CN115444986B - Nano-ceramic bioactive degradable bone grafting bed and preparation method thereof - Google Patents
Nano-ceramic bioactive degradable bone grafting bed and preparation method thereof Download PDFInfo
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- CN115444986B CN115444986B CN202210947766.5A CN202210947766A CN115444986B CN 115444986 B CN115444986 B CN 115444986B CN 202210947766 A CN202210947766 A CN 202210947766A CN 115444986 B CN115444986 B CN 115444986B
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 75
- 239000000919 ceramic Substances 0.000 title claims abstract description 16
- 230000000975 bioactive effect Effects 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 5
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 113
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 112
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000010079 rubber tapping Methods 0.000 claims abstract description 22
- 230000004071 biological effect Effects 0.000 claims abstract description 18
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 230000001054 cortical effect Effects 0.000 claims abstract description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- 229960003638 dopamine Drugs 0.000 claims description 27
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- 238000001035 drying Methods 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 2
- 230000033558 biomineral tissue development Effects 0.000 abstract description 9
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- 238000002513 implantation Methods 0.000 description 6
- 230000011164 ossification Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 4
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/44—Joints for the spine, e.g. vertebrae, spinal discs
- A61F2/4455—Joints for the spine, e.g. vertebrae, spinal discs for the fusion of spinal bodies, e.g. intervertebral fusion of adjacent spinal bodies, e.g. fusion cages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/46—Special tools for implanting artificial joints
- A61F2/4603—Special tools for implanting artificial joints for insertion or extraction of endoprosthetic joints or of accessories thereof
- A61F2/4611—Special tools for implanting artificial joints for insertion or extraction of endoprosthetic joints or of accessories thereof of spinal prostheses
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
-
- 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
- A61L2300/604—Biodegradation
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Transplantation (AREA)
- Biomedical Technology (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Epidemiology (AREA)
- Neurology (AREA)
- Dermatology (AREA)
- Cardiology (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Physical Education & Sports Medicine (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Prostheses (AREA)
Abstract
The invention discloses a degradable bone grafting bed endowed with biological activity by nano ceramic, which comprises a netlike main body, wherein both sides of the netlike main body are respectively provided with a fixed wing, each fixed wing is provided with a plurality of nail hole pairs, each nail hole pair is internally provided with a self-tapping cortical bone screw and a self-tapping locking screw in a matching way, and the netlike main body is formed by hinging a plurality of connecting plates adjacent left and right; the net-shaped main body and each fixing wing are made of PLLA/HA composite powder through selective laser sintering. According to the PLLA/HA composite powder, PLLA particles are wrapped by polydopamine, HA is generated on the surface of the PLLA in situ in a biomimetic mineralization mode to prepare the PLLA/HA composite powder, and then the powder is subjected to 3D printing and molding, so that the PLLA/HA composite powder not only HAs the degradability of PLLA, but also HAs good biological activity and bone conductivity of HA, and complementary advantages can be realized.
Description
Technical Field
The invention relates to the technical field of biological pharmacy, in particular to a degradable bone grafting bed endowed with biological activity by nano ceramic and a preparation method thereof.
Background
The spinal column posterior laminectomy and vertebral canal decompression operation is the most common operation mode for treating spinal column diseases such as spinal canal stenosis, spinal fracture, intervertebral disc protrusion, hyperosteogeny, intrathecal tumor and occupation, serious spinal deformity, and the like. The aim is to relieve or alleviate the compression of the dural sac, spinal cord or nerve root caused by the shrinkage of the vertebral canal and each radial line of the side recess and the volume reduction caused by various reasons, and more than half of spinal operations can use the surgical means of laminectomy vertebral canal decompression to different degrees. At present, an implant bone bed which can be used for repairing bone defect after the vertebral canal decompression operation in spinal surgery is generally made of inert metal or a degradable polymer material, and can not exert osteoinduction, bone conduction and osteogenesis effects due to lack of good biological activity after implantation, so that effective fusion among vertebral bodies is difficult to realize, and the requirement of bone regeneration at the defect part of the spinal column is met.
