CN111268916A - Preparation method of selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder - Google Patents
Preparation method of selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder Download PDFInfo
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- CN111268916A CN111268916A CN202010189244.4A CN202010189244A CN111268916A CN 111268916 A CN111268916 A CN 111268916A CN 202010189244 A CN202010189244 A CN 202010189244A CN 111268916 A CN111268916 A CN 111268916A
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- 239000000843 powder Substances 0.000 title claims abstract description 34
- 239000011521 glass Substances 0.000 title claims abstract description 30
- BXYHXVIURNMBJM-UHFFFAOYSA-N [P].[Si].[Ca] Chemical compound [P].[Si].[Ca] BXYHXVIURNMBJM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000000975 bioactive effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011669 selenium Substances 0.000 claims abstract description 19
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 230000008439 repair process Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910018162 SeO2 Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000002386 leaching Methods 0.000 abstract description 2
- ZMCVOPZMEHFFPQ-UHFFFAOYSA-H calcium silicon(4+) diphosphate Chemical compound [Si+4].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMCVOPZMEHFFPQ-UHFFFAOYSA-H 0.000 abstract 1
- 238000000338 in vitro Methods 0.000 abstract 1
- 230000011164 ossification Effects 0.000 abstract 1
- 239000005313 bioactive glass Substances 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000012620 biological material Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000033115 angiogenesis Effects 0.000 description 2
- 210000001185 bone marrow Anatomy 0.000 description 2
- 230000010478 bone regeneration Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 210000000130 stem cell Anatomy 0.000 description 2
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000037180 bone health Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000037451 immune surveillance Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000036244 malformation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000025053 regulation of cell proliferation Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
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- C03C12/00—Powdered glass; Bead compositions
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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Abstract
The invention discloses a preparation method of selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder. The method uses SeO as selenium element2The method is used for doping the mesoporous glass, and the preparation steps are as follows: using P123 as template agent, TEP as phosphorus source, Ca (NO)3)2.4H2O is a calcium source, TEOS is a silicon source, powder obtained by hydrothermal reaction is washed by absolute ethyl alcohol, dried and calcined to remove a template agent to obtain the selenium-doped calcium silicon phosphate bioactive mediumPorous glass powder. The test shows that: the selenium-doped bioactive mesoporous glass prepared by the invention has the advantages that the selenium doping molar mass accounts for 1-8%, and the specific surface area (S) is higherBET>500m2The average mesoporous diameter is about 67nm, and the leaching liquor can obviously induce and promote osteogenesis. Based on good in vitro bioactivity and bone effect promotion, the material has wide application prospect in the field of bone tissue engineering.
Description
Technical Field
The invention relates to the field of manufacturing of microelement-doped mesoporous glass powder for bone repair, in particular to a method for preparing a mesoporous glass powder by using P123 as a template agent, TEP as a phosphorus source and Ca (NO)3)2.4H2O is a calcium source, SeO2Is a selenium source, TEOS is a silicon source, and is synthesized into a selenium-doped organism through a hydrothermal reactionA preparation method of active mesoporous glass powder.
Background
Bone tissue defects of human bodies caused by congenital malformation, diseases, trauma, aging and the like become common diseases in orthopedics clinic, and a large amount of bone repair materials are needed for treating the bone tissue defects. The ideal bone repair material should have good biocompatibility, the degradation products are non-toxic and do not cause long-term inflammatory reactions; can recruit related cells such as bone marrow stem cells; good biological degradation performance, degradation rate and tissue growth rate are well matched with each other, and biological activity is good. (Acta biomaterials, 2013, 9(1): 4457-4486.). The ability of bone repair materials to induce bone regeneration and promote angiogenesis is particularly important for the formation and growth of new bone.
Based on SiO2-CaO-P2O5The bioactive mesoporous glass (MBG) of the system has a highly ordered mesoporous structure, and the pore diameter is between 5 and 20 nm. The dissolution of calcium and phosphorus ions in the material is beneficial to the formation of hydroxyapatite, and because of higher surface area and porosity, MBG shows better bone bonding, degradation and absorption characteristics, and is a promising bone defect filling material (Journal of biological Materials Research Part B Applied Biomaterials,2018, 106 (30).
Selenium (Se) is a trace element essential to human body, and the ingestion of a proper amount of selenium is essential to bone health, mainly manifested in the aspects of antioxidation, enhancement of immune surveillance, regulation of cell proliferation and the like (nutriments, 2013, 5(1): 97-110.). Se is doped into the mesoporous bioactive glass, so that the MBG can be endowed with antibacterial property, oxidation resistance and cancer inhibition, and the bone regeneration capability of the MBG is enhanced. At present, the sol-gel method (ceramics International, 2015, 42(2):3609-BET=230~250m2/g) are detrimental to bone tissue binding and angiogenesis, thereby limiting the use of MBG in bone repair.
