in the biomedical application at present. The hydroxyapatite has good physical and chemical properties, and the properties are influenced by the surface appearance, the size, the crystallinity and the like of the crystal. These factors lead to differences in the surface properties, mechanical properties and biological properties of hydroxyapatite, which leads to differences in application.
The traditional synthetic method comprises the following steps: precipitation methods, hydrothermal methods, sol-gel methods, and the like. The chemical precipitation method has simple process and has the defects of low crystallinity of the synthesized crystal grains and long synthesis period. The synthesis process of the sol-gel method is simple and the cost is low. However, many factors affect the preparation of hydroxyapatite by the sol-gel method, and it is difficult to obtain particles with good crystallization, uniform particles, high purity and controllable shape and size. The crystallinity of the crystal grains prepared by the hydrothermal method is high and controllable, and the required high-temperature and high-pressure conditions make the large-scale production difficult. Moreover, the hydroxyapatite prepared by the prior art still has certain biological toxicity, can cause additional side effects on human bodies, and the physicochemical property and the cell compatibility are required to be improved.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for controlling the preparation of hydroxyapatite having excellent cell compatibility.
In order to achieve the purpose, the invention adopts the following scheme:
the invention provides a method for regulating and preparing hydroxyapatite with excellent cell compatibility, which is characterized by comprising the following steps: step 1, according to the molar ratio of calcium ions to phosphorus ions of 1.5: 1, respectively preparing Ca (NO)3)2·4H2Aqueous O solution and (NH)4)2HPO4In aqueous solution, and in Ca (NO)3)2·4H2Adding micromolecular amino acid into the O aqueous solution, wherein the concentration ratio of the amino acid to the calcium ion is 4: 1 or 8: 1; step 2, setting parameters during dropwise adding and mixing, and adding (NH)4)2HPO4The mixed aqueous solution of the amino acid and Ca (NO) is slowly dripped into the stirred Ca by a peristaltic pump3)2·4H2O in water solution; step 3, putting the obtained precursor into a microwave digestion instrument, and setting microwave hydrothermal parameters for reaction; and 4, centrifugally washing the solid obtained after the reaction, and then freeze-drying to remove redundant water to obtain the hydroxyapatite.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 1, the small-molecule amino acid added to the solution is glycine or serine, preferably glycine.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 1, the ratio of amino acid to calcium ion concentrations is 8: 1.
preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 2, the rate of the peristaltic pump was set to 20 mL/min.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: during the dropwise addition in step 2, the pH in the reaction system was adjusted to 9 with aqueous ammonia.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 3, the reaction parameters of the microwave hydrothermal reaction are as follows: the microwave power is 300W, the temperature is increased from room temperature to 160 ℃ at the speed of 10 ℃/min, the reaction is carried out for 40min at the temperature of 160 ℃, and then the reaction is carried out with the furnace cooling.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 4, the centrifugation speed is 8000rpm, the time is 3min, and the washing is carried out 3 times by centrifugation with deionized water.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: in step 4, the freeze-drying process is: freezing the product after centrifugal washing in a refrigerator at-20 deg.C for 12h, and drying in a freeze dryer at-45 deg.C for 12 h.
Preferably, the method for regulating and preparing hydroxyapatite with excellent cell compatibility provided by the invention can also have the following characteristics: the length of the prepared hydroxyapatite is 50-130 nm, and the width of the hydroxyapatite is 20-30 nm.
Action and Effect of the invention
The preparation method provided by the invention uses a microwave hot water method, and adopts amino acid as a regulating agent to prepare the hydroxyapatite, the whole process is simple to operate, the preparation period is short, and the obtained product hydroxyapatite has high phase purity and crystallinity and good dispersibility; the product hydroxyapatite powder HAs positive effect on cell proliferation and differentiation, can reach 2.39 times of pure HA at most, and HAs excellent cell compatibility and degradability.
