CN112618794A - Bone defect repair material based on modified perovskite quantum dots and preparation method thereof - Google Patents

Bone defect repair material based on modified perovskite quantum dots and preparation method thereof Download PDF

Info

Publication number
CN112618794A
CN112618794A CN202011555829.XA CN202011555829A CN112618794A CN 112618794 A CN112618794 A CN 112618794A CN 202011555829 A CN202011555829 A CN 202011555829A CN 112618794 A CN112618794 A CN 112618794A
Authority
CN
China
Prior art keywords
perovskite quantum
stirring
quantum dot
quantum dots
modified perovskite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202011555829.XA
Other languages
Chinese (zh)
Inventor
王文爽
沈文齐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bengbu Taixin Material Technology Co ltd
Original Assignee
Bengbu Taixin Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bengbu Taixin Material Technology Co ltd filed Critical Bengbu Taixin Material Technology Co ltd
Priority to CN202011555829.XA priority Critical patent/CN112618794A/en
Publication of CN112618794A publication Critical patent/CN112618794A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/24—Collagen
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/20—Polysaccharides
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412—Tissue-regenerating or healing or proliferative agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow
    • 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

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dermatology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Transplantation (AREA)
  • Biophysics (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a bone defect repairing material based on modified perovskite quantum dots and a preparation method thereof, wherein the bone defect repairing material comprises the following raw materials in percentage by mass: 20-30% of hydroxyapatite, 10-20% of octacalcium phosphate, 0.5-2% of bone morphogenetic protein, 1-5% of collagen, 0.5-2% of chondroitin sulfate, 3-5% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution; the preparation method comprises the following steps: s101: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reaction for 0.5-1 h to obtain a dispersion A; s102: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 3-6 hours, and uniformly stirring to obtain dispersion liquid B; s103: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 2-6 h at 45-60 ℃. According to the invention, perovskite quantum dots are introduced into a bone defect repair material for the first time, the calcium titanium quantum dots are utilized to mediate the transfection of stem cells, and the behavior change of the stem cells is monitored by fluorescence; at the same time, stem cells are induced to differentiate in the direction of osteoblasts and chondroblasts.

