CN117180522B - ZIF-8 coating modified zinc substrate implant and preparation method thereof - Google Patents
ZIF-8 coating modified zinc substrate implant and preparation method thereof Download PDFInfo
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 114
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000000576 coating method Methods 0.000 title claims abstract description 96
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- 150000003751 zinc Chemical class 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title abstract description 6
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a zinc substrate implant modified by a ZIF-8 coating and a preparation method thereof, wherein the zinc substrate implant is soaked in an organic solvent for ultrasonic cleaning; then soaking the zinc substrate implant in a dilute hydrochloric acid solution until bubbles are generated on the surface of the zinc substrate implant; soaking the zinc substrate implant in 2-methylimidazole methanol solution to enable zinc ions on the zinc substrate implant to fully react with the 2-methylimidazole aqueous solution; adding a zinc nitrate hexahydrate methanol solution with the same volume as the 2-methylimidazole aqueous solution into the reaction solution, and placing the solution in a 37 ℃ environment for reaction to generate a ZIF-8 coating with a preset thickness on the zinc substrate implant; immersing the zinc substrate implant with the ZIF-8 coating with preset thickness into methanol for ultrasonic cleaning, and drying to obtain the zinc substrate implant modified by the ZIF-8 coating. The invention effectively protects the surface of the metal zinc, effectively regulates and controls the degradation rate of the metal zinc, improves the cell compatibility of the metal zinc, and enables the metal zinc to be matched with the repair process of the surrounding damaged vascular tissues.
Description
Technical Field
The invention relates to a method for preparing a metallic zinc surface coating and application thereof in biomedical engineering, in particular to a ZIF-8 coating modified zinc substrate implant and a preparation method thereof.
Background
According to world health organization predictions, the number of people worldwide who die from cardiovascular disease in 2030 will reach 2200 tens of thousands. Among them, coronary heart disease caused by cardiovascular stenosis or obstruction has extremely high morbidity and mortality. Compared with drug treatment and surgery, the stent implantation has high success rate and small trauma, thus showing obvious advantages, and has become a treatment method commonly adopted in clinic. In the implantation process, the vascular stent compressed on the balloon is conveyed to a vascular lesion section through the balloon catheter system and then is expanded along with the expansion of the balloon, at the moment, the metal stent generates plastic deformation, and after the balloon is contracted and recovered, radial supporting force is continuously provided, so that the smoothness of the blood vessel is maintained. In recent years, with the aging of the population in China, and the trend of younger cardiovascular diseases, the demand of vascular stents is increasing. At the end of 2020, china formally brings the coronary stent into medical insurance, the unit price of the stent after collection is reduced to hundreds of yuan, and the burden of patients is greatly reduced.
The vascular stent applied clinically at present is made of corrosion-resistant inert medical metals, such as 316L stainless steel, cobalt-based alloy, nickel-titanium alloy and the like. The permanent stent is in the body of a patient after implantation for a long time, and is easy to cause adverse events such as chronic inflammation of blood vessels, late thrombus, restenosis in the stent and the like, thereby threatening the life and health of the patient. The ideal solution is to develop a biodegradable stent which provides sufficient support for the diseased vessel at the early stage of implantation, and after the diseased vessel resumes normal function, the stent material is gradually degraded and absorbed or removed by the human body, and if necessary, a secondary implantation can be performed. Because of good biocompatibility, mechanical properties and processing advantages, degradable metals represented by magnesium, zinc and alloys thereof are widely applied to the field of manufacturing degradable vascular stents. Zinc is one of the microelements necessary for human body, and plays an important role in regulating cell growth and differentiation, immune system and nervous system. In addition, zinc alloys are more suitable as materials for stents due to their lower degradation rate, which is more moderate, than magnesium alloys. However, too fast release of zinc ions is detrimental to cell adhesion, growth and proliferation and even leads to cell death. Therefore, how to regulate the degradation rate and degradation behavior of the degradable metal, so that the degradation process of the degradable metal is matched with the repair process of the surrounding damaged vascular tissue, becomes a key problem for limiting the clinical application of the degradable stent.
