CN110665772B - Preparation method of composite coating containing metal organic framework MOF and polycaprolactone PCL on surface of degradable magnesium alloy - Google Patents
Preparation method of composite coating containing metal organic framework MOF and polycaprolactone PCL on surface of degradable magnesium alloy Download PDFInfo
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Abstract
The invention provides a preparation method of a composite coating containing metal organic framework MOF and polycaprolactone PCL on the surface of a degradable magnesium alloy, which comprises the following steps: (1) mechanical polishing treatment of magnesium alloy, (2) preparation of folic acid modified MOF powder, and (3) preparation of PCL-MOF composite coating. The invention mixes folic acid modified HKUST-1(MOF-FA) with PCL solution, and drops the mixed solution on the surface of AZ31 magnesium alloy to form composite coating (PCL-MOF). In the coating, the MOF can form hydrogen bonds with the PCL so as to improve the compactness of the PCL and achieve the effect of delaying corrosion of the magnesium alloy. Meanwhile, MOF-FA can also be used as a carrier of copper ions, and the copper ions are slowly released in the coating degradation process to promote the proliferation and differentiation of osteoblasts.
Description
Technical Field
The invention relates to the technical field of metal organic framework materials, polymer coatings and biodegradable metal materials, in particular to a preparation method of a composite coating containing metal organic framework MOF and polycaprolactone PCL on the surface of a degradable magnesium alloy.
Background
Due to the proper mechanical property and special biological function, magnesium (Mg) and alloy thereof have great potential in the field of biological materials and have good prospects in the aspects of orthopedic implants and cardiovascular stents. The biodegradability of magnesium alloys has a significant advantage over other orthopedic implant materials, since the implanted magnesium alloy can slowly degrade while tissue reforms during healing and provides sufficient mechanical properties, thus avoiding a second removal procedure. In addition, magnesium is an essential element in the human body, and it participates in almost all metabolic pathways. Approximately 60% of the magnesium is stored in the bone matrix, which also aids in bone healing. However, magnesium is very easy to lose electrons in aqueous solution to form cations, so that magnesium alloy is very easy to corrode, and the corrosion rate is not controllable. Corrosion of magnesium alloys can cause premature loss of mechanical properties of the material, a local increase in pH and the generation of large amounts of hydrogen, which can have an effect on osteogenic capacity. Therefore, controlling the degradation rate of magnesium alloys is very important for developing applications of magnesium alloys in biomedical materials.
Among surface modification methods of magnesium alloys, coating a polymer is a common method in which Polycaprolactone (PCL) is widely spotlighted because of its unique properties. PCL has excellent biocompatibility, has been approved by the food and drug administration, and is a biodegradable polyester. In the in vivo environment, polycaprolactone can be hydrolyzed by phagocytes, the only metabolite of which is 6-hydroxyhexanoic acid. In addition, PCL can improve the bonding force between bone and implant and prevent the matrix from releasing gas, and its crystallinity can also provide good corrosion resistance for the matrix. However, experiments have shown that PCL coated magnesium alloys lose about 23% of their weight after 72 hours of immersion and do not meet the longer degradation requirement. In addition, PCL also needs to further improve its bone conduction capability.
In recent years, Metal Organic Frameworks (MOFs) have attracted a wide range of attention. MOFs are composed of metal nodes and organic ligands, and have porosity and crystallinity. In addition, some MOFs have good biosafety and bioactivity and have been applied to the field of biomaterials, such as drug loading, anticancer, antibacterial, and wound healing. HKUST-1 is a member of the MOF material, which consists of copper nodes and organic ligands of trimesic acid. During the hydrolysis of HKUST-1, it acts as a carrier of copper ions to slowly release copper ions, which have been shown to enhance osteoblast proliferation and differentiation. However, HKUST-1 contains more carboxyl groups, and water molecules easily enter the pores to destroy the structure. Thus, studies have shown that HKUST-1 can be modified with folic acid to improve its water stability.
