CN112451742A - Preparation method of degradable metal-organic matter composite bone repair material - Google Patents
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Abstract
The invention relates to the technical field of biomedical engineering, in particular to a preparation method of a degradable metal-organic compound bone repair material. According to the invention, the porous or reticular metal-organic composite bone repair material with significantly reduced degradation rate and significantly improved compressive strength and compressive modulus is prepared by performing surface modification treatment on the degradable metal and then performing polymerization reaction on the modified metal and the hydrogel prepolymerization solution.
Description
Technical Field
The invention relates to the technical field of biomedical engineering, in particular to a preparation method of a degradable metal-organic compound bone repair material.
Background
The incidence of bone defects is 5-7% according to statistics, and about 3 hundred million people all over the world currently suffer from the diseases of bone defects caused by various reasons. The regeneration capability of large-section bone defects is poor, and how to effectively repair the bone defects is one of the problems to be solved in the medical and material industries.
External intervention therapy is a necessary and effective means, and the clinical bone defect treatment methods mainly comprise autologous bone transplantation and allogeneic bone transplantation. The autogenous bone has good osteogenesis capacity and extremely small immunological rejection, is the 'gold standard' for repairing bone defects, but has the defects of small bone supply amount, multiple operations, increased operation and infection risks, large wound, easy complication caused by bone supply parts and the like. The allogenic bone transplantation has obvious defects of immunological rejection, potential host tissue infection, tissue necrosis and the like. With the development of regenerative medicine and biological materials, a novel functional material capable of replacing and repairing bone defects is designed in a bionic manner, so that a feasible scheme is provided for treating the bone defects. An ideal bone repair material should have the following properties: 1. has good biocompatibility and safety; 2. the bone defect support has certain mechanical strength and provides mechanical support for bone defects with certain bearing parts; 3. has good osteogenic activity and induces bone regeneration; 4. the degradable property is realized, and the degradation rate is adjustable; 5. has a certain bionic micro-nano porous structure to provide space for the growth of new bones and blood vessels.
Currently, a large number of bone repair materials are widely reported, in a wide variety, aimed at providing synergistic enhancement of osteogenic activity, mechanical strength, or both. Such as ceramic bone repair materials, ceramic/polymer bone repair materials, ceramic/hydrogel composite bone repair materials and the like; high molecular bone repairing materials, such as high molecular/bioactive glass composite materials, magnesium-containing high molecular bone repairing materials and the like; the bone repair material comprises hydrogel materials, a micro-nano fiber support, a 3D printing support, a porous metal support and the like, and the materials show good bone repair effect to a certain extent and show good application prospect. The hydrogel prepared by taking the natural polysaccharide as the base material has the characteristics of good biological safety, biocompatibility, degradability, an extracellular matrix structure imitation and the like, so that the material has obvious advantages in bone defect repair, and is widely used for bone repair material research and becomes a research hotspot in recent years. But the single natural polysaccharide hydrogel has insufficient mechanical strength and is difficult to be used for repairing bone defects at certain bearing parts.
Degradable metals, such as magnesium-based alloys and zinc-based alloys, are potential bone repair materials and are hot spots of research in recent years. Magnesium and zinc are essential elements of human body and participate in various important metabolic processes of human body. The magnesium alloy and the zinc alloy have elastic modulus matched with human cortical bone, can provide mechanical support for bone defect parts and avoid stress shielding effect caused by overlarge stress of other non-degradable metals. The magnesium alloy and the zinc alloy can be degraded in human body, and magnesium ions or zinc ions generated in the degradation process have good osteogenesis and angiogenesis activity under proper concentration. Although the advantages are achieved, the block degradable metal is difficult to be directly used for bone defect repair, the block metal occupies a large amount of space and influences the growth of new bones and blood vessels, and a large amount of local corrosion products are accumulated after the block metal is degraded to influence the bone defect repair. Therefore, degradable metals having a porous structure or a mesh structure will be more advantageous in bone defect repair than bulk metals. However, although the porous structure is beneficial to tissue and blood vessel ingrowth, the specific surface area of the porous degradable metal is large, and the degradation of the porous degradable metal is further accelerated in the degradation process, particularly the porous magnesium alloy. How to effectively slow down the degradation rate of the porous degradable metal is a key problem to be solved in the practical application process of the porous degradable metal.