Metal-organic frameworks (MOFs) are porous nanomaterials formed by self-assembly of organic compounds as ligands through coordination bonds with Metal atoms or clusters as the center. As one of the most well-known MOFs, a zeolitic imidazolate framework material (Zeolitic Imidazolate Frame-8, ZIF-8) consists of a zinc (II) salt and 2-methylimidazole, which has the advantages of high specific surface area, regular crystal structure and the like. ZIF-8 can be regarded as a very effective corrosion inhibitor, and as a nanofiller for organic coatings, it is effective in enhancing its corrosion resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for modifying a zinc substrate implant by using a ZIF-8 coating, and a preparation method and application thereof, wherein the modification of the zinc substrate implant is realized by preparing the ZIF-8 coating so as to delay degradation of the zinc substrate implant in vivo. The invention aims to effectively regulate the degradation rate of metallic zinc and improve the cell compatibility of the metallic zinc by the protection effect of the ZIF-8 coating so that the metallic zinc can be matched with the repair process of surrounding damaged vascular tissues.
A method of preparing a ZIF-8 coating modified zinc base implant comprising:
Step one: soaking the zinc substrate implant in an organic solvent for ultrasonic cleaning to remove organic substances on the surface of the zinc substrate implant;
Step two: then soaking the zinc substrate implant in a dilute hydrochloric acid solution, and generating zinc ions on the zinc substrate implant when bubbles are generated on the surface of the zinc substrate implant;
Step three: soaking the zinc substrate implant in 2-methylimidazole methanol solution to enable zinc ions on the zinc substrate implant to fully react with the 2-methylimidazole aqueous solution;
Step four: adding a zinc nitrate hexahydrate methanol solution with the same volume as the 2-methylimidazole aqueous solution into the reaction solution, and placing the solution in a 37 ℃ environment for reaction to generate a ZIF-8 coating with a preset thickness on the zinc substrate implant;
Wherein the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 1:7.
Step five: immersing the zinc substrate implant with the ZIF-8 coating with preset thickness into methanol for ultrasonic cleaning, and drying to obtain the zinc substrate implant modified by the ZIF-8 coating.
Further, the organic solvent is absolute ethyl alcohol or acetone.
Further, the mass concentration of the dilute hydrochloric acid solution is 0.005% -0.01%.
Further, the concentration of the 2-methylimidazole methanol solution was 0.5mM.
Further, the reaction time for producing a ZIF-8 coating of a predetermined thickness on the zinc-based implant in the fourth step is 72 hours.
Further, the zinc base implant is a zinc guide wire.
A ZIF-8 coating modified zinc base implant prepared by the above method.
An implantable zinc-based vascular stent made from a zinc-based implant modified with a ZIF-8 coating.
The beneficial effects of the invention are as follows:
(1) The preparation method can generate the ZIF-8 coating with preset thickness on the zinc-based implant, thereby increasing the controllability and flexibility of the material and providing more accurate material for specific application.
(2) The ZIF-8coating can be used as a protective layer to protect zinc-based implants from excessive degradation and corrosion, thereby improving the stability and lifetime of the implant.
(3) By forming the ZIF-8 coating on the zinc-based implant, the degradation speed of zinc in the body can be effectively reduced, so that the compatibility of the zinc-based implant with human tissues is enhanced, and the potential inflammation or adverse reaction is reduced.
(4) The method mentions the use of zinc guide wires as a substrate, but in theory it can be extended to other types of zinc-based implants, with a broader application potential.
(5) The technology can be used for preparing an implantable zinc-based vascular stent, and the novel stent possibly has better biocompatibility and better treatment effect, thereby providing a new choice for clinical application.
Drawings
FIG. 1 is a topographical representation of metal organic framework (ZIF-8) nanoparticles; wherein, the left image is a Scanning Electron Microscope (SEM) image of ZIF-8 nano particles; the middle graph is a Transmission Electron Microscope (TEM) graph of ZIF-8 nanoparticles; the right panel shows the results of particle size analysis of ZIF-8 nanoparticles.
FIG. 2 is a morphology characterization of ZIF-8 coating modified zinc sheets; wherein, figures a and b are Scanning Electron Microscope (SEM) images of the ZIF-8 coating surface; panels c and d are Scanning Electron Microscope (SEM) images of ZIF-8 coating cross sections.
FIG. 3 is a compositional characterization of ZIF-8 coating modified zinc sheets; wherein FIG. a is an energy dispersive X-ray spectroscopy (EDS) plot of a ZIF-8 coating; FIG. b is a Fourier infrared (FT-IR) plot of a ZIF-8 coating; panel c is the x-ray diffraction (XRD) pattern of the ZIF-8 coating.