Disclosure of Invention
The invention overcomes the defect of small specific surface area of mesoporous glass prepared by the traditional sol-gel method, completes the doping of selenium while synthesizing the mesoporous glass by a one-step method, and simplifies the synthesis process. The invention aims to provide a preparation method of selenium-doped silicon-calcium-phosphorus mesoporous bioglass. The function of inducing the transformation of stem cells into osteoblasts can be realized by utilizing the high specific surface area and the high bioactivity of MBG and the property of Se for promoting bones.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of selenium-doped silicon-calcium-phosphorus mesoporous bioactive glass is characterized by comprising the following steps:
1) preparing concentrated hydrochloric acid: preparing 2mol/L concentrated hydrochloric acid at room temperature;
2) dispersing the template agent: weighing template agent P123, adding into the hydrochloric acid, and stirring at constant speed at 35-40 ℃ until the P123 is uniformly dispersed in the system;
3) synthesizing silicon-calcium-phosphorus mesoporous glass: sequentially adding a phosphorus source, a calcium source, a selenium source and a silicon source, continuously stirring for 12 hours, transferring the mixed liquid into an inner container of a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 24 hours at 90-110 ℃;
4) removing the template agent: and (3) washing the mixed solution after the reaction in the step (3) with absolute ethyl alcohol, drying in an electric heating forced air drying box, and finally calcining in a box-type furnace at 600 ℃ to remove P123 to obtain white mesoporous glass powder.
Compared with the prior art, the invention has the following remarkable advantages:
1. the preparation method of the selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powder disclosed by the invention realizes the synthesis of the silicon-calcium-phosphorus bioactive mesoporous glass powder and the doping of selenium element in one step, and has the advantages of simple preparation conditions, simple method and convenience and effectiveness in operation.
2. The selenium-doped mesoporous bioactive glass powder prepared by the invention has SBET>500m2The glass has high specific surface area per gram, and the average mesoporous diameter is distributed between 6nm and 7nm, which indicates that the glass is mesoporous glass with high specific surface area.
3. Se in the selenium-doped mesoporous silicon-calcium-phosphorus glass prepared by the invention mainly replaces Si to enter a glass framework, so that the slow dissolution of Se element can be realized. 4. The selenium-doped mesoporous bioactive glass powder prepared by the invention has obvious bone-promoting effect and can be used as a bone repair material.
Drawings
FIG. 1 is a WAXRD and SAXRD pattern of the present invention;
FIG. 2 is a BET plot of the present invention;
FIG. 3 is an SEM image of the present invention;
FIG. 4 is a FITR map of the present invention;
FIG. 5 is a graph showing the effect of the leaching solution of the present invention on ALP secretion of bone marrow mesenchymal stem cells (BMSCs).
Detailed Description
Example 1: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. Measuring 0.308ml TEP, slowly adding dropwise into the above liquid, stirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2Dissolving O completely, adding 0.028g SeO2Then, 3.05ml TEOS is slowly dropped into the mixture, and after all the TEOS is added, the mixture is stirred in a water bath at 37 ℃ for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, thus finally obtaining the white mesoporous bioactive glass. Fig. 1 is a wafxrd spectrum and a SAXRD spectrum of the mesoporous bioactive glass obtained in this example.
Example 2: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. 0.308ml of TEP was measured and slowly added dropwise to the above liquid,stirring for 30min, weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.056g of SeO was added2And then slowly dripping TEOS, and after all the TEOS is added, keeping the temperature of the water bath at 37 ℃ and stirring for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, thus finally obtaining the white mesoporous bioactive glass. FIG. 2 is a BET spectrum of the mesoporous bioactive glass obtained in the present example.
Example 3: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. Measuring 0.308ml TEP, slowly adding dropwise into the above liquid, stirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.112g of SeO was added2And then slowly dripping TEOS, and after all the TEOS is added, keeping the temperature of the water bath at 37 ℃ and stirring for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, thus finally obtaining the white mesoporous bioactive glass. Fig. 3 is an SEM spectrum of the mesoporous bioactive glass obtained in the present example.
Example 4: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. 0.308ml of TEP is measured and slowly dripped into the solutionStirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.224g of SeO was added2And then slowly dripping TEOS, and after all the TEOS is added, keeping the temperature of the water bath at 37 ℃ and stirring for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, thus finally obtaining the white mesoporous bioactive glass. Fig. 4 is an FTIR spectrum of the mesoporous bioactive glass obtained in the present example.
