CN115444986A - Degradable bone grafting bed with bioactivity endowed by nano ceramic and preparation method thereof - Google Patents

Degradable bone grafting bed with bioactivity endowed by nano ceramic and preparation method thereof Download PDF

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CN115444986A
CN115444986A CN202210947766.5A CN202210947766A CN115444986A CN 115444986 A CN115444986 A CN 115444986A CN 202210947766 A CN202210947766 A CN 202210947766A CN 115444986 A CN115444986 A CN 115444986A
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plla
limiting
powder
dopamine
bed
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CN115444986B (en
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帅词俊
戚方伟
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NANCHANG CAMPUS OF JIANGXI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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NANCHANG CAMPUS OF JIANGXI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F2/00Filters 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
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/44Joints for the spine, e.g. vertebrae, spinal discs
    • A61F2/4455Joints 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F2/00Filters 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
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/46Special tools or methods for implanting or extracting artificial joints, accessories, bone grafts or substitutes, or particular adaptations therefor
    • A61F2/4603Special tools or methods for implanting or extracting artificial joints, accessories, bone grafts or substitutes, or particular adaptations therefor for insertion or extraction of endoprosthetic joints or of accessories thereof
    • A61F2/4611Special tools or methods for implanting or extracting artificial joints, accessories, bone grafts or substitutes, or particular adaptations therefor for insertion or extraction of endoprosthetic joints or of accessories thereof of spinal prostheses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46Composite 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow
    • A61L2300/604Biodegradation

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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)
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  • Prostheses (AREA)

Abstract

The invention discloses a degradable bone grafting bed with nano-ceramic endowed with bioactivity, which comprises a net-shaped main body, wherein two sides of the net-shaped main body are respectively provided with a fixing wing, each fixing 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 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. According to the invention, the PLLA particles are coated with polydopamine, HA is generated in situ on the surface of the PLLA in a biomimetic mineralization mode to prepare PLLA/HA composite powder, and then the powder is subjected to 3D printing and forming, so that the PLLA/HA composite powder not only HAs the degradability of the PLLA, but also HAs good bioactivity and osteoconductivity of the HA, and advantage complementation can be realized.

Description

Degradable bone grafting bed with bioactivity endowed by nano ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of biological pharmacy, in particular to a degradable bone grafting bed with bioactivity endowed by nano ceramic and a preparation method thereof.
Background
A posterior vertebral laminectomy spinal canal decompression operation is the most common operation mode for treating spinal diseases such as spinal canal stenosis, spinal fracture, intervertebral disc protrusion, hyperosteogeny, intraspinal tumor and occupation, serious spinal deformity and the like. Aims to relieve or alleviate the compression on the dural sac, the spinal cord or nerve roots caused by the shortening of the radial lines of the vertebral canal and the lateral crypt and the volume reduction caused by various reasons, and over half of the spinal surgeries use the surgical means of vertebral plate resection vertebral canal decompression to different degrees. At present, a bone grafting bed for repairing bone defects can be used after vertebral laminectomy and spinal canal decompression in spinal surgery, is generally made of inert metal or degradable high polymer materials, cannot play roles of bone induction, bone conduction and bone generation due to lack of good biological activity after being implanted, and is difficult to realize effective fusion among vertebral bodies so as to meet the requirement of bone regeneration of spinal defect parts.
The bone graft bed needs to be bonded with bone formation and provide strong support at the back after laminectomy spinal decompression, and fully embedded and pressed on the bone graft, so that excellent mechanical strength is needed. If the bone graft bed is not tightly bonded to the bone graft and the compressive strength is not sufficient to provide support, the joint may be easily separated, resulting in implant failure. The conventional method for directly compounding the high polymer material PLLA and the bioceramic HA can make up the defects of a single material to a certain extent, but HAs the problems that the organic high polymer material and the inorganic ceramic have larger difference in physical and chemical properties, the inorganic ceramic and the high polymer interface have poor compatibility and low interface bonding strength in the compounding process of the organic high polymer material and the inorganic ceramic, and the inorganic filler is easy to be debonded from the matrix under lower load to generate a large number of cavities which cannot play a role in transferring force, so that the mechanical reinforcing effect of the inorganic filler is seriously weakened. In addition, the HA nanoparticles have huge specific surface area and surface energy, and are easily agglomerated in a polymer matrix, which may cause the overall macroscopic performance of the composite material to be reduced. Therefore, as a bone grafting bed material, the improvement of the interface bonding of PLLA and HA is very important.
