CN116407687A - Surface modified porous iron-based bracket and preparation method and application thereof - Google Patents
Surface modified porous iron-based bracket and preparation method and application thereof Download PDFInfo
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- CN116407687A CN116407687A CN202111664394.7A CN202111664394A CN116407687A CN 116407687 A CN116407687 A CN 116407687A CN 202111664394 A CN202111664394 A CN 202111664394A CN 116407687 A CN116407687 A CN 116407687A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 41
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 22
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- 238000012795 verification Methods 0.000 abstract 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/06—Etching of iron or steel
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention relates to the field of biomedical materials, in particular to a surface modified porous iron-based bracket, a preparation method and application thereof. The invention carries out surface modification aiming at the existing porous Fe-based scaffold, regulates and controls the surface morphology structure of the scaffold, has higher degradation rate on the premise of not damaging the mechanical property of the scaffold, has better biocompatibility through experimental verification, can promote the proliferation and differentiation of osteoblasts on the surface of the scaffold, and further realizes perfect matching of the degradation rate and the bone regeneration rate of the scaffold in vivo.
Description
Technical Field
The invention relates to the field of biomedical materials, in particular to a surface modified porous iron-based bracket, a preparation method and application thereof.
Background
Bone defects caused by diseases, wounds, traffic accidents, etc. have become a common clinical disease. Most of bone defect repair needs the assistance of endophytes, and the problems of limited sources, secondary operation and the like of autologous bones serving as gold standards are difficult to meet clinical requirements, so that the rapid development of artificial bone repair materials is promoted. Among the many orthopedic materials that have been marketed, traditional medical metals such as titanium and titanium alloys, stainless steel, etc. are widely used in the field of orthopedic implants due to their good mechanical properties. However, these materials still have some problematic problems, such as that they may generate scraps and release harmful metal ions during the human oral use, resulting in the potential risk of inflammation and osteolysis, often requiring secondary surgery for extraction, increasing patient risk and economic burden. Therefore, there is a need to develop degradable metallic materials with excellent mechanical properties and good biocompatibility to replace conventional medical metals.
The current degradable metal materials mainly comprise magnesium-based, zinc-based and iron-based materials, wherein the related researches on the magnesium-based materials are the most extensive, but the mechanical strength of the magnesium-based materials and the zinc-based materials is lower, and the magnesium-based materials cannot be used for repairing bone defects of bearing parts. Iron-based materials have good biocompatibility and excellent mechanical strength, and are capable of effectively fixing and supporting bone tissue of a load-bearing part, and attention has been paid in recent years.
Although iron-based implants can better promote bone tissue regeneration and repair at the load-bearing bone site, their excessively low degradation rate causes a mismatch with the rate of formation of new bone around the implant, severely affecting the rate of healing and repair of the bone defect. The conventional method is to add alloy elements into the substrate material to accelerate degradation, but the degradation promotion degree of the method on the iron-based material can not meet the in-vivo degradation requirement of the iron-based material, and the method can also have great influence on the mechanical properties of the material. In addition, pore structures are introduced into the iron matrix by a template method, a space-occupying filler method and a 3D printing technology, and the degradation rate is improved by increasing the contact effective area with corrosive environment, but the degradation rate cannot be obviously improved by only preparing porous iron.
Disclosure of Invention
Aiming at the problems in the process, the invention aims to provide the surface modified porous Fe-based bracket with good mechanical property and high degradation speed.
Previous studies by the inventors (In vitro and 48 weeks In vivo performances of 3D printed porous Fe-30Mn biodegradable scaffolds (Acta Biomaterialia,2021,121,724-740) indicate that 3D printed Fe-based scaffolds exhibit better biocompatibility during bone defect repair, but there is still a problem that the degradation rate of Fe-based materials is too slow, resulting In a mismatch between the material degradation rate and the new bone regeneration rate.
The inventors hoped to increase the degradation rate by again surface modifying the existing porous structure of the Fe-based scaffold. Chemical etching based on liquid-phase solution soaking is often used for surface modification of a porous bracket, but the etching speed is low, and uniform and controllable bracket surface morphology structure is difficult to realize. Dealloying is a common method for realizing nano-alloying of metal alloys (such as Mn-Cu, mg-Al, etc.), but the nano-porous iron-based material prepared directly by dealloying is not suitable for being used as an implantation stent, and no dealloying related research on Fe-Mn-based porous stents has been reported so far. The inventor finds that different medium solutions are selected, nanometer topological structures with different morphologies can be constructed on the surface of the Fe-based bracket through electrochemical dealloying, the contact area between the Fe-based bracket and the solution is increased, and the degradation rate of the Fe-based bracket is obviously improved on the premise of not affecting the mechanical property of the bracket. In addition, the construction of the nanometer topological structure on the surface of the bracket can play a certain role in promoting the proliferation and differentiation of osteoblasts, promote the bone-promoting capacity of the bracket and finally realize the dynamic adaptation of the degradation rate and the osteogenesis rate in the service period of the Fe-based bracket.
