CN116832215A - Polydopamine composite graphene quantum dot grafted hydroxyapatite coating, and preparation method and application thereof - Google Patents
Polydopamine composite graphene quantum dot grafted hydroxyapatite coating, and preparation method and application thereof Download PDFInfo
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- CN116832215A CN116832215A CN202210296717.XA CN202210296717A CN116832215A CN 116832215 A CN116832215 A CN 116832215A CN 202210296717 A CN202210296717 A CN 202210296717A CN 116832215 A CN116832215 A CN 116832215A
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- graphene quantum
- hydroxyapatite coating
- quantum dot
- coating
- polydopamine
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a polydopamine composite graphene quantum dot grafted hydroxyapatite coating, and a preparation method and application thereof. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating comprises a hydroxyapatite coating prepared by plasma spraying and a functional grafting layer for grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating in situ. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating has good biocompatibility and biological oxidation resistance, can effectively promote cell proliferation and adhesion on the surface of a material under normal culture conditions and under oxidative stress conditions simulated by hydrogen peroxide of MC3T3-E1, has a scavenging effect on various active oxygen in the cells, promotes bone tissue repair in an oxidative stress environment, is a potential biomedical material, and can be used for research and development of hard tissue repair and replacement biological materials.
Description
Technical Field
The invention relates to a biological oxidation-resistant coating in an oxidation stress environment and preparation and application thereof, in particular to a polydopamine composite graphene quantum dot grafted hydroxyapatite coating and a preparation method and application thereof.
Background
With the acceleration of the aging process of population and the increase of bone injury accidents caused by traffic accidents, diseases, natural disasters and the like, the demand of artificial bone implant materials is increasing. Compared with the bone defect patient in normal physiological state, in the micro-environment of the patient suffering from bone metabolic diseases (such as diabetes, hypertension, osteoporosis and the like), the active oxygen, active nitrogen and various free radicals have higher levels, so that the oxidation capability of the body exceeds the oxidation resistance, the oxidative stress injury of tissues is easily caused around bone implantation materials, the activity of osteoblasts is inhibited, and the repair of bone tissues after operation is seriously influenced. Therefore, the development of bone implant materials with good biological oxidation resistance has important clinical significance for promoting bone repair under oxidative stress and improving bone mass.
Plasma sprayed hydroxyapatite (HAp) coating is the most widely used bone implant coating material in clinic, however, HAp coating does not have biological oxidation resistance and cannot protect osteoblasts from oxidative stress. Dopamine as a non-enzymatic antioxidant has high activity on scavenging active oxygen free radicals. And dopamine can generate oxidation polymerization-deposition effect in alkaline aqueous solution, and the formed polydopamine can be grafted to almost any substance surface along with oxidation of catechol structure, so that tight connection with HAp can be formed. The aminated graphene quantum dot has excellent free radical scavenging capability, can react with polydopamine in alkaline environment to reverse oxidation of polydopamine, so that the polydopamine retains more phenol structures, plays roles in supplying hydrogen and scavenging free radicals by electrons, and provides possibility for research and development of novel high-efficiency biological antioxidation coatings.
Disclosure of Invention
The invention provides a coating material with good biological oxidation resistance, a preparation method and application thereof, and aims to solve the defects existing in the prior art. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating has good biocompatibility and biological oxidation resistance, can effectively promote cell proliferation and adhesion on the surface of a material under normal culture conditions and under oxidative stress conditions simulated by hydrogen peroxide of MC3T3-E1, has a scavenging effect on various active oxygen in the cells, promotes bone tissue repair in an oxidative stress environment, is a potential biomedical material, and can be used for research and development of hard tissue repair and replacement biological materials.
In a first aspect, the invention provides a polydopamine composite graphene quantum dot grafted hydroxyapatite coating (HAp-PDA-GQD composite coating), which comprises a hydroxyapatite coating prepared by plasma spraying and a functional grafting layer for grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating in situ. The polydopamine coated with the graphene quantum dots is grafted to the surface of the hydroxyapatite coating prepared by the plasma spraying process, so that the hydroxyapatite is subjected to functional modification, the biological oxidation resistance of the implant is improved, and the probability of aseptic loosening in the oxidation-stressed human body environment is reduced.
