CN115120782B - Biodegradable bone grafting bed for back of vertebral body - Google Patents

Biodegradable bone grafting bed for back of vertebral body Download PDF

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CN115120782B
CN115120782B CN202210937654.1A CN202210937654A CN115120782B CN 115120782 B CN115120782 B CN 115120782B CN 202210937654 A CN202210937654 A CN 202210937654A CN 115120782 B CN115120782 B CN 115120782B
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bone grafting
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CN115120782A (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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    • 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/34Macromolecular materials
    • 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
    • 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
    • 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
    • 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention discloses a biodegradable bone grafting bed for the back of a vertebral body, which comprises the following components: the device comprises a net-shaped main body and fixed wings arranged on two sides of the net-shaped main body, wherein the net-shaped main body and the fixed wings are formed by laser sintering; the net-shaped main body is semi-cylindrical, and a plurality of through holes which are regularly distributed are formed in the net-shaped main body. The invention solves the difficult problem that the effective and degradable bone grafting bed is lacking after the vertebral canal decompression operation. The bone grafting bed has good biocompatibility, the mechanical strength is matched with that of human bone, and the bone grafting bed can realize the full compaction of the bone grafting. And the implant can be naturally degraded, and degradation products are safe and nontoxic and can be absorbed by human bodies.

Description

Biodegradable bone grafting bed for back of vertebral body
Technical Field
The invention belongs to the technical field of medical materials, and particularly relates to a biodegradable bone grafting bed for the back of a vertebral body.
Background
Spinal canal stenosis is a disease that causes a series of nerve dysfunction such as pain, numbness, weakness of limbs, lameness, and dysuria by shortening the diameter of each line of the spinal canal, pressing the dura mater, spinal cord or nerve root. The spinal canal stenosis can be divided into central stenosis, side crypt stenosis and nerve root orifice stenosis according to anatomical parts; the cervical spinal stenosis, the lumbar spinal stenosis and the thoracic spinal stenosis are classified according to the parts. Because of the complex spinal physiological structure, some surgical complications may exist after spinal stenosis surgery, in the surgical treatment, a cutting mode is generally selected, and a nail plate is used for fixing after the surgery. Large bone defects can develop in the body during treatment, requiring the use of bone implants to repair the bone defect and fuse with the adjacent cone.
At present, bone defect repairing after spinal surgery vertebral canal decompression operation mostly adopts transverse process bone grafting fusion, a small amount of cancellous bone is implanted at the original vertebral plate position at the rear, and the bone grafting often cannot be fully compacted because the rear of the resected vertebral body is not supported, so that complete fusion is difficult to realize for the most critical rear vertebral plate position. Meanwhile, the vertebral canal stenosis operation often needs to cut vertebral plates behind a plurality of vertebral bodies, so that the difficulty of repairing bone defects is increased, if the bone defects cannot be completely repaired, the vertebral bodies cannot be completely fused, and the failure of postoperative rehabilitation can be caused. Bone grafting beds for repairing bone defects after spinal stenosis have become particularly important. Repair of bone defects after spinal stenosis often requires good bone grafting conditions: the bone grafting bed has good biological performance, meets the requirements of required osteoinduction, bone conduction and bone formation, and enables vertebral bodies to be completely fused; the bone grafting bed needs to have excellent mechanical properties, can provide strong support, and can fully press and fill the bone graft. In addition, most of the materials of the traditional bone grafting bed are non-degradable materials, so that the bone grafting bed can remain in the body for a long time and can cause secondary injury to the human body, and therefore the bone grafting bed also needs to be degradable.
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 graft bed for a rear of a vertebral body, comprising:
The device comprises a net-shaped main body and fixing wings arranged on two sides of the net-shaped main body, wherein the net-shaped main body and the fixing wings are formed by laser sintering;
the net-shaped main body is semi-cylindrical, and a plurality of through holes which are regularly distributed are formed in the net-shaped main body.
Preferably, the fixing wings are provided with symmetrically distributed screw holes, threads are arranged in the screw holes, and corresponding screws are arranged in the screw holes.
Preferably, the outer surface of the net-shaped main body is a frosted surface, and the inner surface is a smooth surface;
The outer surface of the fixed wing is a frosted spraying surface, and the inner surface is a bone-adhering spraying surface.