Description

Bone defect repair material based on modified perovskite quantum dots and preparation method thereof
Technical Field
The invention belongs to the field of medical materials, and particularly relates to a bone defect repairing material based on modified perovskite quantum dots and a preparation method thereof.
Background
Bone defects are a shortage of bone mass caused during pathological or surgical procedures, such that the structural integrity of the bone is compromised. Clinically, bone defects may be caused by trauma, tumor, osteomyelitis, various congenital diseases, surgical operations, and the like. Due to the presence of bone defects, nonunion, delayed or no healing of the resulting bone, and localized dysfunction are often caused. At present, methods for treating bone defects include autologous bone and allogeneic bone transplantation, a tissue engineering technology, a gene therapy rejection method, a physical factor therapy and the like, but the autologous bone transplantation can cause secondary trauma, the allogeneic bone transplantation can cause an immune rejection phenomenon, the tissue engineering technology and the gene therapy rejection method are still in a laboratory stage, the clinical application difficulty is high, and the physical factor therapy is adjuvant therapy and is mainly used for later-stage rehabilitation. Therefore, various bionic bone repair materials are produced to meet the requirements of clinical application.
The bone repair material is a novel bone repair material which is artificially synthesized, is self-cured and molded, has high mechanical strength, convenient use and biological characteristics (no toxic or side effect, absorption and degradation, good biocompatibility, capability of inducing the growth of osteocytes and blood vessels and the like). The bone repair material is mainly compounded by biological ceramic particles such as hydroxyapatite, bioactive glass, nano alumina and the like and gelatin, chitosan, polylactic acid or polyglycolic acid and the like, has the capability of promoting the growth of bone tissues and realizing osseointegration, and can be degraded after new bones are regenerated for replacement and repair. However, the problem of how to follow and monitor the location and differentiation of bone stem cells and the repair of bone tissue after the bone repair material is implanted into damaged bone tissue is still a difficult problem in clinical application.
The perovskite quantum dot as a semiconductor material has the characteristics of simple synthesis, narrow emission peak, high fluorescence quantum efficiency, adjustable luminescence peak position and the like, has huge biological imaging advantages, and can be used for light-emitting diodes, biological markers, fluorescence detection and the likeThe field has application prospect. However, perovskite quantum dots are highly sensitive to the environment due to strong ionic property, high surface energy and metastable structure, and are easy to cause phase transition, agglomeration and even degradation under the action of polar solvent or water and oxygen, thereby causing fluorescence quenching, especially Sn2+Is B-site element, and is easily oxidized into Sn in humid air4+The main defects of halogen vacancies and interstitial metals are intensified, and the collapse of the perovskite structure is further accelerated. Due to the poor stability of perovskite quantum dots, the practical application thereof is greatly limited.
Based on the above, the bone defect repairing material with a fluorescence detection effect is prepared by using the modified perovskite quantum dots with high stability and biological safety for the first time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a bone defect repairing material based on modified perovskite quantum dots and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
a bone defect repair material based on modified perovskite quantum dots comprises the following raw materials in percentage by mass: 20-30% of hydroxyapatite, 10-20% of octacalcium phosphate, 0.5-2% of bone morphogenetic protein, 1-5% of collagen, 0.5-2% of chondroitin sulfate, 3-5% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution;
the modified perovskite quantum dot solution comprises the following reaction raw materials in parts by mass: 0.5-1.5 parts of perovskite quantum dots, 8-16 parts of dipalmitoyl phosphatidylethanolamine, 3-7 parts of acidic amino acid, 1-3 parts of reduced glutathione, 0.5-1 part of EDC & HCl, 20-30 parts of chloroform and 100 parts of deionized water; the preparation method of the modified perovskite quantum dot solution comprises the following steps:
i: adding dipalmitoyl phosphatidylethanolamine into a chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, then adding perovskite quantum dots, uniformly stirring, and performing rotary evaporation at the temperature of 60-70 ℃ to remove chloroform, thereby obtaining a quantum dot lipid film;
ii: adding acidic amino acid and reduced glutathione into deionized water, stirring and dispersing, then dropwise adding an HCl solution to adjust the pH value to 6.0-6.5, and stirring in a water bath at 40-50 ℃ until the pH value is fully dissolved to obtain a reaction solution;
iii: and adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 50-60 ℃, adding EDC & HCl, continuously stirring and reacting for 2-4 h, and neutralizing to obtain the modified perovskite quantum dot solution.
Preferably, the perovskite quantum dots comprise CsPbBr3、CsPbI3、CsPbBr3-xIx、CsSnBr3、CsSnI3、CsSnBr3-xIxOne or more of (a).
Preferably, 0 < x < 3.
Preferably, the concentration of the HCl solution is 0.1-0.5 mol/L.
Preferably, the acidic amino acid is one or both of aspartic acid and glutamic acid.
A preparation method of a bone defect repair material based on modified perovskite quantum dots comprises the following steps:
s101: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reaction for 0.5-1 h to obtain a dispersion A;
s102: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 3-6 hours, and uniformly stirring to obtain dispersion liquid B;
s103: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 2-6 h at 45-60 ℃ to obtain the bone defect repairing material.
The invention has the beneficial effects that:
1. according to the invention, perovskite quantum dots are introduced into a bone defect repairing material for the first time, calcium titanium quantum dots are utilized to mediate the transfection of bone stem cells and bone marrow mesenchymal stem cells, and a fluorescence microscopic imaging technology is utilized to monitor the positioning and differentiation conditions of the stem cells, so that the whole process of repairing a defect bone tissue part is tracked and monitored; meanwhile, stem cells are induced to differentiate towards osteoblasts and chondroblasts, and the proliferation and regeneration of the osteocytes are stimulated.