Preferably, the graphene quantum dots are aminated graphene quantum dots. Although the graphene quantum dot contains abundant functional groups such as amino, carboxyl and hydroxyl, the amino-substituted graphene quantum dot has larger specific gravity amino in the edge structure of the graphene quantum dot, the introduced amino forms a hydrogen bond with the phenol of PDA to inhibit oxidation of the phenol structure, and the amino and the quinone of PDA generate Schiff base reaction to reduce the quinone into the phenol, so that the amino-substituted graphene quantum dot and polydopamine have more sufficient interaction, and the free radical scavenging activity of the whole coating can be improved.
Preferably, the thickness of the hydroxyapatite coating is 60-120 microns; the thickness of the polydopamine composite graphene quantum dot grafted layer is 50-150 nm.
In a second aspect, the invention also provides a preparation method of the polydopamine composite graphene quantum dot grafted hydroxyapatite coating. The method comprises the following steps:
(1) Preparing a hydroxyapatite coating by adopting a plasma spraying technology: spraying hydroxyapatite powder plasma on the surface of a substrate to form a hydroxyapatite coating;
(2) Preparing the polydopamine composite graphene quantum dot grafted hydroxyapatite coating on the surface of the hydroxyapatite coating by a solution polymerization method: adding graphene quantum dot solution and tris (hydroxymethyl) aminomethane into a dopamine solution, regulating the pH of the solution to 8-10, immersing a hydroxyapatite coating prepared by plasma spraying into the solution for polymerization reaction, and thus forming the polydopamine composite graphene quantum dot grafted hydroxyapatite coating by grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating.
Preferably, the particle size of the hydroxyapatite powder is 15-90 microns.
Preferably, the technological parameters of the plasma spraying are as follows: the Ar flow of the plasma gas is 32 to 50slpm, H 2 The flow is 5-12 slpm; the Ar flow of the powder carrier gas is 1.5 to 5.0slpm; the spraying distance is 100-330 mm; the spraying power is 30-45 kW.
Preferably, the base material is medical metal or medical alloy material of pure titanium, titanium alloy, stainless steel and cobalt-chromium-molybdenum alloy.
Preferably, the polymerization time is 18 to 24 hours.
Preferably, the concentration of the dopamine solution is 0.5-2.0 mg/mL, preferably 1.5-2 mg/mL; the concentration of the graphene quantum dot solution is 1.32-6.80 mg/mL.
In a third aspect, the invention provides an application of the polydopamine composite graphene quantum dot grafted hydroxyapatite coating in biological antioxidation.
The HAp-PDA-GQD composite coating has good biocompatibility and biological oxidation resistance, can effectively reduce oxidative stress damage of bone cells, and can promote repair of bone tissues in an oxidative stress environment; the preparation method has the advantages of low cost, simple operation, good repeatability, suitability for large-scale production and the like.
Drawings
FIG. 1 is an XRD pattern for three coating samples of HAp, HAp-PDA, HAp-pDA-GQD;
FIG. 2 is XPS full spectrum of three coating samples of HAp, HAp-PDA, HAp-pDA-GQD;
FIG. 3 is an SEM photograph of three coating samples of HAp, HAp-PDA, HAp-pDA-GQD;
FIG. 4 is a graph comparing the scavenging ability of three coating samples of HAp, HAp-PDA, HAp-pDA-GQD for DPPH and ABTS+ two radicals;
FIG. 5 is an SEM image of adhesion of MC3T3-E1 cells to HAp, HAp-PDA, HAp-pDA-GQD coating samples under hydrogen peroxide-simulated oxidative stress conditions; the first row of fig. 5 has a scale of 150 μm and the second row has a scale of 25 μm;
FIG. 6 (A) shows the proliferation of MC3T3-E1 cells on the surface of HAp, HAp-PDA, HAp-pDA-GQD coating in normal culture environment, (B) shows the proliferation of MC3T3-E1 cells on the surface of HAp, HAp-PDA, HAp-pDA-GQD coating in hydrogen peroxide-simulated oxidative stress environment, (C) shows the effect of HAp, HAp-PDA, HAp-pDA-GQD coating material on the ROS content in MC3T3-E1 cells in oxidative stress environment, and (D) shows immunofluorescence image of ROS in cells; the scales of (D) were 50 μm each.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent. The following illustrates the polydopamine composite graphene quantum dot grafted hydroxyapatite coating, and the preparation method and application thereof.