Disclosure of Invention
Aiming at the situation, the invention provides a preparation method of a composite coating containing metal organic framework MOF and polycaprolactone PCL on the surface of a degradable magnesium alloy, which comprises the steps of mixing folic acid modified HKUST-1(MOF-FA) with a PCL solution, and dropwise adding the mixed solution to the surface of AZ31 magnesium alloy to form the composite coating (PCL-MOF). In the coating, the MOF can form hydrogen bonds with the PCL so as to improve the compactness of the PCL and achieve the effect of delaying corrosion of the magnesium alloy. Meanwhile, MOF-FA can also be used as a carrier of copper ions, and the copper ions are slowly released in the coating degradation process to promote the proliferation and differentiation of osteoblasts.
The problems in the prior art can be effectively solved.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a preparation method of a composite coating containing metal organic framework MOF and polycaprolactone PCL on the surface of a degradable magnesium alloy is characterized by comprising the following steps:
1) mechanical polishing treatment of magnesium alloy
Polishing the AZ31 magnesium alloy on a polishing machine by using 2400-mesh sand paper, placing the polished AZ31 magnesium alloy in absolute ethyl alcohol for ultrasonic cleaning for 14-16 minutes, and naturally drying at room temperature for later use;
2) preparation of folate-modified MOF powders
Dissolving 35-40mL of folic acid in dimethyl sulfoxide to obtain a folic acid solution, stirring and mixing the folic acid solution and 0.5-1mL of ethanol solution of trimesic acid, adding 30-35mL of ethanol, then dropwise adding 0.5-2mL of copper acetate monohydrate aqueous solution, stirring and reacting for 40 minutes under the condition of 300rpm to obtain a mixed solution, centrifuging the mixed solution for 2 minutes at the rotation speed of 8000rpm by using a centrifuge, then washing for three times by using a mixed solvent of dimethyl sulfoxide, absolute ethyl alcohol and deionized water, finally washing for three times by using the absolute ethyl alcohol, and drying in a vacuum drying oven to obtain powder MOF-FA;
3) preparation of PCL-MOF composite coating
Adding the MOF-FA powder obtained in the step 2) into a dichloromethane solvent, ultrasonically dispersing for 20 minutes, mixing the solution with a dichloromethane solution of PCL to obtain a uniform PCL-MOF solution, dropwise adding the PCL-MOF solution to the surface of the magnesium alloy obtained in the step 1), then placing the magnesium alloy in a drying oven for drying, after the magnesium alloy is completely dried, dropwise adding the PCL-MOF solution to the surface of the magnesium alloy again, and drying to obtain a sample Mg-PCL-MOF.
Preferably, the folic acid concentration in the step 2) is 1-2mmol/L, the ethanol solution concentration of the trimesic acid is 250-300mol/L, the ethanol volume fraction is 50%, and the copper acetate monohydrate aqueous solution concentration is 350-400 mol/L.
Preferably, the volume ratio of the mixed solvent in the step 2) is dimethyl sulfoxide 2: absolute ethyl alcohol 1: deionized water 1.
Preferably, the final concentrations of MOF and PCL in the PCL-MOF mixed solution in step 3) are 0.5 wt% and 6 wt%, respectively.
Preferably, the volume of each dropwise adding of the PCL-MOF solution in the step 3) is 50 μ L.
Preferably, the oven drying temperature in step 3) is 37 ℃.
The invention has the following beneficial effects:
(1) according to the invention, the composite coating is prepared on the surface of the AZ31 magnesium alloy by using the mixed solution of the MOF and the PCL, and the MOF can be connected with the PCL through a hydrogen bond, so that the composite coating has good compactness and can provide long-term corrosion resistance for the AZ31 magnesium alloy.
(2) The folic acid modified HKUST-1 in the invention is hydrolyzed along with the degradation of the coating, so as to release copper ions, and can promote the proliferation and differentiation of osteoblasts.
(3) The preparation method is simple and easy to implement, low in implementation difficulty and low in equipment investment.
