CN114618014A - Bone repair scaffold and preparation method thereof - Google Patents
Bone repair scaffold and preparation method thereof Download PDFInfo
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- CN114618014A CN114618014A CN202011464578.4A CN202011464578A CN114618014A CN 114618014 A CN114618014 A CN 114618014A CN 202011464578 A CN202011464578 A CN 202011464578A CN 114618014 A CN114618014 A CN 114618014A
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- bone repair
- repair scaffold
- shape memory
- memory polyurethane
- bone
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Abstract
The invention provides a bone repair bracket, which is made of shape memory polyurethane and metal magnesium, wherein the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (1-10). The preparation method of the bone repair scaffold comprises the following steps: dissolving shape memory polyurethane in an organic solvent, adding metal magnesium, and stirring and mixing to obtain a printing precursor solution; obtaining a support blank by the printing precursor liquid through a 3D printing process; and freeze-drying the support embryo body to obtain the bone repair support. According to the bone repair scaffold provided by the invention, the mechanical strength of the bone repair scaffold is improved by adding the metal magnesium, and the bone repair scaffold has good bone regeneration promoting performance; the preparation method of the bone repair scaffold has the advantages of simple process flow and easy industrial implementation, and has wide applicability.
Description
Technical Field
The invention belongs to the technical field of biomedicine, and particularly relates to a bone repair stent and a preparation method thereof.
Background
The repair of wide-range bone defects caused by fractures, wounds, etc. has long been one of the most interesting problems in the field of public health. In order to solve the limitation of autologous bone grafting, bone tissue engineering has been continuously developed in recent years. Bone repair scaffolds have been given much attention as an important means for internal fixation of bone defects due to bone fracture, osteoporosis, etc., and when a bone defect occurs, the decrease in bone mass directly affects the stability and holding force of the fixture. The traditional scaffold material is a three-dimensional scaffold with certain stability, such as a rectangle, a cube, a cylinder and the like, so that a stable new tissue growth space is formed after the traditional scaffold material is implanted into a body, but many bone defects are irregular defects clinically, and the defect space is difficult to completely repair by using a shape-fixed material. In addition, at present, a plurality of surgical schemes are clinically pursued for minimally invasive treatment, and the traditional stent material is difficult to implement.
In recent years, with the rapid development of medical technology and material technology, more polymer materials are applied to bone repair and the manufacture of bone repair scaffolds, and a better fixation and repair effect is achieved. Compared with metal internal fixation, it is the most clinically attractive that the high molecular material has excellent biocompatibility so as not to cause secondary infection and the like. However, for the common bone defect internal fixation made of polymer materials, the weak mechanical property limits the wide application of the bone defect internal fixation. According to the article published by Rezwan, Kurosh et al in 2006 (Biomaterials 27.18(2006):3413-3431), there is a problem of insufficient mechanical properties in the bone scaffold product of a high molecular polymer that is degradable in vivo.
The shape memory polymer is used as an intelligent medical material with biocompatibility and a shape memory function, the material can be deformed and compressed to a smaller size as required, and the original shape can be recovered in a specific environment after the shape memory polymer is implanted into a human body. How to improve the mechanical property of the bone repair scaffold made of the shape memory polymer is a problem to be solved in the industry.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a bone repair scaffold and a preparation method thereof, and aims to solve the problem that the existing shape memory polymer bone repair scaffold is poor in mechanical property.
In order to achieve the purpose, the invention provides a bone repair scaffold, wherein the bone repair scaffold is made of shape memory polyurethane and metal magnesium, and the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (1-10).
Preferably, the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (3-5).
Preferably, the particle size of the metal magnesium is 40-100 μm.
More preferably, the metallic magnesium has a particle size of 50 to 80 μm.