The invention solves the problem that the coating cannot remove free radicals in practical application to cause poor osseointegration by utilizing the performance of removing free radicals of polydopamine and graphene quantum dots on the basis of the existing hydroxyapatite coating with good biocompatibility. Specifically, the biological oxidation resistant coating provided by the invention is a Polydopamine (PDA) composite amination Graphene Quantum Dot (GQD) grafted layer deposited in situ on the surface of a plasma sprayed hydroxyapatite biological coating. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating comprises a hydroxyapatite coating prepared by plasma spraying and a functional grafting layer for grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating. The coating has excellent biocompatibility and biological oxidation resistance, can effectively reduce the oxidative damage of oxidative stress to bone tissues, and can promote the bone repair of bone defect parts of patients suffering from bone metabolic diseases. In addition, compared with an unmodified hydroxyapatite coating, the coating grafted with polydopamine and graphene quantum dots has better scavenging performance on DPPH, ABTS & lt+ & gt and other free radicals.
The thickness of the polydopamine composite graphene quantum dot grafted hydroxyapatite coating is tens of micrometers to hundreds of micrometers.
The composite coating has a unique structural design, and is characterized in that a hydroxyapatite layer and polydopamine composite graphene quantum dots grafted on the surface of the hydroxyapatite are sequentially arranged from the (titanium) substrate outwards, wherein the graphene quantum dots are embedded in a (spherical) polydopamine polymer. Ca of the phenol Structure of the grafted substance Polydopamine and hydroxyapatite 2+ Coordination chelation, the amino groups of the aminated graphene quantum dots respectively form hydrogen bonds with the phenol of polydopamine and generate Schiff base reaction with quinone. The amination edge structure of the amination graphene quantum dot can damage a compact microstructure in the dopamine oligomer, so that the oxidation resistance of the dopamine oligomer is improved; sp of simultaneously aminated graphene quantum dots 2 The C domain forms a radical scavenging site by adduct formation or electron transfer.
The preparation method of the polydopamine composite graphene quantum dot grafted hydroxyapatite coating is also shown. The bone implant coating material with good biological antioxidation function is obtained on the surface of the base material by adopting a plasma deposition method and a solution reaction method which are simple in operation and can be produced in a large scale.
And preparing the hydroxyapatite coating by adopting a plasma spraying technology. And spraying hydroxyapatite powder plasma on the surface of the substrate to obtain the HAp ceramic coating. The particle size of the hydroxyapatite powder is 15-90 microns, the particles within the size range have enough fluidity, and the powder blocking phenomenon in the spraying process is avoided, so that the spraying efficiency is improved, the cohesive force of the coating is enhanced, and the hydroxyapatite powder is promoted to be deposited on the surface of the substrate. As an example, the process parameters of the plasma spraying are: the Ar flow of the plasma gas is 32 to 50slpm, H 2 The flow is 5-12 slpm; the Ar flow of the powder carrier gas is 1.5 to 5.0slpm; the spraying distance is 100-330 mm; the spraying power is 30-45 kW. The slpm is the reference standard liters per minute. By selecting proper technological conditions, the bonding strength of the coating and the substrate can be improved, so that the coating has a micron-sized rough surface.
