CN101671032A - Calcium silicate multi-level nano-structure mesoporous microsphere and preparation method thereof - Google Patents
Calcium silicate multi-level nano-structure mesoporous microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a calcium silicate multi-level nano-structure mesoporous microsphere and a preparation method thereof, and belongs to the field of biomaterials. The method provided by the invention comprises the steps of mixing Ca(NO3)2 water solution and NaOH water solution uniformly in a stirring condition, then adding ethyl orthosilicate to react under ultrasonication, and then centrifugally separating, washing by water and alcohol and at last drying to obtain the product. The mole ratio of calcium to silicon of the calcium silicate multi-level nano-structure mesoporous microsphereis 3:2. The particle size of cellular spherical-like particles packaged by nano-plates is 0.6-1.5 mu m and the cellular spherical-like particles are in a mesoporous structure, and the bore diameter distribution of the mesopore ranges from 4 to 30nm. The invention has the advantages of large specific surface area, large pore space, high drug-loading rate and excellent medicine slow release property for medicines insoluble in water, and wide application prospects in the field of biomedicine.
Description
Technical field
The present invention relates to a kind of calcium silicate multi-level nano-structure mesoporous microsphere and preparation method thereof, belong to technical field of biological material.
Background technology
Mesoporous microsphere is the vesicular micron-size spherical particles of aperture between 2-50nm.Mesoporous material is widely used in fields such as catalysis because its specific surface area is big, and at aspects such as separating purification, novel assembled material and biomaterial good application potential is arranged.
Over past ten years, the application of silicon-based mesoporous material aspect drug delivery system has been subjected to paying close attention to widely.Silicon-based mesoporous material not only specific surface area and void content is big, and has excellent biological compatibility.The silicon-based mesoporous material that is used for drug carrier system research at present mainly is based on hollow ball, nucleocapsid structure, porous particle and the polymer composite thereof etc. of amorphous silica.Yet in the preparation process of these materials, tensio-active agent is widely used, and its residue has certain toxicity to biomass cells, and the drug loading of these materials remains further to be improved.In addition, the biological activity of silicon-dioxide neither be very desirable.
At present, in the orthopaedics field, (polymethylmethacrylate PMMA) is the most frequently used clinically pharmaceutical carrier to polymethylmethacrylate.Long-term clinical application shows that there are some shortcomings in it, and for example: the microbiotic release that (1) is lower than treatment level for a long time causes resistance and the breeding of bacterium easily, and drug release is incomplete; (2) biocompatibility is poor, and tissue can not be grown in the above, and the tissue of formation and the gap of material can cause the residual of bacterium; (3) polykaryocyte there is restraining effect, influences body's immunological function; (4) can not be always foreign matter by the organism degraded and absorbed, hinder the formation of new bone, thereby often need second operation to take out material.In this case, be badly in need of a kind of new equivalent material at present, this material not only will have good biological activity, biocompatibility and biodegradability, and will have bigger medicine loading capacity to reach clinical safety preferably.
Calucium Silicate powder is the novel biomaterial that rose in recent years, and the traditional silica-based biomaterial (such as amorphous silica) of its calcium silicon ratio of components has better biological activity, consistency and degradability.It can be organized reuptakes utilization, and finally is converted into osteoid apatite, does not therefore have the residual problem of foreign matter.A large amount of calcium ions on its surface can improve its medicine loading capacity by the active adsorption to general anti-inflammation analgesis medicament molecule.However, the raising of its medicine loading capacity also needs to have big specific surface area and void content.Calcium silicate multi-level nano-structure mesoporous microsphere integrates above advantage, and it has very big application potential in the drug delivery field.
Traditional preparation process method (as coprecipitation method, sol-gel method, hydrothermal method etc.) must use tensio-active agent just may obtain the Calucium Silicate powder meso-hole structure under as the condition of template.And supersonic method is owing to have the formation that cavitation effect helps vesicular structure.But, prepare most of materials with supersonic method and still need the auxiliary of various tensio-active agents.The preparation calcium silicate multi-level nano-structure mesoporous microsphere is not also reported at present under the surfactant-free condition.