The technical scheme adopted by the invention is as follows:
the preparation method of the surface modified porous iron-based bracket comprises the following specific processes:
an electrochemical workstation is used, a porous iron-based bracket is used as a working electrode, an Ag/AgCl electrode in a 3.33mol KCl solution is used as a reference electrode, and a platinum plate is used as a counter electrode. Placing the surface-treated porous Fe-Mn scaffold in electrolyte solution, and passing through open-circuit potential and potentiodynamic polarization curve (900 s, potentiodynamic polarization scanning rate 1mVs -1 ) The electrochemical properties of the Fe-based alloy were characterized to determine the critical voltage. Constant potential dealloying treatment is carried out for different time (20 min-120 min) and different temperature (25-45 ℃) in the critical voltage range (-0.85V, -0.2V).
Wherein the electrolyte is an acidic sodium chloride solution or a dilute hydrochloric acid solution.
The type and concentration of the electrolyte used for dealloying and the dealloying voltage, temperature and time can influence the surface morphology structure of the bracket, if the excessive dealloying can influence the bracket structure, the mechanical property is reduced, and if the dealloying degree is insufficient, a proper nano structure cannot be formed, and the degradation rate cannot be improved.
The porous iron-based scaffold can be prepared by common porous metal preparation methods, such as a template method, a space-occupying filler method, 3D printing, an organic sponge impregnation method and the like. The difference of the porosities can influence the mechanical properties of the stent, so the stent prepared by different methods needs to meet the basic mechanical property requirement of the in-vivo implant, and the porosity of the stent used in the embodiment of the invention is about 70-80%.
Further, na in the acidic sodium chloride solution: h=10:1-20:1, the concentration of the dilute hydrochloric acid solution is 0.5% -5%.
Further, na in the acidic sodium chloride solution: h=20:1; the concentration of the dilute hydrochloric acid solution was 1.5%.
Further, the porous Fe-based bracket is one of Fe-Mn alloy and Fe-Mn-Si alloy, and further is Fe-30Mn.
Fe-30Mn is an Fe-Mn alloy containing 30wt% Mn.
The Fe-Mn alloy has better biocompatibility than other iron alloys, wherein Fe-30Mn can keep better balance between the inhibition effect of cell viability and mechanical property.
Further, when the electrolyte solution is a dilute hydrochloric acid solution, constant voltage of-0.4V and constant potential dealloying treatment at 25 ℃ for 20min are selected. When the electrolyte solution is an acidic sodium chloride solution, constant voltage of-0.65V and temperature of 25 ℃ are selected, and constant potential dealloying treatment is carried out for 30 min.
The invention also provides a surface microporous iron-based bracket adopting the method.
The invention also provides application of the surface modified porous iron-based scaffold in bone repair materials.
Further, the bone repair material is an auxiliary endophyte for bone defect repair.
Compared with the prior art, the invention has the beneficial effects that:
the invention carries out dealloying treatment on the existing porous Fe-based bracket, builds a proper nano structure within the range of 100nm on the surface of the porous bracket through screening the types of electrolyte and dealloying voltage, temperature and time, does not influence the mechanical property of the porous bracket, and can effectively increase the surface area of the porous bracket and improve the degradation rate of the iron-based bracket through the cooperation of the original micropores and nano structure of the porous bracket. Experiments prove that the scaffold has better biocompatibility, can promote proliferation and differentiation of osteoblasts on the surface of the scaffold, and further realizes perfect matching of the degradation rate of the scaffold in vivo and the regeneration rate of bones.
