CN109432514B - Degradable magnesium alloy bone nail with scaly bone-imitating nano-structure coating and preparation method thereof - Google Patents
Degradable magnesium alloy bone nail with scaly bone-imitating nano-structure coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a degradable magnesium alloy bone nail with a scaly bone-imitating nano-structure coating on the surface and a preparation method thereof, and the degradable bone nail consists of an AZ31B magnesium alloy bone nail matrix and a magnesium oxide biological ceramic coating of the scaly bone-imitating nano-structure loaded with PLGA-bone morphogenetic protein BMP. The magnesium oxide biological ceramic coating with the scaly bone-like nano structure is combined with the surface of a metal substrate, and the scaly nano structure with the nano size is constructed on the surface of the substrate by a micro-arc oxidation technology. The BMP is filled and loaded among magnesium oxide scaly bone-imitating nano-structure laminas through centrifugal force and capillary action. The preparation method comprises the following steps: firstly, processing AZ31B magnesium alloy into bone nails; then adopting micro-arc oxidation technology to obtain a magnesium oxide ceramic coating with the characteristics of a scaly bone-like nano structure on the surface of the substrate; and finally loading PLGA-bone morphogenetic protein between the magnesium oxide scaly bone-imitating nano structure layer sheets by adopting a centrifugal loading technology.
Description
Technical Field
The invention relates to a degradable magnesium alloy bone nail with a scale-shaped bone-imitating nano-structure coating and a preparation method thereof, in particular to a bone nail which selects AZ31B magnesium alloy to process a substrate, adopts a micro-arc oxidation method to construct a magnesium oxide biological ceramic coating with a scale-shaped bone-imitating nano-structure on the surface, loads PLGA-bone morphogenetic protein BMP through a centrifugal load technology and a preparation method thereof, and belongs to the technical field of orthopedic implant materials.
Background
The bone nail is a commonly used orthopedic implant material, and is widely applied to the treatment operation of orthopedic diseases at present. However, the commonly used stainless steel and titanium alloy bone nails are not degradable in the human body, so that the patient needs to take out the implant after the regeneration of the bone tissue is completed, and secondary pain is caused. The absorbable and degradable magnesium alloy is a new biomedical orthopedic material, has excellent mechanical property and biological absorbable and degradable capability, and can avoid secondary operation so as to reduce the body burden of a patient and the risk of secondary infection.
Magnesium element has multiple important physiological functions and wide pharmacological action, and can participate in energy metabolism of organisms and control emotion; magnesium is an indispensable element for the human body, and the content of magnesium in the human body is 25 g; the excessive magnesium can be discharged out of the body through urine, and has no toxic or side effect on a physiological system.
However, the standard potential of magnesium is-2.363V. The magnesium and the alloy thereof are decomposed too fast in the physiological environment of the human body, so that the magnesium alloy bone nail is difficult to match the growth and healing speed of the bone tissue of the human body and is cracked prematurely. In addition, magnesium alloy is used as a metal implant material, has certain biological inertia, is difficult to rapidly form osseous combination with bone tissues after being implanted, and finally leads to implantation failure.
The coating with bioactivity is constructed on the surface of the magnesium alloy, so that the degradation rate of the magnesium alloy can be effectively adjusted, and the binding capacity of a matrix and bone tissues is improved. It is well known that regular structures in mineralized tissues are all derived from regular self-assembly of biological macromolecules, which serve as templates for controlling crystallization, growth, size and morphology of minerals. The bone tissue has a hierarchical structure and is microscopically composed of collagen nanofibers and plate-shaped apatite nanocrystals biomineralized thereon. Therefore, the scaly nano structure with the similar bone tissue is formed on the surface of the magnesium alloy, the growth of the bone tissue can be induced in a physiological environment, the crystallization, growth, size and morphology of apatite minerals are controlled, a regular self-assembly inorganic material template is provided, and finally the osseous bonding of the implant and the bone tissue is enhanced. In addition, the scaly nanostructure can effectively increase the specific surface area of the coating, which provides a natural place for loading and slowly releasing substances for promoting bone tissue growth.