FIG. 4 is an SEM image of a ZIF-8 coated modified zinc sheet after three repeated bends.
FIG. 5 is an SEM photograph of a pure zinc sheet (upper panel Bare Zn) and a ZIF-8 coated modified zinc sheet (lower panel) before and after immersion in Hanks balanced salt solution.
FIG. 6 shows the pH and zinc ion concentration changes of the solution of pure zinc flake (Bare Zn) and ZIF-8 coated modified zinc flake (ZIF-8 coating) immersed in Hanks balanced salt solution; wherein figure a is the solution pH change; FIG. b shows the result of detecting the concentration of zinc ions in the solution.
FIG. 7 is a hemolysis test of the leachate after ZIF-8 coated modified zinc sheets (ZIF-8 coating) are immersed in Hanks balanced salt solution for 72 hours.
FIG. 8 is a SEM image of cells after culturing umbilical vein endothelial cells (HUVECs) for 48 hours on pure zinc plates (Bare Zn) and ZIF-8 coated modified zinc plates (ZIF-8 coating).
FIG. 9 is a graph showing the cytotoxicity test results of the leachate after immersing pure zinc sheets (Bare Zn) and ZIF-8 coated modified zinc sheets (ZIF-8 coating) in Hanks balanced salt solution for 72 hours.
FIG. 10 is a micro-CT image of a pure zinc guidewire (Bare Zn) and ZIF-8 coated modified zinc guidewire (ZIF-8 coating) implanted in the abdominal aorta of a rat for 1 month.
FIG. 11 is a chart of HE staining of vascular tissue sections of rats after 1 month of implantation of pure zinc guide wires (Bare Zn) and ZIF-8 coated modified zinc guide wires (ZIF-8 coating) into the abdominal aorta.
Detailed Description
The objects and effects of the present invention will become more apparent from the following detailed description of the preferred embodiments and the accompanying drawings, it being understood that the specific embodiments described herein are merely illustrative of the invention and not limiting thereof.
1. Physical and chemical property detection
First, a zinc sheet having a thickness of 2mm was cut to a size of 10mm by 15mm, and then the following steps were performed: 3M (1500 mesh) sand paper is polished for 1 minute, then the sand paper is soaked in absolute ethyl alcohol for ultrasonic cleaning for 5 minutes, organic substances on the surface of a zinc sheet are removed, then the zinc sheet is soaked in 0.01M dilute hydrochloric acid solution for 1 minute, and when bubbles are generated on the surface of the zinc sheet, zinc ions are generated on the zinc sheet; soaking zinc sheets in a 2-methylimidazole methanol solution with the concentration of 0.5mM for 60 minutes to fully react zinc ions on a zinc substrate with the 2-methylimidazole; adding zinc nitrate hexahydrate methanol solution with the concentration of 3.5mM, which has the same volume as the 2-methylimidazole methanol solution, into the reaction solution, standing at room temperature for 60 minutes, and finally placing the solution in a 37 ℃ environment for reaction for 72 hours to generate a ZIF-8 coating with preset thickness on a zinc sheet; immersing the zinc sheet with the ZIF-8 coating with preset thickness into methanol for ultrasonic cleaning, and drying to obtain the zinc sheet modified by the ZIF-8 coating. And respectively carrying out physicochemical detection on the ZIF-8 nano particles and the zinc sheet modified by the ZIF-8 coating in the solution.
(1) ZIF-8 nanoparticle characterization: observing the morphology of the ZIF-8 material by a transmission electron microscope (Transmission electron microscopy, TEM) and a Scanning Electron Microscope (SEM); the particle size and Zeta potential of ZIF-8 nanoparticles were measured using a dynamic light scattering instrument (DYNAMIC LIGHT SCATTERING, DLS).
(2) ZIF-8 coating characterization: observing the surface morphology of the zinc substrate modified by the ZIF-8 coating by using SEM, and analyzing the element composition and distribution of the sample surface by using a matched energy dispersive X-ray spectrometer (EDS); analyzing the composition of the nanoparticles using an energy spectrometer (ENERGY DISPERSIVE spectrometer, EDS); analyzing the chemical composition and structure of the ZIF-8 coating by using an X-ray diffraction (XRD) and a Fourier transform infrared spectrometer (Fourier transforminfrared spectroscopy, FT-IR); and (3) characterizing the water contact angle of the surface of the zinc sheet modified by the ZIF-8 coating on the pure zinc substrate by adopting an optical video contact angle analyzer.