Drawings
Fig. 1 Scanning Electron Microscope (SEM) observations: a, d is an untreated porous Fe-Mn scaffold; b, e is a HCl treated porous Fe-Mn scaffold; c, f is NaCl treated porous Fe-Mn rack
Fig. 2 Scanning Electron Microscope (SEM) observations: a, HCl solution concentration 1.25%, b: HCl solution concentration 2.5%, c: HCl solution concentration 5%
Fig. 3 Scanning Electron Microscope (SEM) observations: a, dealloying time is 10min, b: dealloying time 20min, c: dealloying time 1h
Fig. 4 Scanning Electron Microscope (SEM) observations: constant voltage-0.4V, b: constant voltage-0.3 v, c: constant voltage-0.2V
Fig. 5 Scanning Electron Microscope (SEM) observations: a, the concentration of the citric acid solution is 1.25%, b: citric acid solution concentration 2.5%, c: citric acid solution concentration 5%
FIG. 6 contact angle test of surfaces of different materials
FIG. 7 open circuit potential (a) and potentiodynamic polarization curve (b) for different scaffolds
FIG. 8 observation by a laser scanning confocal microscope (CLSM) of MC3T3-E1 incubated for 3 days on different material surfaces
FIG. 9 analysis of proliferation of MC3T3-E1 cells on days 1, 3 and 5 co-culture with different materials
FIG. 10 cell proliferation assay of different stent extracts
FIG. 11 results of osteogenic related gene expression after Co-culture of different scaffolds extracts with MC3T3-E1 cells
FIG. 12 mechanical strength comparison of Fe-Mn stents before and after dealloying
Detailed Description
The porous iron-based scaffolds used In the examples of the present invention were prepared according to the method of literature In vitro and 48 weeks In vivo performances of 3D printed porous Fe-30Mn biodegradable scaffolds (Acta Biomaterialia,2021,121,724-740). The iron-based material used was Fe-30Mn.
Example 1
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/NaCl scaffolds
Weighing NaCl and HCl according to the proportion (Na: H=20:1), then placing into a beaker, adding deionized water, and fully stirring for 10 minutes to prepare an acidic sodium chloride solution; electrochemical was used at room temperature (25 ℃ C.)The chemical workstation takes a porous Fe-30Mn bracket as a working electrode, takes an Ag/AgCl electrode in 3.33mol KCl solution as a reference electrode and takes a platinum plate as a counter electrode. Placing the surface-treated porous Fe-Mn scaffold in an acidic sodium chloride solution, and passing through an open-circuit potential (900 s) and an electrokinetic polarization curve (electrokinetic polarization scanning rate is 1 mVs) -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, constant voltage of-0.65V is selected, and constant potential dealloying treatment is carried out for 30min at the temperature of 25 ℃.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain the Fe-Mn material (Fe-Mn/NaCl).
Example 2
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/HCl scaffolds
HCl was diluted with deionized water and mixed well for 10 minutes to prepare a 1.5% HCl solution. An electrochemical workstation was used at room temperature (25 ℃) with a porous Fe-30Mn scaffold as the working electrode, an Ag/AgCl electrode in 3.33M KCl solution as the reference electrode, and a platinum plate as the counter electrode. Placing the surface-treated porous Fe-Mn scaffold in 1.5% HCl solution, and passing through open circuit potential (900 s) and potentiodynamic polarization curve (potentiodynamic polarization scanning rate is 1mVs -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, constant voltage of-0.4V is selected, and constant potential dealloying treatment is carried out for 20min at 25 ℃.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain the Fe-Mn material (Fe-Mn/HCl).
The scanning electron microscope results of examples 1 and 2 and the untreated porous iron-based scaffold are shown in fig. 1, the contact angle test is shown in fig. 6, and the compressive stress test result is shown in fig. 12.
According to fig. 1 and 6, after dealloying treatment, the morphology and micro-nano structure of the porous Fe-based scaffold are obviously changed, and the contact angle is smaller and the hydrophilicity is better. Hydrophilic surfaces facilitate the adherent growth of cells. Meanwhile, the test result of the compressive stress in fig. 12 shows that the surface modified iron-based stent has smaller compressive stress drop, namely the method of the invention can maintain better mechanical property while improving the degradation rate, and meets the requirement of in vivo implantation of the stent.
Examples comparison of different dealloying conditions
1. Solutions of medium of different concentrations
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/HCl scaffolds
HCl was diluted with deionized water and stirred well for 10 minutes to prepare HCl solutions with concentrations of 1.25%, 2.5% and 5%, respectively. An electrochemical workstation was used at room temperature (25 ℃) with a porous Fe-30Mn scaffold as the working electrode, an Ag/AgCl electrode in a 3.33mol KCl solution as the reference electrode, and a platinum plate as the counter electrode. The porous Fe-Mn scaffold after surface treatment is respectively placed in HCl solutions with different concentrations, and is subjected to open-circuit potential (900 s) and electrokinetic potential polarization curve (electrokinetic potential polarization scanning rate is 1 mVs) -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, constant voltage of-0.4V and temperature of 25 ℃ are selected, and constant potential dealloying treatment is carried out for 20 min.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain the Fe-Mn material treated by the HCl medium solution with different concentrations. The scanning electron microscope result is shown in fig. 2.