Chinese patent CN201810694134 mentions that BMP can promote the proliferation of bone marrow stromal mesenchymal cells in vitro and induce the differentiation of the bone marrow stromal mesenchymal cells into osteogenic precursor cells, but has the defects of short burst release, easy inactivation, instability, short half-life and the like. Bone morphogenetic protein BMP is a low molecular glycoprotein polypeptide widely existing in bone matrix, and can induce undifferentiated mesenchymal cells and bone marrow stromal cells to be transformed into osteocytes so as to promote the formation of bone tissues. The bone nail surface loading with BMP can obviously improve the bone forming ability in the early period of implantation. However, since BMP is rapidly absorbed and decomposed in a physiological environment, it is required to load BMP on the surface of an implant to prolong its release period.
The coating is prepared on the surface of the magnesium alloy matrix through the micro-arc oxidation technology to regulate the degradation period and the bone induction forming capability of the coating, and the coating has great biomedical application potential. However, no report has been found so far that the technology is used for preparing a scaly nano coating with a bone tissue structure similar to that of the nano coating and loading bone morphogenetic proteins among the scaly structures so as to improve the bone induction forming capability of the nano coating. In view of the above, the invention provides a degradable magnesium alloy bone nail with a scaly bone-like nano-structure coating and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the artificial hard tissue substitute material, provides a degradable magnesium alloy with a scaly bone-imitating nano-structure coating on the surface and a preparation method thereof, and provides a bone nail capable of obviously improving the surface bioactivity, the cell regulation and control capability and various beneficial functions at the initial stage of implantation and a micro-arc oxidation preparation method thereof.
A magnesium oxide biological ceramic coating with a shape characteristic adjustable scaly bone-like nano structure is constructed on the surface of a metal matrix of the degradable magnesium alloy bone nail by utilizing a micro-arc oxidation technology, and the surface of the magnesium oxide biological ceramic coating is compounded with bone morphogenetic protein BMP by utilizing a centrifugal load technology. In the micro-arc oxidation process, the oxide layer is generated and simultaneously breakdown is carried out and then ceramic is carried out at high temperature, so that the magnesium oxide biological ceramic coating with the scaly bone-like nano structure has high bonding strength with a metal matrix, the scaly bone-like nano structure grown on the surface of the magnesium oxide structure has good bioactivity and can promote nucleation and deposition growth of a apatite layer, and meanwhile, the scaly lamellar staggered interval area is also an ideal carrier of BMP. BMP can be filled and loaded between the scaly nano-layer sheets through centrifugal force and capillary effect, so that the carrying capacity of the BMP on the surface of the bone nail is greatly improved, and a slow release effect is realized; the centrifugal load can effectively remove residual BMP which is not tightly adsorbed on the surface. After the bone nail is implanted into a human body, the release period of BMP on the surface of the bone nail is prolonged, which is beneficial to the full play of the BMP induced osteogenesis effect.
The invention is realized by the following technical scheme:
the degradable magnesium alloy bone nail with the scaly bone-imitating nanostructure coating and the preparation method thereof are characterized in that the degradable magnesium alloy bone nail with the scaly bone-imitating nanostructure coating consists of an AZ31B magnesium alloy bone nail matrix and a magnesium oxide bioceramic coating of a scaly bone-imitating nanostructure loaded with PLGA-bone morphogenetic protein BMP, and the magnesium oxide bioceramic coating of the scaly bone-imitating nanostructure is combined with the surface of the AZ31B magnesium alloy bone nail matrix and is formed by stacking the bone-imitating nanostructure generated by micro-arc oxidation of the AZ31B magnesium alloy matrix surface and an electrolyte solution by a micro-arc oxidation technology; the preparation method of the degradable magnesium alloy bone nail with the scaly bone-imitating nano-structure coating comprises the following steps:
(1) providing an AZ31B magnesium alloy bone nail;
(2) providing an electrolyte solution comprising sodium phosphate and sodium hydroxide;
(3) polishing the surface of the AZ31B magnesium alloy bone nail, performing micro-arc oxidation on the surface of an AZ31B magnesium alloy bone nail matrix by adopting a bipolar pulse micro-arc oxidation device in the electrolyte solution by taking the AZ31B magnesium alloy bone nail as an anode and a stainless steel electrolytic cell wall as a cathode, and constructing a magnesium oxide ceramic coating with an adjustable and controllable characteristic scaly bone-like nano structure on the surface of the AZ31B magnesium alloy bone nail matrix;
(4) loading PLGA-bone morphogenetic protein BMP between the magnesium oxide scaly bone-like nanostructure laminas of the AZ31B magnesium alloy bone nail obtained in the step (3) by adopting a centrifugal loading technology;
(5) and (4) finally, washing the AZ31B magnesium alloy bone nail obtained in the step (4) with alcohol, drying in vacuum, sterilizing and preserving aseptically for later use to obtain the degradable magnesium alloy bone nail with the scaly bone-imitating nano-structure coating.
