CN111870736A - Preparation method of novel photo-thermal anti-bone-tumor coating on surface of magnesium alloy - Google Patents
Preparation method of novel photo-thermal anti-bone-tumor coating on surface of magnesium alloy Download PDFInfo
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Abstract
The invention provides a preparation method of a novel photo-thermal anti-bone tumor coating on a magnesium alloy surface, which comprises the steps of selenium doping of hydroxyapatite microparticles, synthesis of beta-TCP (Transmission control protocol) nano fibers, loading of black phosphorus nano sheets on the beta-TCP nano fibers, selenium doping of hydroxyapatite particles and Ca on the surfaces of the black phosphorus nano sheets @ beta-TCP nano fibers2+Selective adsorption of,And carrying out gradient electrophoretic codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber so as to form the black phosphorus nanosheet @ beta-TCP nanofiber coating with the embedded selenium-doped hydroxyapatite and gradient change in volume fraction. The black phosphorus nanosheet has excellent photo-thermal performance and a selenium-doped hydroxyapatite inhibiting effect on bone tumor cells, so that the black phosphorus nanosheet has a good bone tumor treatment function. In addition, the selenium-doped hydroxyapatite coating with gradient change of pore volume fraction is formed by degrading the beta-TCP nano fibers, so that the coating has excellent osteogenesis performance.
Description
Technical Field
The invention relates to the field of bone implantation medical materials, in particular to a preparation method of a selenium-doped hydroxyapatite @ nanofiber photothermal anti-bone-tumor coating on the surface of a magnesium alloy.
Background
The bone tumor seriously harms human health, the mainstream treatment method of the bone tumor is a mode of combining surgical resection with radiotherapy/chemotherapy, but the surgical resection cannot completely and effectively remove tiny focuses and residual bone tumor cells and can cause bone defect, and the radiotherapy/chemotherapy has serious toxic and side effects and still has the risks of relapse and metastasis. The photothermal therapy is to place a material with excellent photothermal conversion performance at the tumor focus, and convert the light energy into heat energy through the irradiation of a near-infrared light source so as to achieve the treatment effect of killing tumor cells. The photothermal therapy is used as a non-invasive tumor treatment method, can realize targeted killing of tumor cells, and obviously reduces damage to normal tissues.
Hitherto, the developed bone implant materials and bone tumor treatment materials are respectively limited to the functions of surgical replacement and repair and bone tumor treatment, and the dual-function integration of bone tumor surgical repair and bone tumor treatment is difficult to realize, so that the treatment effect of bone tumor is restricted.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a novel photo-thermal anti-bone-tumor coating on the surface of a magnesium alloy, and the magnesium alloy selenium-doped hydroxyapatite @ nanofiber photo-thermal anti-bone-tumor coating prepared by the preparation method is characterized in that: the selenium-doped hydroxyapatite coating formed on the surface of the magnesium alloy by the black phosphorus nanosheet @ beta-TCP nanofiber is in gradient distribution of volume fraction, and as the degradation speed of the beta-TCP nanofiber is far higher than that of the selenium-doped hydroxyapatite, the selenium-doped hydroxyapatite coating with gradient change of pore volume fraction is formed by the selenium-doped hydroxyapatite embedded black phosphorus nanosheet @ beta-TCP nanofiber due to the degradation of the beta-TCP nanofiber in the process of forming bone tissues. The black phosphorus nanosheet has excellent photo-thermal property, has a strong killing effect on bone tumors, and combines the obvious inhibition effect of the selenium-doped hydroxyapatite on bone tumor cells, so that the coating has a good bone tumor treatment function.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a novel photo-thermal anti-bone tumor coating on the surface of a magnesium alloy comprises the following preparation steps:
step one, selenium doping of hydroxyapatite micron particles;
step two, synthesizing beta-TCP nano fibers and loading black phosphorus nano sheets on the beta-TCP nano fibers;
step three, selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber surface Ca2+Selective adsorption of (2);
and step four, carrying out gradient electrophoresis codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber on the surface of the magnesium alloy.
