CN112358317A - Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof - Google Patents

Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof Download PDF

Info

Publication number
CN112358317A
CN112358317A CN202011309699.1A CN202011309699A CN112358317A CN 112358317 A CN112358317 A CN 112358317A CN 202011309699 A CN202011309699 A CN 202011309699A CN 112358317 A CN112358317 A CN 112358317A
Authority
CN
China
Prior art keywords
repair
ceramic
nano
calcium phosphate
bone regeneration
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.)
Pending
Application number
CN202011309699.1A
Other languages
Chinese (zh)
Inventor
吕玉光
张琳琳
吴江
张国梁
任恒鑫
李俏
程雨晴
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.)
Jiamusi University
Original Assignee
Jiamusi University
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 Jiamusi University filed Critical Jiamusi University
Priority to CN202011309699.1A priority Critical patent/CN112358317A/en
Publication of CN112358317A publication Critical patent/CN112358317A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/067—Macromolecular compounds
    • 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
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/50—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing 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
    • A61L2300/10—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
    • A61L2300/10—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
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/408—Noble metals

Abstract

The invention discloses a medical bone regeneration and repair nano biological ceramic material and a preparation method and application thereof, wherein the material is prepared from Ag-doped nano zinc oxide powder and biphase calcium phosphate ceramic, wherein: in Ag-doped nano zinc oxide powder, Zn2+And Ag+The molar ratio of (A) to (B) is 2-4: 1; the two-phase calcium phosphate ceramic is formed by two-phase components of hydroxyapatite and beta-tricalcium phosphate, and the mass ratio of the hydroxyapatite to the beta-tricalcium phosphate is 1: 1-3. The invention constructs the porous calcium phosphate nano ceramic microspheres with the function of cooperatively and controllably releasing Ag and ZnO, and the porous spherical calcium phosphate nano ceramic particles have excellent bone defect repair capacity, so that the aims of inducing regeneration repair of infectious bone defect tissues and long-acting antibiosis are fulfilled, and the possibility is provided for realizing high-efficiency loading of antibacterial drugs.