Further, the electrolyte solution in the step (2) comprises 5-20 g/L of Na3PO4 and 1-10 g/L of NaOH, and the micro-arc oxidation mode is a constant-voltage mode.
Further, the magnesium oxide ceramic coating with the adjustable and controllable characteristics of the scaly bone-like nanostructure in the step (3) can adjust the morphological characteristics of the scaly structure by controlling the process parameters of micro-arc oxidation, wherein the process parameter range of the micro-arc oxidation is as follows: the working voltage adjusting range is 200-800V of positive voltage and 0-300V of negative voltage, the pulse frequency adjusting range is 50 Hz-800 Hz of positive pulse frequency and 50 Hz-800 Hz of negative pulse frequency, the duty ratio adjusting range is 4% -80% of positive duty ratio and 4% -50% of negative duty ratio, and the reaction time is 0.5-20 min.
Further, the centrifugal loading technology of step (4) is specifically operated as follows: preparing a mixed solution of 20-100 mg of PLGA, 1 mL of dichloromethane, 0.5-10 mu g of bone morphogenetic protein and 0.2-0.8 mmol of phosphate buffer salt, immersing the magnesium alloy bone nail obtained in the step (3) into the mixed solution for 5-30 s, then placing the bone nail into a spin coater, rotating the bone nail at a speed of 100-1000 rpm for 10-200 s, and controlling the working temperature to be 20-30 ℃.
Has the advantages that:
(1) the degradable magnesium alloy bone nail with the scaly bone-like nanostructure on the surface is formed by loading PLGA-bone morphogenetic protein BMP on a magnesium oxide bioceramic coating with the scaly bone-like nanostructure generated by a magnesium alloy matrix, has good beneficial effects of bioactivity, cell regulation, bacteriostasis and the like and an induced osteogenesis effect, and can safely form firm physiological combination with bone tissues in a short time.
(2) The magnesium oxide biological ceramic coating on the surface of the bone nail has high bonding strength with a metal matrix, has a scaly bone-like nano structure, is compact in coating contacted with the metal surface, has high biological activity and can promote the deposition and growth of a apatite layer; the coating with the squamous bone-imitating nano structure is an ideal place for cell adhesion, proliferation and BMP growth, and can induce undifferentiated mesenchymal cells and marrow stromal cells to be converted into osteocytes so as to promote the formation of bone tissues. The bone nail surface loading with BMP can obviously improve the bone forming ability in the early period of implantation.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a low magnification of the surface morphology of the coating layer of the magnesium alloy surface having the scaly bone-like nanostructure in example 1.
Fig. 2 is a high-magnification Scanning Electron Microscope (SEM) picture of the surface morphology of the coating layer of the magnesium alloy surface having the scaly bone-like nanostructure in example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) picture of the surface morphology of the coating layer having a small amount of scaly bone-like nanostructures on the surface of the magnesium alloy in example 2.
Detailed Description
Example 1
(1) Firstly, processing a bone nail by using AZ31B magnesium alloy;
(2) bone nail pretreatment: and grinding and polishing AZ31B magnesium alloy bone nails by using metallographic abrasive paper with the marks of 600#, 800#, and 1000# in sequence from coarse sand to fine sand, then ultrasonically cleaning by using acetone, 70% alcohol and distilled water, and drying for later use.
