CN107601827B - Magnetic bioactive glass ceramic hollow microsphere and preparation method thereof - Google Patents
Magnetic bioactive glass ceramic hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
A multifunctional biological glass ceramic hollow material which has good biological activity and integrates magnetic targeting, magnetic thermal treatment, drug loading and sustained-release treatment and a preparation method thereof. The glass ceramic hollow microspheres with porous structures are obtained by a hard template method through a sol-gel-coprecipitation method and subsequent heat treatment. The related hollow microsphere component is xSiO2‑yCaO‑zP2O5‑nFe3O4(x-0-1, y-0-1, z-0-1, n-0-1). Dispersing the template microspheres into a dispersing agent to obtain a suspension of the template microspheres; and adding a surfactant and a catalyst into the suspension, then adding silicon and phosphorus alkoxide, stirring for a period of time, adding aqueous solution of ferric salt and calcium salt, and reacting for a period of time to obtain the glass-coated core-shell structure material. Washing the obtained precipitate with absolute ethyl alcohol and water respectively, drying at 30-100 ℃, and then removing the template microspheres by heat treatment at 500-800 ℃ to obtain the hollow glass microspheres. The obtained hollow glass microspheres are subjected to heat treatment for 1-10 hours at the temperature of 700-1000 ℃ in a reducing atmosphere to obtain the magnetic glass ceramic hollow microspheres.
Description
Technical Field
The invention relates to the field of biological glass ceramics, in particular to a preparation method of magnetic biological hollow glass ceramics and application thereof in tumor magnetic heat treatment.
Background
Cancer is one of the major diseases threatening human health at present, and the development of a novel material integrating cancer cell diagnosis, monitoring and targeted therapy, the pain relief of patients and the improvement of the living quality of patients are the key points of the development of the material at present.
Magnetic hyperthermia (Magnetic hyperthermia) is a new thermotherapy technology which enables a heat generating material to directionally gather at a tumor part by means of direct injection, intravenous injection or intervention and the like, and generates a Magnetic heat generating effect under the action of an alternating Magnetic field to heat tumor tissues to 42-48 ℃ so as to kill tumor cells. Medical studies have found that cancer cells are less heat resistant than normal cells of the human body. Cancer cells die when heated above 43 ℃, while normal cells do not die even when heated to 48 ℃. Therefore, thermotherapy is considered as a new method for treating cancer without side effects. The hot seed materials used at present mainly include ferrite, ferromagnetic alloy, ferromagnetic microcrystalline glass and the like. The main problem to be solved urgently in the technology of heating and treating tumors by using the magnetocaloric seed material is that the biological activity of the material is not enough, especially the metal and the alloy thermotolerant seed material thereof cannot be well combined with human tissues, and in addition, the material also cannot have the function of a drug carrier, cannot well combine thermotherapy and chemotherapy together, and influences the overall treatment effect.
Aiming at the problem of drug-loading performance of the existing thermal seed material, ferromagnetic microcrystalline glass can be prepared into hollow microspheres. The hollow microspheres have large specific surface area and specific pore volume, can fixedly embed various medicines in pore channels of the material, play a role in controlling the release of the medicines and improve the durability of the medicine effect; and the magnetic guiding function can be utilized to effectively and accurately hit target cells and lesion parts, so that the curative effect of the medicine is fully exerted. However, the research of the microcrystalline glass hollow microspheres as drug carriers still has a flexible index, and only MgO-Al is found2O3-SiO2The preparation method of the hollow microsphere of the microcrystalline glass is researched. The hollow microsphere has a larger inner cavity and a higher specific surface area, and the inner surface and the outer surface of the sphere and the sphere wall of the sphere can be simultaneously attached with the medicine, so that the medicine-carrying capacity is larger, and when the medicine is released, the medicine on the surface of the hollow microsphere is released firstly, and then the medicine in the inner cavity is slowly released. For example, validamycin loaded by silicon dioxide hollow microspheres, ibuprofen loaded by nano-structure calcium carbonate hollow spheres and amoxicillin loaded by hydroxyapatite hollow microspheres, the research results show that the hollow microspheres have high drug loading capacity and long drug release duration.