The bone graft bed needs to be bonded to bone after laminectomy and provide strong support posteriorly, fully embedding the bone graft, and thus requires excellent mechanical strength. If the bone graft bed is not tightly combined with the bone graft, the compressive capacity is not enough to provide support, separation is easily caused at the joint, and the implantation is failed. The conventional method can make up the defect of a single material to a certain extent by directly compounding the PLLA and the HA, but HAs the problems that the organic polymer material and the inorganic ceramic have larger physical and chemical property difference, the inorganic ceramic HAs poor interfacial compatibility with the polymer in the compounding process, the interfacial bonding strength is low, and the inorganic filler is easy to debond from the matrix when being subjected to lower load, so that a large number of holes are generated, the effect of transferring force is not achieved, and the mechanical reinforcing effect is seriously weakened. In addition, HA nanoparticles have a huge specific surface area and surface energy, which are very susceptible to agglomeration in the polymeric matrix, which can lead to a decrease in the overall macroscopic performance of the composite. Therefore, as bone grafting bed material, it is important to improve the interface combination between PLLA and HA.
In the prior art, in order to ensure that the bone grafting bed can provide strong support for the spine, the bone grafting bed usually adopts an integrated structure, however, because the installed vertebral positions are different and the physiological curvatures of the vertebral bodies are different, the bone grafting bed can not be well bonded with the vertebral bodies, so that the bone grafting bed can not ensure that the bone grafting bed provides strong support for the spine after being implanted, and is not beneficial to inducing and promoting the growth of new bone tissues on the surface.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a biodegradable bone grafting bed endowed with bioactivity by nano-ceramics, comprising a netlike main body, two sides of which are respectively provided with a fixed wing, a plurality of nail hole pairs are arranged on each fixed wing, and a self-tapping cortical bone screw and a self-tapping locking screw are arranged in each nail hole pair in a matching manner;
the net-shaped main body is formed by hinging a plurality of connecting plates which are adjacent left and right;
the net-shaped main body and each fixing wing are made of PLLA/HA composite powder through selective laser sintering.
Preferably, a plurality of large holes and a plurality of small holes are symmetrically arranged on each connecting plate in a penetrating way, the large holes and the small holes are staggered, the aperture of each large hole is 4-6mm, and the aperture of each small hole is 1-3mm.
Preferably, the plurality of connecting plates are hinged in the following manner:
one side of each connecting plate is provided with a plurality of first connecting bulges in an integrated forming way, the other side of each connecting plate is provided with a plurality of second connecting bulges in an integrated forming way, the second connecting bulges are staggered with the first connecting bulges, and the middle positions of the first connecting bulges are hinged with the middle positions of the adjacent second connecting bulges.
Preferably, a plurality of first limiting holes are symmetrically and circumferentially arranged in the middle position of each first connecting protrusion in a penetrating manner, a plurality of second limiting holes are symmetrically and circumferentially arranged in the middle position of each second connecting protrusion in a penetrating manner, and each first limiting hole corresponds to each second limiting hole; a thread groove is formed in the middle of the top end of each first connecting protrusion at the top, and each thread groove is communicated with each corresponding first limiting hole;
the device comprises a threaded groove, a plurality of limiting pieces, a plurality of limiting rods, a plurality of first limiting holes, a plurality of second limiting holes, a plurality of limiting screws, a plurality of limiting plate bodies and a plurality of limiting plate bodies, wherein the limiting plate bodies are integrally formed at the bottom ends of the limiting plate bodies in a protruding mode, the limiting plate bodies are respectively sleeved at the bottoms of the threaded grooves, the limiting plate bodies are respectively sleeved with the corresponding first limiting holes and the second limiting holes, the limiting screw bodies are respectively connected in the threaded grooves in a sleeved mode, and the limiting screw bodies are respectively connected in the threaded grooves in a threaded mode, and the bottom ends of the limiting screw bodies are abutted to the top ends of the limiting plate bodies through screwing.
Preferably, the two fixing wings are hinged with the connecting plates at two sides respectively, and each fixing wing is detachably connected with each side of the connecting plate through the limiting piece respectively.