(3) Preparation of electrolyte solution: preparing 10L of sodium phosphate solution with the concentration of 5g/L and 2g/L of sodium hydroxide solution by adopting a sodium phosphate solution system for later use;
(4) micro-arc oxidation of the bone nail: and (3) placing the AZ31B magnesium alloy bone nail into an electrolytic bath of a bipolar pulse micro-arc oxidation device, adding a prepared electrolyte solution, and adjusting process parameters to perform micro-arc oxidation on the AZ31B magnesium alloy bone nail by taking the AZ31B magnesium alloy bone nail as an anode and a stainless steel electrolytic bath as a cathode. The technological parameters are as follows: in the constant voltage mode, the working voltage is regulated to be a positive voltage of 600V and a negative voltage of 100V, the pulse frequency is regulated to be a positive pulse frequency of 100Hz and a negative pulse frequency of 80Hz, the duty ratio is regulated to be a positive duty ratio of 12 percent and a negative duty ratio of 50 percent, the reaction time is 10min, and the magnesium oxide biological ceramic coating with the scaly bone-like nano structure is constructed on the surface of the substrate;
(5) centrifugal loading treatment of BMP: fixing a bone nail with a magnesium oxide biological ceramic coating with a scaly bone-imitating nano structure on the surface in a centrifuge tube, pouring a mixed solution of 20-100 mg PLGA, 1 mL dichloromethane, 0.5-10 mug bone morphogenetic protein and 0.2-0.8 mmol phosphate buffer salt, immersing the magnesium alloy bone nail in the mixed solution for 5-30 s, then placing the bone nail in a spin coater, rotating the bone nail at a speed of 100-1000 rpm for 10-200 s at a working temperature of 20-30 ℃, and taking out;
(6) and (3) washing the AZ31B magnesium alloy bone nail with alcohol, drying in vacuum, sterilizing and preserving aseptically for later use to obtain the degradable magnesium alloy bone nail with the scaly bone-like nanostructure coating on the surface.
Fig. 1 and 2 are SEM images of the low and high power of a successful complete scaly biomimetic bone nanostructure coating built on the surface of AZ31B magnesium alloy, illustrating that this example can successfully build the teachings of the present invention.
Example 2
(1) Firstly, processing a bone nail by using AZ31B magnesium alloy;
(2) bone nail pretreatment: and grinding and polishing AZ31B magnesium alloy bone nails by using metallographic abrasive paper with the marks of 600#, 800#, and 1000# in sequence from coarse sand to fine sand, then ultrasonically cleaning by using acetone, 70% alcohol and distilled water, and drying for later use.
(3) Preparation of electrolyte solution: preparing 10L of sodium phosphate solution with the concentration of 10g/L and 1g/L of sodium hydroxide solution by adopting a sodium phosphate solution system for later use;
(4) micro-arc oxidation of the bone nail: and (3) placing the AZ31B magnesium alloy bone nail into an electrolytic bath of a bipolar pulse micro-arc oxidation device, adding a prepared electrolyte solution, and adjusting process parameters to perform micro-arc oxidation on the AZ31B magnesium alloy bone nail by taking the AZ31B magnesium alloy bone nail as an anode and a stainless steel electrolytic bath as a cathode. The technological parameters are as follows: in the constant voltage mode, the working voltage is regulated to be positive voltage 700V and negative voltage 120V, the pulse frequency is regulated to be positive pulse frequency 200Hz and negative pulse frequency 300Hz, the duty ratio is regulated to be positive duty ratio 30% and negative duty ratio 40%, the reaction time is 20min, and the magnesium oxide biological ceramic coating with a small amount of scaly bone-like nano structures is constructed on the surface of the substrate.