The thickness of the hydroxyapatite biological coating can be 60-120 microns. If the coating thickness is too thin, the coating will degrade completely in a short period of time, thereby failing to achieve complete bonding of the coating to the bone tissue; if the coating thickness is too thick, the bond strength of the coating to the substrate may be significantly reduced, risking spalling of the coating from the substrate surface.
The substrate is a metal substrate including, but not limited to, a medical metal or medical alloy material of pure titanium, titanium alloy, stainless steel, cobalt chromium molybdenum alloy. Such a substrate may provide better strength, toughness and excellent processability. The substrate may be a substrate on which a bioceramic layer typified by calcium phosphate is deposited on the surface of a metal substrate. Thus not only improving the problem of insufficient oxidation resistance of the ceramic, but also improving the bioactivity of the base material.
Graphene, graphene oxide, and reduced graphene oxide are generally of a two-dimensional lamellar structure, and are insoluble in water. The graphene quantum dot is a zero-dimensional material and has different structures and functions with graphene, graphene oxide and reduced graphene oxide. The three-dimensional dimensions of the graphene quantum dots used in the specific embodiments are all 100nm or less (preferably less than 10 nm), and the water solubility is good.
And preparing the aminated graphene quantum dots by adopting a hydrothermal method. The trinitropyrene is obtained through pyrene nitration reaction for 12-16 hours, then the trinitropyrene is subjected to hydrothermal reaction with hydrazine hydrate, ammonia water and the like for 8-10 hours, a product is subjected to suction filtration by a PTFE filter membrane with the size of 0.22 microns and is dialyzed for more than 24 hours in a dialysis bag with the retention molecular weight of more than 3500Da, and the yield of the obtained aminated graphene quantum dots is 40-55%. The aminated graphene quantum dot prepared from bottom to top by a hydrothermal method has good water solubility and biocompatibility. As an example, 2g of pyrene was weighed, dissolved in 160mL of concentrated nitric acid, and stirred at 80℃under reflux for 12h. After the reaction, the mixture was cooled to room temperature, diluted with deionized water, and suction-filtered through a 0.22 μm PTFE filter to recover the product 1,3, 6-Trinitropyrene (TNP) on the filter. TNP was dried at 60℃for 24 hours. 0.5g of TNP is mixed with 0.4mol/L of ammonia water and 1.5mol/L of hydrazine hydrate aqueous solution, and the mixture is dispersed for 2 hours by ultrasonic. Then, the temperature was set at 200℃and the hydrothermal reaction was carried out for 8 hours. After cooling, filtering insoluble carbon product with PTFE filter membrane of 0.22 μm, loading the obtained filtrate into dialysis bag (retention molecular weight > 3500 Da), dialyzing for 24 hr to remove small molecular substances such as salts, constant volume to 100mL, and preserving at 4deg.C for use.
Further obtaining the biological oxidation resistant functional coating (HAp-PDA-GQD composite coating) by a solution polymerization method. The solution polymerization reaction is carried out in an air environment at normal temperature and normal pressure, a special reaction device is not needed, toxic and irritant gas is not generated or released in the reaction process, and the method is green, safe, energy-saving and environment-friendly. In some technical schemes, dopamine hydrochloride powder is prepared into a dopamine solution with the concentration of 0.5-2.0 mg/mL, graphene quantum dot solution with the graphene quantum dot concentration of 1.32-6.80 mg/mL is added into the dopamine solution, the pH value of the solution is regulated to 8-10 by adopting tris (hydroxymethyl) aminomethane, a hydroxyapatite coating prepared by plasma spraying is immersed in the solution, and polydopamine coated with graphene quantum dots is grafted on the surface of the hydroxyapatite coating through polymerization, so that the polydopamine composite graphene quantum dot grafted hydroxyapatite coating is formed. The content of polydopamine and the aminated graphene quantum dots in the composite coating can be adjusted according to the concentration and the reaction time of the polymerization reaction solution. As an example, 0.5g of hydrochloric acid-dopamine powder was weighed, dissolved in water, 20mL of GQD solution (0.0132 g/mL) and 4mL of 1mol/L Tris were added dropwise, and the volume was fixed to 200mL with deionized water. Immersing the plasma sprayed HAp coating sample into the solution, and stirring and polymerizing for 24 hours to obtain the PDA-GQD grafted HAp coating.