A preparation method of a degradable bone grafting bed endowed with biological activity by nano ceramic comprises the following steps:
wrapping dopamine on the surface of PLLA powder to obtain dopamine PLLA particles;
soaking the dopamine PLLA particles in an SBF solution, and generating HA in situ on the surface of the PLLA powder after the dopamine on the surfaces of the dopamine PLLA particles fully reacts with the SBF solution, so as to form PLLA/HA composite particles;
step three, separating the PLLA/HA composite particles from SBF solution, centrifugally washing the PLLA/HA composite particles by deionized water, performing dry-wet separation after washing, collecting the PLLA/HA composite particles subjected to dry-wet separation, and placing the PLLA/HA composite particles in an electrothermal blowing drying oven for drying treatment to obtain PLLA/HA composite powder;
and fourthly, placing the PLLA/HA composite powder into a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering is finished to obtain the degradable bone grafting bed endowed with biological activity by the nano ceramic.
Preferably, the method for wrapping dopamine on the surface of PLLA powder comprises the following steps:
mixing the PLLA powder with the mass concentration of 0.5-1 g/L in deionized water, and performing ultrasonic dispersion for 60-120 min to obtain PLLA aqueous solution;
preparing a dopamine hydrochloride solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 10-30 min to obtain a reaction solution;
and heating the reaction liquid, adding a certain amount of Tris solution when the temperature of the reaction liquid is raised to 40-60 ℃, adjusting the pH value of the reaction liquid to about 8.5, stirring and reacting for 10-14 hours to finally obtain a uniform solution, and then centrifugally washing and drying at a high speed to obtain the dopamine PLLA particles.
Preferably, the PLLA powder has a particle size of 40 to 60 μm and a melting point of 175 to 185 ℃.
Preferably, the concentration of the dopamine PLLA particles soaked in the SBF solution is 0.5-1 g/L, and the soaking time is 1-5 days.
Preferably, the parameters of the selective laser sintering system are as follows: the laser power is 1-3W, the scanning speed is 100-200mm/s, the scanning interval is 0.5-2.0 mm, the spot diameter is 0.3-0.5 mm, the powder layer thickness is 0.1-0.2 mm, and the powder bed preheating temperature is 140-160 ℃.
The invention at least comprises the following beneficial effects:
firstly, PLLA particles are wrapped by polydopamine, HA is generated on the surface of PLLA in situ in a biomimetic mineralization mode to prepare PLLA/HA composite powder, and then the powder is subjected to 3D printing and molding, so that the PLLA/HA composite powder not only HAs the degradability of PLLA, but also HAs good bioactivity and bone conductivity of HA, and can realize complementary advantages.
Secondly, the invention provides that the HA and the PLLA form perfect interface combination in an in-situ growth mode, and the mechanical strength is not affected by the problems of low interface bonding strength, agglomeration of nano particles in a polymer matrix and the like after implantation, so that a strong support is provided for the spine.
Thirdly, in the invention, the reticular main body part consists of two hinged semicircular arch plates, and the radian can be adjusted according to different vertebral bodies and different physiological curvatures of a human body so as to better match with the damaged part and provide effective support for the rear part of the vertebral body; the big holes and the small holes are mutually staggered and arranged in parallel, so that the overall weight of the device is reduced without losing the mechanical strength of the device, and enough gaps are reserved to enable epidural blood to be fully combined with the bone graft, thereby playing the best osteogenesis effect.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Fig. 2 is a schematic structural view of another embodiment of the present invention.
Fig. 3 is a schematic view of a connecting plate according to another embodiment of the present invention.
Fig. 4 is a schematic view of a fixed wing structure according to another embodiment of the present invention.
Fig. 5 is a schematic view of a stopper according to another embodiment of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
It should be noted that, in the description of the present invention, the orientation or positional relationship indicated by the term is based on the orientation or positional relationship shown in the drawings, which are merely for convenience of describing the present invention and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "configured to," "engaged with," "connected to," and the like are to be construed broadly, and for example, "connected" may be a fixed connection, may be a detachable connection, or may be integrally connected, may be mechanically connected, may be electrically connected, may be directly connected, may be indirectly connected through an intermediate medium, may be communication between two members, and may be understood in a specific manner by those skilled in the art.