Example 5: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. Measuring 0.308ml TEP, slowly adding dropwise into the above liquid, stirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.112g of SeO was added2And then slowly dripping TEOS, and after all the TEOS is added, keeping the temperature of the water bath at 37 ℃ and stirring for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 90 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, so that the white mesoporous bioactive glass can be obtained.
Example 6: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. Measuring 0.308ml TEP, slowly adding dropwise into the above liquid, stirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.056g of SeO was added2And then slowly dripping TEOS, and after all the TEOS is added, keeping the temperature of the water bath at 37 ℃ and stirring for 12 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction at 110 ℃ for 24 h. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, so that the white mesoporous bioactive glass can be obtained.
Example 7: 1g of analytically pure P123 was weighed out on an analytical balance and dispersed in 2mol/L concentrated hydrochloric acid having a volume of 50ml, and stirred at 37 ℃ in a water bath for 30min until the solution was clear and colorless. Measuring 0.308ml TEP, slowly adding dropwise into the above liquid, stirring for 30min, and weighing 1.98 g Ca (NO)3)2.4H2Adding O into the above liquid until Ca (NO) is reached3)2.4H2O was completely dissolved, and 0.056g of SeO was added2And then slowly dropwise adding TEOS, and after all the TEOS is added, keeping the temperature of a water bath at 37 ℃ and stirring for 18 hours. Then the liquid is transferred to a 100ml polytetrafluoroethylene reaction kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And (3) cooling to room temperature, removing the supernatant, adding absolute ethyl alcohol, stirring properly, standing, removing the supernatant, transferring the powder to a porcelain boat, and drying at 60 ℃ in an electrothermal blowing drying oven. And (4) placing the completely dried powder in a box furnace to calcine and remove the template agent. The heating rate is 1 ℃/min, the temperature is kept at 200 ℃ for 2h, the temperature is kept at 600 ℃ for 6h, then the temperature is kept, and the product is cooled along with the furnace, so that the white mesoporous bioactive glass can be obtained.
The method can be used for preparing the selenium-doped mesoporous bioactive silicon-calcium-phosphorus glass within the parameter range related to the technical scheme of the invention, wherein the parameter range comprises the doping concentration of Se element, the hydrothermal temperature, the hydrothermal time and the aging time.
Claims (4)
1. Selenium-doped silicon-calcium-phosphorus bioactive mesoporous glass powderA method for preparing a powder, characterized by: taking a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) as a template agent, taking triethyl phosphate (TEP) as a phosphorus source, and taking Ca (NO)3)2.4H2O is calcium source, Tetraethoxysilane (TEOS) is silicon source, SeO2Sequentially adding a phosphorus source, a calcium source, a selenium source and a silicon source as a selenium source, and carrying out hydrothermal reaction at 90-110 ℃ to realize the synthesis of the silicon-calcium-phosphorus bioactive mesoporous glass powder and the doping of selenium element in one step.
2. The preparation method of the selenium-doped calcium silicon phosphorus bioactive mesoporous glass powder of claim 1, which is characterized by comprising the following steps: the chemical composition of the synthesized selenium-doped calcium silicon phosphorus bioactive mesoporous glass powder is 59.5SiO2:36.6CaO:3.9P2O5:xSeO2The selenium is doped in the ratio of 1-8 mol% and has cluster or chain structure formed by adhering and twisting vermicular structures, the grain diameter of the vermicular structure is 1-3 μm, and the specific surface area (S) is higherBET>500m2(g) the average mesoporous diameter is distributed between 6 and 7nm, is mainly applied to bone repair and has the effect of promoting bone.
3. The hydrothermal preparation method of the selenium-doped calcium silicon phosphorus bioactive mesoporous glass as claimed in claim 1, characterized in that the method comprises the following steps:
1) preparing concentrated hydrochloric acid: preparing 2mol/L concentrated hydrochloric acid at room temperature;
2) dispersing the template agent: weighing template agent P123, adding into the hydrochloric acid, and stirring at 35-40 ℃ at a constant speed of 2000-3000r/min until the P123 is uniformly dispersed in the system;
3) synthesizing silicon-calcium-phosphorus mesoporous glass: sequentially adding a phosphorus source, a calcium source, a selenium source and a silicon source, continuously stirring for 12 hours, transferring the mixed liquid into an inner container of a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 24 hours at 90-110 ℃;
4) removing the template agent: washing the mixed liquid after the reaction in the step 3) with absolute ethyl alcohol, drying in an electric heating forced air drying oven, and finally calcining in a box-type furnace to remove P123 to obtain white mesoporous glass powder.
4. The method for preparing the selenium-doped silicon-calcium-phosphorus biological mesoporous active glass powder as recited in claim 1, wherein P123 adopts analytically pure solid, Ca (NO)3)2And SeO2Analytically pure powder was used, and analytically pure liquid was used for TEP and TEOS.
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