Preferably, the step one is specifically operated as:
a1. preparing a selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with potassium phenylselenate concentration of 0.1-120mmol/L, sodium hydroxide concentration of 80-350mmol/L and tributylmethylammonium chloride concentration of 5-40 mmol/L.
a2. Preparing a concoction solution: adding urea into deionized water to form a prepared solution with the urea concentration of 0.5-38 mmol/L.
a3. Selenium doping of hydroxyapatite microparticles: adding 120-450g of hydroxyapatite microparticles into 1L of the selenium-doped treatment solution, stirring for 30 minutes by using a magnetic stirrer, then adding 40-180mL of the preparation solution, reacting for 4-18 hours at 20-40 ℃, filtering a suspension solid phase substance, and drying for 8-20 hours at 20-40 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
Preferably, the second step is specifically operated as follows:
b1. synthesis of beta-TCP nanofibers: adding 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form 60% synthetic treatment liquid with the concentrations of the phosphoric acid, the calcium acetate, the calcium fluoride and the tetrahydropyrrole being 9.6-336mL/L, 155-390g/L, 20-270g/L and 60-340mL/L respectively, pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 2-5 hours at the temperature of 100-160 ℃, filtering a suspension solid phase substance, and drying for 3-7 hours at room temperature to obtain the beta-TCP nanofiber;
b2. the loading of the black phosphorus nanosheet on the beta-TCP nanofiber is as follows: adding black phosphorus nanosheets and beta-TCP nanofibers into deionized water to form treatment solutions with the concentrations of the black phosphorus nanosheets and the beta-TCP nanofibers being respectively 120-340mg/L and 170-410g/L, stirring for 30 minutes to form a uniform dispersion system, adding hexadecyl sulfobetaine to enable the concentration of the hexadecyl sulfobetaine to reach 2-30g/L, keeping the system for 16-24 hours, collecting precipitates at the lower layer to obtain solid phase substances in the system, cleaning with anhydrous acetic acid, and drying at 15-40 ℃ for 6-15 hours to complete the loading of the black phosphorus nanosheets on the beta-TCP nanofibers and obtain the black phosphorus nanosheets @ beta-TCP nanofibers.
Preferably, the third step is specifically performed by:
adding calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers into deionized water to form adsorption solutions with the concentrations of the calcium dihydrogen phosphate, the calcium gluconate, the selenium-doped hydroxyapatite particles and the black phosphorus nanosheet @ beta-TCP nanofibers being 15-60g/L, 5-18g/L, 350-480g/L and 15-46g/L respectively, standing for 1-3 hours, and filtering and adsorbing a solid phase substance, wherein the solid phase substance is a substance with the surface on which Ca is adsorbed2+The selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber mixture is characterized in that the mass ratio of the selenium-doped hydroxyapatite to the black phosphorus nanosheet @ beta-TCP nanofiber in the mixture is 8-32: 1.
Preferably, the step four is specifically operated as follows:
adding the mixture prepared in the third step into an N, N-dimethylformamide organic solvent to enable the concentration of the mixture to be 170-380g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 10-42g/L, and stirring for 30 minutes by using a magnetic stirrer; the magnesium alloy is used as a cathode, stainless steel is used as an anode, the electrodeposition temperature is 20-40 ℃, 5-20V is used as an initial electrophoretic deposition voltage value, the electrophoretic deposition voltage is increased by 0.5-2V every 0.2-1 minute of deposition, and the electrophoretic codeposition step of selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber is completed when the final electrophoretic deposition voltage is 40-55V, so that the magnesium alloy selenium-doped hydroxyapatite @ nanofiber photothermal anti-bone tumor coating is obtained on the surface of the magnesium alloy.
The invention has the following positive effects: the magnesium alloy selenium-doped hydroxyapatite @ nanofiber photothermal anti-bone tumor coating prepared according to the method has the following structural characteristics: the selenium-doped hydroxyapatite coating formed on the surface of the magnesium alloy by the black phosphorus nanosheet @ beta-TCP nanofiber is in gradient distribution of volume fraction; because the degradation speed of the beta-TCP nanofiber is far higher than that of the selenium-doped hydroxyapatite, in the process of forming bone tissues, the selenium-doped hydroxyapatite coating with the black phosphorus nanosheet @ beta-TCP nanofiber structure embedded in the selenium-doped hydroxyapatite is formed by degrading the beta-TCP nanofiber, wherein the pore volume fraction gradient change is formed, the black phosphorus nanosheet has excellent photo-thermal performance and has a strong killing effect on bone tumors, and meanwhile, the coating has a good bone tumor treatment function by combining the obvious inhibition effect of the selenium-doped hydroxyapatite on bone tumor cells. In addition, the coating has excellent osteogenic properties due to its composition and structural characteristics that degrade during the formation of bone tissue.