In prior art, for the guarantee bone grafting bed can provide the firm support for the vertebra, bone grafting bed adopts integral type structure usually, nevertheless because the centrum position of installation is different, the difference of centrum physiological curvature for bone grafting bed can not form better bonding with the centrum, thereby can not ensure bone grafting bed and implant the back and provide the firm support for the backbone, be unfavorable for induction and promotion new bone tissue and grow on the surface.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a biodegradable bone graft bed with nano-ceramic endowed with bioactivity, comprising a mesh-shaped main body, both sides of which are respectively provided with a plurality of fixation wings, each fixation wing being provided with a plurality of nail hole pairs, each nail hole pair being provided with a self-tapping cortical bone screw and a self-tapping locking screw 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 reticular main body and each fixed wing are both made of PLLA/HA composite powder through selective laser sintering.
Preferably, each connecting plate is symmetrically provided with a plurality of large holes and a plurality of small holes in a penetrating manner, the large holes and the small holes are arranged in a staggered manner, the aperture of each large hole is 4-6mm, and the aperture of each small hole is 1-3mm.
Preferably, wherein the plurality of connecting plates are hinged in a manner that:
each the equal integrated into one piece protrusion in one side of connecting plate is provided with a plurality of first and connects protrudingly, each the equal integrated into one piece protrusion in opposite side of connecting plate is provided with a plurality of second and connects protrudingly, and is a plurality of second connect protrudingly and a plurality of first connect protruding crisscross setting, and is a plurality of first connect bellied intermediate position and adjacent a plurality of second connect bellied intermediate position articulated.
Preferably, a plurality of first limiting holes are symmetrically arranged in a penetrating manner around the middle position of each first connecting protrusion, a plurality of second limiting holes are symmetrically arranged in a penetrating manner around the middle position of each second connecting protrusion, and each first limiting hole corresponds to each second limiting hole; threaded grooves are formed in the middle of the top ends of the first connecting bulges at the tops of the first connecting bulges, and the threaded grooves are communicated with the corresponding first limiting holes;
the limiting device comprises a plurality of limiting pieces and is characterized by further comprising limiting discs, a plurality of limiting rods are convexly arranged at the bottom ends of the limiting discs in an integrated mode, the limiting discs are sleeved at the bottoms of the thread grooves respectively, the limiting rods are connected with the corresponding first limiting holes and the second limiting holes in a sleeved mode respectively, limiting screws are further connected into the thread grooves in a threaded mode, and the bottom ends of the limiting screws are screwed through threads and abut against the top ends of the limiting discs.
Preferably, the two fixed wings are respectively hinged to the connecting plates located at two sides, and each fixed wing is detachably connected to the connecting plate at each side through the limiting piece.
A preparation method of a degradable bone grafting bed with biological activity endowed by nano ceramics comprises the following steps:
step one, coating dopamine on the surface of PLLA powder to obtain dopamine PLLA particles;
step two, soaking the dopamine PLLA particles in an SBF solution, and generating HA on the surface of the PLLA powder in situ after dopamine on the surface of the dopamine PLLA particles fully reacts with the SBF solution so as to form PLLA/HA composite particles;
separating the PLLA/HA composite particles from an SBF solution, centrifugally washing the PLLA/HA composite particles by using 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 electric heating air blowing drying box for drying treatment to obtain PLLA/HA composite powder;
and 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 with bioactivity endowed by the nano ceramic.
Preferably, the method for coating dopamine on the surface of the 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 a PLLA aqueous solution;
preparing a dopamine hydrochloride aqueous solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride aqueous solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 10-30 min to obtain a reaction solution;
and then heating the reaction solution, adding a certain amount of Tris solution when the temperature of the reaction solution is raised to 40-60 ℃, adjusting the pH value of the reaction solution to about 8.5, stirring for reaction for 10-14 hours to finally obtain a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the dopamine PLLA particles.
Preferably, wherein 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, wherein the parameters of the selective laser sintering system are: 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 thickness of the powder layer is 0.1-0.2 mm, and the preheating temperature of the powder bed is 140-160 ℃.