2. According to the invention, dipalmitoyl phosphatidylethanolamine, acidic amino acid and reduced glutathione are used for treating perovskite quantum dots in a combined manner for the first time, the stability and the biological safety of the quantum dots are improved, the dipalmitoyl phosphatidylethanolamine is used for embedding the perovskite quantum dots to form quantum dot liposomes, and the perovskite quantum dots and O are avoided2Directly contacting with polar solvent to improve the fluorescence stability of perovskite quantum dots, and using-NH2and-COOH, so that the acidic amino acid and the reduced glutathione are further modified on the surfaces of the quantum dot liposome and the amino carbon quantum dot, the reduced glutathione has reducibility, oxygen free radicals are removed, the B-site metastable element of the perovskite quantum dot is further prevented from being oxidized, the collapse of the perovskite structure is avoided, the fluorescence quantum efficiency is improved, and meanwhile, the acidic amino acid also has excellent metal chelating property, and free heavy metal ions Pb are fixed2+、Sn2 +Prevent the heavy metal ions from diffusing outwards, and further improve the biological safety.
3. The invention takes hydroxyapatite and octacalcium phosphate as a skeleton structure of a bone defect repair material and as carriers of active pharmaceutical ingredients such as quantum dots, growth-like proteins and the like, and the hydroxyapatite and the octacalcium phosphate utilize the action of electrostatic attraction, hydrogen bonds and van der Waals force between the hydroxyapatite and the octacalcium phosphate and bone morphogenetic proteins, collagen, chondroitin sulfate and modified perovskite quantum dots to ensure that the active pharmaceutical ingredients such as the quantum dots, the growth-like proteins and the like are adsorbed on the surfaces of the hydroxyapatite and the octacalcium phosphate to achieve the effect of slow release of drugs, and simultaneously ensure that the hydroxyapatite and the octacalcium phosphate are enriched with a large amount of-COOH and-NH2-COOH with-NH in carboxymethyl chitosan2Amidation reaction and esterification reaction with-OH to form cross-linked network structure, and can raise the stability of bone defect material and the slow releasing effect of medicine.
4. The bone defect repairing material can effectively bond an interface of damaged bone tissues, participate in metabolic circulation of an organism, and has stimulation or induction effects on bone cell proliferation and bone tissues, thereby realizing the repair of the damaged bone tissues.
Drawings
FIG. 1 is a flow chart of a preparation method of the bone defect repair material based on modified perovskite quantum dots.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
A bone defect repair material based on modified perovskite quantum dots comprises the following raw materials in percentage by mass: 20% of hydroxyapatite, 10% of octacalcium phosphate, 0.5% of bone morphogenetic protein, 1% of collagen, 0.5% of chondroitin sulfate, 3% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution;
the modified perovskite quantum dot solution comprises the following reaction raw materials in parts by mass: CsPbBr30.5 part of perovskite quantum dot, 8 parts of dipalmitoyl phosphatidylethanolamine, 3 parts of aspartic acid, 1 part of reduced glutathione, 0.5 part of EDC & HCl, 20 parts of chloroform and 100 parts of deionized water.
A preparation method of a bone defect repair material based on modified perovskite quantum dots comprises the following steps:
s101: preparing a modified perovskite quantum dot solution:
i: adding dipalmitoyl phosphatidylethanolamine into chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, and adding CsPbBr3Uniformly stirring the perovskite quantum dots, and then carrying out rotary evaporation at 60 ℃ to remove chloroform, thereby obtaining a quantum dot lipid film;
ii: adding aspartic acid and reduced glutathione into deionized water, stirring and dispersing, then dropwise adding 0.1mol/L HCl solution to adjust the pH value to 6.5, stirring in water bath at 40 ℃ until the solution is fully dissolved, and obtaining reaction liquid;
iii: adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 50 ℃, adding EDC & HCl, continuing stirring and reacting for 2h, and neutralizing to obtain a modified perovskite quantum dot solution;
s102: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reaction for 0.5h to obtain a dispersion liquid A;
s103: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 3 hours, and uniformly stirring to obtain dispersion liquid B;
s104: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 2 hours at 45 ℃ to obtain the bone defect repairing material.
Example 2
A bone defect repair material based on modified perovskite quantum dots comprises the following raw materials in percentage by mass: 25% of hydroxyapatite, 15% of octacalcium phosphate, 1% of bone morphogenetic protein, 3% of collagen, 1% of chondroitin sulfate, 4% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution;
the modified perovskite quantum dot solution comprises the following reaction raw materials in parts by mass: 1 part of perovskite quantum dot, 12 parts of dipalmitoyl phosphatidylethanolamine, 5 parts of glutamic acid, 2 parts of reduced glutathione, 1 part of EDC & HCl, 25 parts of chloroform and 100 parts of deionized water.
A preparation method of a bone defect repair material based on modified perovskite quantum dots comprises the following steps:
s101: preparing a modified perovskite quantum dot solution:
i: adding dipalmitoyl phosphatidylethanolamine into chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, and adding CsPbBr3Uniformly stirring the perovskite quantum dots, and then carrying out rotary evaporation at 65 ℃ to remove chloroform, thereby obtaining a quantum dot lipid film;
ii: adding glutamic acid and reduced glutathione into deionized water, stirring and dispersing, then dropwise adding 0.3mol/L HCl solution to adjust the pH value to 6.0, stirring in a water bath at 45 ℃ until the solution is fully dissolved, and obtaining a reaction solution;
iii: adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 55 ℃, adding EDC & HCl, continuing stirring and reacting for 3 hours, and neutralizing to obtain a modified perovskite quantum dot solution;
s102: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reacting for 1h to obtain a dispersion liquid A;
s103: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 4.5 hours, and uniformly stirring to obtain dispersion liquid B;
s104: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 4 hours at 55 ℃ to obtain the bone defect repairing material.
Example 3