2. Different dealloying times
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/HCl scaffolds
HCl was diluted with deionized water and stirred well for 10 minutes to prepare three sets of HCl solutions at 1.25% strength. An electrochemical workstation was used at room temperature (25 ℃) with a porous Fe-30Mn scaffold as the working electrode, an Ag/AgCl electrode in a 3.33mol KCl solution as the reference electrode, and a platinum plate as the counter electrode. The porous Fe-Mn scaffold after surface treatment is respectively placed in HCl solutions with different concentrations, and is subjected to open-circuit potential (900 s) and electrokinetic potential polarization curve (electrokinetic potential polarization scanning rate is 1 mVs) -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, constant voltage of-0.4V and temperature of 25 ℃ are selected, and constant potential dealloying treatment is respectively carried out for 10min, 20min and 1 h.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain Fe-Mn (HCl) materials with different treatment times. The scanning electron microscope result is shown in fig. 3.
3. Different dealloying currents
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/HCl scaffolds
HCl was diluted with deionized water and stirred well for 10 minutes to prepare three sets of HCl solutions at 1.25% strength. An electrochemical workstation was used at room temperature (25 ℃) with a porous Fe-30Mn scaffold as the working electrode and an Ag/AgCl electrode in 3.33mol KCl solution as the reference electrodeThe electrode uses a platinum plate as a counter electrode. The porous Fe-Mn scaffold after surface treatment is respectively placed in HCl solutions with different concentrations, and is subjected to open-circuit potential (900 s) and electrokinetic potential polarization curve (electrokinetic potential polarization scanning rate is 1 mVs) -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, constant voltage of-0.4V, -0.3V, -0.2V and temperature of 25 ℃ are respectively selected, and constant potential dealloying treatment is carried out for 20 min.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain the Fe-Mn (HCl) material treated by different dealloying currents. The scanning electron microscope result is shown in fig. 4.
4. Different medium solution types
1) Surface treatment of porous Fe-30Mn scaffold
The porous Fe-30Mn bracket is sequentially cleaned by absolute ethyl alcohol, acetone and deionized water respectively through ultrasonic waves (the temperature is 25 ℃, the ultrasonic power is 120W, and the ultrasonic frequency is 40 KHz) for 15min, and then is placed in a high-temperature drying oven for drying at 60 ℃ for 1h, and is used for subsequent surface modification.
2) Surface modification of porous Fe-Mn/citric acid scaffolds
Citric acid was diluted with deionized water and stirred well for 10 minutes to prepare 1.25%, 2.5% and 5% citric acid solutions, respectively. An electrochemical workstation was used at room temperature (25 ℃) with a porous Fe-30Mn scaffold as the working electrode, an Ag/AgCl electrode in a 3.33mol KCl solution as the reference electrode, and a platinum plate as the counter electrode. Placing the surface-treated porous Fe-Mn scaffold in 1.5% citric acid solution, and passing through open circuit potential (900 s) and potentiodynamic polarization curve (potentiodynamic polarization scanning rate is 1mVs -1 ) The electrochemical properties of the Fe-Mn alloy are characterized. After the critical potential is obtained, the constant potential dealloying treatment is carried out for 1 hour at 25 ℃ with the voltage of-0.6V.
And after the electrochemical reaction is finished, taking out the sample, slightly and repeatedly washing the sample by using deionized water and ethanol until the sample is neutral, and then placing the sample in a high-temperature drying oven at 60 ℃ for drying for 1h to obtain the Fe-Mn material (Fe-Mn/citric acid). The scanning electron microscope result is shown in fig. 5.
As can be seen from fig. 2, 3 and 4, the concentration of the medium solution, the dealloying time, the dealloying current intensity, etc. are different, the dealloying effect is obviously different, when the concentration of the HCl medium solution is more than 5%, the dealloying time is 10min and 1h, and the dealloying voltage is-0.3V and-0.2V, the structural distribution of the obtained stent surface is irregular, no uniform nanostructure is formed, and therefore, only the proper concentration of the medium solution, the dealloying time and the dealloying voltage are selected, the stent surface can form the lamellar nanostructure with uniform distribution.
As can be seen from a comparison of fig. 5 and fig. 2, when citric acid is selected as the medium solution, although dealloying can be achieved, the lamellar nanostructures cannot be formed in a uniform distribution regardless of the concentration thereof, and thus, only a suitable medium solution is selected to form a suitable nanostructure.