The prior art can prepare porous or reticular degradable metals, but after the porous or reticular degradable metals are prepared, the degradation of the porous or reticular degradable metals is further accelerated due to the increase of the specific surface area (the increase of the contact area with corrosive media), so that how to effectively regulate the degradation rate of the porous or reticular metals is the key of practical clinical application of the porous or reticular metals, but reports on effectively regulating the degradation of the porous or reticular metals and providing good microenvironment (such as compounding with the simulated extracellular matrix hydrogel) for bone cells and blood vessel ingrowth are few.
Disclosure of Invention
Aiming at the problems of the existing porous or reticular degradable metals, the invention provides a method for preparing the degradable metal-organic composite bone repair material by firstly carrying out surface modification treatment on the degradable metal and then carrying out polymerization reaction on the modified metal and hydrogel prepolymerization solution.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a degradable metal-organic compound bone repair material comprises the following steps:
s1, placing the degradable metal in the surface treatment solution, soaking for 24h, taking out, washing with water, and drying to obtain the modified degradable metal;
the surface treatment solution is a solution formed by preparing a solution with the polyphenol compound content of 0.5-5.0mg/mL by using a Tris aqueous solution with the concentration of 1.0-1.5mg/mL and then adding an amine compound into the solution, wherein the amine compound content is 1.0-2.0 mg/mL.
Preferably, the polyphenol compound is selected from catecholamine, catechol, tannic acid, gallic acid, anthocyanin and procyanidine. More preferably, the polyphenolic compound is dopamine.
Preferably, the amine compound is 2-aminoethyl methacrylate or ethylenediamine.
More preferably, the surface treatment solution is a solution prepared by preparing a solution having a dopamine content of 2.0mg/mL with a 1.2mg/mL Tris aqueous solution and then adding 2-aminoethyl methacrylate to the solution, wherein the 2-aminoethyl methacrylate content is 2.0 mg/mL.
More preferably, the surface treatment solution is a solution prepared by preparing a solution having a dopamine content of 5.0mg/mL with a 1.2mg/mL Tris aqueous solution and then adding ethylenediamine to the solution, wherein the ethylenediamine content is 1.0 mg/mL.
Preferably, the degradable metal is magnesium, magnesium alloy, zinc alloy, iron or iron alloy.
More preferably, the degradable metal is a porous or reticulated degradable metal.
Preferably, before the degradable metal is soaked in the surface treatment liquid, the degradable metal is cleaned; the cleaning treatment comprises the following steps: the degradable metal is firstly placed in acetone for ultrasonic cleaning, then placed in absolute ethyl alcohol for ultrasonic cleaning, and then dried.
Preferably, the drying treatment is to blow dry the degradable metal with a dry nitrogen gas flow, and then place the degradable metal in a vacuum drying oven for standby.
S2, pouring the hydrogel prepolymerization solution into a container filled with the modified degradable metal, and placing the container in a vacuum box for vacuumizing for more than 0.5 h;
the hydrogel pre-polymerization solution is a solution containing 5-40mg/mL of acrylic double bond and 1mg/mL of ultraviolet initiator in the aqueous solution of the natural polysaccharide modified by phosphoric acid; or the hydrogel pre-polymerization solution is 18-22mg/mL solution containing 1mg/mL ultraviolet initiator in methacrylic acid modified natural polysaccharide water solution.
Preferably, the natural polysaccharide is chitosan, hyaluronic acid, gelatin or sodium alginate.
Preferably, the ultraviolet photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
And S3, irradiating the hydrogel pre-polymerized liquid and the modified degradable metal processed in the step 2 by using ultraviolet light to obtain the degradable metal-organic compound composite bone repair material.
Compared with the prior art, the invention has the beneficial effects that:
the invention firstly constructs a coating which is corrosion resistant and contains acrylic acid functional groups on the degradable metal, and the modified degradable metal composite hydrogel pre-polymerization liquid initiates acrylic acid double bond polymerization under ultraviolet light to form the degradable metal-organic composite bone repair material. The degradable metal in the bone repair material can provide mechanical support for the bone repair material, so that the bone repair material can meet the requirement of bone defect repair; the surface coating of the modified degradable metal can provide a corrosion protection function and provide a polymerization site for subsequent compounding with a hydrogel prepolymerization solution; the hydrogel can provide a good microenvironment for the ingrowth of bone cells and vascular cells, and is beneficial to bone ingrowth and angiogenesis; meanwhile, the hydrogel filled in the degradable metal can play a certain physical barrier role, and the contact between a corrosive medium and the degradable metal is slowed down, so that the corrosion rate of the degradable metal is further slowed down; in addition, metal ions released by the degradable metal in the degradation process can be chelated with functional groups (such as phosphate groups) in the hydrogel, so that the metal ions can be slowly released, and the slow release effect is achieved.