Description

Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of medical material preparation, and relates to a medical bone regeneration and repair nano biological ceramic material, and a preparation method and application thereof.
Background
Bioceramics (Bioceramies) refer to a class of ceramic materials used as specific biological or physiological functions, i.e., ceramic materials used directly in the human body or in biological, medical, biochemical, etc. related to the human body. In a broad sense, ceramic materials of bioengineering are collectively referred to as bioceramics. As the biological ceramic material, the following conditions are required: (1) biocompatibility; (2) mechanical compatibility; (3) excellent affinity with biological tissues; (4) anti-thrombosis; (5) has good sterilization performance and good physical and chemical stability.
The biological ceramic material can be divided into three types of biological inert ceramic, biological active ceramic and biological composite material. Since the biological ceramic material is closely related to human life, it has been paid much attention by the material scientists. Calcium phosphate ceramics such as tricalcium phosphate (TCP) and Hydroxyapatite (HA) are common artificial bone substitute materials, bioceramics consisting of calcium phosphate salts such as hydroxyapatite, fluorapatite, tricalcium phosphate and carbonic apatite or composites thereof. The Ca/P atomic ratio and the material structure determine whether the surface thereof has bioactivity or bioabsorbability. The bone-inducing calcium phosphate ceramic material is a ceramic formed by two-phase components of hydroxyapatite and beta-tricalcium phosphate, and the chemical composition of the ceramic is similar to the inorganic component of bone tissue. At present, in vivo and in vitro researches show that the biphasic calcium phosphate ceramic has good biocompatibility, bioactivity and osteoconductivity and also has osteoinductivity, so that the biphasic calcium phosphate ceramic is expected to become an ideal bone substitute material.
Disclosure of Invention
The invention aims to provide a medical bone regeneration and repair nano biological ceramic material and a preparation method and application thereof. The research of combining advanced material characterization technology and cell and molecular biology technology shows that the nano ZnO-Ag biological ceramic material prepared by the invention has good antibacterial activity on staphylococcus aureus and escherichia coli.
The purpose of the invention is realized by the following technical scheme:
a medical nano biological ceramic material for bone regeneration and repair is prepared from Ag-doped nano zinc oxide powder and biphase calcium phosphate ceramic, wherein: in Ag-doped nano zinc oxide powder, Zn2+And Ag+The molar ratio of (a) is 2-4: 1, preferably 3: 1; the two-phase calcium phosphate ceramic is formed by two-phase components of hydroxyapatite and beta-tricalcium phosphate, and the mass ratio of the hydroxyapatite to the beta-tricalcium phosphate is 1: 1-3, preferably 1: 2.
A preparation method of the medical bone regeneration and repair nano biological ceramic material comprises the following steps:
step one, preparing a biphase calcium phosphate ceramic blank:
the naturally formed two-phase calcium phosphate powder hydroxyapatite/beta-tricalcium phosphate is directly obtained by adopting a wet process through controlling the calcium-phosphorus ratio, and the preparation steps are as follows:
stearic acid is selected as a macroporous pore-forming agent, hydrogen peroxide is selected as a microporous pore-forming agent, polyvinyl alcohol is selected as an adhesive, nanoscale HA and nanoscale beta-TCP powder are selected as raw materials, and the raw materials are hydroxy HA: beta-TCP: pore-forming agent: polyvinyl alcohol: hydrogen peroxide =1: 1-3: 0.5-1.5: 0.1-0.3 mixing ratio, pressing and forming to obtain a ceramic blank, and drying overnight to remove residual hydrogen peroxide and stearic acid;
step two, preparing the bone regeneration and repair nano biological ceramic material:
the Ag-doped nano zinc oxide powder and the biphase calcium phosphate ceramic are mixed and sintered and formed at 1000-1200 ℃ to prepare the bone regeneration repair nano biological ceramic material which can be used for bone defect tissue regeneration repair.
Compared with the prior art, the invention has the following advantages:
(1) porous calcium phosphate nano ceramic microspheres with the function of cooperatively and controllably releasing Ag and ZnO are constructed;
(2) the porous spherical calcium phosphate nano ceramic particles have excellent bone defect repair capacity, so that the aims of inducing regeneration repair of infectious bone defect tissues and long-acting antibiosis are fulfilled, and the possibility is provided for realizing efficient loading of antibacterial drugs.
Drawings
FIG. 1 shows the structure under an Ag-ZnO scanning electron microscope;
FIG. 2 shows the morphology of the nano-bioceramic particles;
FIG. 3 is a schematic diagram of a gradient ZnO-Ag/CS/LST nano biological ceramic material and cooperative antibacterial effects of the gradient LST and nano ZnO-Ag released by the material, CS: chitosan, LST: a staphylococcal enzyme.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1 preparation of nano ZnO-Ag:
step 1: 50ml of 0.2mol/L zinc nitrate aqueous solution and a certain amount of Ag ion-doped nitric acid solution (namely, Ag nitrate is dissolved in 2mol/L nitric acid) are measured and added into an erlenmeyer flask.
Step 2: uniformly dropwise adding 0.5mol/L (NH) under magnetic stirring4)2CO3And obtaining a precipitate after the solution is aged for 12 hours.
And step 3: and (2) performing centrifugal separation, washing the obtained precipitate with deionized water for three times, washing with absolute ethyl alcohol for three times, drying at 70 ℃ in vacuum for 4 hours to obtain a precursor, and then putting the precursor into a tubular resistance furnace to anneal for 4 hours at 400 ℃ to obtain Ag-doped nano zinc oxide powder, wherein: the molar ratio of Zn ions to Ag ions is 3: 1.
Example 2 preparation of biphasic calcium phosphate ceramic body:
in this embodiment, the biphasic calcium phosphate ceramic is a ceramic composed of two-phase components of hydroxyapatite and β -tricalcium phosphate, and the bioactivity of the biphasic calcium phosphate ceramic is higher than that of the hydroxyapatite ceramic. In this embodiment, a naturally formed two-phase calcium phosphate powder hydroxyapatite/β -tricalcium phosphate is directly obtained by controlling the calcium-phosphorus ratio using a wet process, and the preparation steps are as follows:
stearic acid is selected as a macroporous pore-forming agent, hydrogen peroxide with the volume fraction of 30% is selected as a microporous pore-forming agent, 5% of polyvinyl alcohol is selected as an adhesive, and nano-scale HA and nano-scale beta-TCP powder are selected as raw materials and are mixed according to the mass ratio of HA/beta-TCP =1: 2. According to the hydroxyl group HA: beta-TCP: pore-forming agent: polyvinyl alcohol: hydrogen peroxide =1: 2: 1: 1: 0.2: 0.2 (mass ratio) mixing ratio, pressing and forming under 2MPa to obtain a ceramic blank, and drying overnight to remove residual hydrogen peroxide and stearic acid.
Example 3 preparation of bone regeneration repair nano-bioceramic material:
and sintering and forming the nano ZnO-Ag powder and the calcium phosphate ceramic blank at the temperature of 1100 ℃ according to the mass ratio of 1: 3 to prepare the bone regeneration and repair nano biological ceramic material.
Example 4 application of bone regeneration repairing nano biological ceramic material
Advanced instruments such as a field emission scanning electron microscope, an X-ray diffraction analyzer, a specific surface area instrument, an inductive coupling plasma spectrometer and the like are comprehensively used for representing and analyzing the surface and section morphology, phase composition, element distribution, micropore distribution and other material characteristics of the bone regeneration and repair nano-bioceramic material and the release behavior of nano-ZnO-Ag, and meanwhile, an enzyme-linked immunosorbent method is used for quantitatively analyzing the loading capacity and the release behavior of Lysostaphin (LST).
As can be seen from the scanning image of the electron microscope of Ag-ZnO shown in figure 1, the synthesized sample has uniform particle size and particle ratio and no obvious agglomeration phenomenon. The average grain size of the Ag-ZnO sample is about 30 nm, and the grain size basically accords with the predicted value of a Scherrer formula. The morphology of the nano-bioceramic material particles is shown in figure 2. As can be seen from fig. 3, in this embodiment, sodium alginate gel method is combined with hydrogen peroxide foaming method to successfully construct nano-bioceramic material particles, the ceramic particles have good sphericity, three-dimensional through pore structure and nano-scale grain size, and the nano-bioceramic material particles are implanted into bone defects with critical dimension of rabbit mandible (9 mm) for repair evaluation, and it is found that bone defects have good regenerative repair effect after being implanted for 100 days, and a large amount of new bone tissues are generated in the defect region and the material. The nano biological ceramic material particles have excellent bone defect repair capability, and lay a good foundation for the construction of materials and the regeneration and repair of infectious bone defects.