Summary of the invention
The object of the present invention is to provide a kind of calcium silicate multi-level nano-structure mesoporous microsphere and preparation method thereof.
Calcium silicate multi-level nano-structure mesoporous microsphere of the present invention is characterized in that, the mol ratio of calcium and silicon is 3: 2 in the chemical constitution;
Described calcium silicate multi-level nano-structure mesoporous microsphere is characterized in that, is the cavernous similar spheroidal particle that is assembled by nanometer sheet, and its particle size is 0.6-1.5 μ m;
Described calcium silicate multi-level nano-structure mesoporous microsphere is characterized in that, has meso-hole structure, and its pore size distribution is between 4-30nm.
The preparation method of described calcium silicate multi-level nano-structure mesoporous microsphere comprises the steps:
(1) compound concentration is the Ca (NO of 0.01-0.2mol/L
3)
2The NaOH aqueous solution of the aqueous solution and 1-4mol/L.
(2) under stirring condition, earlier with Ca (NO described in the step (1)
3)
2The aqueous solution and the NaOH aqueous solution are to mix in 1: 1 to 10: 3 by calcium constituent and sodium element mol ratio, add tetraethoxy then, and make that the mol ratio of calcium and element silicon is 1: 1 to 2: 1 in the final blending liquid.
(3) be that 10-50kHz, power are the ultrasonic wave effect 10-120min of 100-1000W with frequency.
(4) with step (3) products therefrom centrifugation, water and washing with alcohol obtain calcium silicate multi-level nano-structure mesoporous microsphere after the drying.
Preferred Ca (NO in the described step (1)
3)
2Concentration of aqueous solution is 0.03-0.05mol/L.
Preferred hyperacoustic power is 350-450W in the described step (3).
The preferred action of ultrasonic waves time is 10-50min in the described step (3).
Calcium silicate multi-level nano-structure mesoporous microsphere of the present invention, recording specific surface area through the BET method is 200-300m
2/ g, recording void content through the BJH method is 1-1.5cm
3/ g.Described calcium silicate multi-level nano-structure mesoporous microsphere can be used as pharmaceutical carrier, poorly water soluble drugs is had the drug loading (loading capacity of Ibuprofen BP/EP is 1.6-2.3g Ibuprofen BP/EP/g carrier) and the good medicament slow release performance of superelevation.Calcium silicate multi-level nano-structure mesoporous microsphere of the present invention and preparation method thereof has the following advantages:
(1) preparation environment for use close friend's raw material can not pollute environment;
(2) preparation is at room temperature to carry out, the productive rate height, and be swift in response, have quick synthetic advantage, output efficiency height, and save energy;
(3) raw material is cheap and easy to get, and is easy to operate, and preparation technology is simple, is easy to realize suitability for industrialized production;
(4) calcium silicate multi-level nano-structure mesoporous microsphere pattern that makes and size be homogeneous relatively, and specific surface area is big, and void content is big.
(5) calcium silicate multi-level nano-structure mesoporous microsphere that makes is suitable for as drug carrier material, poorly water soluble drugs is had the drug loading (loading capacity of Ibuprofen BP/EP is 1.6-2.3g Ibuprofen BP/EP/g carrier) and the good medicament slow release performance of superelevation.
(6) calcium silicate multi-level nano-structure mesoporous microsphere has good biological activity and degradability, and its medicine-carried system discharges in the medicine under the simulated body fluid environment, has hydroxyapatite and forms, and finally can be converted into class bone hydroxyapatite fully.
In sum, compare with other method of the prior art, calcium silicate multi-level nano-structure mesoporous microsphere specific surface area of the present invention is big, void content is big, the useful as drug carrier, poorly water soluble drugs is had the drug loading of superelevation and good medicament slow release performance, have broad application prospects at biomedicine field.