The invention at least comprises the following beneficial effects:
firstly, the PLLA particles are wrapped by polydopamine, HA is generated in situ on the surface of the PLLA in a biomimetic mineralization mode to prepare PLLA/HA composite powder, and then the powder is subjected to 3D printing and forming, so that the PLLA/HA composite powder not only HAs the degradability of the PLLA, but also HAs good bioactivity and osteoconductivity of the HA, and advantage complementation can be realized.
Secondly, the invention provides a method for forming perfect interface combination between HA and PLLA by in-situ growth, and the mechanical strength is not influenced by the problems of low interface bonding strength, agglomeration of nano-particles in a polymer matrix and the like after implantation, thereby providing strong support for a spine.
Thirdly, in the invention, the reticular main body part is composed of two hinged semi-circular arch plates, the radian can be adjusted according to different vertebral bodies and different physiological curvatures of a human body, so as to better match the damaged part and provide effective support for the back of the vertebral bodies; the large holes and the small holes are arranged in a staggered and parallel way, so that the whole weight of the device is reduced without losing the mechanical strength of the device, and meanwhile, enough gaps are reserved to fully combine epidural blood with transplanted bones, thereby playing the best role of bone healing.
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 diagram of the present invention.
FIG. 2 is a schematic structural diagram of another embodiment of the present invention.
Fig. 3 is a schematic view of a connection plate structure according to another embodiment of the present invention.
Fig. 4 is a schematic view of a stationary wing according to another embodiment of the present invention.
Fig. 5 is a schematic view of a limiting member according to another embodiment of the invention.
Detailed Description
The present invention is described in further detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
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 is to be understood that in the description of the present invention, the terms indicating orientation or positional relationship are based on the orientation or positional relationship shown in the drawings, and are used only for convenience in describing the present invention and for simplification of the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" 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 otherwise specifically stated or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are used broadly, and for example, "connected" may be a fixed connection, a detachable connection, or an integral connection, a mechanical connection, an electrical connection, a direct connection, an indirect connection via an intermediate medium, or a communication between two elements, and those skilled in the art will understand the specific meaning of the terms in the present invention specifically.
Further, in the present invention, unless otherwise explicitly specified or limited, a first feature "on" or "under" a second feature may be directly contacted with the first and second features, or indirectly contacted with the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature "under," "beneath," and "under" a second feature may be directly under or obliquely under the second feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
Fig. 1 shows an implementation form of the present invention, which includes: the self-tapping type bone screw comprises a net-shaped main body 1, wherein two sides of the net-shaped main body are respectively provided with a fixing wing 2, each fixing wing 2 is provided with a plurality of nail hole pairs 21, and a self-tapping type cortical bone screw 22 and a self-tapping type locking screw 23 are arranged in each nail hole pair 21 in a matching manner;
the reticular main body 1 is formed by hinging a plurality of connecting plates 11 which are adjacent left and right;
the net-shaped main body 1 and the fixed wings 2 are made of PLLA/HA composite powder through selective laser sintering.
The working principle is as follows: when the bone is implanted to repair the bone defect, the plurality of connecting plates 11 are adjusted to deflect according to different vertebral bodies and different physiological curvatures of a human body, so that the inner sides of the plurality of connecting plates 11 are attached to the damaged part, and each fixing wing 2 is fixed with the adjacent vertebral body of the damaged part through the matching of a self-tapping cortical bone screw 22 and a self-tapping locking screw 23, so that strong support is provided for the spine. The self-tapping cortical bone screw 22 and the self-tapping locking screw 23 are matched for use, so that the net-shaped main body 1 can be conveniently and firmly fixed at the back of a human vertebral body to rebuild 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 each have a tapered configuration with a self-tapping blade tip to facilitate direct screwing-in after drilling without manual tapping. The self-tapping cortical bone screw 22 and the self-tapping locking screw 23 are both designed as hexagonal screw heads, which on the one hand match conventional instruments and on the other hand are not prone to thread-slip failure. The fixing positions of the self-tapping cortical bone screw 22 and the self-tapping locking screw 23 can be fixed on the inner side of the pedicle of vertebral arch or can be directly fixed on the transverse process position according to different vertebral bodies and different requirements, and the diameters of the self-tapping cortical bone screw 22 and the self-tapping locking screw 23 are smaller because the net-shaped main body 1 is very thin. The net-shaped main body 1 made of PLLA/HA composite powder through selective laser sintering is used for repairing bone defects after vertebral laminectomy and spinal decompression in spinal surgery so as to achieve the biological reconstruction effect of the defect part. The PLLA/HA composite powder is prepared by coating 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 HAs the degradability of PLLA, and also HAs good bioactivity and osteoconductivity of HA. And the interface formed by HA and PLLA is combined in an in-situ growth mode, so that strong support can be provided for the spine after implantation, the surface growth of new bone tissues can be induced and promoted, and the HA and PLLA are firmly combined with bone formation at the interface. In the technical scheme, the deflection angles of the connecting plates 11 and the two fixing wings 2 can be adjusted through hinging, so that the adjustment can be conveniently carried out according to different centrums and different physiological curvatures of a human body, and the beneficial effects of enhancing the applicability and guaranteeing the structural strength are achieved.