According to the invention, the composition and the component content of the surface treatment liquid are optimized, so that the coating formed on the surface of the degradable metal is firm and has good corrosion resistance; by optimizing the concentration of the acrylic double bond and the natural polysaccharide modified by phosphoric acid in the hydrogel prepolymerization solution, the hydrogel prepolymerization solution can easily enter the pores of the reticular/porous degradable metal to fully fill the pores, and the formation of hydrogel with loose pores after crosslinking reaction can be avoided.
Tests prove that the bone repair material has certain mechanical strength and can provide mechanical support for a bone defect part, the hydrogel filled in the reticular or porous degradable metal has a three-dimensional bionic structure and can provide a good microenvironment for the growth of bone cells and blood vessel cells, and the coating on the surface of the degradable metal and the filled hydrogel can regulate the degradation rate of the degradable metal and the release rate of osteogenic active metal ions so as to meet the purposes of material degradation, bone growth rate matching and metal ion osteogenic activity.
Drawings
FIG. 1 is a macro-topography of the degradable metal-organic composite bone repair material prepared in example 4;
fig. 2 is a graph comparing the compressive strength and compressive modulus of the degradable metal-organic composite bone repair material prepared in example 4 with those of a hydrogel bone repair material without a magnesium mesh.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.
The preparation method of the phosphoric acid modified methacrylated natural polysaccharide comprises the following steps:
(1) dissolving natural polysaccharide in a solvent, adding methacrylic anhydride, and reacting at room temperature to obtain a mixture A;
(2) dissolving phosphoric acid or phosphonic acid modified raw materials in deionized water, sequentially adding MES, EDC and NHS, fully dissolving, and uniformly stirring at room temperature to obtain a mixture B;
(3) and adding the mixture A into the mixture B, reacting at room temperature, adding deionized water for dilution, placing the diluent into a dialysis bag, dialyzing in the deionized water at room temperature, dialyzing, and freeze-drying to obtain the phosphoric acid modified methacrylic acid natural polysaccharide.
Preferably, the natural polysaccharide is one of chitosan, hyaluronic acid and sodium alginate.
Preferably, the ratio of the natural polysaccharide, the solvent for dissolving the natural polysaccharide and the methacrylic anhydride is 1-5g:100mL:0-1 mL.
More preferably, the ratio of the natural polysaccharide, the solvent for dissolving the natural polysaccharide and the methacrylic anhydride is 1g:100mL: 367. mu.L.
Preferably, when the natural polysaccharide is chitosan, the solvent for dissolving the chitosan in the step (1) is acetic acid water solution, and the volume fraction of the acetic acid water solution is 0.5-10%
Preferably, when the natural polysaccharide is hyaluronic acid or sodium alginate, the solvent for dissolving the hyaluronic acid or the sodium alginate is deionized water, and after the hyaluronic acid or the sodium alginate is dissolved, the pH value is adjusted to 7.3-8.5 by adding a sodium hydroxide solution.
Preferably, the mass ratio of the natural polysaccharide to the phosphoric acid or phosphonic acid modified raw material in the step (1) and the step (2) is 10:1-1: 5.
More preferably, the mass ratio of the natural polysaccharide to the phosphoric acid or phosphonic acid modified raw material in the step (1) and the step (2) is 2: 1.
Preferably, in the step (2), the phosphoric acid or phosphonic acid modified raw material is one of 3-phosphonic acid propionic acid, phosphocreatine, alene phosphoric acid or phosphoethanolamine; the mass ratio of the phosphoric acid or phosphonic acid modified raw material to the MES, the EDC and the NHS is 0.1-10:50-80:3-9: 1-3.
More preferably, the mass ratio of phosphoric acid or phosphonic acid modified feedstock, MES, EDC and NHS is 5:53.3:9: 3.