According to the preparation method disclosed by the invention, the hydroxyapatite coating is obtained by depositing on the surface of the substrate through vacuum plasma spraying, and then the solution copolymerization method is adopted, so that two substances, namely polydopamine and amino graphene quantum dots, can be uniformly introduced into the surface of the hydroxyapatite coating, and the obtained coating not only has excellent biocompatibility, but also has biological oxidation resistance, has an obvious protection effect on osteoblast proliferation under an oxidation stress state, and can reduce the adverse effect of active oxygen free radicals on the osteoblast proliferation. The preparation method has the advantages of simple operation, high efficiency, good repeatability, wide application and the like, and provides an effective solution for improving the oxidation resistance of the biological coating.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Examples
A: preparation of hydroxyapatite coating by plasma spraying process
After carrying out sand blasting treatment (pressure of 0.3 MPa) on the surface of the Ti-6Al-4V alloy, carrying out ultrasonic cleaning in an absolute ethyl alcohol solution for 2 times, each time for 4 minutes, and then drying at 110 ℃ for 1 hour for standby.
Spraying commercial hydroxyapatite powder (particle diameter: about 90 μm) onto the treated titanium alloy surface by using a plasma spraying process to obtain HAp ceramic coating. Wherein, the plasma spraying process parameters are as follows: the Ar flow of the plasma gas is 50slpm, and the H flow of the plasma gas is 50slpm 2 The flow rate was 8slpm, the powder carrier gas Ar flow rate was 1.5slpm, the spray distance was 250mm, the spray power was 32.9kW, the spray voltage was 59.8V, and the spray current was 550A. The resulting coating thickness was about 90 μm.
As shown in fig. 1, the XRD pattern of the HAp coating after the plasma spraying was compared with the PDF card (PDF # 74-0565) of the corresponding hydroxyapatite, and the purity of the hydroxyapatite coating prepared by the plasma spraying was higher. As can be seen from SEM scanning pictures shown in fig. 3, the HAp coating exhibits a rough surface morphology combined in a molten and semi-molten state, which is advantageous for bonding to bone tissue in the human body.
B: preparation of HAp-PDA biological antioxidation coating and HAp-PDA-GQD biological antioxidation coating by solution polymerization
Immersing the HAp sample in alcohol, ultrasonically cleaning for 2min, drying at 60 ℃, cooling, placing in 2mg/mL dopamine hydrochloride solution (the pH of the solution is regulated by Tris buffer solution=8.5), and stirring and polymerizing for 24h to obtain the HAp-PDA sample. Preparation of HAp-PDA-GQD coating samples was similar to the procedure described above: 0.5g of dopamine hydrochloride powder is weighed, water is added for dissolution, 20mL of the amination graphene quantum dot solution with the solution concentration of 1.32mg/mL is added, the pH=8.5 is regulated by using Tris buffer solution, and deionized water is used for constant volume to 200mL. Immersing the plasma sprayed HAp coating sample into the solution, and stirring and polymerizing for 24 hours to obtain the HAp-PDA-GQD coating.
As shown in FIG. 1, grafting PDA and PDA-GQD on the surface of the hydroxyapatite coating hardly affects the phase structure of the coating. As can be seen from the XPS full spectrum shown in FIG. 2, the content of C, N element in the sample grafted with PDA and PDA-GQD was sequentially increased, which indicates that PDA and PDA-GQD were successfully grafted on the HAp surface.
As can be seen from the SEM scanning pictures shown in fig. 3, the sample surface of HAp grafted PDA exhibited nano-scale spherical small particles uniformly covered on the HAp surface. While the introduction of GQDs has little effect on the sample surface morphology.