Preferably, the shape memory polyurethane is formed by reacting the following raw material components based on 100% of the mass of the shape memory polyurethane: 23.0 to 25.0 percent of diphenylmethane diisocyanate, 7.0 to 8.0 percent of chain extender and 67.0 to 70.0 percent of polycaprolactone diol.
Preferably, the ratio of isocyanate groups contained in the diphenylmethane diisocyanate to hydroxyl groups of all the raw materials participating in the reaction is (1.0-1.2): 1.
Preferably, the chain extender is selected from any one of 1, 4-butanediol, 1, 6-hexanediol and ethylene glycol.
Preferably, the number average molecular weight of the polycaprolactone diol is 3000-8000.
Another aspect of the present invention is to provide a method for preparing a bone repair scaffold as described above, which comprises:
dissolving shape memory polyurethane in an organic solvent, adding metal magnesium, and stirring and mixing to obtain a printing precursor solution;
obtaining a support blank by the printing precursor liquid through a 3D printing process;
and freeze-drying the support embryo body to obtain the bone repair support.
Preferably, the printing speed in the 3D printing process is 0.1-1.5 mm/s, and the temperature of a printing nozzle is 10-20 ℃; the temperature of the freeze drying is-80 ℃ to-70 ℃, and the time is 48h to 72 h.
The bone repair scaffold provided by the embodiment of the invention comprises Shape Memory Polyurethane (SMPU) and magnesium metal (Mg), and has the following beneficial effects by adding the magnesium metal: (1) the mechanical strength of the bone repair bracket is improved; (2) the magnesium ions can stimulate the sensory nerve terminals in the natural periosteum so as to release more neurotransmitters, and further promote the osteogenic differentiation of stem cells in the periosteum, so that the bone repair scaffold has good bone regeneration promoting performance; (3) magnesium has a photothermal effect, and under the irradiation of near infrared light, magnesium in the composite material converts light energy into heat energy, activates a thermal response mechanism of SMPU, realizes shape recovery in vivo, and provides feasibility for realizing remote stimulation-response regulation and control for the bone repair scaffold.
The preparation method of the bone repair scaffold provided by the embodiment of the invention is used for quickly forming the bone repair scaffold under a low-temperature condition through a 3D printing process, the morphology structure of the bone repair scaffold can be variously controlled, and the porous scaffold with controllable and uniform pore diameter can be prepared and formed.
Drawings
FIG. 1 is a graph illustrating photothermal effects of a bone repair scaffold in an embodiment of the present invention;
FIG. 2 is a graph of a test for stress-strain of a bone repair scaffold in an embodiment of the present invention;
FIG. 3 is a graph of a test of shape memory performance of a bone repair scaffold in an embodiment of the present invention;
fig. 4 is a graph of cell viability staining of a bone repair scaffold in an example of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a bone repair scaffold, wherein the bone repair scaffold is made of Shape Memory Polyurethane (SMPU) and magnesium metal (Mg), and the mass ratio of the shape memory polyurethane to the magnesium metal is 100 (1-10).
The material of the bone repair bracket is formed by adding metal magnesium into the shape memory polyurethane, so that the mechanical strength of the bone repair bracket is improved firstly; secondly, the magnesium ions can stimulate the sensory nerve terminals in the natural periosteum so as to release more neurotransmitters, further promote the osteogenic differentiation of stem cells in the periosteum, so that the bone repair scaffold has good bone regeneration promoting performance; and thirdly, the magnesium has a photothermal effect, and under the irradiation of near infrared light, the magnesium in the composite material converts the light energy into heat energy, so that the thermal response mechanism of the SMPU is activated, the shape recovery is realized in vivo, and the feasibility of realizing remote stimulation-response regulation and control is provided for the bone repair scaffold.
In a preferable scheme, the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (3-5). More preferably, the mass ratio of the two is selected to be 100: 4.
In a preferred embodiment, the metal magnesium has a particle size of 40 to 100 μm. In a more preferable scheme, the particle size of the metal magnesium is 50-80 μm, the metal magnesium in a more particle size range is more easily dispersed in the shape memory polyurethane, and the molded bone repair scaffold has higher mechanical strength.