Claims (6)

1. The medical bone regeneration and repair nano biological ceramic material is characterized by being prepared from Ag-doped nano zinc oxide powder and biphase calcium phosphate ceramic, wherein: in Ag-doped nano zinc oxide powder, Zn2+And Ag+The molar ratio of (A) to (B) is 2-4: 1; the two-phase calcium phosphate ceramic is formed by two-phase components of hydroxyapatite and beta-tricalcium phosphate, and the mass ratio of the hydroxyapatite to the beta-tricalcium phosphate is 1: 1-3.
2. The medical bone regeneration repair nano bio-ceramic material according to claim 1, characterized in that said Zn2+And Ag+Is 3: 1.
3. The medical bone regeneration and repair nano-bioceramic material according to claim 1, wherein the mass ratio of the hydroxyapatite to the beta-tricalcium phosphate is 1: 2.
4. A method for preparing the medical bone regeneration and repair nano biological ceramic material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
step one, preparing a biphase calcium phosphate ceramic blank:
directly obtaining naturally formed two-phase calcium phosphate powder hydroxyapatite/beta-tricalcium phosphate by controlling the calcium-phosphorus ratio by adopting a wet process;
step two, preparing the bone regeneration and repair nano biological ceramic material:
mixing Ag-doped nano zinc oxide powder with the biphase calcium phosphate ceramic, and sintering and forming at 1000-1200 ℃ to obtain the bone regeneration repair nano biological ceramic material.
5. The preparation method of the medical bone regeneration and repair nano-bioceramic material according to claim 4, wherein the biphasic calcium phosphate ceramic body is prepared by the following steps:
stearic acid is selected as a macroporous pore-forming agent, hydrogen peroxide is selected as a microporous pore-forming agent, polyvinyl alcohol is selected as an adhesive, nanoscale HA and nanoscale beta-TCP powder are selected as raw materials, and the raw materials are hydroxy HA: beta-TCP: pore-forming agent: polyvinyl alcohol: hydrogen peroxide =1: 1-3: 0.5-1.5: 0.1-0.3 mixing ratio, pressing and forming to obtain a ceramic blank, and drying overnight to remove residual hydrogen peroxide and stearic acid.
6. The medical bone regeneration and repair nano biological ceramic material as claimed in any one of claims 1 to 3 is applied to regeneration and repair of bone defect tissues.
CN202011309699.1A 2020-11-20 2020-11-20 Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof Pending CN112358317A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011309699.1A CN112358317A (en) 2020-11-20 2020-11-20 Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011309699.1A CN112358317A (en) 2020-11-20 2020-11-20 Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN112358317A true CN112358317A (en) 2021-02-12