C: radical scavenging performance detection of oxidation resistant coatings
Ultraviolet-visible spectrophotometry was used to test the scavenging properties of the coating samples against DPPH (1, 1-diphenyl-2-trinitrophenylhydrazine) and ABTS + (2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt) radicals. After a sample is placed in DPPH and ABTS+ solutions with certain concentrations for a period of time, the absorbance values of the solutions at 517nm and 734nm are respectively tested, and the lower the absorbance (the more the absorbance is reduced compared with a control group), the stronger the activity of the sample for scavenging free radicals and the better the oxidation resistance.
As shown in fig. 4, the radical scavenging efficiency of the conversion of absorbance values of different samples at DPPH and abts·+ maximum absorption wavelength is known, for DPPH scavenging, HAp-PDA and HAp-PDA-GQD samples are significantly higher than HAp coating, with good scavenging ability, while HAp hardly scavenges DPPH radicals; the clearance effect of HAp-PDA-GQD was most pronounced for ABTS · clearance, HAp had some clearance capacity but was inferior to HAp-PDA samples. Overall, HAp-PDA-GQD after GQD addition showed the highest scavenging ability for both radicals.
D: biocompatibility of the coating and facilitating bone performance testing
Cell adhesion, proliferation and intracellular active oxygen level detection were performed using mouse preosteoblast MC3T 3-E1.
(1) Cell adhesion morphology observation
Sterilizing HAp, HAp-PDA, and HAp-PDA-GQD coating sample at 121deg.C under 1.5MPa, placing into 48-well plate, and inoculating with 1×10 density 4 cells/pre-osteoblasts of wells. After incubation for 24h, samples were washed 3 times with PBS. Samples were immersed in glutaraldehyde solution overnight and treated with alcohol at different concentration gradients. And (3) after the sample is dried, observing the adhesion morphology of the cells on the surface of the coating by adopting an FE-SEM.
As can be seen from the SEM scanning image shown in fig. 5, after the hydrogen peroxide treatment, the cells showed an elongated morphology on the surface of HAp, and the spreading condition was not ideal; the cells are fully spread on the surfaces of HAp-PDA and HAp-PDA-GQD, and platy and filopodia exist, wherein the cell spreading area on the surface of the HAp-PDA-GQD is maximum, the cell boundary is tightly attached to the surface of the material, and the spreading is most sufficient.
(2) Cell proliferation
Samples were sterilized using a steam sterilizer (121 ℃ C., 30 min) and each group of sterile material was carefully placed in a 48-well cell culture plate. MC3T3-E1 cells with good growth state are collected, digested and cell suspension concentration is regulated. 1mL of the cell suspension (10000 cells/mL) was planted on the surface of the sample, and hydrogen peroxide was added to a portion of the wells at a final concentration of 0.3 mM. At 37 ℃ CO 2 After culturing in 5% cell culture incubator for 1, 4 and 7 days, respectively, the culture medium was discarded. 1mL of fresh culture medium and 0.1mL of CCK-8 solution were added to each well. 37 ℃ and 5% CO 2 After 3 hours of continued incubation in the cell incubator, the well solutions were carefully aspirated and added to the 48-well plate. OD values of each well were measured at 450nm using an enzyme-labeled instrument.
As can be seen from (a) in fig. 6, HAp-PDA and HAp-PDA-GQD exhibit a certain ability to promote proliferation of osteoblasts as compared to HAp samples even under normal growth conditions. As can be seen from fig. 6 (B), the proliferation capacity of the MC3T3-E1 preosteoblasts on the surfaces of HAp-PDA and HAp-PDA-GQD coatings was significantly better than that of the HAp coating control group under the oxidative stress condition simulated by hydrogen peroxide, indicating that HAp-PDA and HAp-PDA-GQD coatings have better biological antioxidant capacity and bone-contributing capacity, wherein the biological antioxidant capacity and bone-contributing capacity of HAp-PDA-GQD coatings are better than those of HAp-PDA coatings.