Drawings
The following figures are all the representations of the results obtained for example 3 and the control groups for the polishing of AZ31 magnesium alloy and Mg-PCL (i.e.the polymer coating obtained by adding two drops of a PCL solution onto the surface of AZ31 magnesium alloy):
FIG. 1 is an X-ray diffraction (XRD) pattern of the MOF-FA powder obtained in step 2) of example 3 and of the HKUST-1 powder obtained in example 4 as a control;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) of the product of FIG. 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of the Mg-PCL-MOF sample obtained in step 3) of example 3, and of a polished AZ31 magnesium alloy and Mg-PCL sample as a control;
FIG. 4 is a microscopic morphology and elemental analysis spectra of AZ31 magnesium alloy, Mg-PCL samples, and Mg-PCL-MOF samples;
FIG. 5 is a polarization curve of AZ31 magnesium alloy, Mg-PCL sample and Mg-PCL-MOF sample;
FIG. 6 is an electrochemical impedance energy Nyquist plot of AZ31 magnesium alloy, Mg-PCL sample and Mg-PCL-MOF sample, showing the magnitude of the electrochemical impedance of the product;
FIGS. 7, 8 and 9 show the pH change and the release of magnesium and copper ions in the long-term immersion of AZ31 magnesium alloy, Mg-PCL sample and Mg-PCL MOF sample, respectively;
FIG. 10 FIG. 11 shows cytotoxicity test and alkaline phosphatase activity test, respectively, showing cell viability and cell differentiation-promoting effect of AZ31 magnesium alloy, Mg-PCL and Mg-PCL-MOF, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
The specific embodiment of the invention is as follows:
example 1:
step one, mechanical polishing treatment of magnesium alloy
The AZ31 magnesium alloy was polished on a polisher with 2400 mesh sandpaper until the surface was smooth and presented with a mirror gloss. Placing the polished AZ31 magnesium alloy in absolute ethyl alcohol for ultrasonic cleaning for 15 minutes, and naturally drying at room temperature for later use;
example 2:
step one, mechanical polishing treatment of magnesium alloy
The AZ31 magnesium alloy was polished on a polisher with 2400 mesh sandpaper until the surface was smooth and presented with a mirror gloss. Placing the polished AZ31 magnesium alloy in absolute ethyl alcohol for ultrasonic cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the PCL coating, which comprises the following specific steps:
1) dissolving PCL in dichloromethane to obtain solution with concentration of 6 wt%
2) And (3) dropwise adding the solution on the surface of the magnesium alloy obtained in the step one, drying in a 37 ℃ oven, after complete drying, dropwise adding a PCL solution on the surface of the magnesium alloy again, and drying to obtain a sample Mg-PCL. The volume of the solution added dropwise was 50. mu.L each time.
Example 3:
step one, mechanical polishing treatment of magnesium alloy
The AZ31 magnesium alloy was polished on a polisher with 2400 mesh sandpaper until the surface was smooth and presented with a mirror gloss. Placing the polished AZ31 magnesium alloy in absolute ethyl alcohol for ultrasonic cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing folic acid modified MOF powder, which comprises the following specific steps:
1) 36mL of a solution of folic acid dissolved in dimethyl sulfoxide (concentration: 1.64mmol/L) was mixed with 0.8mL of an ethanol solution of trimesic acid (concentration: 260mol/L) under stirring, 34mL of 50% ethanol was added to the above solution, and 1mL of an aqueous solution of copper acetate monohydrate (concentration: 375mol/L) was added dropwise. The rotation speed was adjusted to 300rpm, and the reaction was stirred for 40 minutes.
2) And centrifuging the obtained solution for 2 minutes at 8000rpm by using a centrifuge, then washing the solution for three times by using a mixed solvent of dimethyl sulfoxide, absolute ethyl alcohol and deionized water (the volume ratio is 2:1:1), finally washing the solution for three times by using the absolute ethyl alcohol, and drying the solution in a vacuum drying oven to obtain powder MOF-FA.