Drawings
FIG. 1 is a flow chart of the preparation of the photothermal anti-bone tumor coating according to the present invention;
FIG. 2 is a graph comparing the mortality of MG63 human osteosarcoma cells planted in comparative example 1, comparative example 2 and example 1 according to the present invention when irradiated with near infrared light (wavelength 808nm, power 0.8W/cm 2).
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Referring to fig. 1, a preferred embodiment 1 of the present invention provides a method for preparing a novel photothermal anti-bone-tumor coating on a magnesium alloy surface, which comprises the following steps:
preparation of selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of potassium phenylselenate of 12mmol/L, the concentration of sodium hydroxide of 90mmol/L and the concentration of tributylmethylammonium chloride of 15 mmol/L.
Preparing a preparation solution: adding urea into deionized water to form a prepared solution with the urea concentration of 18 mmol/L.
③ selenium doping of hydroxyapatite microparticles: adding 150g of hydroxyapatite microparticles into 1L of the selenium-doped treatment solution, stirring for 30 minutes by using a magnetic stirrer, then adding 90mL of the prepared solution, reacting for 8 hours at 30 ℃, filtering a suspension liquid solid phase substance, and drying for 15 hours at 30 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
And fourthly, synthesizing the beta-TCP nano fiber: respectively adding 60% phosphoric acid (60% by mass of phosphoric acid), calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form synthetic treatment solutions with the concentrations of 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole being 96mL/L, 170g/L, 150g/L and 120mL/L respectively; pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 3 hours at 140 ℃, then filtering the suspension liquid solid phase matter, and drying for 4 hours at room temperature to prepare the beta-TCP nano fiber.
Loading the black phosphorus nanosheets on the beta-TCP nanofiber: forming black phosphorus nanosheets and beta-TCP nanofiber deionized water into treatment solutions with the concentrations of the black phosphorus nanosheets and the beta-TCP nanofibers being 140mg/L and 180g/L respectively, stirring for 30 minutes to form a uniform dispersion system, adding hexadecyl sulfobetaine to enable the concentration of the hexadecyl sulfobetaine to reach 15g/L, keeping the system for 18 hours, collecting precipitates at a lower layer to obtain solid phase substances in the system, cleaning the solid phase substances with anhydrous acetic acid, and drying at 20 ℃ for 7 hours to finish loading of the black phosphorus nanosheets on the beta-TCP nanofibers and obtain the black phosphorus nanosheets @ beta-TCP nanofibers.
Sixth, Ca on the surface of selenium-doped hydroxyapatite particles and black phosphorus nano-sheets @ beta-TCP nano-fibers2+Selective adsorption of (2): adding calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers into deionized water to form adsorption solutions with the concentrations of the calcium dihydrogen phosphate, the calcium gluconate, the selenium-doped hydroxyapatite particles and the black phosphorus nanosheet @ beta-TCP nanofibers being 30g/L, 7g/L, 420g/L and 20g/L respectively, standing for 2 hours, and filtering to adsorb a solid phase substance, wherein the solid phase substance is a substance with Ca adsorbed on the surface2+The selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber mixture is characterized in that the mass ratio of the selenium-doped hydroxyapatite to the black phosphorus nanosheet @ beta-TCP nanofiber in the mixture is 12: 1.