Furthermore, in the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be a direct contact of the first and second features, or an indirect contact of the first and second features through an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
Fig. 1 shows an implementation of the invention comprising: the bone screw comprises a netlike main body 1, wherein both sides of the netlike main body are respectively provided with a fixed wing 2, each fixed wing 2 is provided with a plurality of nail hole pairs 21, and each nail hole pair 21 is internally provided with a self-tapping cortical bone screw 22 and a self-tapping locking screw 23 in a matching way;
the net-shaped main body 1 is formed by hinging a plurality of connecting plates 11 adjacent left and right;
the net-shaped main body 1 and each fixing wing 2 are made of PLLA/HA composite powder through selective laser sintering.
Working principle: when the bone grafting is used for repairing bone defects, the deflection of the connecting plates 11 is adjusted according to different vertebral bodies and different physiological curvatures of a human body, the inner sides of the connecting plates 11 are attached to the damaged parts, and the fixing wings 2 are fixed with the vertebral bodies adjacent to the damaged parts through the matching of the self-tapping cortical bone screws 22 and the self-tapping locking screws 23, so that strong support is provided for the vertebral column. The self-tapping cortical bone screw 22 and the self-tapping locking screw 23 are matched for use, so that the reticular main body 1 is firmly fixed behind the vertebral body of a human body to reconstruct the integrity of the vertebral body and protect the spinal cord and nerve roots of the human body. The self-tapping cortical screw 22 and the self-tapping locking screw 23 both have a tapered configuration of the tip of the self-tapping blade, facilitating direct threading after drilling without manual tapping. Both the self-tapping cortical screw 22 and the self-tapping locking screw 23 are designed as hexagonal screw heads, on the one hand, matching with conventional instruments and, on the other hand, being less prone to slide failure. The fixing positions of the self-tapping cortical screw 22 and the self-tapping locking screw 23 can be fixed on the inner side of the pedicle according to different vertebral bodies and different needs, and can also be directly fixed on the transverse process position, and the diameters of the self-tapping cortical screw 22 and the self-tapping locking screw 23 are smaller because the reticular main body 1 is very thin. The mesh-shaped main body 1 prepared by PLLA/HA composite powder through selective laser sintering is used for repairing bone defects after vertebral canal decompression surgery of spinal surgery, so as to achieve the biological reconstruction effect of defect parts. The PLLA/HA composite powder is prepared by wrapping PLLA particles with polydopamine and generating HA on the surface of the PLLA in situ in a biomimetic mineralization mode. Therefore, the prepared PLLA/HA composite powder not only HAs the degradability of PLLA, but also HAs good biological activity and bone conductivity of HA. And the HA is combined with the PLLA through an in-situ growth mode, so that a strong support can be provided for the spine after implantation, the growth of the new bone tissue on the surface can be induced and promoted, and the new bone tissue is firmly combined with the bone at the interface. In the technical scheme, the deflection angles of the connecting plates 11 and the two fixed wings 2 can be adjusted through hinging, so that the deflection angles can be adjusted conveniently according to different vertebral bodies and different physiological curvatures of a human body, and the device has the beneficial effects of enhancing applicability and guaranteeing structural strength.
In the above scheme, a plurality of large holes 12 and a plurality of small holes 13 are symmetrically and penetratingly arranged on each connecting plate 11, the large holes 12 and the small holes 13 are staggered, the aperture of each large hole 12 is 4-6mm, and the aperture of each small hole 13 is 1-3mm. The big holes 12 and the small holes 13 are mutually staggered and arranged in parallel, so that the overall weight of the device is reduced without losing the mechanical strength of the device, and enough gaps are reserved to fully combine the epidural blood and the bone graft, thereby playing the best osteogenesis effect.
In another example, a plurality of said connection plates 11 are hinged in such a way that:
a plurality of first connecting protrusions 14 are formed on one side of each connecting plate 11 in a uniform and formed manner, a plurality of second connecting protrusions 15 are formed on the other side of each connecting plate 11 in a uniform and formed manner, the second connecting protrusions 15 are staggered with the first connecting protrusions 14, and the middle positions of the first connecting protrusions 14 are hinged with the middle positions of the adjacent second connecting protrusions 15.
Working principle: when the bone grafting is used for repairing bone defects, the plurality of connecting plates 11 are adjusted to deflect according to different vertebral bodies and different physiological curvatures of a human body through the hinged connection relation between the plurality of first connecting protrusions 14 and the plurality of second connecting protrusions 15, so that the inner sides of the plurality of connecting plates 11 are attached to damaged parts, and the connection strength of the plurality of connecting plates 11 is ensured while the flexibility of each connecting plate 11 is ensured through the hinged connection relation between the plurality of first connecting protrusions 14 and the plurality of second connecting protrusions 15; this way has the advantage of guaranteeing the connection stability and facilitating the adjustment.