Preferably, in step (3), dialysis is performed using a dialysis bag having an excess molecular weight of 12 to 14 kDa.
Taking phosphoric acid modified methacrylated chitosan as an example, the preparation of phosphoric acid modified methacrylated chitosan comprises the following steps:
(1) 1g of chitosan was dissolved in 100mL of an aqueous solution of acetic acid with a volume fraction of 1%, 367. mu.L of Methacrylic Anhydride (MA) was added dropwise after dissolution, and the reaction was carried out at room temperature for 24 hours to obtain methacrylated Chitosan (CSMA).
(2) 0.5g of 3-phosphonopropionic acid was dissolved in 50mL of deionized water, and 5.33g of 2- (N-morpholine) ethanesulfonic acid monohydrate (MESonohydrate) and 0.9g of EDC (1-Ethyl-3- (3' -methylenepropyl) carbodiimide) and 0.3g of NHS (N-hydroxysuccinimide) were added thereto, and the mixture was sufficiently dissolved and stirred at room temperature for 30 min.
(3) Dropwise adding the liquid obtained after the reaction of the chitosan and the methacrylic acid in the step (1) into the 3-phosphonic acid propionic acid solution in the step (2), stirring while dropwise adding, reacting at room temperature for 24 hours after all dropwise adding, adding 100mL of deionized water for dilution, placing the diluted solution into a 12-14kDa dialysis bag, dialyzing in the deionized water at room temperature for 5 days, changing the deionized water once in the morning and at night every day, continuously stirring, dialyzing, and freeze-drying to obtain white loose phosphoric acid modified methacrylic acid Chitosan (CSMAP).
The MES is 2- (N-morpholine) ethanesulfonic acid monohydrate, the EDC is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and the NHS is N-hydroxysuccinimide.
Example 1
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example is a reticulated AZ31 magnesium alloy, the hollow mesh is square, the side length of the square is 1.5mm, the width of the metal ribs of the mesh is 0.25mm, and the thickness of the magnesium mesh is 0.25 mm.
The method comprises the following specific steps:
(1) ultrasonically cleaning degradable metal in acetone for 3 times, 5min each time, then ultrasonically cleaning in absolute ethyl alcohol for 3 times, 5min each time, taking out, drying under dry nitrogen flow, and storing in a vacuum drying oven for later use.
(2) Preparing a dopamine solution with the concentration of 2mg/mL by using a Tris aqueous solution with the concentration of 1.2mg/mL in an open beaker, adding 2-aminoethyl methacrylate with the concentration of 2mg/mL into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and 2-aminoethyl methacrylate, namely the surface treatment solution.
(3) And (2) soaking the degradable metal cleaned in the step (1) in the surface treatment liquid prepared in the step (2), taking out the degradable metal after the surface treatment liquid is soaked for 24 hours at the open room temperature of a beaker, washing the degradable metal by deionized water, and blow-drying the degradable metal under dry nitrogen flow to obtain the modified degradable metal. And (3) placing the modified degradable metal in a vacuum drying oven for storage for later use.
(4) Dissolving phosphoric acid modified methacrylated chitosan in deionized water at the concentration of 20mg/mL, and adding 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution to obtain the hydrogel pre-polymerization solution.
(5) And (3) placing the modified degradable metal obtained in the step (3) into a beaker, pouring the hydrogel prepolymerization solution obtained in the step (4) into the beaker to completely cover the degradable metal, and then placing the beaker into a vacuum box to be vacuumized for half an hour.
(6) And (4) placing the beaker in the step (5) under ultraviolet light (the wavelength is 400nm-10nm), and irradiating for 20min to obtain the reticular degradable metal-organic composite bone repair material.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 26.8. mu.A/cm2The unmodified AZ31 self-etching current density was 269.1. mu.A/cm2. The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared in the embodiment are 49MPa and 80 MPa.
In other embodiments, pure magnesium, as well as biomedical magnesium alloys such as AZ91, WE43, etc., may also be used; and a porous degradable metal with the pore communication rate of more than 80 percent and the pore size favorable for the inflow of the hydrogel pre-polymerization liquid and the communication of the hydrogel pre-polymerization liquid in a porous structure can also be used.