Drawings
Fig. 1 is an XRD (X-ray diffraction analysis) pattern of the method of preparing hydroxyapatite according to an example of the present invention;
fig. 2 is a transmission electron microscope microscopic morphology image of hydroxyapatite prepared in the example of the present invention, wherein (a) is a morphology image of HAG4, (b) is a morphology image of HAG8, (c) is a morphology image of HAS4, and (d) is a morphology image of HAS 8;
FIG. 3 is a graph showing cytotoxicity tests of each group of the leaching solution and MC3T3-11 cell culture in the example of the present invention;
FIG. 4 is a cell morphology chart of each group of leaching solution and MC3T3-11 cells after 1, 3 and 5 days of culture in the embodiment of the invention;
in the above figures, HAG4, HAG8, HAS4 and HAS8 correspond to the products obtained in the first to fourth examples, respectively, the control group is a blank group without materials, and HA is a pure hydroxyapatite group without controlled synthesis.
Detailed Description
The following description will explain in detail specific embodiments of the method for regulating and preparing hydroxyapatite having excellent cell compatibility according to the present invention with reference to the accompanying drawings.
< example one >
As shown in fig. 1, the method for preparing hydroxyapatite with excellent cell compatibility according to the first embodiment of the present invention includes:
3.5423g of calcium nitrate tetrahydrate and 4.5042g of glycine are dissolved in 50ml of deionized water and stirred for 10 minutes; 1.3206g of diammonium phosphate is dissolved in 50ml of deionized water and stirred for 10 minutes; slowly dropping diammonium phosphate into a stirred mixed solution of calcium nitrate tetrahydrate and glycine at the speed of 20mL/min by using a peristaltic pump, keeping the temperature at 25 ℃, adjusting the pH value of the whole dropping process to be 9 by using ammonia water, completing dropping within 10min, and continuously stirring for 20min after completing dropping to ensure that a solution system is uniform. And pouring the obtained precursor into a microwave reaction kettle, and setting the wattage of a microwave digestion instrument to be 300W, the temperature to be 160 ℃ and the time to be 40 min. And after the microwave hydrothermal reaction is finished, pouring the mixture into a 50ml centrifugal tube, carrying out centrifugal washing for 3 times by using deionized water, setting the rotating speed of a centrifugal machine to be 8000rpm, and washing redundant ammonium ions and glycine for 3 min. After washing, putting the mixture into a refrigerator with the temperature of 20 ℃ below zero for freezing for 12 hours; then taking out, putting into a freeze drying oven with the temperature of minus 45 ℃ for freeze drying for 12h to remove water, and obtaining the product of the hydroxyapatite powder. This product was labeled HAG 4.
< example two >
As shown in fig. 1, the method for preparing hydroxyapatite with excellent cell compatibility according to the second embodiment of the present invention includes:
3.5423g of calcium nitrate tetrahydrate and 9.0084g of glycine are dissolved in 50ml of deionized water and stirred for 10 minutes; 1.3206g of diammonium phosphate is dissolved in 50ml of deionized water and stirred for 10 minutes; slowly dropping diammonium phosphate into a stirred mixed solution of calcium nitrate tetrahydrate and glycine at the speed of 20mL/min by using a peristaltic pump, keeping the temperature at 25 ℃, adjusting the pH value of the whole dropping process to be 9 by using ammonia water, completing dropping within 10min, and continuously stirring for 20min after completing dropping to ensure that a solution system is uniform. And pouring the obtained precursor into a microwave reaction kettle, and setting the wattage of a microwave digestion instrument to be 300w, the temperature to be 160 ℃ and the time to be 40 min. And after the microwave hydrothermal reaction is finished, pouring the mixture into a 50ml centrifugal tube, carrying out centrifugal washing for 3 times by using deionized water, setting the rotating speed of a centrifugal machine to be 8000rpm, and washing redundant ammonium ions and glycine for 3 min. After washing, putting the mixture into a refrigerator with the temperature of 20 ℃ below zero for freezing for 12 hours; then taking out, putting into a freeze drying oven with the temperature of minus 45 ℃ for freeze drying for 12h to remove water, and obtaining the product of the hydroxyapatite powder. This product was labeled HAG 8.