The experimental results are as follows: through the morphological characterization of the nano particles collected in the solution, the ZIF nano particles synthesized under the system are better in dispersibility and are in regular dodecahedron structure particles (shown as a left graph and a middle graph of figure 1), and the particle size is about 500nm (shown as a right graph of figure 1); the morphological features of the composite ZIF-8 structure are shown in the left diagram of FIG. 1; the Zeta potential of the ZIF-8 nano particles detected by DLS is 14.37 +/-0.94 mV, which proves that the ZIF-8 nano particles have good dispersibility and are electropositive.
Carrying out appearance characterization on the zinc substrate modified by the ZIF-8coating by using a scanning electron microscope, wherein the surface of the zinc substrate modified by the ZIF-8coating is flat and smooth as shown by the appearance of the coating surface shown by a and b in fig. 2; as shown in the cross-sectional morphology of the coating shown in FIGS. 2, c and d, the ZIF-8coating thickness was about 400nm. Analysis of the composition of the nanoparticles using an energy spectrometer (EDS) found that the ZIF-8coating consisted of C, N, O and Zn (fig. 3 a); fourier transform infrared spectroscopy (FTIR) analysis of pure zinc substrate (Bare Zn) and ZIF-8coating modified zinc substrate (ZIF-8 coating), respectively, the spectra of ZIF-8coating showed characteristic absorption peaks of ZIF-8: zn-N peaks appear at 421cm -1, and the stretching vibrations at 1110 and 1580cm -1 are attributed to C-N and C-N of the imidazole ring (b in FIG. 3); x-ray diffraction (XRD) analysis is carried out on a pure zinc sheet (Bare Zn) and a zinc sheet modified by a ZIF-8coating, and the result shows that the spectrogram of the ZIF-8coating is identical with a ZIF-8 standard spectrogram (Stimulated ZIF-8), so that the synthesized coating is proved to be ZIF-8.
2. Coating stability detection
(1) To investigate the firmness of the coating, we repeatedly bent a zinc sheet sample modified with ZIF-8 coating 3 times and observed the surface morphology of the coating using SEM.
(2) To investigate the degradation behavior and degradation rate of pure zinc flakes and ZIF-8 coating modified zinc flakes, samples of pure zinc flakes and ZIF-8 coating modified zinc flakes of the same size were immersed in 20mL balanced salt solution (Hanks, pH 6.7), respectively, and then kept at 37±0.5 ℃ for immersion. Observing the morphology of the pure zinc sheet and the zinc sheet modified by the ZIF-8 coating by utilizing a scanning electron microscope, and measuring the concentration of Zn 2+ in the leaching solution by utilizing ICP-MS; meanwhile, the pH change condition of the soaking liquid is detected by a pH test paper.
The experimental results are as follows: as shown in FIG. 4, after the zinc sheet sample modified by the ZIF-8 coating is repeatedly bent for 3 times, the coating is not broken and falls off, which indicates that the ZIF-8 coating has very good firmness.
In order to study the long-acting corrosion resistance of the ZIF-8coating in vitro, static soaking experiments were performed by soaking pure zinc sheets and zinc sheet samples modified by the ZIF-8coating in Hanks. FIG. 5 shows the surface morphology of pure zinc flakes (Bare Zn) and ZIF-8coating modified zinc flakes (ZIF-8 coating) before and after immersion. As can be seen from the figure, after 72 hours of immersion, the surface of the pure zinc sheet is covered by flocculent corrosion products, and a foam structure appears, which indicates that the pure zinc sheet is corroded; while ZIF-8coating surfaces were not visibly damaged by corrosion and remained overall intact with only small amounts of corrosion products attached.
As a result of the two ions generated by zinc corrosion during the soaking process, OH - and Zn 2+ gradually accumulate in the leach liquor. Thus, the pH and Zn 2+ concentrations of the various sample leaches were monitored during the test to evaluate the degradation rate of pure zinc flakes and zinc flakes modified with ZIF-8 coatings, the test results are shown in FIG. 6. It can be observed that the pH value of the leaching solution of the pure zinc substrate shows a change trend of rising and then falling, while the pH value of the leaching solution of the zinc substrate modified by the ZIF-8 coating is basically unchanged, which indicates that the ZIF-8 coating can delay the corrosion of the pure zinc substrate; similarly, the zinc ion concentration of the leaching solution three days before soaking is detected, so that the zinc ion concentration in the leaching solution of the zinc substrate modified by the ZIF-8 coating is lower, and the ZIF-8 can slow down the degradation of the zinc substrate to a certain extent.