(3) Detection of active oxygen level in osteoblast under oxidative stress state
MC3T3-E1 cells with good growth state are collected, digested and cell suspension concentration is regulated. 1mL of cell suspension (10000 cells/mL) was planted on the surface of each well material and according to the experimental protocol, a portion of the wells was added with H at a final concentration of 0.3mM 2 O 2 ，37℃、5％CO 2 Incubate in cell incubator for 24h. The supernatant was discarded, the cells were washed 2 times with PBS, and DCFH-DA solution was added to each well at a final concentration of 10. Mu.M. Incubate at 37℃for 20min. The supernatant was discarded and the cells were washed 3 times with PBS. 0.3mL of cell lysate was added to each well, and after shaking table lysis of cells at 37℃for 10min, the well-mixed lysate was added to a 96-well plate. Excitation light of 485nm is emitted by a fluorescence enzyme-labeling instrument, the fluorescence intensity value at 525nm is read, and laser confocal display is usedAnd (5) observing by a micro mirror.
As can be seen from the intracellular ROS level (C) and ROS fluorescence photograph (D) of FIG. 6, the fluorescent signal of active oxygen species in osteoblasts on the surface of HAp material is relatively weak under normal conditions, while the ROS signal in osteoblasts on the surface of HAp material is strong under oxidative stress conditions. But HAp-PDA and HAp-PDA-GQD materials after being introduced into PDA and GQD show sequentially enhanced antioxidation protection effect on osteoblasts, and the ROS level in the cells is correspondingly weakened.
Claims (10)
1. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating is characterized by comprising a hydroxyapatite coating prepared by plasma spraying and a functional grafting layer for grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating in situ.
2. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating according to claim 1, wherein said graphene quantum dots are aminated graphene quantum dots.
3. The polydopamine composite graphene quantum dot grafted hydroxyapatite coating according to claim 1 or 2, wherein the thickness of the hydroxyapatite coating is 60-120 microns; the thickness of the polydopamine composite graphene quantum dot grafted layer is 50-150 nm.
4. A method for preparing the polydopamine composite graphene quantum dot grafted hydroxyapatite coating according to any of the claims 1 to 3, characterized in that the method comprises the following steps:
(1) Preparing a hydroxyapatite coating by adopting a plasma spraying technology: spraying hydroxyapatite powder plasma on the surface of a substrate to form a hydroxyapatite coating;
(2) Preparing the polydopamine composite graphene quantum dot grafted hydroxyapatite coating on the surface of the hydroxyapatite coating by a solution polymerization method: adding graphene quantum dot solution and tris (hydroxymethyl) aminomethane into a dopamine solution, regulating the pH of the solution to 8-10, immersing a hydroxyapatite coating prepared by plasma spraying into the solution for polymerization reaction, and thus forming the polydopamine composite graphene quantum dot grafted hydroxyapatite coating by grafting polydopamine coated with graphene quantum dots on the surface of the hydroxyapatite coating.
5. The method of claim 4, wherein the hydroxyapatite powder has a particle size of 15 to 90 microns.
6. The method according to claim 4 or 5, wherein the process parameters of the plasma spraying are: the Ar flow of the plasma gas is 32 to 50slpm, H 2 The flow is 5-12 slpm; the Ar flow of the powder carrier gas is 1.5 to 5.0slpm; the spraying distance is 100-330 mm; the spraying power is 30-45 kW.
7. The method according to any one of claims 4 to 6, wherein the substrate is a medical metal or medical alloy material of pure titanium, titanium alloy, stainless steel, cobalt chromium molybdenum alloy.
8. The process according to any one of claims 4 to 7, wherein the polymerization time is 18 to 24 hours.
9. The method according to any one of claims 4 to 8, wherein the concentration of the dopamine solution is 0.5-2.0 mg/mL, preferably 1.5-2 mg/mL; the concentration of the graphene quantum dot solution is 1.32-6.80 mg/mL.
10. Use of the polydopamine composite graphene quantum dot grafted hydroxyapatite coating according to any of claims 1 to 3 in biological antioxidation.
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