Disclosure of Invention
The invention aims to develop a multifunctional bioglass ceramic hollow material which has good bioactivity and integrates magnetic targeting, magnetocaloric therapy, drug loading and sustained-release therapy, and provides a method for preparing bioglass ceramic hollow microspheres, which is based on a hard template method and is used for obtaining the glass ceramic hollow microspheres with porous structures by a sol-gel-coprecipitation method and subsequent heat treatment.
The hollow microsphere glass ceramic comprises the following components: SiO 22-CaO-P2O5-Fe3O4
The invention adopts the following technical scheme:
1) dispersing the template microspheres into a dispersing agent to obtain a suspension of the template microspheres;
2) and adding a surfactant and a catalyst into the suspension, then adding silicon and phosphorus alkoxide, stirring for a period of time, adding aqueous solution of ferric salt and calcium salt, and reacting for a period of time to obtain the glass-coated core-shell structure material.
3) And (3) separating the product obtained in the step (2), washing with absolute ethyl alcohol and water respectively, and drying at the temperature of 30-100 ℃.
4) And (4) carrying out heat treatment on the powder obtained in the step (3) at the temperature of 500-800 ℃ to remove the template microspheres, so as to obtain the hollow glass microspheres.
5) And (4) carrying out heat treatment on the hollow glass microspheres obtained in the step (4) at the temperature of 700-1000 ℃ for 1-10 hours in a reducing atmosphere to obtain the glass ceramic hollow microspheres.
According to the invention, the dispersant used in step 1) is water, ethanol or a mixture thereof, preferably a water/ethanol mixture. The volume ratio of water to ethanol in the water/ethanol mixed solution may be 0 to 100, and is preferably 1.
According to the present invention, the template microspheres used in step 1) are organic microspheres that can be decomposed at a certain temperature, such as polystyrene microspheres, poly-organic microspheres, etc.
According to the invention, the concentration of template microspheres in the template microsphere suspension in step 1) is 0.001-0.1mg/ml, preferably 0.05mg/ml, more preferably 0.01 mg/ml.
According to the present invention, in step 1), the template microspheres are dispersed in a dispersing agent by means of, for example, stirring, sonication, etc.
According to the present invention, in step 2), the surfactant added may be a cationic surfactant, an anionic surfactant such as cetyltrimethyl ammonium bromide, polyethylene glycol, etc.
According to the invention, the catalyst used in step 2) is a basic inorganic substance, which can be ammonia, ethylenediamine, triethylamine, sodium hydroxide, preferably ammonia.
According to the invention, in step 2), the silicon and phosphorus alkoxides may be alkoxides of different carbon chains, preferably tetraethoxysilane, triethyl phosphate. The added salts of iron and calcium can be inorganic salts such as nitrate, chloride, acetate and the like.
According to the invention, in step 2), the silicon alkoxide is added in a concentration of 0.01 to 0.1mol/L, preferably 0.05 mol/L. The concentration of the phosphorus alkoxide is preferably 0.001 to 0.01mol/L, more preferably 0.0065 mol/L. The concentration of the iron salt is preferably 0.01-0.1mol/L, preferably 0.04 mol/L. The concentration of the calcium salt is preferably 0.01 to 0.1mol/L, preferably 0.06 mol/L. The concentration of the added surfactant is 0.001-0.01mol/L, preferably 0.04 mol/L. The concentration of the catalyst is 0.01 to 1mol/L, preferably 0.2 mol/L.
According to the invention, in step 2), the stirring is continued for 1 to 60 minutes after the addition of the silicon alkoxide. Preferably 40 minutes, more preferably 30 minutes, most preferably 25 minutes.
According to the invention, the reaction temperature in step 2) is 20 to 80 ℃, preferably 60 ℃, more preferably 30 ℃ and most preferably 40 ℃.