Step three, preparing the PCL-MOF composite coating, which comprises the following specific steps:
1) and adding the synthesized MOF-FA powder into a dichloromethane solvent, ultrasonically dispersing for 20 minutes, and mixing the solution with a dichloromethane solution of PCL to obtain a uniform PCL-MOF solution. The final concentrations of MOF and PCL in the mixed solution were 0.5 wt% and 6 wt%, respectively.
2) And (3) dropwise adding the mixed solution on the surface of the magnesium alloy obtained in the step one, drying in a 37 ℃ drying oven, after complete drying, dropwise adding a PCL-MOF solution on the surface of the magnesium alloy again, and drying to obtain a sample Mg-PCL-MOF. The volume of the solution added dropwise was 50. mu.L each time.
Example 4
Step one, preparing MOF (HKUST-1) powder
The method comprises the following specific steps: an aqueous solution of copper acetate monohydrate (375 mol/L) and an ethanol solution of trimesic acid (260 mol/L) were mixed in equal volumes and stirred for 30 minutes. The obtained product was centrifuged, washed three times with 50% ethanol, and dried to obtain powder HKUST-1.
The corresponding assay results of example 3 were analyzed as follows: (Mg-PCL obtained by coating a layer of PCL on a magnesium alloy and a magnesium alloy polished with AZ31, as a control group)
A series of characterizations were carried out on four samples of polished AZ31 magnesium alloy (Mg) obtained in example 1, Mg-PCL sample obtained by adding PCL to the surface of AZ31 magnesium alloy in example 2, and Mg-PCL-MOF constructed by adding PCL-MOF solution to the surface of AZ31 magnesium alloy in example 3.
As shown in FIG. 1, the MOF-FA sample was shown to have characteristic peaks of the HKUST-1 sample by X-ray diffraction (XRD) detection, indicating that the modification of folic acid did not affect the crystal structure of HKUST-1.
As shown in FIG. 2, analysis by X-ray photoelectron spectroscopy (XPS) showed that both MOF-FA and HKUST-1 contained C, H, O and Cu elements, whereas only the MOF-FA powder contained N elements, which are derived from folic acid, demonstrating the successful modification of folic acid.
As shown in FIG. 3, the three samples are detected by X-ray diffraction (XRD) and have a characteristic peak of magnesium alloy and a characteristic peak of crystalline polymer PCL, and a characteristic peak of MOF-FA powder can be observed in the Mg-PCL-MOF sample and is positioned at 11.76 degrees, which indicates that MOF-FA is successfully prepared in the PCL coating layer to form the composite coating layer.
As shown in FIG. 4, parallel scratches were present on the polished AZ31 magnesium alloy surface, and after PCL and PCL-MOF coating, the scratches were completely covered, and a flat coating was observed.
Fig. 5 is an electrochemical polarization curve of a product, from which the corrosion current (Icorr) of a sample can be obtained, and specific values thereof are summarized as follows:
the corrosion current of the AZ31 magnesium alloy can be reduced by three orders of magnitude after the PCL coating is covered, and the corrosion current of the AZ31 magnesium alloy can be further reduced by one order of magnitude after the PCL and the MOF-FA form a composite coating.
FIG. 6 is a Nyquist plot of the electrochemical impedance of the product, which shows that Mg-PCL has a larger arc of impedance compared to polished AZ31 magnesium alloy, while Mg-PCL-MOF has the largest arc of impedance among the three samples, indicating that the maximum arc of impedance of Mg-PCL-MOF can further retard corrosion of AZ31 magnesium alloy.
FIGS. 7 and 8 show the pH change and magnesium ion release during 21 days of soaking, and it can be seen that in the long-term soaking, the pH values of the PCL and PCL-MOF coating samples are lower than that of the polished AZ31 magnesium alloy, and the release amount of magnesium ions is lower, so that the PCL and PCL-MOF coating can inhibit the corrosion of the magnesium alloy substrate, and the PCL-MOF inhibiting effect is better.