In the above scheme, a plurality of large holes 12 and a plurality of small holes 13 are symmetrically arranged on each connecting plate 11 in a penetrating manner, 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 large holes 12 and the small holes 13 are arranged in a staggered and parallel way, so that the whole weight of the device is reduced without losing the mechanical strength of the device, and meanwhile, enough gaps are reserved to fully combine epidural blood with transplanted bones, thereby playing the best role of osteogenesis healing.
In another example, the connection plates 11 are hinged in a manner that:
a plurality of first connecting protrusions 14 are convexly formed on one side of each connecting plate 11, a plurality of second connecting protrusions 15 are convexly formed on the other side of each connecting plate 11, the plurality of second connecting protrusions 15 and the plurality of first connecting protrusions 14 are arranged in a staggered mode, and the middle positions of the plurality of first connecting protrusions 14 are hinged with the middle positions of the plurality of adjacent second connecting protrusions 15.
The working principle is as follows: when the bone defect is repaired through bone grafting, the plurality of connecting plates 11 are adjusted to deflect according to different centrums and different physiological curvatures of a human body through the hinged connection relationship between the plurality of first connecting bulges 14 and the plurality of second connecting bulges 15, so that the inner sides of the plurality of connecting plates 11 are attached to the damaged part, 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 relationship between the plurality of first connecting bulges 14 and the plurality of second connecting bulges 15; the adoption of the mode has the advantages of ensuring the connection stability and facilitating the adjustment.
In another example, a plurality of first limiting holes 16 are symmetrically arranged around the middle of each first connecting protrusion 14, a plurality of second limiting holes 17 are symmetrically arranged around the middle of each second connecting protrusion 15, and each first limiting hole 16 corresponds to each second limiting hole 17; the middle position of the top end of each first connecting protrusion 14 at the top is provided with a thread groove 18, and each thread groove 18 is communicated with each corresponding first limiting hole 16;
the limiting device further comprises a plurality of limiting pieces 3 which comprise limiting discs 31, a plurality of limiting rods 32 are arranged at the bottom ends of the limiting discs 31 in an integrally formed protruding mode, the limiting discs 31 are sleeved at the bottoms of the thread grooves 18 respectively, the limiting rods 32 are connected with the corresponding first limiting holes 16 and the corresponding second limiting holes 17 in a sleeved mode respectively, limiting screws 4 are connected in the thread grooves 18 in a threaded mode, and the bottom ends of the limiting screws 4 are screwed through threads and abutted to the top ends of the limiting discs 31.
The working principle is as follows: when the bone defect is repaired through bone grafting, the plurality of connecting plates 11 are adjusted to deflect according to different centrums and different physiological curvatures of a human body through the hinged connection relationship between the plurality of first connecting bulges 14 and the plurality of second connecting bulges 15, so that the inner sides of the plurality of connecting plates 11 are attached to the damaged part, 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 relationship between the plurality of first connecting bulges 14 and the plurality of second connecting bulges 15; after the insides of the connecting plates 11 are attached to the damaged parts, the corresponding limiting rods 31 of the limiting parts 3 are sleeved with the corresponding limiting holes 16 and 17 to be connected so as to limit the moving positions of the connecting plates 11 respectively, so that the net-shaped main body 1 keeps a fixed shape, strong support can be provided for the spine after implantation, and the limiting parts 3 are prevented from being separated from the moving positions by limiting screws 4. The adoption of the mode has the advantages of ensuring the structural strength, being convenient for adjustment and having strong applicability.