A method for preparing a biodegradable bone grafting bed for the back of a vertebral body, comprising the following steps:
Dispersing PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles;
Preparing a certain concentration of dopamine solution, mixing the dopamine solution with the PLLA particle aqueous suspension system obtained in the step one, stirring at room temperature, heating, adding a certain amount of Tris solution, regulating the pH value of the reaction solution, stirring for reaction, carrying out self-polymerization reaction on dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the PLLA particles wrapped by polydopamine;
Step three, soaking the PLLA particles wrapped by the polydopamine prepared in the step two in an SBF solution, fully reacting polydopamine on the surfaces of the PLLA particles wrapped by polydopamine with the SBF solution, soaking the PLLA particles in a constant-temperature water bath at 37 ℃ for a certain time, replacing the SBF solution once a day, and growing HA on the surfaces of the PLLA powder in situ to form PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging, then carrying out solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body.
Preferably, in the first step, the mass concentration of PLLA powder in deionized water is 0.5-1 g/L, the ultrasonic power during ultrasonic treatment is 500-1000W, and the ultrasonic time is 20-40 min.
Preferably, in the second step, the concentration of the dopamine solution is 1-3 g/L, the volume ratio of the dopamine solution to the PLLA particle water suspension system is 1-2:1-2, the mixture is stirred at room temperature for 10-30 min, the temperature of the reaction solution is 40-60 ℃, the stirring reaction time for synthesizing the polydopamine coated PLLA particles is 8-14 h, and the pH value of the reaction solution is adjusted to 8.5.
Preferably, in the third step, the soaking time of the polydopamine-coated PLLA particles in the SBF solution is 1-5 days, the solid-liquid volume ratio of the polydopamine-coated PLLA particles to the SBF solution is 1-2:1-2, and the SBF solution adopts different multiples, namely 1.5x,2x,2.5x and 3x.
Preferably, in the fourth step, the centrifugal speed is 3000-6000 r/min, the drying temperature is 60 ℃, and the heat preservation time is 24h.
Preferably, in the fifth step, the process parameters of the selective laser sintering are as follows: the laser power is 1-3W, the scanning speed is 100-200 mm/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 ℃.
Preferably, before the PLLA powder is dispersed in deionized water, polyvinyl alcohol and sodium dodecyl sulfate are used to modify the PLLA powder, and the modification method is as follows: 1.2 to 8 parts of polyvinyl alcohol are weighed according to parts by weight and dissolved in deionized water to obtain 0.5 to 1.5g/L of polyvinyl alcohol solution, 20 to 30 parts of PLLA powder is added into the polyvinyl alcohol solution, ultrasonic dispersion is carried out for 10 to 20 minutes, ultrasonic power is 500 to 800W, mixed slurry is obtained, the temperature of the mixed slurry is raised to 50 to 65 ℃, and heat preservation is carried out for 20 to 60 minutes; and cooling the mixed slurry to room temperature, adding 0.6-4 parts of sodium dodecyl sulfate, carrying out ultrasonic treatment for 1-1.6 h, carrying out ultrasonic power of 600-1000W, standing for 4-8 h, carrying out solid-liquid separation, washing and drying the solid, and thus obtaining the modified PLLA powder.
The invention at least comprises the following beneficial effects: the invention solves the difficult problem that the effective and degradable bone grafting bed is lacking after the vertebral canal decompression operation. The bone grafting bed has good biocompatibility, the mechanical strength is matched with that of human bone, and the bone grafting bed can realize the full compaction of the bone grafting. And the implant can be naturally degraded, and degradation products are safe and nontoxic and can be absorbed by human bodies.
Before preparing the poly-dopamine-coated PLLA (L-polylactic acid) particles, the poly-dopamine-coated PLLA particles are modified by using polyvinyl alcohol and sodium dodecyl sulfate, so that the interfacial force between the poly-dopamine and the PLLA particles is obviously enhanced, the compactness and stability of the poly-dopamine-coated PLLA particles are improved, and when hydroxyapatite powder (HA powder) grows on the surfaces of the poly-dopamine-coated PLLA particles in situ, the combination is more compact, the mechanical property of the PLLA/HA composite degradable bone grafting bed is further improved, and the prepared PLLA/HA composite degradable bone grafting bed HAs high toughness and compression strength while having degradability and good biocompatibility.
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 view of the structure of a biodegradable bone grafting bed for the rear of a vertebral body according to 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.