3. Hemolysis test
The haemocompatibility of ZIF-8 coated modified zinc sheets was tested according to ISO 10993-4 using an anti-coagulated rabbit blood (containing 2.5% sodium citrate by weight) for haemolysis experiments. First, 5mL of physiological saline and 4mL of anticoagulated pig-rabbit blood were mixed to prepare diluted blood. Subsequently, ZIF-8 coated modified zinc sheet samples were placed in 15mL centrifuge tubes, each of which had a different volume of saline (sample surface area/saline volume of 3:1), and saline and ultrapure water without the samples served as negative/positive controls, respectively. The centrifuge tubes are placed in a constant temperature water bath at 37 ℃ for 0.5h, then 0.2mL of diluted blood is added into each centrifuge tube and is fully and uniformly mixed, and the centrifuge tubes are continuously soaked under the water bath condition at 37 ℃. Finally, the supernatant was centrifuged at 3000rpm for 5min, and the absorbance of the supernatant was measured with an enzyme-labeled instrument at a test wavelength of 540nm. The Hemolysis Rate (HR) of each sample was calculated by the following formula:
wherein Ai is the absorbance (%) of the sample, an is the absorbance (%) of the negative control group, and Ap is the absorbance (%)
The experimental results are as follows: as shown in the test result of the hemolysis rate of the zinc sheet modified by the ZIF-8 coating in FIG. 7, the hemolysis rate is lower than 5%, the standard implementation procedure (ASTM F756-08) for evaluating the hemolysis performance of the standard material is adopted, no obvious destructive effect on erythrocytes is seen, and the requirement of the biological material on the percentage of the hemolysis rate is met.
4. Cell compatibility test
The biological material is used for the vascular stent to be implanted into a blood vessel and is bound to be connected with endothelial cells, so that Human Umbilical Vein Endothelial Cells (HUVECs) are selected as research objects, and the tolerance of the HUVEC cells to leaching liquor is evaluated, so that the biological material has certain reference significance for guiding the selection of the biological material for the stent. The medium used in the experiment was DMEM medium containing 10% Fetal Bovine Serum (FBS) and 1% diabody (penicillin-streptomycin); cell culture was performed in a cell incubator containing 5% CO 2, a relative humidity of 95% and a temperature of 37 ℃. The in vitro cell compatibility of the coated samples was studied by direct and indirect cell experiments.
(1) The direct method comprises the following steps: the pure zinc sheet and zinc sheet sample modified by ZIF-8 coating are sterilized by double-sided ultraviolet irradiation for 30min, and are respectively placed in 24-hole cell culture plates. 1mL of a HUVEC cell suspension containing 6.0X10 4 cells was then inoculated onto the surface of each sample. After 48h incubation, cells were gently washed twice with PBS and fixed by addition of paraformaldehyde. Cell morphology was characterized using scanning electron microscopy.
(2) And (3) an indirect method: the extract collected in the in vitro soaking experiments was filter sterilized and used to indirectly evaluate cytotoxicity of pure zinc sheet and ZIF-8 coating modified zinc sheet samples. Specifically, first 100 μl of HUVEC cell suspension (1×10 4 cells per ml) was added per well in a 96-well cell culture plate. After 24h of culture, the culture medium of each well was replaced with a leaching solution of different concentrations, and after 48h of culture, the cell viability of the different leaching solutions was determined by CCK-8 method. At least 5 parallel test groups were secured per sample.
The experimental results are as follows: the cell compatibility of the surface of the vascular implant material is one of the important factors affecting the endothelialization process of the stent surface. Due to the rapid corrosion of metallic zinc, the released excess OH - and Zn 2+ not only inhibit cell adhesion and growth on the material surface, but can even cause cell death. Therefore, in order to evaluate the effect of ZIF-8 coating modification on the compatibility of metallic zinc surface cells, the adhesion and growth state of pure zinc sheets and ZIF-8 coating modified zinc sheet sample surface cells were first studied. HUVEC cells were inoculated directly onto the surface of pure zinc sheet and zinc sheet modified with ZIF-8 coating, after 48h of culture, cell washing and fixation were performed, and the morphology of adherent cells on different surfaces was observed using a scanning electron microscope. As shown in FIG. 8, the pure zinc sheet showed a small cell size and an adherent state, while the ZIF-8 coating-modified zinc sheet showed a large cell size and an adherent state. These results indicate that the ZIF-8 coating modified zinc sheet surface favors cell adhesion due to its excellent corrosion protection properties.
