CN114404655A - Porous scaffold with photo-thermal effect and preparation method thereof - Google Patents

Porous scaffold with photo-thermal effect and preparation method thereof Download PDF

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CN114404655A
CN114404655A CN202210107309.5A CN202210107309A CN114404655A CN 114404655 A CN114404655 A CN 114404655A CN 202210107309 A CN202210107309 A CN 202210107309A CN 114404655 A CN114404655 A CN 114404655A
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powder
solution
later use
porous scaffold
preparing
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CN114404655B (en
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马瑜磊
马瑜瑾
李光大
李晓芳
张子林
张开丽
赵三团
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Luoyang Hospital Of Traditional Chinese Medicine
Henan University of Science and Technology
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Luoyang Hospital Of Traditional Chinese Medicine
Henan University of Science and Technology
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/08—Carbon ; Graphite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • 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
    • A61L27/56—Porous materials, e.g. foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/325—Preparation by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/327—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0063—Mixed oxides or hydroxides containing zinc
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a porous bracket with a photo-thermal effect and a preparation method thereof, wherein the preparation method comprises the following steps: mixing beta-calcium phosphate and Ca (H)2PO4)2·H2Mixing O powder, putting into a mortar, and grinding uniformly; adding the nano manganese-zinc ferrite into the mixed powder, and grinding uniformly for later use; continuously adding carbon powder into the mixed powder, and uniformly grinding for later use; adding a citric acid solution into the prepared mixed powder according to the proportion of 3g/mL, and stirring for 2-4 min; sixthly, obtaining a porous support product after the material is solidified; the material prepared by the method has no cytotoxicity, and the material has photo-thermal property due to the addition of the carbon powder.

Description

Porous scaffold with photo-thermal effect and preparation method thereof
Technical Field
The invention relates to the technical field of biomedical scaffolds, in particular to a porous scaffold with a photothermal effect and a preparation method thereof.
Background
With the development of socio-economic, bone tissue defects caused by various diseases, high-energy trauma, etc. have become common clinical diseases. When the defect reaches a critical state, the bone tissue can not be repaired by self, the bone nonunion can be formed, the tissue function and the shape are attractive, and the dual damage of the body and the mind of a patient is brought. Autologous bone grafting and allogeneic bone grafting are the common means of bone grafting in clinical practice to repair bone defects. Although autologous bone grafting is from the self, has good repairing effect and good compatibility, can not generate rejection, but has limited source and is easy to cause secondary damage to patients. Allograft bone grafts, taken from cadavers or xenogeneic bone, are more abundant in origin than autologous bone, but are at risk for disease transmission and immune rejection. Therefore, the development of a novel artificial bone grafting material with excellent functions can reduce the pain of human beings, and is the direction of efforts in the medical and scientific fields.
Among many bone repair biomaterials, calcium phosphate materials have received much attention because of their similar histochemical composition to human bone, good biocompatibility and strong bone repair ability. The calcium phosphate of the brushite class has good biocompatibility and excellent degradation performance, and can be synthesized at low temperature, so that the calcium phosphate becomes a good choice for preparing bone repair materials. The bone tissue has a porous structure, particularly cancellous bone, the porosity is high, the pores are communicated, and the pore diameter is mainly distributed between 300 and 800 microns. Therefore, when designing bone grafting materials, it is desirable to have a biomimetic porous structure with a height similar to that of bone tissue, i.e. a high porosity, through-going pore structure, with a pore size mainly distributed at 300-800 μm.
At present, the preparation method of the porous brushite bracket material mainly adopts the modes of pore-forming by using active metal such as magnesium and the like or pore-forming by leaching soluble solid. The method of using active metal to prepare porous material brings difficulties in operation and aperture control due to the fast reaction speed. The pore is formed by using a leaching method, generally, salt is introduced into the material preparation process, and after the material is formed, the salt is dissolved and separated out by soaking for a long time to obtain a porous structure. The method is simple and feasible, but has long production period, and the residual salt can affect biocompatibility.
Disclosure of Invention
In order to solve the existing problems, the invention provides a porous support with a photothermal effect and a preparation method thereof.