According to the invention, in step 2), the stirring is continued for a period of time of from 1 to 50 hours, preferably 10 hours, more preferably 48 hours, most preferably 24 hours after the addition of the starting materials.
According to the invention, in step 3), the temperature of drying is 30 to 100 ℃, preferably 80 ℃, more preferably 60 ℃.
According to the invention, in step 4), the template microspheres are removed by a heat treatment at a temperature of 500-. The temperature rise rate is 0.5-20 deg.C/min, preferably 10 deg.C/min, more preferably 5 deg.C/min, and most preferably 2 deg.C/min.
According to the invention, the atmosphere of the heat treatment in step 4) is an air atmosphere.
According to the invention, the heat treatment temperature of the hollow glass microspheres in the step 5) is 700-1200 ℃, preferably 800 ℃, more preferably 1000 ℃, and most preferably 900 ℃, and the holding time is 1-10 hours, preferably 5 hours, more preferably 2 hours, and most preferably 3 hours. The temperature rise rate is 0.5-20 deg.C/min, preferably 10 deg.C/min, more preferably 5 deg.C/min, and most preferably 2 deg.C/min.
According to the invention, the atmosphere of the heat treatment in step 5) is a reducing atmosphere, which may be N2/H2Mixed gas, activated carbon and carbon monoxide.
The hollow microspheres obtained by the method of the invention have micron-scale or nanometer-scale dimensions, and the microspheres are fully distributed with nanometer-scale holes. Therefore, the pore canal and the hollow cavity of the hollow microsphere can be used as a transmission medium of the drug and used for the slow release of the drug. While SiO in the composition of the microsphere2-CaO-P2O5Is the main component of bone repair bioglass, so the material has good bioactivity and can be used as a bone repair material. In addition, the magnetic mineral phase obtained by crystallization in the glass ceramic can be used as a magnetocaloric seed and can generate heat under an alternating magnetic field, so that the hollow microsphere can be used for magnetocaloric therapy.
The bioglass ceramic hollow microsphere integrates good bioactivity, magnetic targeting, magnetic heat treatment and drug slow release treatment, and has important significance in treating tumors, repairing bones and improving treatment effect.
Drawings
FIG. 1 shows SiO heat-treated at 850 deg.C2-CaO-P2O5-Fe3O4X-ray powder diffraction pattern of the glass ceramic hollow microspheres.
FIG. 2 is SiO by a heat treatment at 850 deg.C2-CaO-P2O5-Fe3O4Scanning electron microscope photo of the glass ceramic hollow microsphere.
FIG. 3 is SiO by a heat treatment at 850 deg.C2-CaO-P2O5-Fe3O4The glass ceramic hollow microspheres are dispersed in simulated body fluid under the action of magnetic fields without (a) and (b)The photographs were dispersed.
FIG. 4 is a drug release curve of the glass ceramic hollow microspheres loaded with methylene blue.
Detailed Description
The present invention is further illustrated by the following examples but it will be understood by those skilled in the art that the examples are not intended to limit the scope of the present invention and that any modifications and variations based on the present invention are within the scope of the present invention.
Example 1
1) Preparation of polystyrene microspheres (PS)
Adding 13mL of styrene into 100mL of distilled water by adopting an emulsion polymerization method, and heating to 40 ℃; then 0.5g PVP-30 was added and N was added2(30min) to discharge O in the reaction system2(ii) a 0.33g of potassium persulfate was weighed, dissolved in 20mL of distilled water, and the above solution was added. The reaction temperature is raised to 70 ℃, stirring is continuously carried out for 24 hours, and products are centrifugally separated to obtain PS pellets.
2) Preparation of glass-coated core-shell structure material by sol-gel-coprecipitation method
0.2mg of PS beads were dispersed in 25mL of H2O/25mL CH3CH2Heating the OH mixed solution to 40 ℃; weighing 0.08g of CTAB, dissolving in 5mL of water, adding the solution, and then adding 1mL of 35% ammonia water; 0.69g TEOS and 0.06g TEP were dissolved in 20mL absolute ethanol, and the above solution was added and stirred at 40 ℃ for another 40 min. 0.34g of CaCl was weighed2，0.34g FeCl3Dissolving in a small amount of water, then dripping into the solution, continuing to react for 48 hours, centrifugally separating the obtained product, washing with absolute ethyl alcohol, and drying at 60 ℃ to obtain the glass-coated core-shell structure material.