A bone defect repair material based on modified perovskite quantum dots comprises the following raw materials in percentage by mass: 30% of hydroxyapatite, 20% of octacalcium phosphate, 2% of bone morphogenetic protein, 5% of collagen, 2% of chondroitin sulfate, 5% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution;
the modified perovskite quantum dot solution comprises the following reaction raw materials in parts by mass: CsSnBr2.5I0.51.5 parts of perovskite quantum dots, 16 parts of dipalmitoyl phosphatidylethanolamine, 7 parts of aspartic acid, 3 parts of reduced glutathione, 1 part of EDC & HCl, 30 parts of chloroform and 100 parts of deionized water.
A preparation method of a bone defect repair material based on modified perovskite quantum dots comprises the following steps:
s101: preparing a modified perovskite quantum dot solution:
i: adding dipalmitoyl phosphatidylethanolamine into chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, and adding CsPbBr3Uniformly stirring the perovskite quantum dots, and then carrying out rotary evaporation at 70 ℃ to remove chloroform, thereby obtaining a quantum dot lipid film;
ii: adding aspartic acid and reduced glutathione into deionized water, stirring and dispersing, then dropwise adding 0.5mol/L HCl solution to adjust the pH value to 6.0, stirring in a water bath at 50 ℃ until the solution is fully dissolved, and obtaining a reaction solution;
iii: adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 60 ℃, adding EDC & HCl, continuing stirring and reacting for 4 hours, and neutralizing to obtain a modified perovskite quantum dot solution;
s102: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reacting for 1h to obtain a dispersion liquid A;
s103: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 6 hours, and uniformly stirring to obtain dispersion liquid B;
s104: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 6 hours at 60 ℃ to obtain the bone defect repairing material.
Comparative example 1 is the same as example 1 except that the modified perovskite quantum dot solution is replaced by deionized water.
Comparative example 2 is the same as example 1 except that the reaction raw materials of the modified perovskite quantum dot do not contain aspartic acid, reduced glutathione, EDC & HCl; the preparation method comprises the following steps:
i: adding dipalmitoyl phosphatidylethanolamine into a chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, then adding CsPbBr3 perovskite quantum dots, uniformly stirring, and carrying out rotary evaporation at 60 ℃ to remove chloroform, thus obtaining a quantum dot lipid film;
ii: and adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 50 ℃, adding EDC & HCl, continuously stirring and reacting for 2h, and neutralizing to obtain the modified perovskite quantum dot solution.
The bone defect repair materials prepared in examples 1-3 and comparative example 2 can be photoluminescent, stem cells can be labeled by using the fluorescence property of the bone defect repair materials, and the behavioral change of the stem cells can be monitored, while the repair material prepared in comparative example 1 has no luminescence property. The luminescent properties of the bone defect repair materials prepared in examples 1 to 3 and comparative example 2 were measured, and the test results are shown in table 1:
TABLE 1
Example 1 Example 2 Example 3 Comparative example 2
Luminescence quantum yield/%) 92.6 92.2 93.1 89.5
Luminescence stability/d 17 18 20 12
As can be seen from table 1, the bone defect repair materials prepared in examples 1 to 3 have high luminescence quantum yield, long fluorescence emission time, and high quantum dot stability.
Embodiments 1 to 3 introduce perovskite quantum dots into a bone defect repair material for the first time, utilize the perovskite quantum dots to mediate the transfection of bone stem cells and bone marrow mesenchymal stem cells, and utilize a fluorescence microscopic imaging technology to monitor the stem cell positioning and differentiation conditions, so as to realize the tracking and monitoring of the whole process of repairing a defective bone tissue part; meanwhile, stem cells are induced to differentiate towards osteoblasts and chondroblasts, and the proliferation and regeneration of the osteocytes are stimulated.
Examples 1 to 3 perovskite quantum dots were first treated with dipalmitoyl phosphatidylethanolamine, acidic amino acids, and reduced glutathione in combination to improve the stability and biosafety of the quantum dots, and the dipalmitoyl phosphatidylethanolamine was used to embed the perovskite quantum dots to form quantum dot liposomes to avoid perovskite quantum dotsPoint and O2Directly contacting with polar solvent to improve the fluorescence stability of perovskite quantum dots, and using-NH2and-COOH, so that the acidic amino acid and the reduced glutathione are further modified on the surfaces of the quantum dot liposome and the amino carbon quantum dot, the reduced glutathione has reducibility, oxygen free radicals are removed, the B-site metastable element of the perovskite quantum dot is further prevented from being oxidized, the collapse of the perovskite structure is avoided, the fluorescence quantum efficiency is improved, and meanwhile, the acidic amino acid also has excellent metal chelating property, and free heavy metal ions Pb are fixed2+、Sn2+Prevent the heavy metal ions from diffusing outwards, and further improve the biological safety.
Embodiments 1 to 3 use hydroxyapatite and octacalcium phosphate as a skeleton structure of a bone defect repairing material and as carriers of active pharmaceutical ingredients such as quantum dots and growth proteins, and the hydroxyapatite and octacalcium phosphate absorb the active pharmaceutical ingredients such as the quantum dots and the growth proteins on the surfaces of the hydroxyapatite and octacalcium phosphate by utilizing the electrostatic attraction, hydrogen bonds and van der waals force between the hydroxyapatite and the octacalcium phosphate and bone morphogenetic proteins, collagen, chondroitin sulfate and modified perovskite quantum dots to achieve a drug release effect and simultaneously enrich the hydroxyapatite and the octacalcium phosphate with a large amount of-COOH and-NH2-COOH with-NH in carboxymethyl chitosan2Amidation reaction and esterification reaction with-OH to form cross-linked network structure, and can raise the stability of bone defect material and the slow releasing effect of medicine.
The bone defect repair materials of the embodiments 1 to 3 can effectively bond with the interface of the damaged bone tissue, participate in the metabolic cycle of the organism, and have stimulation or induction effects on the proliferation of bone cells and the bone tissue, thereby realizing the repair of the defective bone tissue.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (6)