In another example, a plurality of first limiting holes 16 are symmetrically and circumferentially arranged at the middle position of each first connecting protrusion 14, a plurality of second limiting holes 17 are symmetrically and circumferentially arranged at the middle position of each second connecting protrusion 15, and each first limiting hole 16 corresponds to each second limiting hole 17; a thread groove 18 is formed in the middle position of the top end of each first connecting protrusion 14 positioned at the top, and each thread groove 18 is communicated with each corresponding first limiting hole 16;
the device further comprises a plurality of limiting pieces 3, each limiting piece comprises a limiting disc 31, a plurality of limiting rods 32 are arranged at the bottom end of each limiting disc 31 in an integrally formed protruding mode, each limiting disc 31 is sleeved at the bottom of each threaded groove 18, each limiting rod 32 is sleeved with a corresponding first limiting hole 16 and a corresponding second limiting hole 17 and connected with each threaded groove 18 in a sleeved mode, each limiting screw 4 is further connected with each threaded groove 18 in a threaded mode, and the bottom end of each limiting screw 4 abuts against the top end of each limiting disc 31 through screwing.
Working principle: when the bone grafting is used for repairing bone defects, the plurality of connecting plates 11 are adjusted to deflect according to different vertebral bodies and different physiological curvatures of a human body through the hinged connection relation between the plurality of first connecting protrusions 14 and the plurality of second connecting protrusions 15, so that the inner sides of the plurality of connecting plates 11 are attached to damaged parts, and the connection strength of the plurality of connecting plates 11 is ensured while the flexibility of each connecting plate 11 is ensured through the hinged connection relation between the plurality of first connecting protrusions 14 and the plurality of second connecting protrusions 15; after the inner sides of the connecting plates 11 are attached to the damaged parts, the corresponding first limiting holes 16 and second limiting holes 17 are sleeved and connected through the limiting rods 31 of the limiting pieces 3, the movable positions of the connecting plates 11 are respectively limited, the net-shaped main body 1 is kept in a fixed shape, strong support can be provided for the spine after implantation, the movable positions of the limiting pieces 3 are limited through the limiting screws 4, and the limiting pieces 3 are prevented from being separated. The method has the advantages of ensuring the structural strength, being convenient to adjust and having strong applicability.
In another example, two fixing wings 2 are hinged to the connecting plates 11 at both sides, respectively, and each fixing wing 2 is detachably connected to each side of the connecting plate 11 through the limiting member 3, respectively.
Working principle: a plurality of third connecting protrusions 24 are integrally formed and protruded on one side of the fixed wing 2, the specifications of the third connecting protrusions 24 and the first connecting protrusions 14 are the same, the third connecting protrusions 24 are hinged with the second connecting protrusions 15 of the connecting plate 11 on one side, and the third connecting protrusions 24 and the second connecting protrusions 15 of the connecting plate 11 on one side are detachably connected through the limiting pieces 3;
the other one side integrated into one piece protrusion of fixed wing 2 is provided with a plurality of fourth connecting protrusion 25, and a plurality of fourth connecting protrusion 25 with a plurality of second connecting protrusion 15 specification is the same, a plurality of fourth connecting protrusion 25 with the opposite side a plurality of first connecting protrusion 14 of connecting plate 11 articulates, and a plurality of fourth connecting protrusion 25 with the opposite side a plurality of first connecting protrusion 14 of connecting plate 11 passes through the locating part 3 can dismantle the connection.
The mode that each fixed wing 2 is articulated with each side connecting plate 11 is the same with the mode that two adjacent connecting plates 11 are articulated, is convenient for adjust the deflection angle of fixed wing 2 for fixed wing 2 can carry out adaptive erection joint according to actual conditions, and can prevent that fixed wing 2 from deflecting and producing great unsmooth with each side connecting plate 11 after adjusting, ensure holistic surface smoothness, prevent that bone grafting bed from producing foreign matter sense after the installation. And the fixing wings 2 are detachably connected with the connecting plates 11 at the sides through the limiting pieces 3, so that the connection strength between the fixing wings 2 and the connecting plates 11 is ensured, and shape change is prevented from being generated again after the bone grafting bed is installed. The method has the advantages of enhancing applicability, guaranteeing structural strength and facilitating installation.