The technical scheme adopted by the invention is as follows: a preparation method of a porous scaffold with a photo-thermal effect comprises the following steps:
step one, beta-calcium phosphate and Ca (H)2PO4 )2·H2Grinding the O powder respectively, and sieving for later use;
step two, mixing the beta-calcium phosphate and Ca (H) in the step one2PO4 )2·H2O powder according to the mol ratio1, (0.9-1.1), placing the mixture in a mortar, and uniformly grinding the mixture;
step three, adding the nano manganese-zinc ferrite into the mixed powder in the step two, and grinding the mixture uniformly for later use;
step four, adding carbon powder into the mixed powder obtained in the step three, and uniformly grinding the mixture for later use;
step five, adding a citric acid solution into the mixed powder prepared in the step four according to the proportion of 3g/mL, and stirring for 2-4 min;
and step six, obtaining a porous support product after the material is solidified.
Further, in the first step, beta-tricalcium phosphate and Ca (H)2PO4 )2·H2And sieving the O powder with a 180-220 mesh sieve.
Further, the preparation method of the beta-tricalcium phosphate in the first step comprises the following steps:
s11, massage dose [ Ca]：[P]Is 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing a solution A and a solution B with the concentration of 0.08-0.12 mol/L at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after dropwise adding, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting at room temperature for 4 hours, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, aging the mixed solution for 20-30 h at the temperature of 38-45 ℃;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven, and drying for 20-30 h at the temperature of 90-105 ℃;
s14, drying the Ca3(PO4)2And (3) placing the powder in a high-temperature furnace, calcining for 1.5-2.5 hours at 1050-1150 ℃ to obtain high-purity beta-TCP powder, and sieving for later use.
Furthermore, the nano manganese-zinc ferrite in the third step accounts for 1-3 wt% of the mixed powder.
Further, the preparation method of the nano manganese-zinc ferrite in the third step comprises the following steps:
s31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O、ZnCl2And MnCl2·4H2O；
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with metal ion concentration of 0.25-0.35M, and heating to 90-100 ℃ for later use;
s33, adding 0.6-1.2M NaOH solution into the solution of S32, adjusting the pH value to 9-10, carrying out 3.5-4.5 h at the temperature of 90-100 ℃, and isolating air in the whole process;
s34, separating the brown-black precipitate obtained in the step S33 by using 3T strong magnet, washing until no white precipitate can be detected by using silver nitrate solution with the concentration of 0.05-0.1M, and washing for 2-4 times by using absolute ethyl alcohol;
and S35, placing the brown precipitate washed by the S34 in a vacuum drying oven, and drying at the temperature of 65-75 ℃ for 35-45 h to obtain the prepared powder for later use.
Furthermore, the mass of the carbon powder in the fourth step is 1-3 wt% of the mass of the mixed powder, and the particle size of the carbon powder is 0.1-0.3 μm.
Further, the concentration of the citric acid solution in the fifth step is 0.4-0.6 mol/L.
A porous scaffold having a photothermal effect, which is prepared by any one of claims 1 to 7.
The invention has the following beneficial effects that:
1) the preparation process is simple and feasible, the production speed is high, and the cost is low;
2) the material has been made to the addition of carbon powder has had the light and heat performance in this patent, and when using infrared light irradiation, the material can become heat energy with light energy conversion, has had the ability of utilizing the light and heat to develop other treatment methods.
Drawings
FIG. 1 is a sample graph of various embodiments of the present invention;
fig. 2 is a graph of a photothermal map and temperature rise for various embodiments of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific examples, but the present invention is not limited thereto.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "lateral", "longitudinal", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
A preparation method of a porous scaffold with a photo-thermal effect comprises the following steps:
step one, beta-calcium phosphate and Ca (H)2PO4 )2·H2Grinding the O powder respectively, and sieving for later use;
step two, mixing the beta-calcium phosphate and Ca (H) in the step one2PO4 )2·H2Mixing O powder according to the molar ratio of 1 (0.9-1.1), placing the mixture in a mortar, and uniformly grinding;
step three, adding the nano manganese-zinc ferrite into the mixed powder in the step two, and grinding the mixture uniformly for later use;
step four, adding carbon powder into the mixed powder obtained in the step three, and uniformly grinding the mixture for later use;
step five, adding a citric acid solution into the mixed powder prepared in the step four according to the proportion of 3g/mL, and stirring for 2-4 min;
and step six, obtaining a porous support product after the material is solidified.