In another example, two of the fixed wings 2 are respectively hinged to the connecting plates 11 at two sides, and each of the fixed wings 2 is detachably connected to each of the connecting plates 11 at one side through the limiting member 3.
The working principle is as follows: a plurality of third connecting protrusions 24 are integrally formed and protruded on one side of the fixed wing 2, the plurality of third connecting protrusions 24 have the same specification as the plurality of first connecting protrusions 14, the plurality of third connecting protrusions 24 are hinged to the plurality of second connecting protrusions 15 of the connecting plate 11 on one side, and the plurality of third connecting protrusions 24 are detachably connected to the plurality of second connecting protrusions 15 of the connecting plate 11 on one side through the limiting member 3;
another one side integrated into one piece protrusion of stationary vane 2 is provided with a plurality of fourth connection arch 25, and is a plurality of fourth connection arch 25 is with a plurality of the protruding 15 specifications of second connection are the same, and is a plurality of fourth connection arch 25 and opposite side connecting plate 11 is a plurality of first connection arch 14 is articulated, and is a plurality of fourth connection arch 25 and opposite side connecting plate 11 is a plurality of first connection arch 14 passes through the connection can be dismantled to locating part 3.
The mode that each fixed wing 2 is articulated with each side connecting plate 11 is the same with two adjacent connecting plates 11 articulated modes, is convenient for adjust the deflection angle of fixed wing 2 for fixed wing 2 can carry out the installation of adaptability according to actual conditions and be connected, and can prevent to produce great unsmooth between the fixed wing 2 after the deflection adjustment and each side connecting plate 11, guarantee holistic surface smoothness, prevent to produce the foreign body sensation after the bone grafting bed is installed. And each fixed wing 2 and each side connecting plate 11 can be dismantled through locating part 3 and be connected, have ensured the joint strength between fixed wing 2 and the connecting plate 11, prevent to produce shape change again after the bone grafting bed installation. The mode has the advantages of enhancing the applicability, ensuring the structural strength and being convenient to install.
Example 1:
step one, mixing PLLA powder with the particle size of 40 mu m and the melting point of 175 ℃ in deionized water according to the mass concentration of 0.5g/L, and performing ultrasonic dispersion for 120min to obtain a PLLA aqueous solution;
preparing a dopamine hydrochloride aqueous solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride aqueous solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 30min to obtain a reaction solution;
heating the reaction solution, adding a certain amount of Tris solution when the temperature of the reaction solution rises to 40 ℃, adjusting the pH value of the reaction solution to be about 8.5, stirring for 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, tripotassium hydrogen phosphate hexahydrate magnesium chloride, calcium chloride, sodium sulfate, trimethylolalkane, hydrochloric acid and pH standard solution, soaking the dopamine PLLA particles in 1.5x SBF solution for 5 days at a soaking concentration of 0.5g/L, and generating HA on the surface of the PLLA powder in situ to form PLLA/HA composite particles after dopamine on the surface of the dopamine PLLA particles and the SBF solution react sufficiently;
separating the PLLA/HA composite particles from an SBF solution, centrifugally washing the PLLA/HA composite particles by using 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 electric heating air blowing drying box for drying treatment to obtain PLLA/HA composite powder;
step four, placing the PLLA/HA composite powder in a selective laser sintering system, wherein the 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 thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 140 ℃. And sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the degradable bone grafting bed with bioactivity endowed by the nano ceramic.
The mineralization performance test shows that the PLLA/HA bone grafting bed HAs excellent mineralization capability compared with the PLLA bone grafting bed, and a small amount of HA layer is formed on the surface;
biological activity tests show that a calcium-phosphorus layer can grow after the PLLA/HA bone grafting bed is soaked in an SBF solution for one week, and the calcium-phosphorus ratio is close to 1.67;
Micro-CT detection and Van-Giesen staining of bone tissues show that the PLLA/HA bone graft bed shows better osteogenesis inducing capacity compared with the PLLA bone graft bed.