Example 1:
step one, PLLA powder with the particle size of 40 mu m and the melting point of 175 ℃ is mixed in deionized water according to the mass concentration of 0.5g/L, and then the PLLA powder is dispersed for 120min by ultrasonic to obtain PLLA aqueous solution;
preparing a dopamine hydrochloride solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride solution with 50mL of the PLLA aqueous solution, and stirring for 30min at room temperature to obtain a reaction solution;
heating the reaction solution, adding a certain amount of Tris solution when the temperature of the reaction solution is raised to 40 ℃, regulating the pH value of the reaction solution to be about 8.5, stirring and reacting for 14 hours to finally obtain a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain dopamine PLLA particles;
preparing 1.5x SBF solution by using sodium chloride, sodium bicarbonate, potassium chloride, dipotassium phosphate hexahydrate, magnesium chloride, sodium sulfate, trimethylol amine alkane, hydrochloric acid and pH standard solution, soaking the dopamine PLLA particles in the 1.5x SBF solution at the concentration of 0.5g/L for 5 days, and fully reacting the dopamine on the surfaces of the dopamine PLLA particles with the SBF solution to generate HA on the surfaces of the PLLA powder in situ so as to form PLLA/HA composite particles;
step three, separating the PLLA/HA composite particles from SBF solution, centrifugally washing the PLLA/HA composite particles by deionized water, performing dry-wet separation after washing, collecting the PLLA/HA composite particles subjected to dry-wet separation, and placing the PLLA/HA composite particles in an electrothermal blowing drying oven for drying treatment to obtain PLLA/HA composite powder;
step four, placing the PLLA/HA composite powder in a selective laser sintering system, wherein parameters of the selective laser sintering system are as follows: the laser power is 1W, the scanning speed is 100mm/s, the scanning interval is 0.5mm, the spot diameter is 0.3mm, the powder layer thickness is 0.1mm, and the powder bed preheating temperature is 140 ℃. And (3) performing layer-by-layer sintering according to the three-dimensional model, and removing the unsintered model after sintering is completed to obtain the degradable bone grafting bed endowed with biological activity by the nano ceramic.
According to mineralization performance tests, the PLLA/HA bone grafting bed HAs excellent mineralization capability compared with the PLLA bone grafting bed, and a small amount of HA layers are formed on the surface of the PLLA/HA bone grafting bed;
biological activity tests show that the PLLA/HA bone grafting bed can grow a calcium-phosphorus layer after being soaked in SBF solution for one week, and the calcium-phosphorus ratio is close to 1.67;
Micro-CT examination and Van-Gieson staining of bone tissue indicated that PLLA/HA bone grafting beds exhibited better osteogenesis inducing capacity than PLLA bone grafting beds.
Example 2:
step one, PLLA powder with the particle size of 50 mu m and the melting point of 180 ℃ is mixed in deionized water according to the mass concentration of 0.8g/L, and then the PLLA powder is dispersed for 90 minutes by ultrasonic to obtain PLLA aqueous solution;
preparing a dopamine hydrochloride solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 20min to obtain a reaction solution;
heating the reaction solution, adding a certain amount of Tris solution when the temperature of the reaction solution is raised to 50 ℃, regulating the pH value of the reaction solution to be about 8.5, stirring and reacting for 12 hours to finally obtain a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain dopamine PLLA particles;
preparing 2x SBF solution by using sodium chloride, sodium bicarbonate, potassium chloride, dipotassium phosphate hexahydrate, magnesium chloride, sodium sulfate, trimethylol amine alkane, hydrochloric acid and pH standard solution, soaking the dopamine PLLA particles in the 2x SBF solution at the concentration of 0.8g/L for 3 days, and fully reacting the dopamine on the surfaces of the dopamine PLLA particles with the SBF solution to generate HA on the surfaces of the PLLA powder in situ so as to form PLLA/HA composite particles;
step three, separating the PLLA/HA composite particles from SBF solution, centrifugally washing the PLLA/HA composite particles by deionized water, performing dry-wet separation after washing, collecting the PLLA/HA composite particles subjected to dry-wet separation, and placing the PLLA/HA composite particles in an electrothermal blowing drying oven for drying treatment to obtain PLLA/HA composite powder;
step four, placing the PLLA/HA composite powder in a selective laser sintering system, wherein parameters of the selective laser sintering system are as follows: the laser power is 2W, the scanning speed is 150mm/s, the scanning interval is 1.5mm, the spot diameter is 0.4mm, the thickness of the powder layer is 0.15mm, and the preheating temperature of the powder bed is 150 ℃. And (3) performing layer-by-layer sintering according to the three-dimensional model, and removing the unsintered model after sintering is completed to obtain the degradable bone grafting bed endowed with biological activity by the nano ceramic.