Example 2
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, which was a reticulated AZ31 magnesium alloy, the hollow mesh was square, the side length of the square was 1.5mm, the width of the mesh metal ribs was 0.25mm, and the thickness of the magnesium mesh was 0.25 mm.
The method comprises the following specific steps:
(1) ultrasonically cleaning degradable metal in acetone for 3 times, 5min each time, then ultrasonically cleaning in absolute ethyl alcohol for 3 times, 5min each time, taking out, drying under a dry nitrogen flow, and placing in a vacuum drying oven for later use.
(2) Preparing a 5mg/mL dopamine solution by using a 1.2mg/mL Tris aqueous solution in an open beaker, then adding 1mg/mL 2-aminoethyl methacrylate into the solution, and stirring the mixture for half an hour in the open at room temperature to obtain a mixed solution containing dopamine and 2-aminoethyl methacrylate, namely a surface treatment solution.
(3) And (3) soaking the clean degradable metal in the step (1) in the mixed solution in the step (2), taking out the degradable metal after the beaker is opened and soaked for 24 hours at room temperature, slightly washing the degradable metal with deionized water, and blow-drying the degradable metal under dry nitrogen flow to obtain the modified degradable metal. And (3) placing the modified degradable metal in a vacuum drying oven for storage for later use.
(4) Dissolving phosphoric acid modified methacrylated chitosan in deionized water at the concentration of 20mg/mL, and adding 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution to obtain the hydrogel pre-polymerization solution.
(5) And (3) placing the modified degradable metal obtained in the step (3) into a beaker, pouring the hydrogel prepolymerization solution obtained in the step (4) into the beaker to completely cover the modified degradable metal, and then placing the beaker into a vacuum box to be vacuumized for half an hour.
(6) And (4) placing the beaker in the step (5) under ultraviolet light (the wavelength is 400nm-10nm), and irradiating for 20min to obtain the reticular degradable metal-organic composite bone repair material.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 28.2. mu.A/cm2. The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 50MPa and 48 MPa.
Example 3
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, which was a reticulated AZ31 magnesium alloy, the hollow mesh was square, the side length of the square was 1.5mm, the width of the mesh metal ribs was 0.25mm, and the thickness of the magnesium mesh was 0.25 mm.
The method comprises the following specific steps:
(1) ultrasonically cleaning degradable metal in acetone for 3 times, 5min each time, then ultrasonically cleaning in absolute ethyl alcohol for 3 times, 5min each time, taking out, drying under a dry nitrogen flow, and placing in a vacuum drying oven for later use.
(2) Preparing a 5mg/mL dopamine solution by using a 1.2mg/mL Tris aqueous solution in an open beaker, then adding 1mg/mL ethylenediamine into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and ethylenediamine, namely a surface treatment solution.
(3) And (3) soaking the clean degradable metal in the step (1) in the mixed solution in the step (2), taking out the degradable metal after the beaker is opened and soaked for 24 hours at room temperature, slightly washing the degradable metal with deionized water, and blow-drying the degradable metal under dry nitrogen flow to obtain the modified degradable metal. And (3) placing the modified degradable metal in a vacuum drying oven for storage for later use.
(4) Dissolving phosphoric acid modified methacrylated chitosan in deionized water at the concentration of 20mg/mL, and adding 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution to obtain the hydrogel pre-polymerization solution.
(5) And (3) placing the modified degradable metal obtained in the step (3) into a beaker, pouring the hydrogel prepolymerization solution obtained in the step (4) into the beaker to completely cover the modified degradable metal, and then placing the beaker into a vacuum box to be vacuumized for half an hour.
(6) And (4) placing the beaker in the step (5) under ultraviolet light (the wavelength is 400nm-10nm), and irradiating for 20min to obtain the reticular degradable metal-organic composite bone repair material.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 29.1. mu.A/cm2. The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 47MPa and 79 MPa.
Example 4
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, which was a reticulated AZ31 magnesium alloy, the hollow mesh was square, the side length of the square was 1.5mm, the width of the mesh metal ribs was 0.25mm, and the thickness of the magnesium mesh was 0.25 mm.
The method comprises the following specific steps:
(1) ultrasonically cleaning degradable metal in acetone for 3 times, 5min each time, then ultrasonically cleaning in absolute ethyl alcohol for 3 times, 5min each time, taking out, drying under a dry nitrogen flow, and placing in a vacuum drying oven for later use.