In a preferred scheme, the shape memory polyurethane is formed by reacting the following raw material components based on 100% of the mass of the shape memory polyurethane: 23.0 to 25.0 percent of diphenylmethane diisocyanate, 7.0 to 8.0 percent of chain extender and 67.0 to 70.0 percent of polycaprolactone diol.
Wherein the ratio of isocyanate groups contained in the diphenylmethane diisocyanate to hydroxyl groups of all the raw materials participating in the reaction is (1.0-1.2): 1, and preferably 1: 1.
Wherein the chain extender is selected from any one of 1, 4-butanediol, 1, 6-hexanediol and ethylene glycol, and 1, 4-butanediol is preferably used.
Wherein the number average molecular weight of the polycaprolactone diol is 3000-8000, and preferably 5000.
The embodiment of the invention also provides a preparation method of the bone repair scaffold, which comprises the following steps:
step one, dissolving shape memory polyurethane in an organic solvent, adding metal magnesium, and stirring and mixing to obtain a printing precursor solution.
In a preferred scheme, the shape memory polyurethane is prepared by the following process:
(1) and respectively placing the diphenylmethane diisocyanate, the chain extender and the polycaprolactone diol in a vacuum drying oven for drying for a certain time to completely remove moisture. The specific drying process conditions are, for example: drying at 105 deg.C in vacuum environment for more than 2 hr.
(2) Mixing and stirring the dried diphenylmethane diisocyanate, the chain extender and the polycaprolactone diol according to a predetermined proportion, heating to the reaction temperature, and continuously stirring. The specific drying process conditions are, for example: the temperature is increased to 85 ℃, the reaction temperature is kept at 85 ℃, the stirring speed is set to be 150rmp/min, and the stirring time is set to be 5 min.
(3) And after stirring, quickly pouring the reaction mixture into a polytetrafluoroethylene mold, and putting the polytetrafluoroethylene mold into an oven for curing to obtain an SMPU solid. Specifically, the temperature of the oven can be set to 85 ℃ and the curing time is 16 h.
In a more preferred embodiment, the ratio of the isocyanate groups contained in diphenylmethane diisocyanate (MDI) to the hydroxyl groups of all the starting materials involved in the reaction is 1:1, the chain extender (BDO) is selected to be 1, 4-butanediol, and the number average molecular weight of the polycaprolactone diol (PCL-diol) is 5000. Wherein, PCL-diol forms the soft segment of SMPU, BDO and MDI form the hard segment of SMPU. The reaction formula is as follows:
In a preferable scheme, the organic solvent is preferably a mixed solvent of 1, 4-dioxane and dimethyl sulfoxide, the volume ratio of the 1, 4-dioxane to the dimethyl sulfoxide is preferably 5:1, metal magnesium is added after the shape memory polyurethane is completely dissolved in the mixed solvent, and the quality of the added metal magnesium is controlled so that the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (1-10), preferably 100 (3-5), and most preferably 100: 4.
And step two, obtaining a support blank by the printing precursor liquid through a 3D printing process.
Specifically, the printing apparatus is preferably a low temperature rapid prototyping (LT-RP) printer, the printing speed may be set to 0.1mm/s to 1.5mm/s, and the temperature of the printing head may be set to 10 ℃ to 20 ℃. In a preferred scheme, the printing speed is 0.2mm/s, and the temperature of the printing nozzle is 12 ℃.
And step three, freeze-drying the support embryonic body to obtain the bone repair support.
Wherein the temperature of the freeze drying is-80 ℃ to-70 ℃, and the time is 48h to 72 h.