According to mineralization performance tests, the PLLA/HA bone grafting bed HAs excellent mineralization capability compared with the PLLA bone grafting bed, and a small amount of HA layers are formed on the surface of the PLLA/HA bone grafting bed;
biological activity tests show that the PLLA/HA bone grafting bed can grow a calcium-phosphorus layer after being soaked in SBF solution for one week, and the calcium-phosphorus ratio is close to 1.67;
Micro-CT examination and Van-Gieson staining of bone tissue indicated that PLLA/HA bone grafting beds exhibited better osteogenesis inducing capacity than PLLA bone grafting beds.
From the above, the PLLA powder is wrapped by polydopamine, the wrapped powder is soaked in SBF in a biomineralization mode to form HA, and then the PLLA/HA composite powder is used for preparing the bone grafting bed by a 3D printing technology so as to endow the bone grafting bed with biological activity. The bone grafting bed introduces HA into PLLA, fully exerts the biological activity of HA, can form good bone bonding with bone tissue in an implant body, and can induce osteogenesis to repair bone defects. On the other hand, through wrapping polydopamine on the PLLA surface, the problem of insufficient interface combination of a high polymer material and a ceramic material can be solved by utilizing a biomimetic mineralization mode to generate HA on the PLLA surface in situ, so that the bone grafting bed is favorable for fully exerting mechanical properties after implantation to provide a supporting effect and realizing firm combination with adjacent vertebral bodies. The principle of the preparation method is that dopamine is utilized to carry out self-polymerization reaction in alkaline solution (pH=8.5) to synthesize polydopamine-coated PLLA nano particles, and then catechol groups of polydopamine are utilized to effectively chelate calcium ions in SBF, so that nucleation and crystallization of HA are promoted, and nano HA is further grown on PLLA in situ. Wherein dopamine is used as bridging medium, on one hand, the dopamine can be combined with PLLA through hydrogen bond action, on the other hand, HA grows in situ due to chelating effect, and finally, the perfect combination of a polymer matrix and a nano ceramic filling phase is realized.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (5)
1. The utility model provides a nanometer pottery gives bioactive degradable bone grafting bed, includes netted main part, and its both sides are provided with the fixed wing respectively, each all be provided with a plurality of nail hole pairs on the fixed wing, each all match in the nail hole pair and be provided with self-tapping cortical bone screw and self-tapping locking screw, its characterized in that:
the net-shaped main body is formed by hinging a plurality of connecting plates which are adjacent left and right;
the net-shaped main body and each fixed wing are made of PLLA/HA composite powder through selective laser sintering;
the mode that a plurality of connecting plates are articulated is:
a plurality of first connecting protrusions are integrally formed and protruded on one side of each connecting plate, a plurality of second connecting protrusions are integrally formed and protruded on the other side of each connecting plate, the second connecting protrusions and the first connecting protrusions are arranged in a staggered mode, and the middle positions of the first connecting protrusions are hinged with the middle positions of the adjacent second connecting protrusions;
a plurality of first limiting holes are symmetrically formed in the middle position of each first connecting protrusion in a penetrating mode, a plurality of second limiting holes are symmetrically formed in the middle position of each second connecting protrusion in a penetrating mode in the surrounding mode, and each first limiting hole corresponds to each second limiting hole; a thread groove is formed in the middle of the top end of each first connecting protrusion at the top, and each thread groove is communicated with each corresponding first limiting hole;
the device comprises a threaded groove, a plurality of limiting pieces, a plurality of limiting rods, a plurality of limiting screw bolts and a plurality of limiting screw bolts, wherein the limiting pieces are respectively provided with limiting plates, the bottom ends of the limiting plates are respectively sleeved at the bottoms of the threaded grooves, the limiting rods are respectively sleeved with the corresponding first limiting holes and second limiting holes, and the limiting screw bolts are respectively connected with the threaded grooves in a threaded manner, and the bottom ends of the limiting screw bolts are abutted against the top ends of the limiting plates through screwing;
the two fixing wings are hinged with the connecting plates at two sides respectively, and each fixing wing is detachably connected with each side of the connecting plate through the limiting piece respectively.