Example 2:
step one, mixing PLLA powder with the particle size of 50 microns and the melting point of 180 ℃ in deionized water according to the mass concentration of 0.8g/L, and performing ultrasonic dispersion for 90min to obtain a PLLA aqueous solution;
preparing a dopamine hydrochloride aqueous solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride aqueous 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 rises to 50 ℃, adjusting the pH value of the reaction solution to be about 8.5, stirring for reaction 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, tripotassium phosphate trihydrate, magnesium chloride hexahydrate, calcium chloride, sodium sulfate, trimethylolalkane, hydrochloric acid and pH standard solution, soaking the dopamine PLLA particles in the 2x SBF solution for 3 days at a soaking concentration of 0.8g/L, and generating HA on the surface of the PLLA powder in situ after dopamine on the surface of the dopamine PLLA particles and the SBF solution react sufficiently, thereby forming PLLA/HA composite particles;
separating the PLLA/HA composite particles from an SBF solution, centrifugally washing the PLLA/HA composite particles by using deionized water, performing dry-wet separation after washing, collecting the PLLA/HA composite particles after dry-wet separation, and placing the PLLA/HA composite particles in an electrothermal blowing drying box for drying treatment to obtain PLLA/HA composite powder;
placing the PLLA/HA composite powder in a selective laser sintering system, wherein the 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 sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the degradable bone grafting bed with bioactivity endowed by the nano ceramic.
The mineralization performance test shows that 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;
biological activity tests show that a calcium-phosphorus layer can grow after the PLLA/HA bone grafting bed is soaked in an SBF solution for one week, and the calcium-phosphorus ratio is close to 1.67;
Micro-CT detection and Van-Giesen staining of bone tissue indicate that PLLA/HA bone graft exhibits better osteogenesis-inducing ability than PLLA bone graft.
According to the invention, the PLLA powder is coated by the polydopamine, the coated 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 through a 3D printing technology so as to endow the bone grafting bed with bioactivity. HA is introduced into PLLA by the bone grafting bed, the bioactivity of HA is fully exerted, and the bone grafting bed can form good bone bonding with bone tissues when being implanted into a body and can induce osteogenesis so as to repair bone defects. On the other hand, by wrapping polydopamine on the surface of the PLLA and generating HA in situ on the surface of the PLLA in a biomimetic mineralization mode, the problem of insufficient interface bonding between a high polymer material and a ceramic material can be solved, and the bone grafting bed is favorable for fully playing the mechanical property after being implanted to provide a supporting effect and realizing firm bonding with an adjacent vertebral body. The principle of the preparation method is that dopamine is subjected to self-polymerization reaction in an alkaline solution (pH = 8.5) to synthesize polydopamine-coated PLLA nanoparticles, and then a catechol group of the polydopamine is utilized to effectively chelate calcium ions in SBF, so that nucleation and crystallization of HA are promoted, and nano HA grows on the PLLA in situ. The dopamine is used as a bridging medium, and can be combined with PLLA through hydrogen bond action on one hand, and HA grows in situ due to chelation effect on the other hand, so that the perfect combination of a polymer matrix and a nano ceramic filling phase is finally realized.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (10)

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 stationary vane respectively, each all be provided with a plurality of nail hole pairs on the stationary vane, each the nail hole is to all matcing internally and is provided with self-tapping type cortical bone screw and self-tapping type 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 reticular main body and each fixed wing are both made of PLLA/HA composite powder through selective laser sintering.
2. The degradable bone grafting bed with the nano-ceramic endowed with bioactivity as claimed in claim 1, wherein a plurality of large holes and a plurality of small holes are symmetrically arranged on each connecting plate in a penetrating manner, the large holes and the small holes are staggered, the pore diameter of each large hole is 4-6mm, and the pore diameter of each small hole is 1-3mm.
3. The degradable bone graft bed with nano-ceramic endowed with bioactivity according to claim 1, wherein the connecting plates are hinged in a way that:
each the equal integrated into one piece protrusion in one side of connecting plate is provided with a plurality of first and connects protrudingly, each the equal integrated into one piece protrusion in opposite side of connecting plate is provided with a plurality of second and connects protrudingly, and is a plurality of second connect protrudingly and a plurality of first connect protruding crisscross setting, and is a plurality of first connect bellied intermediate position and adjacent a plurality of the bellied intermediate position is connected to the second and is articulated.