(2) Preparing a 5mg/mL dopamine solution by using a 1.2mg/mL Tris aqueous solution in an open beaker, then adding 1mg/mL ethylenediamine into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and ethylenediamine, namely a surface treatment solution.
(3) And (3) soaking the clean degradable metal in the step (1) in the mixed solution in the step (2), taking out the degradable metal after the beaker is opened and soaked for 24 hours at room temperature, slightly washing the degradable metal with deionized water, and blow-drying the degradable metal under dry nitrogen flow to obtain the modified degradable metal. And (3) placing the modified degradable metal in a vacuum drying oven for storage for later use.
(4) Dissolving methacrylated chitosan in deionized water at the concentration of 20mg/mL, and adding 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution to obtain hydrogel pre-polymerization liquid.
(5) And (3) placing the modified degradable metal obtained in the step (3) into a beaker, pouring the hydrogel prepolymerization solution obtained in the step (4) into the beaker to completely cover the modified degradable metal, and then placing the beaker into a vacuum box to be vacuumized for half an hour.
(6) And (4) placing the beaker in the step (5) under ultraviolet light (the wavelength is 400nm-10nm), and irradiating for 20min to obtain the reticular degradable metal-organic composite bone repair material.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 27.0. mu.A/cm2. The macroscopic morphology of the degradable metal-organic composite bone repair material prepared in this example is shown in fig. 1, and the compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared in this example are 49MPa and 78MPa, respectively, as shown in fig. 2. In FIG. 2, the material without the magnesium mesh is a hydrogel bone repair material formed by irradiating the hydrogel pre-polymerization solution described in this example with ultraviolet light.
Example 5
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the component concentrations of the surface treatment liquid used were different, that is, the method of preparing the surface treatment liquid in step (2) was as follows:
preparing a dopamine solution with the concentration of 6mg/mL by using a Tris aqueous solution with the concentration of 1.2mg/mL in an open beaker, adding 2mg/mL of 2-aminoethyl methacrylate into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and 2-aminoethyl methacrylate, namely the surface treatment solution.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 45.5. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 42MPa and 65MPa respectively.
Example 6
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the component concentrations of the surface treatment liquid used were different, that is, the method of preparing the surface treatment liquid in step (2) was as follows:
preparing 0.3mg/mL dopamine solution by using 1.2mg/mL Tris aqueous solution in an open beaker, then adding 2mg/mL 2-aminoethyl methacrylate into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and 2-aminoethyl methacrylate, namely the surface treatment solution.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 102.2. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 42MPa and 49 MPa.
Example 7
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 4, and the preparation method of this example was substantially the same as that of example 4, except that the component concentrations of the surface treatment liquid used were different, that is, the method of preparing the surface treatment liquid in step (2) was as follows:
preparing a 6mg/mL dopamine solution by using a 1.2mg/mL Tris aqueous solution in an open beaker, then adding 1mg/mL ethylenediamine into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and ethylenediamine, namely a surface treatment solution.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 80.5. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 48MPa and 76MPa respectively.
Example 8
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 4, and the preparation method of this example was substantially the same as that of example 4, except that the component concentrations of the surface treatment liquid used were different, that is, the method of preparing the surface treatment liquid in step (2) was as follows:
preparing 0.3mg/mL dopamine solution by using 1.2mg/mL Tris aqueous solution in an open beaker, then adding 1mg/mL ethylenediamine into the solution, and stirring the mixture for half an hour in an open atmosphere at room temperature to obtain a mixed solution containing dopamine and ethylenediamine, namely a surface treatment solution.
The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 75.5. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 45MPa and 74 MPa.
Example 9
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the hydrogel pre-polymerization solution was used at different concentrations of the components, i.e., the method of preparing the hydrogel pre-polymerization solution in step (4) was as follows:
the same phosphoric acid-modified methacrylated chitosan as in example 1 was used, and the phosphoric acid-modified methacrylated chitosan was dissolved in deionized water at a concentration of 3mg/mL, and after dissolution, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, which is an ultraviolet initiator, was added to the solution at a concentration of 1mg/mL, to obtain a hydrogel pre-polymerization solution.
The concentration of the hydrogel pre-polymerization solution is too low, the viscosity is too low, and the hydrogel cannot be formed.