FIG. 9 shows the release of copper ions in 21 days of immersion of the product Mg-PCL-MOF, which shows that in long-term immersion, the copper ions are slowly released along with the degradation of the coating, and the concentration of the released copper ions reaches 1.1ppm when the product is immersed for about 500 hours.
FIG. 10 is a cytotoxicity assay characterized using cell fluorescence and cell viability. Osteoblasts co-cultured with polished magnesium alloy appeared circular, while cells co-cultured with Mg-PCL and Mg-PCL-MOF samples appeared polygonal and spread well. Cytotoxicity tests show that the materials have no obvious toxicity, and the Mg-PCL-MOF sample group shows the highest cell activity.
FIG. 11 is an alkaline phosphatase activity assay showing that Mg-PCL-MOF has the best ability to promote osteoblast differentiation.
The functional verification steps are not described in detail above, and are obtained in a conventional manner (for example, the steps of fig. 1 to 11 and the parameter summary table are obtained in a conventional manner, and thus, the detailed description thereof is omitted)
Although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. A preparation method of a composite coating containing metal organic framework MOF and polycaprolactone PCL on the surface of a degradable magnesium alloy is characterized by comprising the following steps:
1) mechanical polishing treatment of magnesium alloy
Polishing the AZ31 magnesium alloy on a polishing machine by using 2400-mesh sand paper, placing the polished AZ31 magnesium alloy in absolute ethyl alcohol for ultrasonic cleaning for 14-16 minutes, and naturally drying at room temperature for later use;
2) preparation of folate-modified MOF powders
Dissolving 35-40mL of folic acid in dimethyl sulfoxide to obtain a folic acid solution, stirring and mixing the folic acid solution and 0.5-1mL of ethanol solution of trimesic acid, adding 30-35mL of ethanol, dropwise adding 0.5-2mL of copper acetate monohydrate aqueous solution, stirring and reacting for 30-50 minutes under the condition of 200-400rpm to obtain a mixed solution, centrifuging the mixed solution for 1-5 minutes by using a centrifuge at the rotation speed of 7000-10000rpm, washing for one to four times by using a mixed solvent of dimethyl sulfoxide, absolute ethyl alcohol and deionized water, finally washing for one to four times by using absolute ethyl alcohol, and placing the washed solution in a vacuum drying box for drying to obtain powder MOF-FA;
3) preparation of PCL-MOF composite coating
Adding the MOF-FA powder obtained in the step 2) into a dichloromethane solvent, ultrasonically dispersing for 20 minutes, mixing the solution with a dichloromethane solution of PCL to obtain a uniform PCL-MOF solution, dropwise adding the PCL-MOF solution to the surface of the magnesium alloy obtained in the step 1), then placing the magnesium alloy in a drying oven for drying, after the magnesium alloy is completely dried, dropwise adding the PCL-MOF solution to the surface of the magnesium alloy again, and drying to obtain a sample Mg-PCL-MOF;
in the step 2), the concentration of folic acid is 1-2mmol/L, the concentration of an ethanol solution of trimesic acid is 300mol/L of 250-ketone, the volume fraction of ethanol is 50%, and the concentration of a copper acetate monohydrate aqueous solution is 400mol/L of 350-ketone;
the volume ratio of the mixed solvent in the step 2) is dimethyl sulfoxide: anhydrous ethanol: deionized water 2:1: 1;
the concentration of MOF and PCL in the PCL-MOF mixed solution in the step 3) is respectively 0.5 wt% and 6 wt%.
2. The method for preparing the composite coating layer of the degradable magnesium alloy surface containing the metal organic framework MOF and the polycaprolactone PCL according to claim 1, wherein the volume of the PCL-MOF solution added in step 3) is 50 μ L.
3. The method for preparing the composite coating layer of the degradable magnesium alloy surface containing the metal organic framework MOF and the polycaprolactone PCL according to claim 1, wherein the drying temperature of the oven in the step 3) is 37 ℃.
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