1. The bone defect repairing material based on the modified perovskite quantum dots is characterized by comprising the following raw materials in percentage by mass: 20-30% of hydroxyapatite, 10-20% of octacalcium phosphate, 0.5-2% of bone morphogenetic protein, 1-5% of collagen, 0.5-2% of chondroitin sulfate, 3-5% of carboxymethyl chitosan and the balance of modified perovskite quantum dot solution;
the modified perovskite quantum dot solution comprises the following reaction raw materials in parts by mass: 0.5-1.5 parts of perovskite quantum dots, 8-16 parts of dipalmitoyl phosphatidylethanolamine, 3-7 parts of acidic amino acid, 1-3 parts of reduced glutathione, 0.5-1 part of EDC & HCl, 20-30 parts of chloroform and 100 parts of deionized water; the preparation method of the modified perovskite quantum dot solution comprises the following steps:
i: adding dipalmitoyl phosphatidylethanolamine into a chloroform solvent, magnetically stirring until the dipalmitoyl phosphatidylethanolamine is completely dissolved, then adding perovskite quantum dots, uniformly stirring, and performing rotary evaporation at the temperature of 60-70 ℃ to remove chloroform, thereby obtaining a quantum dot lipid film;
ii: adding acidic amino acid and reduced glutathione into deionized water, stirring and dispersing, then dropwise adding an HCl solution to adjust the pH value to 6.0-6.5, and stirring in a water bath at 40-50 ℃ until the pH value is fully dissolved to obtain a reaction solution;
iii: and adding the obtained quantum dot lipid film into the reaction solution, stirring and dispersing, then heating to 50-60 ℃, adding EDC & HCl, continuously stirring and reacting for 2-4 h, and neutralizing to obtain the modified perovskite quantum dot solution.
2. The bone defect repair material based on the modified perovskite quantum dot as claimed in claim 1, wherein the perovskite quantum dot comprises CsPbBr3、CsPbI3、CsPbBr3-xIx、CsSnBr3、CsSnI3、CsSnBr3-xIxOne or more of (a).
3. The bone defect repair material based on the modified perovskite quantum dots, which is characterized in that: x is more than 0 and less than 3.
4. The bone defect repair material based on the modified perovskite quantum dots, according to claim 1, wherein the concentration of the HCl solution is 0.1-0.5 mol/L.
5. The bone defect repair material based on the modified perovskite quantum dots, which is characterized in that the acidic amino acid is one or two of aspartic acid and glutamic acid.
6. The preparation method of the bone defect repairing material based on the modified perovskite quantum dots as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
s101: adding bone morphogenetic protein, collagen and chondroitin sulfate into the modified perovskite quantum dot solution, and stirring for reaction for 0.5-1 h to obtain a dispersion A;
s102: adding hydroxyapatite and octacalcium phosphate into the dispersion liquid A, soaking and adsorbing for 3-6 hours, and uniformly stirring to obtain dispersion liquid B;
s103: and adding carboxymethyl chitosan into the dispersed slurry B, and stirring and reacting for 2-6 h at 45-60 ℃ to obtain the bone defect repairing material.
CN202011555829.XA 2020-12-23 2020-12-23 Bone defect repair material based on modified perovskite quantum dots and preparation method thereof Withdrawn CN112618794A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011555829.XA CN112618794A (en) 2020-12-23 2020-12-23 Bone defect repair material based on modified perovskite quantum dots and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011555829.XA CN112618794A (en) 2020-12-23 2020-12-23 Bone defect repair material based on modified perovskite quantum dots and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112618794A true CN112618794A (en) 2021-04-09