< example three >
The method for preparing hydroxyapatite with excellent cell compatibility by regulation and control provided by the third embodiment comprises the following steps:
3.5423g of calcium nitrate tetrahydrate and 6.3054g of serine are dissolved in 50ml of deionized water and stirred for 10 minutes; 1.3206g of diammonium phosphate is dissolved in 50ml of deionized water and stirred for 10 minutes; slowly dropping diammonium phosphate into a stirred mixed solution of calcium nitrate tetrahydrate and serine at the speed of 20mL/min by using a peristaltic pump, keeping the temperature at 25 ℃, adjusting the pH value of the whole dropping process to be 9 by using ammonia water, completing dropping within 10min, and continuously stirring for 20min after completing dropping to ensure that a solution system is uniform. And pouring the obtained precursor into a microwave reaction kettle, and setting the wattage of a microwave digestion instrument to be 300w, the temperature to be 160 ℃ and the time to be 40 min. And after the microwave hydrothermal reaction is finished, pouring the mixture into a 50ml centrifugal tube, carrying out centrifugal washing for 3 times by using deionized water, setting the rotating speed of a centrifugal machine to be 8000rpm and the time to be 3min, and washing redundant ammonium ions and serine. After washing, putting the mixture into a refrigerator with the temperature of 20 ℃ below zero for freezing for 12 hours; then taking out, putting into a freeze drying oven with the temperature of minus 45 ℃ for freeze drying for 12h to remove water, and obtaining the product of the hydroxyapatite powder. This product was labeled HAS 4.
< example four >
As shown in fig. 1, the method for preparing hydroxyapatite with excellent cell compatibility by regulation provided in the fourth embodiment is as follows:
3.5423g of calcium nitrate tetrahydrate and 12.6108g of serine are dissolved in 50ml of deionized water and stirred for 10 minutes; 1.3206g of diammonium phosphate is dissolved in 50ml of deionized water and stirred for 10 minutes; slowly dropping diammonium phosphate into a stirred mixed solution of calcium nitrate tetrahydrate and serine at the speed of 20mL/min by using a peristaltic pump, keeping the temperature at 25 ℃, adjusting the pH value of the whole dropping process to be 9 by using ammonia water, completing dropping within 10min, and continuously stirring for 20min after completing dropping to ensure that a solution system is uniform. And pouring the obtained precursor into a microwave reaction kettle, and setting the wattage of a microwave digestion instrument to be 300w, the temperature to be 160 ℃ and the time to be 40 min. And after the microwave hydrothermal reaction is finished, pouring the mixture into a 50ml centrifugal tube, carrying out centrifugal washing for 3 times by using deionized water, setting the rotating speed of a centrifugal machine to be 8000rpm and the time to be 3min, and washing redundant ammonium ions and serine. After washing, putting the mixture into a refrigerator with the temperature of 20 ℃ below zero for freezing for 12 hours; then taking out, putting into a freeze drying oven with the temperature of minus 45 ℃ for freeze drying for 12h to remove water, and obtaining the hydroxyapatite powder. This product was labeled HAS 8.
The products prepared in examples one to four were taken as samples HAG4, HAG8, HAS4, HAS8 in that order for performance testing:
as shown in FIG. 1, the diffraction peaks of the products obtained in examples one to four match with JCPDS (09-0432) which is the hydroxyapatite PDF standard card, and the crystallinity and purity are good as can be seen from the X-ray diffraction pattern. After the regulation of the added amino acids, diffraction peaks of HAG8 and HAS8 are widened relative to those of HAG4 and HAS4, and the crystallinity of the crystal is reduced.
As shown in FIG. 2, it can be seen from the SEM images of the products, the grains of the products prepared in examples one to four have dispersivity and are in obvious rod-like morphology. And as the amount of amino acid substances added into the precursor is increased, the crystal grains are changed from long rods of HAG4 and HAS4 into short rods of HAG8 and HAS8 and rice grains. For two different amino acids, serine has a more pronounced effect on shortening the aspect ratio of the crystals than glycine.