The preparation method of the bone repair scaffold provided by the embodiment is used for quickly forming the bone repair scaffold under a low-temperature condition through a 3D printing process, the morphology and the structure of the bone repair scaffold can be variously controlled, the porous scaffold with controllable and uniform pore diameter can be prepared, and the preparation method has the advantages of simple process flow, limitation of easy industrial implementation and wide applicability.
When the bone repair stent provided by the embodiment of the invention is used, deformation compression treatment is carried out at 55-65 ℃, standing, cooling and shaping are carried out at room temperature, the bone repair stent is implanted into a bone defect part through an operation, and then the bone repair stent is irradiated by near infrared light (the wavelength is 808nm, and the power density range is P-0.5 w/cm)2～2w/cm2The power density is preferably 1w/cm2) The bone repair scaffold is gradually restored to a natural state, and further fixes and supports the bone defect site and promotes the growth and healing of bone tissues.
Example 1
(1) And drying the PCL-diol, MDI and BDO in a vacuum drying oven in a vacuum environment at 105 ℃ for more than 2 hours to completely remove the water.
(2) After the drying is finished, mixing and stirring the PCL-diol, the MDI and the BDO according to the proportion, keeping the reaction temperature at 85 ℃, and stirring at the speed of 150rmp/min for 5 min.
(3) And after stirring, quickly pouring the mixture into a polytetrafluoroethylene mold, putting the polytetrafluoroethylene mold into an oven for curing for 16 hours, and keeping the temperature at 85 ℃ to obtain the SMPU solid.
(4) Stirring and dissolving the prepared SMPU by using a mixed solution of 1, 4-dioxane and dimethyl sulfoxide (the volume ratio is 5:1), adding metal Mg after the SMPU is completely dissolved, and uniformly mixing to prepare a printing liquid. The metal Mg added in this example makes the mass percentage of Mg relative to SMPU 2%, i.e., the mass ratio of SMPU to Mg is 100: 2.
(5) And (3) performing 3D printing on the printing liquid obtained in the step (4) by using an LT-RP printer, wherein the filling speed of a nozzle is 0.2mm/s, and the temperature of the nozzle is 12 ℃.
(6) And after printing, carrying out freeze drying at-80 ℃ for 2 days to obtain the SMPU composite bone repair scaffold sample S-1 with the shape memory function.
Example 2
This example is different from example 1 in that the metal Mg added in step (4) of example 1 is such that the mass percentage of Mg with respect to SMPU is 4%, that is, the mass ratio of SMPU to Mg is 100:4, and the rest of the process is the same as that of example 1. This example prepares a bone repair scaffold sample S-2.
Example 3
This example is different from example 1 in that the metal Mg added in step (4) of example 1 is such that the mass percentage of Mg with respect to SMPU is 6%, i.e., the mass ratio of SMPU to Mg is 100:6, and the rest of the process is the same as that of example 1. This example prepares a bone repair scaffold sample S-3.
Example 4
This example is different from example 1 in that the metal Mg added in step (4) of example 1 is such that the mass percentage of Mg with respect to SMPU is 8%, i.e., the mass ratio of SMPU to Mg is 100:8, and the rest of the process is the same as that of example 1. This example prepares a bone repair scaffold sample S-4.
Comparative example
The comparative example is different from examples 1 to 4 in that Mg was not added in step (4), that is, the Mg content was 0%, and the rest of the process was the same as in examples 1 to 4. Comparative example preparation of bone repair scaffold sample S-0 was obtained.
The raw materials and their amounts used in the comparative and examples 1-4 are shown in the following table:
examples 1-4 and comparative examples bone repair scaffoldsPhotothermal effect testing of the racks is shown in figure 1. Wherein the wavelength of the irradiated near infrared light is 808nm, and the power density is 1w/cm2. The samples of the comparative examples have substantially no temperature rise, the temperature of the samples of examples 1-4 all increase with increasing irradiation time, the temperature of the sample of example 4 rises relatively fastest, the rise is greatest, and the photothermal effect is best.