Example 1
As shown in fig. 1: the present embodiment provides a biodegradable bone graft bed for the rear of a vertebral body, comprising:
the net-shaped main body 1 and the fixed wings 3 arranged on two sides of the net-shaped main body 1 are formed by sintering the net-shaped main body 1 and the fixed wings 3 by laser;
The net-shaped main body 1 is semi-cylindrical, and a plurality of through holes 2 which are regularly arranged are arranged on the net-shaped main body 1.
The fixing wings 3 are provided with symmetrically distributed screw holes 4, threads are arranged in the screw holes 1, and corresponding screws 5 are arranged in the screw holes 4.
The outer surface of the net-shaped main body is a frosted surface, and the inner surface of the net-shaped main body is a smooth surface;
The outer surface of the fixed wing is a frosted spraying surface, and the inner surface is a bone-adhering spraying surface.
The application process of the invention comprises the steps of customizing a proper PLLA/HA composite degradable bone grafting bed according to the actual condition of a patient, fixing the PLLA/HA composite degradable bone grafting bed behind a pathological cone after a vertebral canal decompression operation, repairing bone defects, and fixing the PLLA/HA composite degradable bone grafting bed by using screws 5 according to the specific fitting positions of fixing wings 3. The plurality of through holes 2 arranged on the reticular main body lighten the whole weight of the bone grafting bed on the basis of ensuring the mechanical strength of the PLLA/HA composite degradable bone grafting bed, and simultaneously, enough gaps are reserved to fully combine the epidural blood and the bone grafting, thereby playing the best osteogenesis effect. The PLLA/HA composite degradable bone grafting bed provided by the embodiment is used for repairing bone defects generated after a vertebral stenosis operation. The bone grafting bed is prepared by using PLLA/HA composite material, and the PLLA/HA composite material is prepared by adopting a method of growing HA powder on the surface of PLLA particles wrapped by polydopamine in situ. As a biomedical polymer material, PLLA HAs good biocompatibility, can realize natural degradation in vivo, can be completely absorbed by human body, is safe and nontoxic to human body, and HAs HA as a main component of human bone, thereby promoting and guiding bone regeneration. The bone grafting bed made of PLLA/HA composite degradable material can be naturally degraded in human body, can not hurt human body, can promote the regeneration of guided bone, and can avoid secondary injury caused by the implantation of non-degradable bone implant. Structurally, the inner surface of the bone grafting bed is provided with a smooth surface, adhesion with the dura mater sac can be avoided, and the outer surface of the bone grafting bed is provided with a frosted surface, so that the bone grafting bed can be better compatible with the bone grafting. The inner and outer surfaces of the fixed wing parts are designed by adopting a spraying structure, so that the fixed wing parts can be better attached to bone tissues.
The preparation method of the biodegradable bone grafting bed for the back of the vertebral body provided by the embodiment comprises the following steps:
Dispersing PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles with the concentration of 0.5g/L, wherein the ultrasonic power is 500W, and the ultrasonic time is 20min;
Preparing a dopamine solution with the concentration of 2g/L, weighing 100mL of the dopamine solution, mixing with 50mL of the PLLA particle aqueous suspension system obtained in the step one, stirring at room temperature for 10min, heating to 40 ℃, adding a certain amount of Tris solution, adjusting the pH value of the reaction solution to 8.5, stirring and reacting for 8h, carrying out self-polymerization reaction on dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain PLLA particles wrapped by polydopamine;
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 0.2g PLLA particles coated with polydopamine prepared in the step two in the SBF solution according to the solid-liquid volume ratio of 10%, placing in a constant-temperature water bath at 37 ℃ for 1 day, replacing the SBF solution once every day, and fully reacting polydopamine coated with the PLLA particles with the SBF solution until HA grows in situ on the surface of PLLA powder, thereby forming PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging at a centrifugal speed of 3000r/min, performing solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder, wherein the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body. The technological parameters of selective laser sintering are as follows: the laser power is 1.8W, the scanning speed is 120mm/s, the scanning interval is 1mm, the spot diameter is 0.3mm, the thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 150 ℃.
The mechanical property test shows that the compression strength and the modulus of the PLLA sample are 25.2MPa and 2.4GPa respectively; the PLLA/HA samples prepared in this example had compressive strengths and moduli of 36.8MPa and 3.5GPa, respectively.