Seventhly, carrying out gradient electrophoretic codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber on the surface of the magnesium alloy: adsorbing Ca on the surface prepared according to the sixth step2+Adding the mixture of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber into an N, N-dimethylformamide organic solvent to enable the concentration of the mixture to be 180g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 12g/L, and stirring for 30 minutes by using a magnetic stirrer; the magnesium alloy is used as a cathode, stainless steel is used as an anode, 15V is used as an initial electrophoretic deposition voltage value at the electrodeposition temperature of 30 ℃, the electrophoretic deposition voltage is increased by 1V every 0.5 minute of deposition, and the electrophoretic codeposition step of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber is completed when the final electrophoretic deposition voltage is 45V, so that the black phosphorus nanosheet @ beta-TCP nanofiber coating with the selenium-doped hydroxyapatite embedded in a volume fraction gradient distribution is obtained on the surface of the magnesium alloy.
Comparative examples are given below to verify the technical effect of the present invention by comparing the comparative examples with example 1:
comparative example 1
The invention provides a preparation method of a magnesium alloy-based selenium-doped hydroxyapatite coating, which comprises the following steps:
preparation of selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of potassium phenylselenate of 12mmol/L, the concentration of sodium hydroxide of 90mmol/L and the concentration of tributylmethylammonium chloride of 15 mmol/L.
Preparing a preparation solution: adding urea into deionized water to form a prepared solution with the urea concentration of 18 mmol/L.
③ selenium doping of hydroxyapatite microparticles: adding 150g of hydroxyapatite microparticles into 1L of selenium-doped treatment solution prepared according to the component concentration, stirring for 30 minutes by using a magnetic stirrer, then adding 90mL of prepared solution, reacting for 8 hours at 30 ℃, filtering a suspension liquid solid phase substance, and drying for 15 hours at 30 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
Selenium-doped hydroxyapatite particle surface Ca2+Selective adsorption of (2): adding calcium dihydrogen phosphate, calcium gluconate and selenium-doped hydroxyapatite particles into deionized water to form 30g/L, 7g/L and 420g/L adsorption solution, standing for 2 hr, filtering to obtain solid phase substance with Ca adsorbed on surface2+The selenium-doped hydroxyapatite particles.
Electrophoretic codeposition of selenium-doped hydroxyapatite on the surface of the magnesium alloy: adsorbing Ca on the surface prepared according to the fourth step2+Adding the selenium-doped hydroxyapatite particles into an N, N-dimethylformamide organic solvent to enable the concentration of the selenium-doped hydroxyapatite particles to be 180g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 12g/L, and stirring for 30 minutes by using a magnetic stirrer; taking magnesium alloy as a cathode and stainless steel as an anode, and finishing the electrodeposition process when the electrodeposition temperature is 30 ℃, the electrodeposition voltage is increased by 1V by taking 15V as an initial electrophoretic deposition voltage value and every 0.5 minute of deposition, and the final electrophoretic deposition voltage is 45V, thereby obtaining the magnesium alloy-based selenium-doped hydroxyapatite coating on the surface of the magnesium alloy.
Comparative example 2
The invention provides a preparation method of a magnesium alloy-based selenium-doped hydroxyapatite embedded beta-TCP nanofiber coating with gradient distribution of volume fraction, which comprises the following steps:
preparation of selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of potassium phenylselenate of 12mmol/L, the concentration of sodium hydroxide of 90mmol/L and the concentration of tributylmethylammonium chloride of 15 mmol/L.
Preparing a preparation solution: adding urea into deionized water to form a prepared solution with the urea concentration of 18 mmol/L.
③ selenium doping of hydroxyapatite microparticles: adding 150g of hydroxyapatite microparticles into 1L of selenium-doped treatment solution prepared according to the component concentration, stirring for 30 minutes by using a magnetic stirrer, then adding 90mL of prepared solution, reacting for 8 hours at 30 ℃, filtering a suspension liquid solid phase substance, and drying for 15 hours at 30 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
And fourthly, synthesizing the beta-TCP nano fiber: adding 60% phosphoric acid (60% phosphoric acid by mass), calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form synthetic treatment solution with 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole respectively being 96mL/L, 170g/L, 150g/L and 120 mL/L; pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 3 hours at 140 ℃, then filtering the suspension liquid solid phase matter, and drying for 4 hours at room temperature to prepare the beta-TCP nano fiber.