3) Preparation of glass ceramic hollow microspheres by thermal treatment
And (3) putting the obtained glass-coated core-shell structure material into a muffle furnace, and carrying out heat treatment for 2h at 850 ℃ in an air atmosphere to obtain the glass ceramic hollow microspheres.
The resulting glass ceramic hollow microspheres were observed using a scanning electron microscope. FIG. 1 shows the XRD spectrum of the hollow glass-ceramic microspheresIt can be seen from the figure that Fe is crystallized from the glass microspheres after heat treatment3O4The crystalline phase of (2). FIG. 2 shows a scanning electron micrograph of the resulting glass ceramic hollow microspheres. As can be seen from FIG. 2, the size of the glass ceramic microspheres is 300nm, the size distribution is uniform, and each microsphere is a hollow structure. FIG. 3 is a photograph showing the dispersion of glass ceramic hollow microspheres in a simulated body fluid. Under the action of no magnetic field (figure 3, left), the glass ceramic can be well dispersed in simulated body fluid, and when a magnetic field is applied, glass ceramic microspheres can be gathered around the magnetic field. FIG. 4 is a graph of the sustained release profile of a prepared glass-ceramic loaded with methylene blue drug in simulated body fluids. It can be seen from the figure that the magnetic glass ceramic hollow microspheres have good drug slow-release behavior.
Example 2
1) Preparation of polystyrene microspheres (PS)
Adding 13mL of styrene into 100mL of distilled water by adopting an emulsion polymerization method, and heating to 40 ℃; then 0.8g PVP-30 was added and N was added2(30min) to discharge O in the reaction system2(ii) a 0.33g of potassium persulfate was weighed, dissolved in 20mL of distilled water, and the above solution was added. The reaction temperature is raised to 70 ℃, stirring is continuously carried out for 24 hours, and products are centrifugally separated to obtain PS pellets.
2) Preparation of glass-coated core-shell structure material by sol-gel-coprecipitation method
Dispersing 0.3mg PS beads in 25mLH2O/25mL CH3CH2Heating the OH mixed solution to 40 ℃; weighing 0.08g CTAB, dissolving in 5mL of water, adding the solution, and then adding 1mL of concentrated ammonia water; 0.78g TEOS and 0.06g TEP were dissolved in 20mL absolute ethanol, and the above solution was added and stirred at 40 ℃ for another 40 min. 0.34g of CaCl was weighed2，0.25g FeCl3Dissolving in a small amount of water, then dripping into the solution, continuing to react for 48 hours, centrifugally separating the obtained product, washing with absolute ethyl alcohol, and drying at 60 ℃ to obtain the glass-coated core-shell structure material.
3) Preparation of glass ceramic hollow microspheres by thermal treatment
And (3) putting the obtained glass-coated core-shell structure material into a muffle furnace, and carrying out heat treatment for 2h at 850 ℃ in an air atmosphere to obtain the glass ceramic hollow microspheres.
Example 3
1) Preparation of polystyrene microspheres (PS)
Adding 13mL of styrene into 100mL of distilled water by adopting an emulsion polymerization method, and heating to 40 ℃; then 0.5g PVP-30 was added and N was added2(30min) to discharge O in the reaction system2(ii) a 0.33g of potassium persulfate was weighed, dissolved in 20mL of distilled water, and the above solution was added. The reaction temperature is raised to 70 ℃, stirring is continuously carried out for 24 hours, and products are centrifugally separated to obtain PS pellets.