Example degradation Rate determination
The material setting: control group: untreated porous Fe-Mn scaffold groups; experimental group: example 1 dealloying Fe-Mn set of stents (Fe-Mn/NaCl), example 2 dealloying Fe-Mn set of stents (Fe-Mn/HCl)
The corrosion resistance of the stent is tested by electrochemistry, and the degradation rate of the material is evaluated, and the results are shown in figure 7, wherein the corrosion potential of the Fe-Mn/NaCl and Fe-Mn/HCl stent is obviously lower than that of a control pure Fe-Mn stent, which shows that the dealloyed stent has lower electrochemical stability and higher corrosion tendency and is easier to degrade in human body.
Example different scaffold surface cell morphology observations and proliferation experiments
The material setting: control group: blank control without scaffold; experimental group: untreated porous Fe-Mn scaffold, example 1 dealloying Fe-Mn scaffold (Fe-Mn/NaCl)
The following cells were used: mouse embryonic osteoblast precursor cells (MC 3T 3-E1)
The culture mode is as follows: indirect culture, cell density: 2X 10 4 Individual/orifice plate
The observation mode is as follows: the cell morphology observation adopts FDA/PI bicolor fluorescence method to dye the cells on the surface of the material, and then the cell morphology observation is performed through laser confocal observation; cell proliferation experiments were tested by the CCK-8 method.
From the results of the staining in FIG. 8, MC3T3-E1 grew well on all material surfaces and exhibited normal cell morphology. Along with the extension of the culture time, the cell density of the MC3T3-E1 inoculated on the surfaces of the three groups of materials is gradually increased, which shows that the dealloying treatment Fe-Mn material has excellent cell compatibility.
FIG. 9 shows the observation of CCK-8 that both material cells had a tendency to proliferate throughout the co-culture period, indicating good cell growth viability. But the proliferation was less than that of the control group relative to the blank. Probably because the Fe-Mn scaffold is degraded, fe is generated 2+ 、Mn 2+ And the local ion concentration is high, which affects the cells.
Examples cell proliferation and osteogenic Gene expression Effect test of different scaffolds extracts
The material setting: control group: blank control; experimental group: example 1 dealloying Fe-Mn set of stents (Fe-Mn/NaCl), example 2 dealloying Fe-Mn set of stents (Fe-Mn/HCl)
The following cells were used: mouse embryonic osteoblast precursor cells (MC 3T 3-E1)
After preparing the stent extract according to GB/T16886 medical device biological evaluation series standard, it was co-cultured with MC3T3-E1 cells.
As shown in fig. 10, although HCl and NaCl scaffolds have different degradation rates, after 5 days of culture, the cell proliferation densities of the two material extracts have not been significantly different from that of the blank, indicating that the surface-modified porous iron-based scaffold prepared according to the present invention has good biocompatibility.
As shown in FIG. 11, from the results of the osteogenic related gene expression after co-culturing different stent extracts with MC3T3-E1 cells, it can be seen that the proliferation and differentiation of osteoblasts on the surface of the stent can be promoted after the micro-nano morphology and structure of the stent surface are regulated by dealloying treatment.
Claims (10)
1. The preparation method of the surface modified porous iron-based bracket is characterized by comprising the following steps: performing constant potential dealloying treatment on the porous iron-based bracket for 20-120 min at the temperature of 25-45 ℃ and the critical voltage of-0.85V to-0.2V; wherein the electrolyte is an acidic sodium chloride solution or a dilute hydrochloric acid solution.
2. The method of claim 1, wherein Na: h=10:1-20:1, the concentration of the dilute hydrochloric acid solution is 0.5% -5%.
3. The method of claim 2, wherein Na: h=20:1; the concentration of the dilute hydrochloric acid solution was 1.5%.
4. The method of claim 1, wherein the porous Fe-based scaffold is any one of an Fe-Mn alloy, an Fe-Mn-Si alloy.
5. The method of claim 4, wherein the porous Fe-based scaffold is Fe-30Mn.
6. The method according to claim 1, wherein when the electrolyte solution is a dilute hydrochloric acid solution, constant voltage of-0.4V is selected and constant potential dealloying treatment is performed at 25 ℃ for 20 minutes.
7. The method according to claim 1, wherein when the electrolyte solution is an acidic sodium chloride solution, constant voltage of-0.65V is selected, and the temperature is 25 ℃ and constant potential dealloying treatment is performed for 30 min.
8. A surface modified porous iron-based scaffold, characterized in that it has been prepared by the method according to any one of claims 1-7.
9. Use of the surface modified porous iron-based scaffold of claim 8 in bone repair materials.
10. The use according to claim 9, wherein the bone repair material is an auxiliary endophyte for repair of bone defects.
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