Example 2
The structure of the biodegradable bone grafting bed for the rear of the vertebral body provided in this example is the same as that of example 1.
The preparation method of the biodegradable bone grafting bed for the back of the vertebral body provided by the embodiment comprises the following steps:
Dispersing PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles with the concentration of 0.5g/L, wherein the ultrasonic power is 500W, and the ultrasonic time is 20min;
Preparing a dopamine solution with the concentration of 2g/L, weighing 100mL of the dopamine solution, mixing with 50mL of the PLLA particle aqueous suspension system obtained in the step one, stirring for 50min at room temperature, heating to 40 ℃, adding a certain amount of Tris solution, adjusting the pH value of the reaction solution to 8.5, stirring for reacting for 12h, carrying out self-polymerization reaction on the dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the PLLA particles wrapped by polydopamine;
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 0.2 g PLLA particles coated with polydopamine prepared in the step two in the SBF solution according to the solid-liquid volume ratio of 10%, placing in a constant-temperature water bath at 37 ℃ for 1 day, replacing the SBF solution once every day, and fully reacting polydopamine coated with polydopamine on the surfaces of the PLLA particles with the SBF solution to grow HA on the surfaces of PLLA powder in situ so as to form PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging at a centrifugal speed of 5000r/min, performing solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder, wherein the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body. The technological parameters of selective laser sintering are as follows: the laser power is 1.8W, the scanning speed is 120mm/s, the scanning interval is 1mm, the spot diameter is 0.3mm, the thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 150 ℃.
The test of mechanical properties shows that the compressive strength and modulus of the PLLA/HA sample prepared by the embodiment are 38.8MPa and 3.6GPa respectively.
Example 3
The structure of the biodegradable bone grafting bed for the rear of the vertebral body provided in this example is the same as that of example 1.
Dispersing PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles with the concentration of 0.5g/L, wherein the ultrasonic power is 500W, and the ultrasonic time is 20min;
Preparing a dopamine solution with the concentration of 2g/L, weighing 100mL of the dopamine solution, mixing with 50mL of the PLLA particle aqueous suspension system obtained in the step one, stirring at room temperature for 10min, heating to 40 ℃, adding a certain amount of Tris solution, adjusting the pH value of the reaction solution to 8.5, stirring and reacting for 8h, carrying out self-polymerization reaction on dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain PLLA particles wrapped by polydopamine;
Preparing 2.5x 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 0.2g PLLA particles coated with polydopamine prepared in the step two in the SBF solution according to the solid-liquid volume ratio of 10%, placing in a constant-temperature water bath at 37 ℃ for 1 day, replacing the SBF solution once every day, and fully reacting polydopamine coated with the PLLA particles with the SBF solution until HA grows in situ on the surface of PLLA powder, thereby forming PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging at a centrifugal speed of 3000r/min, performing solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder, wherein the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body. The technological parameters of selective laser sintering are as follows: the laser power is 1.8W, the scanning speed is 120mm/s, the scanning interval is 1mm, the spot diameter is 0.3mm, the thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 150 ℃.
The test of mechanical properties shows that the compressive strength and modulus of the PLLA/HA sample prepared by the embodiment are respectively 40.3MPa and 3.9GPa.
Example 4
The structure of the biodegradable bone grafting bed for the rear of the vertebral body provided in this example is the same as that of example 1.