2. The degradable bone grafting bed for endowing biological activity with nano ceramic according to claim 1, wherein a plurality of macropores and a plurality of small holes are symmetrically arranged on each connecting plate in a penetrating way, the macropores and the small holes are staggered, the pore diameter of each macropore is 4-6mm, and the pore diameter of each small hole is 1-3mm.
3. The method for preparing the degradable bone grafting bed endowed with biological activity by the nano ceramic according to any one of claims 1-2, which is characterized by comprising the following steps:
wrapping dopamine on the surface of PLLA powder to obtain dopamine PLLA particles;
soaking the dopamine PLLA particles in an SBF solution, and generating HA in situ on the surface of the PLLA powder after the dopamine on the surfaces of the dopamine PLLA particles fully reacts with the SBF solution, so as to form PLLA/HA composite particles;
step three, separating the PLLA/HA composite particles from SBF solution, centrifugally washing the PLLA/HA composite particles by deionized water, performing dry-wet separation after washing, collecting the PLLA/HA composite particles subjected to dry-wet separation, and placing the PLLA/HA composite particles in an electrothermal blowing drying oven for drying treatment to obtain PLLA/HA composite powder;
step four, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to a three-dimensional model, and removing an unsintered model after sintering is completed to obtain the degradable bone grafting bed endowed with biological activity by the nano ceramic;
the method for wrapping dopamine on the surface of PLLA powder comprises the following steps:
mixing the PLLA powder in deionized water according to the mass concentration of 0.5-1 g/L, and performing ultrasonic dispersion for 60-120 min to obtain PLLA aqueous solution;
preparing a dopamine hydrochloride solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 10-30 min to obtain a reaction solution;
heating the reaction liquid, adding a certain amount of Tris solution when the temperature of the reaction liquid is raised to 40-60 ℃, adjusting the pH value of the reaction liquid to be about 8.5, stirring and reacting for 10-14 hours to finally obtain a uniform solution, and then centrifugally washing and drying at a high speed to obtain the dopamine PLLA particles;
the concentration of the dopamine PLLA particles soaked in the SBF solution is 0.5-1 g/L, and the soaking time is 1-5 days.
4. The method for preparing the biodegradable bone grafting bed endowed with biological activity by the nano ceramic according to claim 3, wherein the particle size of the PLLA powder is 40-60 microns, and the melting point is 175-185 ℃.
5. The method for preparing a biodegradable bone grafting bed endowed with biological activity according to claim 3, characterized in that the parameters of the selective laser sintering system are as follows: the laser power is 1-3W, the scanning speed is 100-200mm/s, the scanning interval is 0.5-2.0 mm, the spot diameter is 0.3-0.5 mm, the powder layer thickness is 0.1-0.2 mm, and the powder bed preheating temperature is 140-160 ℃.
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| US11284925B2 (en) * | 2019-08-15 | 2022-03-29 | Central South University Xiangya Hospital | Internal fixation system of spine posterior screw-plate |
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| WO2009071813A1 (en) * | 2007-11-22 | 2009-06-11 | Henry Graf | Device for interconnection of at least three vertebrae |
| CN109350208A (en) * | 2018-11-06 | 2019-02-19 | 中南大学湘雅二医院 | A titanium alloy bone grafting bed device for the rear of the vertebral body |
| CN111184916A (en) * | 2018-11-15 | 2020-05-22 | 中南大学 | Method for preparing hydroxyapatite/levorotatory polylactic acid composite bone scaffold |
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