Selenium doped hydroxyapatite particles and Ca on the surface of beta-TCP nano-fiber2+Selective adsorption of (2): adding analytically pure calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and beta-TCP (Transmission control protocol) nano fibers into deionized water to form adsorption solutions with the concentrations of calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and beta-TCP nano fibers being respectively 30g/L, 7g/L, 420g/L and 20g/L, standing for 2 hours, and filtering an adsorption solution solid phase substance which is a solid phase substance with Ca adsorbed on the surface2+The selenium-doped hydroxyapatite and beta-TCP nanofiber mixture.
Sixthly, the selenium-doped hydroxyapatite and the beta-TCP nano-fiber are subjected to gradient electrophoresis codeposition on the surface of the magnesium alloy: adsorbing Ca on the surface prepared according to the fifth step2+The mixture of selenium-doped hydroxyapatite and beta-TCP nanofibers was added to an N, N-dimethylformamide organic solvent to a concentration of 180g/L, and ammonium bicarbonate was added to a concentration of 12g/L, and stirred with a magnetic stirrer for 30 minutes. Taking magnesium alloy as a cathode and stainless steel as an anode, taking 15V as an initial electrophoretic deposition voltage value at the electrodeposition temperature of 30 ℃, increasing the electrophoretic deposition voltage by 1V every 0.5 minute of deposition, and finishing the electrophoretic codeposition step of selenium-doped hydroxyapatite and beta-TCP nanofiber when the final electrophoretic deposition voltage is 45V, thereby obtaining the beta-TCP nanofiber coating with selenium-doped hydroxyapatite embedded with volume fraction gradient distribution on the surface of the magnesium alloyAnd (3) a layer.
In order to study and compare the effect of photothermal therapy on the death rate of MG63 human osteosarcoma cells, human sarcomatosis cells MG63 were cultured in RPMI1640 culture medium in comparative example 1, comparative example 2 and example 1, and MG63 human osteosarcoma cells were cultured, and example 1, comparative example 1 and comparative example 2 were divided into three groups: no illumination, 5 minutes illumination and 10 minutes illumination, wherein the illumination group adopts near infrared light (wavelength is 808nm, power is 0.8W/cm)2). The MTT method is used for detecting the influence of photothermal treatment on the MG63 human osteosarcoma cell death rate, and the experimental result is shown in figure 2, and the near infrared illumination has no significant influence on the human bone and meat cell MG63 death rate of comparative example 1 and comparative example 2, and the death rate is lower than 5%. The near infrared light has a decisive effect on the death rate of the human bone and flesh cell MG63 in the example 1, under the condition of no light, the death rate of the human bone and flesh cell MG63 in the example 1 is less than 4%, when the light is irradiated for 5 minutes, the death rate of the human bone and flesh cell MG63 in the example 1 reaches 72%, and when the light is irradiated for 10 minutes, the death rate of the human bone and flesh cell MG63 in the example 1 reaches 96%, so that the invention has a good bone tumor photothermal treatment function.
Culturing rabbit bone marrow stromal stem cells and mixing 1 × 108The cell concentration of/L is planted on the surfaces of comparative example 1, comparative example 2 and example 1, and the research result is 5 days of culture, and the research result shows that the osteoblasts after induction have division and proliferation on the surfaces of comparative example 1, comparative example 2 and example 1, and have stronger osteogenic differentiation capacity on the surfaces of comparative example 2 and example 1, so that example 1 has excellent osteogenic performance. Experimental results show that the magnesium alloy selenium-doped hydroxyapatite @ nanofiber photothermal anti-bone tumor coating prepared according to the invention has a good bone tumor treatment function and excellent bone formation performance.
For further detailed illustration, two further embodiments are now provided.
Example 2
The preferred embodiment 2 of the invention provides a preparation method of a novel photothermal anti-bone tumor coating on the surface of a magnesium alloy, which is carried out according to the following steps:
preparation of selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of the potassium phenylselenate being 15mmol/L, the concentration of the sodium hydroxide being 90mmol/L and the concentration of the tributylmethylammonium chloride being 20 mmol/L.
Preparing a preparation solution: adding urea into deionized water to form a prepared solution with the urea concentration of 3 mmol/L.