Description of drawings
Preparation technology's schema of Fig. 1 calcium silicate multi-level nano-structure mesoporous microsphere.
Fig. 2 adopts scanning electron microscope (SEM) photo of the calcium silicate multi-level nano-structure mesoporous microsphere that the inventive method makes.As can be seen from Figure 2, the calcium silicate multi-level nano-structure mesoporous microsphere size is about 1 μ m, is to be about the multi-level nano-structure that the nanometer sheet of 30nm assembles by thickness, and has vesicular structure.
Fig. 3 adopts X-ray powder diffraction (XRD) spectrogram of the calcium silicate multi-level nano-structure mesoporous microsphere that the inventive method makes.Fig. 3 shows that the chemical ingredients of the Calucium Silicate powder calcium silicate multi-level nano-structure mesoporous microsphere that makes is Ca
3Si
2O
7XH
2O (JCPDS 33-0306).
Fig. 4 adopts the nitrogen adsorption desorption curve and the corresponding pore size distribution curve of the calcium silicate multi-level nano-structure mesoporous microsphere that the inventive method makes.Fig. 4 has illustrated the mesoporous characteristic of the Calucium Silicate powder calcium silicate multi-level nano-structure mesoporous microsphere that makes, and its aperture mainly is distributed in the 2-50nm scope, and mean pore size is about 11nm.
Fig. 5 has loaded the medicament slow release curve of calcium silicate multi-level nano-structure mesoporous microsphere in simulated body fluid of shipwreck soluble drug Ibuprofen BP/EP.
Fig. 6 has loaded X-ray powder diffraction (XRD) spectrogram of calcium silicate multi-level nano-structure mesoporous microsphere after simulated body fluid Chinese traditional medicine slowly-releasing is finished of shipwreck soluble drug Ibuprofen BP/EP.
Embodiment
Further describe calcium silicate multi-level nano-structure mesoporous microsphere of the present invention and preparation method thereof below by specific embodiment.Should illustrate that these embodiment only are used to the present invention is described and are not used in and limit the scope of the invention.
Embodiment 1
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 2
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 10mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 3
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 3mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 4
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 10min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 5
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 30min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 6
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 300W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 7
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 30min under the power of 300W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 8
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 200W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 9
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 30min under the power of 200W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 10min under the power of 600W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 11
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 20min under the power of 600W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 12
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.046mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.046mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.34mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 30min under the power of 600W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 13
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 1mol/L and the Ca (NO of 0.03mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.03mol/L toward 65mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 0.45mL tetraethyl silicate of 1mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 30min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 14
The preparation calcium silicate multi-level nano-structure mesoporous microsphere
Compound concentration is the NaOH aqueous solution of 4mol/L and the Ca (NO of 0.03mol/L respectively
3)
2The aqueous solution.Under room temperature, stirring condition, be the Ca (NO of 0.03mol/L toward 500mL concentration
3)
2Adding 5mL concentration in the aqueous solution successively is the NaOH aqueous solution and the 2mL tetraethyl silicate of 4mol/L, obtains an emulsion.Then ultrasound probe is immersed emulsion, ultrasonication 50min under the power of 400W.Reaction is used the centrifuging separated product after finishing, and isolating product washs respectively three times with deionized water and ethanol, and 60 ℃ of air atmosphere dryings obtain calcium silicate multi-level nano-structure mesoporous microsphere.
Embodiment 15
Calcium silicate multi-level nano-structure mesoporous microsphere is used for the loading and the slowly-releasing of poorly water soluble drugs Ibuprofen BP/EP
Load: the 0.75g calcium silicate multi-level nano-structure mesoporous microsphere joins in the Ibuprofen BP/EP hexane solution that 50mL concentration is 40mg/mL, sealing back shakes up 24 hours under 37 ℃ of conditions, then the calcium silicate multi-level nano-structure mesoporous microsphere behind the medicine carrying is separated, with normal hexane washing, dry, compressing tablet (every 0.2g).