Example 10
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the hydrogel pre-polymerization solution was used at different concentrations of the components, i.e., the method of preparing the hydrogel pre-polymerization solution in step (4) was as follows:
the same phosphoric acid-modified methacrylated chitosan as in example 1 was used, and the phosphoric acid-modified methacrylated chitosan was dissolved in deionized water at a concentration of 5mg/mL, and after dissolution, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, which is an ultraviolet initiator, was added to the solution at a concentration of 1mg/mL, to obtain a hydrogel pre-polymerization solution.
According to the degradable metal-organic composite bone repair material prepared by the embodiment, the hydrogel can fully enter the holes of the modified degradable metal, the filling effect is good, and loose holes do not appear in the hydrogel.
Example 11
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the hydrogel pre-polymerization solution was used at different concentrations of the components, i.e., the method of preparing the hydrogel pre-polymerization solution in step (4) was as follows:
the same phosphoric acid-modified methacrylated chitosan as in example 1 was used, and the phosphoric acid-modified methacrylated chitosan was dissolved in deionized water at a concentration of 40mg/mL, and after dissolution, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, which is an ultraviolet initiator, was added to the solution at a concentration of 1mg/mL, to obtain a hydrogel pre-polymerization solution.
According to the degradable metal-organic composite bone repair material prepared by the embodiment, the hydrogel can fully enter the holes of the modified degradable metal, the filling effect is good, and loose holes do not appear in the hydrogel.
Example 12
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 1, and the preparation method of this example was substantially the same as that of example 1 except that the hydrogel pre-polymerization solution was used at different concentrations of the components, i.e., the method of preparing the hydrogel pre-polymerization solution in step (4) was as follows:
the same phosphoric acid-modified methacrylated chitosan as in example 1 was used, and the phosphoric acid-modified methacrylated chitosan was dissolved in deionized water at a concentration of 45mg/mL, and after dissolution, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, which is an ultraviolet initiator, was added to the solution at a concentration of 1mg/mL, to obtain a hydrogel pre-polymerization solution.
The concentration of the hydrogel pre-polymerization solution is too high, the viscosity of the hydrogel pre-polymerization solution is too high, the hydrogel pre-polymerization solution is difficult to enter the holes of the modified degradable metal and is difficult to be fully filled, and the uniformity of the composite material is poor.
Example 13
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 4, and the preparation method of this example was substantially the same as that of example 1, except that the concentrations of the components of the hydrogel prepolymer solution used were different, that is, the method of preparing the hydrogel prepolymer solution in step (4) was as follows:
dissolving methacrylated chitosan in deionized water at the concentration of 3mg/mL, and adding 2mg/mL dopamine Tris aqueous solution and 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution after dissolving to obtain the hydrogel pre-polymerization solution. (aqueous dopamine Tris solution was the same as in example 4.)
The concentration of the hydrogel pre-polymerization solution is too low, the viscosity is too low, and the hydrogel cannot be formed.
Example 14
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example was the same as that of example 4, and the preparation method of this example was substantially the same as that of example 1, except that the concentrations of the components of the hydrogel prepolymer solution used were different, that is, the method of preparing the hydrogel prepolymer solution in step (4) was as follows:
dissolving methacrylated chitosan in deionized water at the concentration of 45mg/mL, and adding 2mg/mL dopamine Tris aqueous solution and 1mg/mL ultraviolet initiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone into the solution after dissolving to obtain the hydrogel pre-polymerization solution. (aqueous dopamine Tris solution was the same as in example 4.)
The concentration of the hydrogel pre-polymerization solution is too high, the viscosity of the hydrogel pre-polymerization solution is too high, the hydrogel pre-polymerization solution is difficult to enter the holes of the modified degradable metal and is difficult to be fully filled, and the uniformity of the composite material is poor.
Example 15
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example is reticulated zinc metal, the hollow mesh is square, the side length of the square is 1.5mm, the width of the metal ribs of the mesh is 0.25mm, and the thickness of the zinc mesh is 0.25 mm.
The preparation method of this example was the same as that of example 4 except that the degradable metal used was different from that of example 4. The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 12.4. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared in the embodiment are 53MPa and 83 MPa.
Example 16
The embodiment provides a preparation method of a degradable metal-organic composite bone repair material. The degradable metal used in this example is a reticular iron alloy, the hollow grid is square, the side length of the square is 1.5mm, the width of the grid metal rib is 0.25mm, and the thickness of the iron mesh is 0.25 mm.