The preparation method of the biodegradable bone grafting bed for the back of the vertebral body provided by the embodiment comprises the following steps:
Step one, modifying PLLA powder by using polyvinyl alcohol and sodium dodecyl sulfate, wherein the modification method comprises the following steps: weighing 5g of polyvinyl alcohol according to parts by weight, dissolving in deionized water to obtain 0.5g/L of polyvinyl alcohol solution, adding 20g of PLLA powder into the polyvinyl alcohol solution, performing ultrasonic dispersion for 10min, obtaining mixed slurry with ultrasonic power of 500W, heating the mixed slurry to 50 ℃, and preserving heat for 20min; cooling the mixed slurry to room temperature, adding 1g of sodium dodecyl sulfate, carrying out ultrasonic treatment for 1h with ultrasonic power of 600W, standing for 4h for reaction, carrying out solid-liquid separation, washing and drying the solid to obtain modified PLLA powder; dispersing the modified PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles with the concentration of 0.5g/L, wherein the ultrasonic power is 500W, and the ultrasonic time is 20min;
Preparing a dopamine solution with the concentration of 2g/L, weighing 100mL of the dopamine solution, mixing with 50mL of the PLLA particle aqueous suspension system obtained in the step one, stirring for 50min at room temperature, heating to 40 ℃, adding a certain amount of Tris solution, adjusting the pH value of the reaction solution to 8.5, stirring for reacting for 12h, carrying out self-polymerization reaction on the dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the PLLA particles wrapped by polydopamine;
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 0.2 g PLLA particles coated with polydopamine prepared in the step two in the SBF solution according to the solid-liquid volume ratio of 10%, placing in a constant-temperature water bath at 37 ℃ for 1 day, replacing the SBF solution once every day, and fully reacting polydopamine coated with polydopamine on the surfaces of the PLLA particles with the SBF solution to grow HA on the surfaces of PLLA powder in situ so as to form PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging at a centrifugal speed of 5000r/min, performing solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder, wherein the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body. The technological parameters of selective laser sintering are as follows: the laser power is 1.8W, the scanning speed is 120mm/s, the scanning interval is 1mm, the spot diameter is 0.3mm, the thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 150 ℃.
The mechanical property test shows that the compression strength and the modulus of the PLLA/HA sample prepared in the embodiment are respectively 60.3MPa and 4.1GPa, and compared with the PLLA/HA sample prepared in the embodiment 2, the compression strength is improved by more than 55.5%.
Example 5
The structure of the biodegradable bone grafting bed for the rear of the vertebral body provided in this example is the same as that of example 1.
The preparation method of the biodegradable bone grafting bed for the back of the vertebral body provided by the embodiment comprises the following steps:
Step one, modifying PLLA powder by using polyvinyl alcohol and sodium dodecyl sulfate, wherein the modification method comprises the following steps: weighing 8g of polyvinyl alcohol according to parts by weight, dissolving in deionized water to obtain 1.5g/L of polyvinyl alcohol solution, adding 30g of PLLA powder into the polyvinyl alcohol solution, performing ultrasonic dispersion for 20min, obtaining mixed slurry with ultrasonic power of 800W, heating the mixed slurry to 65 ℃, and preserving heat for 60min; cooling the mixed slurry to room temperature, adding 4g of sodium dodecyl sulfate, performing ultrasonic treatment for 1.6h with ultrasonic power of 1000W, standing for 8h, performing solid-liquid separation, washing and drying the solid to obtain modified PLLA powder; dispersing the modified PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles with the concentration of 0.5g/L, wherein the ultrasonic power is 500W, and the ultrasonic time is 20min;
Preparing a dopamine solution with the concentration of 2g/L, weighing 100mL of the dopamine solution, mixing with 50mL of the PLLA particle aqueous suspension system obtained in the step one, stirring at room temperature for 10min, heating to 40 ℃, adding a certain amount of Tris solution, adjusting the pH value of the reaction solution to 8.5, stirring and reacting for 8h, carrying out self-polymerization reaction on dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain PLLA particles wrapped by polydopamine;
Preparing 2.5x 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 0.2g PLLA particles coated with polydopamine prepared in the step two in the SBF solution according to the solid-liquid volume ratio of 10%, placing in a constant-temperature water bath at 37 ℃ for 1 day, replacing the SBF solution once every day, and fully reacting polydopamine coated with the PLLA particles with the SBF solution until HA grows in situ on the surface of PLLA powder, thereby forming PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging at a centrifugal speed of 3000r/min, performing solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder, wherein the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
And fifthly, placing the PLLA/HA composite powder in a selective laser sintering system, sintering layer by layer according to the three-dimensional model, and removing the unsintered model after sintering to obtain the biodegradable bone grafting bed for the rear of the vertebral body. The technological parameters of selective laser sintering are as follows: the laser power is 1.8W, the scanning speed is 120mm/s, the scanning interval is 1mm, the spot diameter is 0.3mm, the thickness of the powder layer is 0.1mm, and the preheating temperature of the powder bed is 150 ℃.