Slowly-releasing: compressing tablet is immersed in the 200mL simulated body fluid (pH 7.4), shake up at 37 ℃.Take out the 2ml release medium every 2 hours, in former mixed solution, add the fresh simulated body fluid of 2mL simultaneously.The release medium of taking out is carried out the ultra-violet absorption spectrum test, and be that the uv-absorbing peak intensity at 264nm place is analyzed to wavelength, obtain loading the medicament slow release curve of calcium silicate multi-level nano-structure mesoporous microsphere in simulated body fluid of Ibuprofen BP/EP, as shown in Figure 5, its pharmaceutical release time can reach 372 hours, and finally almost medicine can be discharged fully.
Fig. 6 is X-ray powder diffraction (XRD) spectrogram of calcium silicate multi-level nano-structure mesoporous microsphere after simulated body fluid Chinese traditional medicine slowly-releasing is finished that has loaded shipwreck soluble drug Ibuprofen BP/EP, and the pairing thing of spectrogram is hydroxyapatite Ca mutually
10(PO
4)
6(OH)
2(JCPDS 74-0565).Fig. 6 shows that the calcium silicate multi-level nano-structure mesoporous microsphere Calucium Silicate powder composition after drug release is finished that has loaded Ibuprofen BP/EP has been converted into hydroxyapatite fully.
Claims (9)
1, calcium silicate multi-level nano-structure mesoporous microsphere is characterized in that:
The mol ratio of calcium and silicon is 3: 2 in the chemical constitution;
By the cavernous similar spheroidal particle that nanometer sheet assembles, particle size is 0.6-1.5 μ m;
Have meso-hole structure, its aperture mainly is distributed between the 4-30nm.
2, the preparation method of calcium silicate multi-level nano-structure mesoporous microsphere comprises the steps:
(1) preparation Ca (NO
3)
2The aqueous solution and the NaOH aqueous solution;
(2) under stirring condition, earlier with Ca (NO in the step (1)
3)
2The aqueous solution and the NaOH aqueous solution are to mix in 1: 1 to 10: 3 by calcium constituent and sodium element mol ratio, add tetraethoxy then, and make that the mol ratio of calcium and element silicon is 1: 1 to 2: 1 in the final blending liquid;
(3) ultrasonic wave effect 10-120min;
(4) with step (3) products therefrom centrifugation, water and washing with alcohol obtain calcium silicate multi-level nano-structure mesoporous microsphere after the drying.
3, by the preparation method of the described calcium silicate multi-level nano-structure mesoporous microsphere of claim 2, it is characterized in that Ca (NO in the described step (1)
3)
2Concentration of aqueous solution is 0.01-0.2mol/L mol/L.
4, by the preparation method of the described calcium silicate multi-level nano-structure mesoporous microsphere of claim 3, it is characterized in that Ca (NO in the described step (1)
3)
2Concentration of aqueous solution is 0.03-0.05mol/L.
By the preparation method of the described calcium silicate multi-level nano-structure mesoporous microsphere of claim 2, it is characterized in that 5, the NaOH concentration of aqueous solution is 1-4mol/L in the described step (1).
By the preparation method of claim 3 or 5 described calcium silicate multi-level nano-structure mesoporous microspheres, it is characterized in that 6, the condition of ultrasonic wave effect is that 10-50kHz, power are 100-1000W for the frequency rate in the described step (3).
7, by the preparation method of the described calcium silicate multi-level nano-structure mesoporous microsphere of claim 6, it is characterized in that hyperacoustic power is 350-450W in the described step (3).
By the preparation method of claim 3 or 5 described calcium silicate multi-level nano-structure mesoporous microspheres, it is characterized in that 8, the time of ultrasonic wave effect is 10-50min in the described step (3).
9, be used for biomedicine field by the described calcium silicate multi-level nano-structure mesoporous microsphere of claim 1.
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