The preparation method of this example was the same as that of example 4 except that the degradable metal used was different from that of example 4. The modified degradable metal prepared in step (3) of this example had a self-corrosion current density of 5.3. mu.A/cm2(ii) a The compressive strength and the compressive modulus of the degradable metal-organic composite bone repair material prepared by the embodiment are 56MPa and 87 MPa.
In other embodiments, the dopamine in the surface treatment fluid used may also be replaced with catechol, tannic acid, gallic acid, anthocyanins, procyanidins, or the like; phosphoric acid in the hydrogel pre-polymerization liquid modifies the methacrylated chitosan or the methacrylated chitosan, wherein the chitosan can be replaced by hyaluronic acid, gelatin or sodium alginate, for example, the phosphoric acid modified methacrylated chitosan can be replaced by phosphoric acid modified methacrylated gelatin, phosphoric acid modified methacrylated hyaluronic acid, phosphoric acid modified methacrylated sodium alginate, and the like.
The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.
Claims (10)
1. A preparation method of a degradable metal-organic compound bone repair material is characterized by comprising the following steps:
s1, placing the degradable metal in the surface treatment solution, soaking for 24h, taking out, washing with water, and drying to obtain the modified degradable metal;
the surface treatment solution is a solution formed by preparing a solution with the polyphenol compound content of 0.5-5.0mg/mL by using a Tris aqueous solution with the concentration of 1.0-1.5mg/mL and then adding an amine compound into the solution, wherein the amine compound content is 1.0-2.0 mg/mL;
s2, pouring the hydrogel prepolymerization solution into a container filled with the modified degradable metal, and placing the container in a vacuum box for vacuumizing for more than 0.5 h;
the hydrogel pre-polymerization solution is a solution containing 1mg/mL of ultraviolet initiator in an aqueous solution of 5-40mg/mL of acrylic double bond and phosphoric acid modified natural polysaccharide, or the hydrogel pre-polymerization solution is a solution containing 1mg/mL of ultraviolet initiator in an aqueous solution of 18-22mg/mL of methacrylic acid modified natural polysaccharide;
and S3, irradiating the hydrogel pre-polymerized liquid and the modified degradable metal processed in the step 2 by using ultraviolet light to obtain the degradable metal-organic compound composite bone repair material.
2. The method for preparing the degradable metal-organic compound bone repair material according to claim 1, wherein the degradable metal is magnesium, magnesium alloy, zinc alloy, iron or iron alloy.
3. The method for preparing the degradable metal-organic compound bone repair material according to claim 2, wherein the degradable metal is porous or reticular.
4. The method for preparing the degradable metal-organic compound bone repair material according to claim 1, wherein the degradable metal is cleaned before being soaked in the surface treatment solution; the cleaning treatment comprises the following steps: the degradable metal is firstly placed in acetone for ultrasonic cleaning, then placed in absolute ethyl alcohol for ultrasonic cleaning, and then dried.
5. The method for preparing the degradable metal-organic composite bone repair material according to claim 4, wherein the drying treatment is to blow dry the degradable metal with a dry nitrogen gas flow, and then to put the degradable metal in a vacuum drying oven for standby.
6. The method for preparing the degradable metal-organic compound composite bone repair material according to claim 1, wherein the polyphenol compound is one selected from catecholamine, catechol, tannic acid, gallic acid, anthocyanidin, and procyanidins.
7. The method for preparing the degradable metal-organic composite bone repair material according to claim 1, wherein the polyphenol compound is dopamine.
8. The method for preparing the degradable metal-organic compound composite bone repair material according to claim 1, wherein the amine compound is 2-aminoethyl methacrylate or ethylenediamine.
9. The method for preparing a degradable metal-organic composite bone repair material according to claim 1, wherein the surface treatment solution is a solution prepared by preparing a solution with a dopamine content of 5.0mg/mL with a 1.2mg/mL aqueous solution of Tris, and then adding ethylenediamine to the solution, wherein the ethylenediamine content is 1.0 mg/mL.
10. The method for preparing the degradable metal-organic composite bone repair material of claim 1, wherein the natural polysaccharide in step S2 is chitosan, hyaluronic acid, gelatin or sodium alginate.
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