Further, in the first step, beta-tricalcium phosphate and Ca (H)2PO4 )2·H2And sieving the O powder with a 180-220 mesh sieve.
Further, the preparation method of the beta-tricalcium phosphate in the first step comprises the following steps:
s11, massage dose [ Ca]：[P]Is 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing a solution A and a solution B with the concentration of 0.08-0.12 mol/L at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after dropwise adding, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting at room temperature for 4 hours, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, aging the mixed solution for 20-30 h at the temperature of 38-45 ℃;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven, and drying for 20-30 h at the temperature of 90-105 ℃;
s14, drying the Ca3(PO4)2And (3) placing the powder in a high-temperature furnace, calcining for 1.5-2.5 hours at 1050-1150 ℃ to obtain high-purity beta-TCP powder, and sieving for later use.
Furthermore, the nano manganese-zinc ferrite in the third step accounts for 1-3 wt% of the mixed powder.
Further, the preparation method of the nano manganese-zinc ferrite in the third step comprises the following steps:
s31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O、ZnCl2And MnCl2·4H2O；
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with metal ion concentration of 0.25-0.35M, and heating to 90-100 ℃ for later use;
s33, adding 0.6-1.2M NaOH solution into the solution of S32, adjusting the pH value to 9-10, carrying out 3.5-4.5 h at the temperature of 90-100 ℃, and isolating air in the whole process;
s34, separating the brown-black precipitate obtained in the step S33 by using 3T strong magnet, washing until no white precipitate can be detected by using silver nitrate solution with the concentration of 0.05-0.1M, and washing for 2-4 times by using absolute ethyl alcohol;
and S35, placing the brown precipitate washed by the S34 in a vacuum drying oven, and drying at the temperature of 65-75 ℃ for 35-45 h to obtain the prepared powder for later use.
Furthermore, the mass of the carbon powder in the fourth step is 1-3 wt% of the mass of the mixed powder, and the particle size of the carbon powder is 0.1-0.3 μm.
Further, the concentration of the citric acid solution in the fifth step is 0.4-0.6 mol/L.
A porous scaffold having a photothermal effect, which is prepared by any one of claims 1 to 7.
Example 1
Preparation of manganese zinc ferrite
S31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O,ZnCl2And MnCl2·4H2And O, chemical raw materials.
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with the metal ion concentration of 0.3M, and heating to 95 ℃ for later use;
s33, adding 1M NaOH solution into the solution of S32, adjusting the pH value to 9-10, reacting at 95 ℃ for 4 hours, and isolating air in the whole process;
s34, separating the brownish black precipitate obtained in the S33 by using 3T strong magnet, washing until no white precipitate can be detected by using 0.1M silver nitrate solution, and washing for 3 times by using absolute ethyl alcohol;
s35, drying the washed tan precipitate obtained in the step S34 in a vacuum drying oven at 70 ℃ for 38 hours to obtain powder for later use;
preparation of di) beta-calcium phosphate
S11, massage dose [ Ca]：[P]= 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing 0.1 mol/L solution A and solution B at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after dropwise adding, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting at room temperature for 4 hours, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, the mixed solution is placed at the temperature of 40 ℃ for aging for 24 hours;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven at 100 ℃ for 24 hours;
s14, drying the Ca3(PO4)2And placing the powder in a high-temperature furnace, calcining for 2 hours at the high temperature of 1100 ℃ to obtain high-purity beta-TCP powder, and sieving by a 200-mesh sieve for later use.