To evaluate cytotoxicity of the degradation products of different samples, the extracts collected in the soaking experiments were mixed with a culture medium to prepare diluted extracts of various concentrations, and then HUVEC cells were cultured therein for 24 hours, and then cell viability was analyzed by CCk-8 method using the culture medium as a negative control group during the experiments. As shown in fig. 9, both the pure zinc sheet and the zinc sheet modified by ZIF-8 coating show a certain proliferation promoting effect at low concentration; at high concentration, the pure zinc sheet extract shows stronger cytotoxicity, and the zinc sheet extract modified by the ZIF-8 coating does not show cytotoxicity, because the ZIF-8 coating delays the degradation speed of the metal zinc sheet, the pH change of the extract of a coating sample is smaller, less Zn 2+ is released, and zinc ions have the function of promoting cell proliferation at low concentration, but Zn 2+ is accumulated in a large amount along with the increase of the concentration of the extract, so that the extract shows obvious cytotoxicity.
5. In vivo degradation analysis
The degradation conditions of the pure zinc substrate and the ZIF-8 coating modified zinc substrate in animal bodies are researched through animal experiments, and the vascular repair conditions of the pure zinc substrate and the ZIF-8 coating modified zinc substrate after the implantation of the samples are characterized. The implants were pure zinc guide wires 10mm long and 0.1mm in diameter and ZIF-8 coating modified zinc guide wires. The two guide wires described above were implanted subcutaneously in SD rats according to ISO 10993-6-2016.
Subcutaneous implantation surgery: all animal experimental procedures were approved by the university of Zhejiang laboratory animal management and animal welfare ethics committee. Experiments randomly selected 6 male SD rats weighing about 200-275 g. Healthy rats were kept in an environmentally appropriate animal laboratory for 1 week prior to surgery and then randomized into two groups of 3 animals. After anesthetizing the rats (the disappearance of the orthotopic reflex of the rats was confirmed as successful anesthesia), the incisors and limbs of the rats were fixed on an operating table, respectively, so that the rats were in a prone position. After shaving and sterilizing, two incisions were made in the back of each rat, and the double-sided uv sterilized samples were placed in subcutaneous tissue of the back of the rat, followed by suturing the incisions. After 12 weeks of feeding, the rats were sacrificed and the implants and surrounding 1cm of tissue were excised. The removed implant was fixed with 10% formaldehyde solution and then dehydrated with gradient ethanol for use.
In vivo degradation test: to evaluate the in vivo degradation of magnesium implants, the removed implants were first scanned by Micro-CT.
HE pathology detection: implants with surrounding tissue on the surface were fixed with 10% formaldehyde solution and dehydrated with gradient ethanol prior to paraffin embedding. Tissue sections (thickness about 5 μm) were then removed, dewaxed, re-hydrated, stained with hematoxylin and eosin, washed with ethanol solution, sealed with neutral resin, and photographed under an inverted microscope.
The experimental results are as follows: as shown in fig. 10, after 4 weeks of implantation, pure zinc guide wires were observed to exhibit severe corrosion (the corroded sites are dark portions) in the 2D reconstruction of micro-CT. In contrast, zinc substrates in ZIF-8 coating modified zinc guidewire samples erode less, which fully demonstrates the long-lasting corrosion protection of ZIF-8 coatings in vivo.
Microscopic pictures of H & E stained sections of tissue surrounding pure zinc guide wire and ZIF-8 coating modified zinc guide wire implants are shown in fig. 11. All tissues tightly bound to the implant surface showed significant proliferation of fibroblasts. Many red blood cells and severe inflammatory cell infiltration phenomena were observed in the tissue surrounding the pure zinc guidewire implant, as well as tissue damage due to hydrogen bubble collapse from corrosion. After modification of the ZIF-8 coating, the tissue surrounding the ZIF-8 coating modified zinc guidewire implant showed only a slight inflammatory response and fewer erythrocytes, and no tissue damage due to hydrogen bubbles was found. The ZIF-8 coating has the optimal long-acting corrosion resistance, so that the toxicity and damage of corrosion products of the metallic zinc to surrounding tissues are effectively reduced, and finally the inflammatory reaction of the surrounding tissues of the modified metallic zinc guide wire of the ZIF-8 coating is effectively reduced.