4. The degradable bone grafting bed with the nano-ceramic endowed with bioactivity according to claim 3, wherein a plurality of first limiting holes are symmetrically arranged around the middle position of each first connecting protrusion in a penetrating manner, a plurality of second limiting holes are symmetrically arranged around the middle position of each second connecting protrusion in a penetrating manner, and each first limiting hole corresponds to each second limiting hole; thread grooves are formed in the middle of the top end of each first connecting protrusion on the top, and each thread groove is communicated with each corresponding first limiting hole;
the limiting device comprises a plurality of limiting pieces and is characterized by further comprising limiting discs, a plurality of limiting rods are convexly arranged at the bottom ends of the limiting discs in an integrated mode, the limiting discs are sleeved at the bottoms of the thread grooves respectively, the limiting rods are connected with the corresponding first limiting holes and the second limiting holes in a sleeved mode respectively, limiting screws are further connected into the thread grooves in a threaded mode, and the bottom ends of the limiting screws are screwed through threads and abut against the top ends of the limiting discs.
5. The degradable bone grafting bed with the bioactivity endowed by the nano-ceramic as claimed in claim 4, wherein two fixing wings are respectively hinged with the connecting plates at two sides, and each fixing wing is respectively detachably connected with the connecting plate at each side through the limiting piece.
6. The method for preparing a bone graft bed according to any one of claims 1 to 5, comprising the steps of:
step one, coating dopamine on the surface of PLLA powder to obtain dopamine PLLA particles;
step two, soaking the dopamine PLLA particles in an SBF solution, and generating HA on the surface of the PLLA powder in situ when the dopamine on the surface of the dopamine PLLA particles fully reacts with the SBF solution, so as to form PLLA/HA composite particles;
separating the PLLA/HA composite particles from an SBF solution, centrifugally washing the PLLA/HA composite particles by using 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 electric heating air blowing drying box for drying treatment to obtain PLLA/HA composite powder;
and 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 with bioactivity endowed by the nano ceramic.
7. The method for preparing the degradable bone grafting bed which is endowed with the bioactivity by the nano-ceramic according to claim 6, is characterized in that the method for wrapping dopamine on the surface of the 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 a PLLA aqueous solution;
preparing a dopamine hydrochloride aqueous solution with the concentration of 2g/L, mixing 100mL of the dopamine hydrochloride aqueous solution with 50mL of the PLLA aqueous solution, and stirring at room temperature for 10-30 min to obtain a reaction solution;
and then heating the reaction solution, adding a certain amount of Tris solution when the temperature of the reaction solution rises to 40-60 ℃, adjusting the pH value of the reaction solution to about 8.5, stirring for reaction for 10-14 h to finally obtain a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the dopamine PLLA particles.
8. The method of claim 6, wherein the PLLA powder has a particle size of 40-60 μm and a melting point of 175-185 ℃.
9. The method for preparing a degradable bone graft bed with nano-ceramic endowed with bioactivity according to claim 6, wherein 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.
10. The method for preparing a degradable bone graft bed with nano-ceramic endowed with bioactivity according to claim 6, wherein 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 thickness of the powder layer is 0.1-0.2 mm, and the preheating temperature of the powder bed is 140-160 ℃.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 kind of titanium alloy bone grafting bed apparatus for centrum rear
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US20210045781A1 (en) * 2019-08-15 2021-02-18 Central South University Xiangya Hospital Internal fixation system of spine posterior screw-plate
CN114027959A (en) * 2021-11-30 2022-02-11 迪恩医疗科技有限公司 Hinge type vertebral lamina fixing plate
CN114376698A (en) * 2020-10-19 2022-04-22 江苏国立医疗器械有限公司 Adjustable bone fracture plate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 kind of titanium alloy bone grafting bed apparatus for centrum rear
CN111184916A (en) * 2018-11-15 2020-05-22 中南大学 Method for preparing hydroxyapatite/levorotatory polylactic acid composite bone scaffold
US20210045781A1 (en) * 2019-08-15 2021-02-18 Central South University Xiangya Hospital Internal fixation system of spine posterior screw-plate
CN114376698A (en) * 2020-10-19 2022-04-22 江苏国立医疗器械有限公司 Adjustable bone fracture plate
CN114027959A (en) * 2021-11-30 2022-02-11 迪恩医疗科技有限公司 Hinge type vertebral lamina fixing plate

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