III) preparation of porous scaffolds
1) Preparing a citric acid solution with the concentration of 0.5mol/L as a synthetic liquid phase for later use;
2) 0.1802g of beta-tricalcium phosphate was weighed in conjunction with 0.1564gCa (H)2PO4 )2·H2Grinding O powder (both of which are sieved by a 200-mesh sieve) in a mortar for 10min to prepare mixed powder for later use;
3) putting 0.009g of the prepared manganese-zinc ferrite powder and the mixed powder prepared in the step 2) into a mortar, grinding for 15min, and uniformly mixing to obtain a solid-phase mixture for later use;
4) adding 0.003g of carbon powder with the particle size of about 0.2um into the mixed powder in the step 3), and uniformly grinding;
5) adding a citric acid solution with the concentration of 0.5mol/L into the mixed powder prepared in the step 4) according to the proportion of 3g/mL, stirring for 3min to obtain uniform slurry, filling the uniform slurry into a mold for foaming, demolding to obtain a material, and performing various detections.
Example 2
Preparation of manganese zinc ferrite
S31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O,ZnCl2And MnCl2·4H2And O, chemical raw materials.
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with the metal ion concentration of 0.3M, and heating to 95 ℃ for later use.
S33, adding 1M NaOH solution into the solution of S32, adjusting the pH value to 9-10, reacting at 95 ℃ for 4 hours, and isolating air in the whole process;
s34, separating the brownish black precipitate obtained in the S33 by using 3T strong magnet, washing until no white precipitate can be detected by using 0.1M silver nitrate solution, and washing for 3 times by using absolute ethyl alcohol;
s35, drying the washed tan precipitate obtained in the S34 in a vacuum drying oven at 70 ℃ for 38 hours to obtain powder for later use.
Preparation of di) beta-calcium phosphate
S11, massage dose [ Ca]：[P]= 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing 0.1 mol/L solution A and solution B at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after the dropwise addition is finished, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting for 4 hours at room temperature, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, the mixed solution is placed at the temperature of 40 ℃ for aging for 24 hours;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven at 100 ℃ for 24 hours;
s14, drying the Ca3(PO4)2And placing the powder in a high-temperature furnace, calcining for 2 hours at the high temperature of 1100 ℃ to obtain high-purity beta-TCP powder, and sieving by a 200-mesh sieve for later use.
III) preparation of porous scaffolds
1) Preparing a citric acid solution with the concentration of 0.5mol/L as a bone cement liquid phase for later use;
2) 0.1802g of beta-tricalcium phosphate was weighed in conjunction with 0.1564gCa (H)2PO4 )2·H2Grinding O powder (both of which are sieved by a 200-mesh sieve) in a mortar for 10min to prepare mixed powder for later use;
3) putting 0.006g of the prepared manganese-zinc ferrite powder and the mixed powder prepared in the step 2) into a mortar, grinding for 15min, and uniformly mixing to obtain a solid-phase mixture for later use;
4) adding 0.006g of carbon powder with the particle size of about 0.2um into the mixed powder in the step 3), and uniformly grinding;
5) adding a citric acid solution with the concentration of 0.5M into the mixed powder prepared in the step 4) according to the proportion of 3g/mL, stirring for 3min to obtain uniform slurry, filling the uniform slurry into a mold for foaming, demolding to obtain a material, and carrying out various detections.
Embodiment 3
Preparation of manganese zinc ferrite
S31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O,ZnCl2And MnCl2·4H2And O, chemical raw materials.
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with the metal ion concentration of 0.3M, and heating to 95 ℃ for later use.
S33, adding 1M NaOH solution into the solution of S32, adjusting the pH value to 9-10, reacting at 95 ℃ for 4 hours, and completely isolating air.
S34, separating the brown-black precipitate obtained in the S33 by using 3T strong magnet, washing until no white precipitate can be detected by using 0.1M silver nitrate solution, and then washing for 3 times by using absolute ethyl alcohol.
S35, drying the washed tan precipitate obtained in the S34 in a vacuum drying oven at 70 ℃ for 38 hours to obtain powder for later use.
Preparation of di) beta-calcium phosphate
S11, massage dose [ Ca]：[P]= 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing 0.1 mol/L solution A and solution B at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after the dropwise addition is finished, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting for 4 hours at room temperature, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, the mixed solution is placed at the temperature of 40 ℃ for aging for 24 hours;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven at 100 ℃ for 24 hours;
s14, drying the Ca3(PO4)2And placing the powder in a high-temperature furnace, calcining for 2 hours at the high temperature of 1100 ℃ to obtain high-purity beta-TCP powder, and sieving by a 200-mesh sieve for later use.