According to the test results of the ZIF-8 coating modified metal zinc guide wire and the zinc sheet, the implantable zinc-based vascular stent made of the zinc substrate modified by the ZIF-8 coating has the same beneficial effects, and the modified coating can effectively regulate and control the degradation rate of metal zinc on the implantable zinc-based vascular stent, so that the modified zinc-based vascular stent can be matched with the repair process of surrounding damaged vascular tissues, and the repair effect is further improved.
It will be appreciated by persons skilled in the art that the foregoing description is a preferred embodiment of the invention, and is not intended to limit the invention, but rather to limit the invention to the specific embodiments described, and that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for elements thereof, for the purposes of those skilled in the art. Modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A method of preparing a ZIF-8 coating modified zinc base implant comprising:
Step one: soaking the zinc substrate implant in an organic solvent for ultrasonic cleaning to remove organic substances on the surface of the zinc substrate implant;
Step two: then soaking the zinc substrate implant in a dilute hydrochloric acid solution, and generating zinc ions on the zinc substrate implant when bubbles are generated on the surface of the zinc substrate implant;
Step three: soaking the zinc substrate implant in 2-methylimidazole methanol solution to enable zinc ions on the zinc substrate implant to fully react with the 2-methylimidazole aqueous solution;
Step four: adding a zinc nitrate hexahydrate methanol solution with the same volume as the 2-methylimidazole aqueous solution into the reaction solution, and placing the solution in a 37 ℃ environment for reaction to generate a ZIF-8 coating with a preset thickness on the zinc substrate implant;
Wherein the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 1:7;
Step five: immersing the zinc substrate implant with the ZIF-8 coating with preset thickness into methanol for ultrasonic cleaning, and drying to obtain the zinc substrate implant modified by the ZIF-8 coating.
2. The method of preparing a ZIF-8 coating modified zinc base implant according to claim 1, wherein the organic solvent is absolute ethanol or acetone.
3. The method of preparing a ZIF-8 coating-modified zinc base implant according to claim 1, wherein the diluted hydrochloric acid solution has a mass concentration of 0.005% to 0.01%.
4. The method of preparing a ZIF-8 coating modified zinc base implant according to claim 1, wherein the concentration of the 2-methylimidazole methanol solution is 0.5mM.
5. The method of preparing a ZIF-8 coating modified zinc base implant according to claim 1, wherein the reaction time for producing a ZIF-8 coating of a predetermined thickness on the zinc base implant in the fourth step is 72 hours.
6. The method of preparing a ZIF-8 coating modified zinc base implant of claim 1, wherein the zinc base implant is a zinc guide wire.
7. A ZIF-8 coating modified zinc base implant prepared by the method of any one of claims 1 to 5.
8. An implantable zinc-based vascular stent made from the ZIF-8 coating modified zinc-based implant of claim 7.
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| CN113813923B (en) * | 2021-10-18 | 2023-02-28 | 中国科学院长春应用化学研究所 | Continuous ZIF-8 membrane material and preparation method thereof |
| CN116103714A (en) * | 2021-11-10 | 2023-05-12 | 天津大学 | ZIF-8 anticorrosive film grown on carbon steel surface in situ and preparation method thereof |
| CN114191610A (en) * | 2021-12-24 | 2022-03-18 | 华中科技大学 | Magnesium-based multifunctional composite active coating and preparation method and application thereof |
| CN114748687B (en) * | 2022-04-01 | 2023-03-21 | 华中科技大学同济医学院附属协和医院 | Preparation and application of in-situ induced biomimetic mineralized ZIF-8 nano material |
| CN114797499A (en) * | 2022-05-16 | 2022-07-29 | 南京工业大学 | Durable ZIF-8 membrane material and preparation method and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| Polydopamine (PDA) coatings with endothelial vascular growth factor (VEGF) immobilization inhibiting neointimal formation post zinc (zn) wire implantation in rat aortas;Guosheng Fu et al;Biomaterials Research;20231204;1-17 * |
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