③ selenium doping of hydroxyapatite microparticles: 230g of hydroxyapatite microparticles are added into 1L of the selenium-doped treatment solution, stirred for 30 minutes by a magnetic stirrer, then 95mL of the above prepared solution is added, the reaction is carried out for 7 hours at 30 ℃, then the suspension solid phase substance is filtered, and the suspension is dried for 10 hours at 30 ℃, thus obtaining the selenium-doped hydroxyapatite microparticles.
And fourthly, synthesizing the beta-TCP nano fiber: respectively adding 60% phosphoric acid (60% by mass of phosphoric acid), calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form synthetic treatment solutions with the concentrations of 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole being 150mL/L, 270g/L, 50g/L and 220mL/L respectively; pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 2.5 hours at 120 ℃, then filtering the suspension liquid solid phase matter, and drying for 5 hours at room temperature to prepare the beta-TCP nano fiber.
Loading the black phosphorus nanosheets on the beta-TCP nanofiber: forming black phosphorus nanosheets and beta-TCP nanofiber deionized water into treatment solutions with the concentrations of the black phosphorus nanosheets and the beta-TCP nanofibers being 200mg/L and 310g/L respectively, stirring for 30 minutes to form a uniform dispersion system, adding hexadecyl sulfobetaine to enable the concentration of the hexadecyl sulfobetaine to reach 6g/L, keeping the system for 20 hours, collecting precipitates at a lower layer to obtain solid phase substances in the system, cleaning the solid phase substances with anhydrous acetic acid, and drying at 30 ℃ for 12 hours to finish loading of the black phosphorus nanosheets on the beta-TCP nanofibers and obtain the black phosphorus nanosheets @ beta-TCP nanofibers.
Sixth, Ca on the surface of selenium-doped hydroxyapatite particles and black phosphorus nano-sheets @ beta-TCP nano-fibers2+Selective adsorption of (2): adding calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers into deionized water to form calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers with concentrations of 23g/L and 16 g/L respectivelyL, 360g/L and 40g/L of the adsorption solution, standing for 2.5 hours, and then filtering and adsorbing a solid phase substance which is Ca adsorbed on the surface2+The selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber mixture is prepared from the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber, wherein the mass ratio of the selenium-doped hydroxyapatite to the black phosphorus nanosheet @ beta-TCP nanofiber is 20: 1.
Seventhly, carrying out gradient electrophoretic codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber on the surface of the magnesium alloy: adsorbing Ca on the surface prepared according to the sixth step2+Adding the mixture of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber into an N, N-dimethylformamide organic solvent to enable the concentration of the mixture to be 260g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 33g/L, and stirring for 30 minutes by using a magnetic stirrer; the magnesium alloy is used as a cathode, stainless steel is used as an anode, the electrodeposition temperature is 35 ℃, 10V is used as an initial electrophoretic deposition voltage value, the electrophoretic deposition voltage is increased by 1.5V every 0.3 minute of deposition, and the electrophoretic codeposition step of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber is completed when the final electrophoretic deposition voltage is 50V, so that the black phosphorus nanosheet @ beta-TCP nanofiber coating with the selenium-doped hydroxyapatite embedded in a volume fraction gradient distribution is obtained on the surface of the magnesium alloy.
Example 3
The preferred embodiment 3 of the present invention provides a method for preparing a novel photothermal anti-bone tumor coating on a magnesium alloy surface, which comprises the following steps:
preparation of selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of the potassium phenylselenate being 92mmol/L, the concentration of the sodium hydroxide being 310mmol/L and the concentration of the tributylmethylammonium chloride being 36 mmol/L.
Preparing a preparation solution: adding urea into deionized water to form a prepared solution with the urea concentration of 33 mmol/L.
③ selenium doping of hydroxyapatite microparticles: adding 420g of hydroxyapatite microparticles into 1L of the selenium-doped treatment solution, stirring for 30 minutes by using a magnetic stirrer, then adding 162mL of the prepared solution, reacting for 16 hours at 35 ℃, filtering a suspension solid phase substance, and drying for 17 hours at 36 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
And fourthly, synthesizing the beta-TCP nano fiber: adding 60% phosphoric acid (60% by mass of phosphoric acid), calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form synthetic treatment solutions with the concentrations of 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole being 305mL/L, 362g/L, 210g/L and 325mL/L respectively; pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 2 hours at 150 ℃, then filtering the suspension liquid solid phase matter, and drying for 6 hours at room temperature to prepare the beta-TCP nano fiber.