Three) preparation of porous scaffolds
1) Preparing a citric acid solution with the concentration of 0.5mol/L as a bone cement liquid phase for later use;
2) 0.1802g of beta-tricalcium phosphate was weighed in conjunction with 0.1564gCa (H)2PO4 )2·H2Grinding O powder (both of which are sieved by a 200-mesh sieve) in a mortar for 10min to prepare mixed powder for later use;
3) putting 0.003g of the prepared manganese-zinc ferrite powder and the mixed powder prepared in the step 2) into a mortar, grinding for 15min, and uniformly mixing to obtain a solid-phase mixture for later use;
4) adding 0.009g of carbon powder with the particle size of about 0.2um into the mixed powder in the step 3), and uniformly grinding;
5) adding a citric acid solution with the concentration of 0.5M into the mixed powder prepared in the step 4) according to the proportion of 3g/mL, stirring for 3min to obtain uniform slurry, filling the uniform slurry into a mold for foaming, demolding to obtain a material, and carrying out various detections.
The porosity, photothermal effect and cytotoxicity of each material prepared in example 1, example 2 and example 3 were measured;
1) and (3) porosity characterization: and (3) detecting the porosity of the material by adopting an Archimedes principle. The results are shown in FIG. 1 and Table 1. The visible material is a porous structure, the pore size is mainly distributed below 800 microns, and the porosity of the material is 52% -58%, so that a better natural bionic porous structure is formed.
2) And (3) detecting the photothermal effect: the material was irradiated perpendicularly with a 1064 nm laser at an intensity of 1W, and the temperature rise curve was recorded. And when the temperature rise is balanced, taking a picture by using an infrared camera. The results are shown in FIG. 2 and Table 1. It can be known that the material has photo-thermal property due to the addition of the carbon powder, and when infrared light is used for irradiation, the material can convert the photo-thermal energy into heat energy, so that the material has the capability of developing other treatment modes by using photo-thermal energy.
3) After the material is soaked in pure water for 8 hours and cleaned, the cytotoxicity of the material is detected by adopting a method for testing the cytotoxicity by adopting a cell leaching solution method according to a national standard GB16886.5-200 method. The cells used were MG63 cells, with an initial concentration of 3000 cells per well in 96-well plates. The results are shown in Table 1. As can be seen from the table, the prepared material was not cytotoxic.
TABLE 1 examples and results of experiments
Figure DEST_PATH_IMAGE001
The invention discloses a method for preparing a brushite porous support, which is simple and easy to implement and has the production speed of about half an hour. When the brushite is prepared at room temperature, a small amount of nano manganese-zinc ferrite is added, and the acidic environment of chemical reaction and the high-activity nano manganese-zinc ferrite are utilized to carry out chemical reaction to generate gas and form holes. Meanwhile, a small amount of high-purity carbon powder is added into the raw materials, and the pore diameter is controlled by utilizing the tension effect generated by the carbon powder. The dosage of the added pore-forming agent is very small, so that the biocompatibility of the material is not influenced, and the material has no cytotoxicity. Meanwhile, the material has photo-thermal property due to the addition of the carbon powder, and when infrared light is used for irradiation, the material can convert the photo-thermal energy into heat energy, so that the material has the capability of developing other treatment modes by using photo-thermal energy.
The above examples are not specifically described, and the reagents used in the present invention are commercially available as chemical reagents or industrial products, the present invention can be realized by the ratios of the raw materials listed in the present invention, the values of the upper and lower limits and the intervals of the raw materials can be realized by the values of the upper and lower limits of the process parameters of the present invention, and the present invention can be realized by the values of the upper and lower limits and the intervals of the process parameters of the present invention, but the examples are not specifically listed here.
The device of the present invention may have other forms than the above-described embodiments, and it should be understood that any simple modification, equivalent change and modification made to the above-described embodiments according to the technical spirit of the present invention fall within the scope of the present invention.