Family

ID=74533022

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011309699.1A Pending CN112358317A (en) 2020-11-20 2020-11-20 Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112358317A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114538914A (en) * 2022-03-14 2022-05-27 成都理工大学 Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028919A1 (en) * 1999-10-18 2001-04-26 Spassova, Else Hydroxyl apatite material containing tricalcium phosphate, having a microporous structure
FR2826281A1 (en) * 2001-06-21 2002-12-27 Jean Paul Adenis Intraorbital ball for implantation in an eye after evisceration and/or enucleation comprises a porous ceramic comprising hydroxyapatite and tricalcium phosphate
CN1488602A (en) * 2003-08-12 2004-04-14 四川大学 Porous calcium phosphate bioceramic material and preparing method thereof
CN1513806A (en) * 2003-04-30 2004-07-21 东南大学 Calcium phosphorus kind ceramic bone structure engineering porous support material
DE102004016065B3 (en) * 2004-03-30 2005-06-09 Zlb Behring Gmbh Bone substitute material comprises a porous material impregnated with a solution containing factor XIII
CN103585672A (en) * 2013-11-18 2014-02-19 西南科技大学 Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material
CN103638556A (en) * 2013-12-03 2014-03-19 四川大学 Surface nano-scale modified calcium phosphate bioactive ceramic as well as preparation method and application thereof
CN103964891A (en) * 2014-05-08 2014-08-06 山东大学 Preparation method of surface porous calcium phosphate ceramic material
CN104548213A (en) * 2014-12-23 2015-04-29 四川大学 Porous spherical calcium phosphate filling material and preparing method thereof
CN105288740A (en) * 2015-11-23 2016-02-03 上海交通大学 Method for preparation of controlled pore size biphasic calcium phosphate composite ceramic scaffold
CN109260525A (en) * 2018-09-12 2019-01-25 四川大学 Controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing and preparation method thereof
CN110054491A (en) * 2019-03-27 2019-07-26 昆明理工大学 A kind of preparation method of nano-zinc oxide doped hydroxyapatite porous bio-ceramic
CN111450325A (en) * 2020-04-23 2020-07-28 四川大学 Icaritin-loaded calcium phosphate ceramic bracket with surface micro-nano structure and preparation method and application thereof
CN114538914A (en) * 2022-03-14 2022-05-27 成都理工大学 Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028919A1 (en) * 1999-10-18 2001-04-26 Spassova, Else Hydroxyl apatite material containing tricalcium phosphate, having a microporous structure
FR2826281A1 (en) * 2001-06-21 2002-12-27 Jean Paul Adenis Intraorbital ball for implantation in an eye after evisceration and/or enucleation comprises a porous ceramic comprising hydroxyapatite and tricalcium phosphate
CN1513806A (en) * 2003-04-30 2004-07-21 东南大学 Calcium phosphorus kind ceramic bone structure engineering porous support material
CN1488602A (en) * 2003-08-12 2004-04-14 四川大学 Porous calcium phosphate bioceramic material and preparing method thereof
DE102004016065B3 (en) * 2004-03-30 2005-06-09 Zlb Behring Gmbh Bone substitute material comprises a porous material impregnated with a solution containing factor XIII
CN103585672A (en) * 2013-11-18 2014-02-19 西南科技大学 Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material
CN103638556A (en) * 2013-12-03 2014-03-19 四川大学 Surface nano-scale modified calcium phosphate bioactive ceramic as well as preparation method and application thereof
CN103964891A (en) * 2014-05-08 2014-08-06 山东大学 Preparation method of surface porous calcium phosphate ceramic material
CN104548213A (en) * 2014-12-23 2015-04-29 四川大学 Porous spherical calcium phosphate filling material and preparing method thereof
CN105288740A (en) * 2015-11-23 2016-02-03 上海交通大学 Method for preparation of controlled pore size biphasic calcium phosphate composite ceramic scaffold
CN109260525A (en) * 2018-09-12 2019-01-25 四川大学 Controllable bone tissue engineering scaffold of a kind of degradation based on 3D printing and preparation method thereof
CN110054491A (en) * 2019-03-27 2019-07-26 昆明理工大学 A kind of preparation method of nano-zinc oxide doped hydroxyapatite porous bio-ceramic
CN111450325A (en) * 2020-04-23 2020-07-28 四川大学 Icaritin-loaded calcium phosphate ceramic bracket with surface micro-nano structure and preparation method and application thereof
CN114538914A (en) * 2022-03-14 2022-05-27 成都理工大学 Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
刘国梅: "半导体氧化物的掺杂及其抗菌性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)信息科技辑》 *
季金苟: "微波等离子体烧结多孔β-TCP/HA生物活性陶瓷的研究", 《中国优秀博硕士学位论文全文数据库(博士)医药卫生科技辑》 *
王祖华等: "载银羟基磷灰石抗菌剂及陶瓷抗菌性能测定", 《人工晶体学报》 *
聂玮: "纳米双相陶瓷人工骨的成骨及降解", 《中国组织工程研究》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114538914A (en) * 2022-03-14 2022-05-27 成都理工大学 Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof

Similar Documents

Publication Publication Date Title
Singh et al. Customized hydroxyapatites for bone-tissue engineering and drug delivery applications: A review
Kalita et al. Nanocrystalline hydroxyapatite doped with magnesium and zinc: Synthesis and characterization
Fiorilli et al. Electrophoretic deposition of mesoporous bioactive glass on glass–ceramic foam scaffolds for bone tissue engineering
Priyadarshini et al. Development of cerium and silicon co-doped hydroxyapatite nanopowder and its in vitro biological studies for bone regeneration applications
Ghomi et al. Preparation of nanostructure hydroxyapatite scaffold for tissue engineering applications
Shuai et al. Processing and characterization of laser sintered hydroxyapatite scaffold for tissue engineering
Koohkan et al. Synthesis, characterization, and in vitro biological evaluation of copper-containing magnetic bioactive glasses for hyperthermia in bone defect treatment
EP2454085A1 (en) Scaffold for tissue regeneration in mammals
Badr-Mohammadi et al. Mechanical properties and in vitro cellular behavior of zinc-containing nano-bioactive glass doped biphasic calcium phosphate bone substitutes
US20140212469A1 (en) Surface functional bioactive glass scaffold for bone regeneration
CN114452439B (en) Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof
KR102553738B1 (en) Nanocements based on bioactive glass nanoparticles
Sobczak-Kupiec et al. Physicochemical and biological properties of hydrogel/gelatin/hydroxyapatite PAA/G/HAp/AgNPs composites modified with silver nanoparticles
Heidari et al. 3D construct of hydroxyapatite/zinc oxide/palladium nanocomposite scaffold for bone tissue engineering
Bozorgi et al. Fabrication, characterization, and optimization of a novel copper-incorporated chitosan/gelatin-based scaffold for bone tissue engineering applications
KR101178204B1 (en) Porous microsphere and manufacturing method thereof
Tithito et al. Fabrication of biocomposite scaffolds made with modified hydroxyapatite inclusion of chitosan-grafted-poly (methyl methacrylate) for bone tissue engineering
CN112358317A (en) Medical bone regeneration and repair nano biological ceramic material and preparation method and application thereof
KR101671585B1 (en) A bioactive nanocomposite calcium phosphate bone cement composition and a kit for preparing the same
US20130165540A1 (en) Porous Calcium Phospate Granules and Methods of Making and Using the Same
Durgalakshmi et al. Structural, morphological and antibacterial investigation of Ag-impregnated Sol–Gel-Derived 45S5 nanoBioglass systems
KR101461161B1 (en) Nanocomposite scaffolds having 3D porous structure for bone reconstruction
Sukhodub et al. Antibacterial and physical characteristics of silver-loaded hydroxyapatite/alginate composites
Sha et al. Physico-chemical and biological properties of novel Eu-doped carbonization modified tricalcium silicate composite bone cement
Saxena et al. Nano hydroxyapatite (nano-HAp): a potential bioceramic for biomedical applications

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210212

WD01 Invention patent application deemed withdrawn after publication