The leaching solution of the product prepared in the first to fourth examples is co-cultured with MC3T3-11 cells, and the absorbance, namely the OD value, of the cells in 1, 3 and 5 days is tested by a CCK8 method, and the OD value is in positive correlation with the survival rate of the cells. As shown in fig. 3, compared to pure hydroxyapatite, the cell survival rate of amino acid-regulated hydroxyapatite was significantly higher than that of the HA-free blank group (control group) and the pure HA group, and the OD value of HAG8 group was about 2.39 times that of the pure HA group, showing good cell compatibility.
As shown in fig. 4, the morphology of the cells was observed by a fluorescence microscope at 1, 3, and 5 days, and the cell density of the group of HAG4 and HAG8 was significantly higher than that of the other groups, in accordance with the cytotoxicity test.
The above embodiments are merely illustrative of the technical solutions of the present invention. The method for regulating and preparing hydroxyapatite with excellent cell compatibility according to the present invention is not limited to the contents described in the above embodiments, but is subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.
Claims (6)
1. A method for regulating and preparing hydroxyapatite with excellent cell compatibility is characterized by comprising the following steps:
step 1, according to the molar ratio of calcium ions to phosphorus ions of 1.5: 1, respectively preparing Ca (NO)3)2·4H2Aqueous O solution and (NH)4)2HPO4In aqueous solution, and in Ca (NO)3)2·4H2Adding micromolecular amino acid into the O aqueous solution, wherein the concentration ratio of the amino acid to the calcium ion is 4: 1 or 8: 1; the added small molecular amino acid is glycine or serine;
step 2, setting parameters during dropwise adding and mixing, and adding (NH)4)2HPO4The aqueous solution was slowly added dropwise to Ca (NO) under stirring by a peristaltic pump3)2·4H2In the mixed aqueous solution of O and amino acid, the speed of a peristaltic pump is set to be 20 mL/min;
step 3, putting the obtained precursor into a microwave digestion instrument, setting microwave hydrothermal parameters for reaction, wherein the microwave power is 300W, the temperature is increased from room temperature to 160 ℃ at the speed of 10 ℃/min, the reaction is carried out for 40min at the temperature of 160 ℃, and then the reaction is carried out along with furnace cooling;
and 4, centrifugally washing the solid obtained after the reaction, and then freeze-drying to remove redundant water to obtain hydroxyapatite with the length of 50-130 nm and the width of 20-30 nm.
2. The method for preparing hydroxyapatite with excellent cell compatibility according to claim 1, characterized in that:
wherein, in the step 1, the small molecular amino acid added into the solution is glycine.
3. The method for preparing hydroxyapatite with excellent cell compatibility according to claim 1, characterized in that:
wherein, in the step 1, the concentration ratio of the amino acid to the calcium ion is 8: 1.
4. the method for preparing hydroxyapatite with excellent cell compatibility according to claim 1, characterized in that:
wherein, in the dropping process of the step 2, the pH value in the reaction system is adjusted to 9 by ammonia water.
5. The method for preparing hydroxyapatite with excellent cell compatibility according to claim 1, characterized in that:
wherein, in the step 4, the centrifugal speed is 8000rpm, the time is 3min, and the centrifugal washing is carried out by deionized water.
6. The method for preparing hydroxyapatite with excellent cell compatibility according to claim 1, characterized in that:
wherein, in the step 4, the freeze drying treatment comprises the following steps: freezing the product after centrifugal washing in a refrigerator at-20 deg.C for 12h, and drying in a freeze dryer at-45 deg.C for 12 h.
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| CN111320470A (en) * | 2020-01-21 | 2020-06-23 | 武汉理工大学 | Method for preparing hydroxyapatite ceramic by combining microwave hydrothermal method and microwave sintering method |
| CN112978695A (en) * | 2021-03-16 | 2021-06-18 | 华东理工大学 | Preparation method of bionic hydroxyapatite nanoparticles with high osteogenic activity |
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