The mechanical property test shows that the compression strength and the modulus of the PLLA/HA sample prepared by the embodiment are respectively 62.7MPa and 4.3GPa, and compared with the PLLA/HA sample prepared by the embodiment 3, the compression strength is improved by more than 55.6%.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
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 (1)

1. A method for preparing a biodegradable bone grafting bed for the back of a vertebral body, which is characterized by comprising the following steps:
Dispersing PLLA powder in deionized water, and performing ultrasonic treatment to obtain an aqueous suspension system of PLLA particles;
Preparing a certain concentration of dopamine solution, mixing the dopamine solution with the PLLA particle aqueous suspension system obtained in the step one, stirring at room temperature, heating, adding a certain amount of Tris solution, regulating the pH value of the reaction solution, stirring for reaction, carrying out self-polymerization reaction on dopamine in the Tris solution, finally obtaining a uniform solution, and then carrying out high-speed centrifugal washing and drying to obtain the PLLA particles wrapped by polydopamine;
Step three, soaking the PLLA particles wrapped by the polydopamine prepared in the step two in an SBF solution, fully reacting polydopamine on the surfaces of the PLLA particles wrapped by polydopamine with the SBF solution, soaking the PLLA particles in a constant-temperature water bath at 37 ℃ for a certain time, replacing the SBF solution once a day, and growing HA on the surfaces of the PLLA powder in situ to form PLLA/HA composite powder;
Step four, separating the PLLA/HA composite powder obtained in the step three from SBF solution, washing with deionized water, centrifuging, then carrying out solid-liquid separation to collect powder, and drying in an electrothermal blowing drying oven to obtain PLLA/HA composite powder;
Step five, placing 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 biodegradable bone grafting bed for the rear of the vertebral body;
Before PLLA powder is dispersed in deionized water, polyvinyl alcohol and sodium dodecyl sulfate are used for modifying the PLLA powder, and the modification method comprises the following steps: 1.2-8 parts of polyvinyl alcohol are weighed according to parts by weight and dissolved in deionized water to obtain 0.5-1.5 g/L of polyvinyl alcohol solution, 20-30 parts of PLLA powder is added into the polyvinyl alcohol solution, ultrasonic dispersion is carried out for 10-20 min, ultrasonic power is 500-800W, mixed slurry is obtained, the temperature of the mixed slurry is raised to 50-65 ℃, and heat preservation is carried out for 20-60 min; cooling the mixed slurry to room temperature, adding 0.6-4 parts of sodium dodecyl sulfate into the mixed slurry, carrying out ultrasonic treatment for 1-1.6 hours, carrying out standing reaction for 4-8 hours at the ultrasonic power of 600-1000W, carrying out solid-liquid separation, and washing and drying solids to obtain modified PLLA powder;
The structure of the biodegradable bone grafting bed for the back of the vertebral body comprises a reticular main body and fixing wings arranged at two sides of the reticular main body, wherein the reticular main body and the fixing wings are formed by laser sintering;
the net-shaped main body is semi-cylindrical, and a plurality of through holes which are regularly arranged are formed in the net-shaped main body;
symmetrically distributed screw holes are formed in the fixing wings, threads are arranged in the screw holes, and screws corresponding to the screw holes are arranged in the screw holes;
The outer surface of the net-shaped main body is a frosted surface, and the inner surface of the net-shaped main body is a smooth surface;
the outer surface of the fixed wing is a frosted spraying surface, and the inner surface is a bone-adhering spraying surface;
In the first step, the mass concentration of PLLA powder in deionized water is 0.5-1 g/L, the ultrasonic power during ultrasonic treatment is 500-1000W, and the ultrasonic time is 20-40 min;
In the second step, the concentration of the dopamine solution is 1-3 g/L, the volume ratio of the dopamine solution to the PLLA particle water suspension system is 1-2:1-2, the mixture is stirred at room temperature for 10-30 min, the temperature rise temperature of the reaction solution is 40-60 ℃, the stirring reaction time for synthesizing the PLLA particles coated with polydopamine is 8-14 h, and the pH value of the reaction solution is regulated to 8.5;
In the third step, the soaking time of the polydopamine-coated PLLA particles in the SBF solution is 1-5 days, the solid-liquid volume ratio of the polydopamine-coated PLLA particles to the SBF solution is 1-2:1-2, and the SBF solution adopts different multiples, namely 1.5x,2x,2.5x and 3x;
in the fourth step, the centrifugal rotating speed is 3000-6000 r/min, the drying temperature is 60 ℃, and the heat preservation time is 24 hours;
In the fifth step, the technological parameters of selective laser sintering are as follows: the laser power is 1-3W, the scanning speed is 100-200 mm/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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