Stress-strain testing of bone repair scaffolds obtained in examples 1-4 and comparative example are shown in fig. 2. The sample of example 4 had the greatest compressive strength, while the samples of example 2 and example 3 had the same compressive strength.
The bone repair scaffolds obtained in examples 1-4 and comparative example were subjected to near infrared light (wavelength of 808nm, power density of 1 w/cm)2) Shape memory performance under illumination is shown in figure 3. The fixation rate of the comparative example was high, but there was almost no recovery. In the samples of examples 1 to 4, the shape fixation rate of the samples was increasing with the increase in the Mg content, but the recovery rate was decreasing.
The cytocompatibility of the bone repair scaffolds obtained in examples 1-4 and comparative example is compared with that of the scaffold obtained in comparative example, see FIG. 4. Compared to the live and dead staining of the blank cells (no sample) and the comparative examples, the cells of examples 1-4 had a more significant number of live cells, with more live cells indicating better sample cytocompatibility, and the number of dead cells (middle column of images) in the comparative examples and examples was also very small, indicating better cytocompatibility of the samples of examples 1-4.
In combination with the above test results, the sample in example 2 has the most balanced photothermal effect, mechanical strength, shape memory property and biocompatibility, and therefore, in the composite bone repair scaffold provided by the embodiment of the present invention, the mass ratio of SMPU to Mg is preferably 100 (3-5), and most preferably 100: 4.
According to the bone repair scaffold provided by the invention, the mechanical strength of the bone repair scaffold is improved by adding the metal magnesium, the bone repair scaffold has good bone regeneration promoting performance, and the feasibility of realizing remote stimulation-response regulation and control can be provided for the bone repair scaffold by utilizing the photothermal effect of the magnesium; the preparation method of the bone repair scaffold has the advantages of simple process flow and easy industrial implementation, and has wide applicability.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. The bone repair scaffold is characterized in that the bone repair scaffold is made of shape memory polyurethane and metal magnesium, and the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (1-10).
2. The bone repair scaffold according to claim 1, wherein the mass ratio of the shape memory polyurethane to the metal magnesium is 100 (3-5).
3. The bone repair scaffold according to claim 1, wherein the metallic magnesium has a particle size of 40 to 100 μm.
4. The bone repair scaffold according to claim 3, wherein the metallic magnesium has a particle size of 50 to 80 μm.
5. The bone repair scaffold according to any one of claims 1 to 4, wherein the shape memory polyurethane is formed by reacting the following raw material components, based on 100% by mass of the shape memory polyurethane: 23.0 to 25.0 percent of diphenylmethane diisocyanate, 7.0 to 8.0 percent of chain extender and 67.0 to 70.0 percent of polycaprolactone diol.
6. The bone repair scaffold according to claim 5, wherein the ratio of isocyanate groups contained in the diphenylmethane diisocyanate to the hydroxyl groups of all the raw materials participating in the reaction is (1.0-1.2): 1.
7. The bone repair scaffold according to claim 5, wherein the chain extender is selected from any one of 1, 4-butanediol, 1, 6-hexanediol and ethylene glycol.
8. The bone repair scaffold according to claim 5, wherein the polycaprolactone diol has a number average molecular weight of 3000 to 8000.
9. A method of preparing a bone repair scaffold according to any one of claims 1 to 8, comprising:
dissolving shape memory polyurethane in an organic solvent, adding metal magnesium, and stirring and mixing to obtain a printing precursor solution;
obtaining a support blank by the printing precursor liquid through a 3D printing process;
and freeze-drying the support embryonic body to obtain the bone repair support.
10. The method for preparing a bone repair scaffold according to claim 9, wherein the printing speed in the 3D printing process is 0.1mm/s to 1.5mm/s, and the temperature of the printing nozzle is 10 ℃ to 20 ℃; the temperature of the freeze drying is-80 ℃ to-70 ℃, and the time is 48h to 72 h.
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