Loading the black phosphorus nanosheets on the beta-TCP nanofiber: forming black phosphorus nanosheets and beta-TCP nanofiber deionized water into treatment solutions with the concentrations of the black phosphorus nanosheets and the beta-TCP nanofibers being 320mg/L and 387g/L respectively, stirring for 30 minutes to form a uniform dispersion system, adding hexadecyl sulfobetaine to enable the concentration of the hexadecyl sulfobetaine to reach 27g/L, keeping the system for 23 hours, collecting precipitates on the lower layer to obtain solid phase substances in the system, washing the solid phase substances with anhydrous acetic acid, and drying the solid phase substances at 35 ℃ for 10 hours to finish the loading of the black phosphorus nanosheets on the beta-TCP nanofibers and obtain the black phosphorus @ beta-TCP nanofibers.
Sixth, Ca on the surface of selenium-doped hydroxyapatite particles and black phosphorus nano-sheets @ beta-TCP nano-fibers2+Selective adsorption of (2): adding calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers into deionized water to form adsorption solutions with the concentrations of the calcium dihydrogen phosphate, the calcium gluconate, the selenium-doped hydroxyapatite particles and the black phosphorus nanosheet @ beta-TCP nanofibers respectively being 51g/L, 7g/L, 450g/L and 35g/L, standing for 3 hours, and filtering and adsorbing a solid-phase substance, wherein the solid-phase substance is a substance with Ca adsorbed on the surface2+The selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber mixture is prepared, wherein the mass ratio of the selenium-doped hydroxyapatite to the black phosphorus nanosheet @ beta-TCP nanofiber is 28: 1.
Seventhly, carrying out gradient electrophoretic codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber on the surface of the magnesium alloy: adsorbing Ca on the surface prepared according to the sixth step2+Adding the mixture of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber into an N, N-dimethylformamide organic solvent to enable the concentration of the mixture to be 358g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 39g/L, and stirring for 30 minutes by using a magnetic stirrer; the magnesium alloy is used as a cathode, stainless steel is used as an anode, 18V is used as an initial electrophoretic deposition voltage value at the electrodeposition temperature of 38 ℃, the electrophoretic deposition voltage is increased by 1.2V every 0.8 minute of deposition, and the electrophoretic codeposition step of the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber is completed when the final electrophoretic deposition voltage is 52V, so that the black phosphorus nanosheet @ beta-TCP nanofiber coating with the selenium-doped hydroxyapatite embedded volume fraction gradient distribution is obtained on the surface of the magnesium alloy.
The above embodiments are only preferred embodiments of the present invention, and it should be understood that the above embodiments are only for assisting understanding of the method and the core idea of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation method of a novel photo-thermal anti-bone tumor coating on the surface of a magnesium alloy is characterized by comprising the following preparation steps:
step one, selenium doping of hydroxyapatite micron particles;
step two, synthesizing beta-TCP nano fibers and loading black phosphorus nano sheets on the beta-TCP nano fibers;
step three, selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber surface Ca2+Selective adsorption of (2);
and step four, carrying out gradient electrophoresis codeposition on the selenium-doped hydroxyapatite and the black phosphorus nanosheet @ beta-TCP nanofiber on the surface of the magnesium alloy.
2. The method for preparing the novel photothermal anti-bone tumor coating on the surface of the magnesium alloy as claimed in claim 1, wherein the step one is specifically operated as follows:
a1. preparing a selenium-doped treatment solution: adding potassium phenylselenate, sodium hydroxide and tributylmethylammonium chloride into deionized water to form selenium-doped treatment solution with the concentration of the potassium phenylselenate being 0.1-120mmol/L, the concentration of the sodium hydroxide being 80-350mmol/L and the concentration of the tributylmethylammonium chloride being 5-40 mmol/L;
a2. preparing a concoction solution: adding urea into deionized water to form a modulating liquid with the urea concentration of 0.5-38 mmol/L;
a3. selenium doping of hydroxyapatite microparticles: adding 120-450g of hydroxyapatite microparticles into 1L of the selenium-doped treatment solution, stirring for 30 minutes by using a magnetic stirrer, then adding 40-180mL of the preparation solution, reacting for 4-18 hours at 20-40 ℃, filtering a suspension solid phase substance, and drying for 8-20 hours at 20-40 ℃ to obtain the selenium-doped hydroxyapatite microparticles.