Claims (8)

1. A preparation method of a porous scaffold with a photothermal effect is characterized by comprising the following steps: the method comprises the following steps:
step one, beta-calcium phosphate and Ca (H)2PO4 )2·H2Grinding the O powder respectively, and sieving for later use;
step two, mixing the beta-calcium phosphate and Ca (H) in the step one2PO4 )2·H2Mixing O powder according to the molar ratio of 1 (0.9-1.1), placing the mixture in a mortar, and uniformly grinding;
step three, adding the nano manganese-zinc ferrite into the mixed powder in the step two, and grinding the mixture uniformly for later use;
step four, adding carbon powder into the mixed powder obtained in the step three, and uniformly grinding the mixture for later use;
step five, adding a citric acid solution into the mixed powder prepared in the step four according to the proportion of 3g/mL, and stirring for 2-4 min;
and step six, obtaining a porous support product after the material is solidified.
2. The method of claim 1 for preparing a porous scaffold with a photothermal effect, wherein: beta-tricalcium phosphate and Ca (H) in step one2PO4 )2·H2And sieving the O powder with a 180-220 mesh sieve.
3. The method of claim 1 for preparing a porous scaffold with a photothermal effect, wherein: the preparation method of the beta-tricalcium phosphate in the first step comprises the following steps:
s11, massage dose [ Ca]：[P]Is 1.5: 1 in a ratio of Ca (NO)3)2·4H2O and (NH)4)2HPO4Respectively adding Ca (NO) as raw material3)2·4H2O and (NH)4)2HPO4Preparing a solution A and a solution B with the concentration of 0.08-0.12 mol/L at room temperature, and then uniformly stirring;
s12, mixing Ca (NO)3)2·4H2O solution is added dropwise to (NH)4)2HPO4In the solution, after dropwise adding, adjusting the pH value of the mixed solution to 7-8 by using ammonia water, then reacting at room temperature for 4 hours, and maintaining the pH value to 7-8 in the whole process; after the reaction is finished, aging the mixed solution for 20-30 h at the temperature of 38-45 ℃;
s13, after aging, respectively performing suction filtration by using deionized water and absolute ethyl alcohol, and then placing a filter cake in an oven, and drying for 20-30 h at the temperature of 90-105 ℃;
s14, drying the Ca3(PO4)2And (3) placing the powder in a high-temperature furnace, calcining for 1.5-2.5 hours at 1050-1150 ℃ to obtain high-purity beta-TCP powder, and sieving for later use.
4. The method of claim 1 for preparing a porous scaffold with a photothermal effect, wherein: and in the third step, the nano manganese-zinc ferrite accounts for 1-3 wt% of the mixed powder.
5. The method of claim 1 for preparing a porous scaffold with a photothermal effect, wherein: the preparation method of the nano manganese-zinc ferrite in the third step comprises the following steps:
s31 Mn in stoichiometric ratio0.2Zn0.8Fe2O4Weighing FeCl in proportion3·6H2O、ZnCl2And MnCl2·4H2O；
S32, adding the raw material S31 into triple distilled water under the condition of air isolation to prepare a clear transparent solution with metal ion concentration of 0.25-0.35M, and heating to 90-100 ℃ for later use;
s33, adding 0.6-1.2M NaOH solution into the solution of S32, adjusting the pH value to 9-10, carrying out 3.5-4.5 h at the temperature of 90-100 ℃, and isolating air in the whole process;
s34, separating the brown-black precipitate obtained in the step S33 by using 3T strong magnet, washing until no white precipitate can be detected by using silver nitrate solution with the concentration of 0.05-0.1M, and washing for 2-4 times by using absolute ethyl alcohol;
and S35, placing the brown precipitate washed by the S34 in a vacuum drying oven, and drying at the temperature of 65-75 ℃ for 35-45 h to obtain the prepared powder for later use.
6. The method of claim 3 for preparing a porous scaffold with a photothermal effect, wherein: in the fourth step, the mass of the carbon powder is 1-3 wt% of the mass of the mixed powder, and the particle size of the carbon powder is 0.1-0.3 μm.
7. The method of claim 3 for preparing a porous scaffold with a photothermal effect, wherein: and in the fifth step, the concentration of the citric acid solution is 0.4-0.6 mol/L.
8. A porous scaffold having a photothermal effect, comprising: the porous scaffold is prepared by any one of claims 1-7.
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