2) Preparation of glass-coated core-shell structure material by sol-gel-coprecipitation method
Dispersing 0.2mg PS beads in 25mLH2O/25mL CH3CH2Heating the OH mixed solution to 40 ℃; weighing 0.08g of CTAB, dissolving in 5mL of water, adding the solution, and then adding 1mL of 35% ammonia water; 0.95g TEOS and 0.06g TEP were dissolved in 20mL absolute ethanol, and the above solution was added and stirred at 40 ℃ for another 40 min. Weighing 0.25g CaCl2，0.25g FeCl3Dissolving in a small amount of water, then dripping into the solution, continuing to react for 48 hours, centrifugally separating the obtained product, washing with absolute ethyl alcohol, and drying at 60 ℃ to obtain the glass-coated core-shell structure material.
3) Preparation of glass ceramic hollow microspheres by thermal treatment
And (3) putting the obtained glass-coated core-shell structure material into a muffle furnace, and carrying out heat treatment for 2h at 850 ℃ in an air atmosphere to obtain the glass ceramic hollow microspheres.
Example 4
1) Preparation of polystyrene microspheres (PS)
Adding 13mL of styrene into 100mL of distilled water by adopting an emulsion polymerization method, and heating to 40 ℃; then 0.5g PVP-30 was added and N was added2(30min) to discharge O in the reaction system2(ii) a 0.33g of potassium persulfate was weighed, dissolved in 20mL of distilled water, and the above solution was added. The reaction temperature is raised to 70 ℃, stirring is continuously carried out for 24 hours, and products are centrifugally separated to obtain PS pellets.
2) Preparation of glass-coated core-shell structure material by sol-gel-coprecipitation method
Dispersing 0.2mg PS beads in 25mLH2O/25mL CH3CH2Heating the OH mixed solution to 40 ℃; weighing 0.08g of CTAB, dissolving in 5mL of water, adding the solution, and then adding 0.6mL of 35% ammonia water; 0.69g TEOS and 0.06g TEP were dissolved in 20mL absolute ethanol, and the above solution was added and stirred at 40 ℃ for another 40 min. 0.34g of CaCl was weighed2，0.34g FeCl3Dissolving in a small amount of water, then dripping into the solution, continuing to react for 48 hours, centrifugally separating the obtained product, washing with absolute ethyl alcohol, and drying at 60 ℃ to obtain the glass-coated core-shell structure material.
3) Preparation of glass ceramic hollow microspheres by thermal treatment
And (3) putting the obtained glass-coated core-shell structure material into a muffle furnace, and carrying out heat treatment for 2h at 900 ℃ in an air atmosphere to obtain the glass ceramic hollow microspheres.
It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (2)
1. The preparation method of the magnetic glass ceramic hollow microsphere is characterized in that the component of the magnetic glass ceramic hollow microsphere is xSiO2-yCaO-zP2O5-nFe3O4The content is as follows: the preparation method of the magnetic glass ceramic hollow microsphere comprises the following steps:
(1) dispersing a polystyrene microsphere or tetrabutyl polyacrylate nanosphere template into a dispersing agent to obtain a suspension of the template microspheres;
(2) adding a surfactant and a catalyst into the suspension, then adding silicon and phosphorus alkoxide, stirring for a period of time, adding aqueous solution of ferric salt and calcium salt, and reacting for a period of time to obtain a glass-coated core-shell structure material, wherein the catalyst is an alkaline inorganic substance;
(3) separating the product obtained in the step 2, washing with absolute ethyl alcohol and water respectively, and then drying at 30-100 ℃;
(4) carrying out heat treatment on the powder obtained in the step 3 at the temperature of 500-800 ℃ to remove the template microspheres to obtain hollow glass microspheres;
(5) carrying out heat treatment on the hollow glass microspheres obtained in the step 4 at the temperature of 700-1000 ℃ for 1-10 hours in a reducing atmosphere to obtain glass ceramic hollow microspheres, wherein the main crystallization phase of the glass ceramic is magnetic Fe3O4The structure of the glass ceramic is a porous hollow structure, and the particle size is 0.05-1 micron.
2. The method for preparing magnetic glass ceramic hollow microspheres according to claim 1, wherein the alkaline inorganic substance used in step (2) can be ammonia or sodium hydroxide.
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