(5) Centrifugal loading treatment of BMP: fixing a bone nail with a small amount of scaly bone-imitating nano-structure magnesium oxide bioceramic coating on the surface in a centrifuge bowl, pouring a mixed solution of 20-100 mg PLGA, 1 mL dichloromethane, 0.5-10 mug bone morphogenetic protein and 0.2-0.8 mmol phosphate buffer salt, immersing the magnesium alloy bone nail in the mixed solution for 5-30 s, then placing the bone nail in a spin-coating machine, rotating the bone nail at a speed of 100-1000 rpm for 10-200 s, and taking out the bone nail at a working temperature of 20-30 ℃;
(6) and (3) washing the AZ31B magnesium alloy bone nail with alcohol, drying in vacuum, sterilizing, and preserving aseptically for later use to obtain the degradable magnesium alloy bone nail with a small amount of scaly bone-like nanostructure coating on the surface.
Fig. 3 is an SEM picture of a small amount of scaly bone-like nanostructure coating built on the surface of AZ31B magnesium alloy.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing disclosure, without departing from the spirit or essential characteristics of the invention, and it is intended to cover all such modifications and variations as fall within the true spirit and scope of the invention.
Claims (2)
1. The preparation method of the degradable magnesium alloy nail with the scaly bone-imitating nanostructure coating is characterized in that the degradable magnesium alloy nail with the scaly bone-imitating nanostructure coating is composed of an AZ31B magnesium alloy nail matrix and a magnesium oxide bioceramic coating of a scaly bone-imitating nanostructure loaded with PLGA-bone morphogenetic protein BMP, and the magnesium oxide bioceramic coating of the scaly bone-imitating nanostructure is combined with the surface of the AZ31B magnesium alloy nail matrix and is formed by stacking the bone-imitating nanostructure generated by micro-arc oxidation of an AZ31B magnesium alloy matrix and an electrolyte solution by a micro-arc oxidation technology; the preparation method of the degradable magnesium alloy bone nail with the scaly bone-imitating nano-structure coating comprises the following steps:
(1) providing an AZ31B magnesium alloy bone nail;
(2) providing an electrolyte solution comprising sodium phosphate and sodium hydroxide;
(3) polishing the surface of the AZ31B magnesium alloy bone nail, performing micro-arc oxidation on the surface of an AZ31B magnesium alloy bone nail matrix by adopting a bipolar pulse micro-arc oxidation device in the electrolyte solution by taking the AZ31B magnesium alloy bone nail as an anode and a stainless steel electrolytic cell wall as a cathode, and constructing a magnesium oxide ceramic coating with an adjustable and controllable characteristic scaly bone-like nano structure on the surface of the AZ31B magnesium alloy bone nail matrix; the process parameter range of the micro-arc oxidation is as follows: the working voltage adjusting range is 200-800V of positive voltage and 0-300V of negative voltage, the pulse frequency adjusting range is 50 Hz-800 Hz of positive pulse frequency and 50 Hz-800 Hz of negative pulse frequency, the duty ratio adjusting range is 4% -80% of positive duty ratio and 4% -50% of negative duty ratio, and the reaction time is 0.5-20 min;
(4) loading PLGA-bone morphogenetic protein BMP between the magnesium oxide scaly bone-like nanostructure laminas of the AZ31B magnesium alloy bone nail obtained in the step (3) by adopting a centrifugal loading technology; the specific operation of the centrifugal load technology is as follows: preparing a mixed solution of 20-100 mg of PLGA, 1 mL of dichloromethane, 0.5-10 mu g of bone morphogenetic protein and 0.2-0.8 mmol of phosphate buffer salt, immersing the magnesium alloy bone nail obtained in the step (3) into the mixed solution for 5-30 s, then placing the bone nail into a spin coater, rotating the bone nail at a speed of 100-1000 rpm for 10-200 s, and controlling the working temperature to be 20-30 ℃;
(5) and (4) finally, washing the AZ31B magnesium alloy bone nail obtained in the step (4) with alcohol, drying in vacuum, sterilizing and preserving aseptically for later use to obtain the degradable magnesium alloy bone nail with the scaly bone-imitating nano-structure coating.
2. The preparation method of the degradable magnesium alloy bone nail with the scaly bone-like nanostructure coating according to claim 1, wherein the electrolyte solution of the step (2) contains 5-20 g/L of Na3PO4And 1-10 g/L NaOH, wherein the working mode of the micro-arc oxidation is a constant-pressure mode.
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