Family

ID=75324637

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011555829.XA Withdrawn CN112618794A (en) 2020-12-23 2020-12-23 Bone defect repair material based on modified perovskite quantum dots and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112618794A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845898A (en) * 2021-10-27 2021-12-28 暨南大学 Multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845898A (en) * 2021-10-27 2021-12-28 暨南大学 Multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof

Similar Documents

Publication Publication Date Title
CN112618788A (en) Bone defect repair material based on modified perovskite quantum dots/amino carbon quantum dots and preparation method thereof
CN104726921B (en) Titanium dioxide/hydroxyapatite bioactive nano-composite coating of fluorine containing strontium and its preparation method and application
KR101461159B1 (en) Preparation method of implant comprising drug delivery layer and implant compostion for living donor transplantation comprising the same
CN105274603B (en) Composite modified coating of magnesium or Mg alloy surface carbon nanotubes and preparation method thereof
CN112206356A (en) Injectable bone repair hydrogel containing human umbilical cord mesenchymal stem cell exosomes and preparation method thereof
CN101994143A (en) Preparation method of titanium alloy/biological ceramic layer composite material
CN107236983B (en) A kind of preparation method of ferroso-ferric oxide/titanium dioxide magnetic bio active coating
CN110478528B (en) Preparation method and application of novel tissue repair promoting material
CN105879115A (en) Dental implant and surface preparation method thereof
CN106606801A (en) Zn-ZnO zinc alloy and its preparation method and application
CN107158465B (en) Preparation method of bone scaffold composite material
CN104192817A (en) Method for preparing mesoporous hydroxyapatite nanometer particle with high specific surface area by virtue of template method
Zhang et al. Chondrogenic preconditioning of mesenchymal stem/stromal cells within a magnetic scaffold for osteochondral repair
CN112618794A (en) Bone defect repair material based on modified perovskite quantum dots and preparation method thereof
CN107129969B (en) Method for inducing bone marrow mesenchymal stem cells to directionally differentiate into osteoblasts
Yang et al. 3D printed porous titanium filled with mineralized UV-responsive chitosan hydrogel promotes cell proliferation and osteogenesis in vitro
CN105327397B (en) A kind of preparation of the degradable implantation material of the mesoporous calcium silicates coating of medical magnesium alloy surface
CN106075589A (en) A kind of heterogeneous hydridization micro-nano structure magnetic composite and preparation method thereof
CN108815571B (en) Preparation method of silver modified crystal form titanium dioxide nanotube layer
CN111514375B (en) Anti-calcification biological valve material and preparation method thereof
Song et al. Mechanics‐resilient HA/SIS‐based composite scaffolds with ROS‐scavenging and bacteria‐resistant capacity to address infected bone regeneration
CN106606806A (en) Zn-Mg1Ca series zinc alloy and preparing method and application of Zn-Mg1Ca series zinc alloy
CN115501387B (en) Titanium implant capable of slowly releasing trace elements and exosomes and preparation method thereof
KR20180054439A (en) Methods for 3D Culturing of Cell
CN1451367A (en) Induction ossified bio-active artificial tooth root implant material and preparing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20210409