3. The method for preparing the novel photothermal anti-bone tumor coating on the surface of the magnesium alloy as claimed in claim 1, wherein the second step is specifically performed by:
b1. synthesis of beta-TCP nanofibers: adding 60% phosphoric acid, calcium acetate, calcium fluoride and tetrahydropyrrole into deionized water to form 60% synthetic treatment liquid with the concentrations of the phosphoric acid, the calcium acetate, the calcium fluoride and the tetrahydropyrrole being 9.6-336mL/L, 155-390g/L, 20-270g/L and 60-340mL/L respectively, pouring the prepared synthetic treatment liquid into a reaction kettle, reacting for 2-5 hours at the temperature of 100-160 ℃, filtering a suspension solid phase substance, and drying for 3-7 hours at room temperature to obtain the beta-TCP nanofiber;
b2. the loading of the black phosphorus nanosheet on the beta-TCP nanofiber is as follows: adding black phosphorus nanosheets and beta-TCP nanofibers into deionized water to form treatment solutions with the concentrations of the black phosphorus nanosheets and the beta-TCP nanofibers being respectively 120-340mg/L and 170-410g/L, stirring for 30 minutes to form a uniform dispersion system, adding hexadecyl sulfobetaine to enable the concentration of the hexadecyl sulfobetaine to reach 2-30g/L, keeping the system for 16-24 hours, collecting precipitates at the lower layer to obtain solid phase substances in the system, cleaning with anhydrous acetic acid, and drying at 15-40 ℃ for 6-15 hours to complete the loading of the black phosphorus nanosheets on the beta-TCP nanofibers and obtain the black phosphorus nanosheets @ beta-TCP nanofibers.
4. The method for preparing the novel photothermal anti-bone tumor coating on the surface of the magnesium alloy as claimed in claim 1, wherein the three steps are specifically:
adding calcium dihydrogen phosphate, calcium gluconate, selenium-doped hydroxyapatite particles and black phosphorus nanosheet @ beta-TCP nanofibers into deionized water to form adsorption solutions with the concentrations of the calcium dihydrogen phosphate, the calcium gluconate, the selenium-doped hydroxyapatite particles and the black phosphorus nanosheet @ beta-TCP nanofibers being 15-60g/L, 5-18g/L, 350-480g/L and 15-46g/L respectively, standing for 1-3 hours, and filtering and adsorbing a solid phase substance, wherein the solid phase substance is a substance with the surface on which Ca is adsorbed2+The selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber mixture is characterized in that the mass ratio of the selenium-doped hydroxyapatite to the black phosphorus nanosheet @ beta-TCP nanofiber in the mixture is 8-32: 1.
5. The method for preparing the novel photothermal anti-bone tumor coating on the surface of the magnesium alloy as claimed in claim 4, wherein the four steps are specifically:
adding the mixture prepared in the third step into an N, N-dimethylformamide organic solvent to enable the concentration of the mixture to be 170-380g/L, adding ammonium bicarbonate to enable the concentration of the ammonium bicarbonate to be 10-42g/L, and stirring for 30 minutes by using a magnetic stirrer; the magnesium alloy is used as a cathode, stainless steel is used as an anode, the electrodeposition temperature is 20-40 ℃, 5-20V is used as an initial electrophoretic deposition voltage value, the electrophoretic deposition voltage is increased by 0.5-2V every 0.2-1 minute of deposition, and the electrophoretic codeposition step of selenium-doped hydroxyapatite and black phosphorus nanosheet @ beta-TCP nanofiber is completed when the final electrophoretic deposition voltage is 40-55V, so that the magnesium alloy selenium-doped hydroxyapatite @ nanofiber photothermal anti-bone tumor coating is obtained on the surface of the magnesium alloy.
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