CN114601972B - Photo-thermal, photo-dynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as matrix and preparation method thereof - Google Patents
Photo-thermal, photo-dynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as matrix and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photo-thermal, photodynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as a matrix, which has a layered structure and sequentially comprises a magnesium/magnesium alloy/zinc alloy matrix, a corrosion product film of the matrix and a calcium-phosphorus-metal porphyrin coating from inside to outside; the calcium-phosphorus-metal porphyrin coating comprises 5-10 layers, all the layers are sequentially stacked, and the next layer is coated on the previous layer; each layer is formed by mutually attaching and assembling calcium-phosphorus coatings induced by metalloporphyrin; the calcium phosphorus-metal porphyrin coating is a crystalline coating. The photo-thermal, photo-dynamic and metal ion synergistic antibacterial material taking the magnesium/magnesium alloy zinc/zinc alloy prepared by the method as the matrix has compact and uniform structure, not only has excellent corrosion resistance, but also has good biocompatibility and photo-thermal antibacterial performance, and can overcome the problems of high production cost, large brittleness, poor corrosion resistance, poor biocompatibility and the like of amorphous magnesium alloy.
Description
Technical Field
The invention relates to the technical field of medical magnesium/magnesium alloy/zinc alloy surface coatings, in particular to a photothermal/photodynamic antibacterial material taking magnesium/magnesium alloy/zinc alloy as a matrix and a preparation method thereof.
Background
The degradation behavior of magnesium and magnesium alloys makes it very attractive as a biodegradable implant material, and it has suitable mechanical properties and good biocompatibility. At present, the application research of magnesium and magnesium alloy as degradable medical materials is basically focused on the research in the aspects of cardiovascular stents, bone fixing materials, porous bone repairing materials, dental implant materials, oral cavity repairing materials and the like. However, the problems of over-high corrosion speed, insufficient biocompatibility and the like exist in the magnesium/magnesium alloy/zinc alloy, so that the direct clinical application of the magnesium/magnesium alloy/zinc alloy is limited. Therefore, the perfection of the magnesium/magnesium alloy/zinc alloy surface modification technology becomes the key of the application of the magnesium/magnesium alloy/zinc alloy in the field of biological materials.
In recent years, surface modification has become the most common major technical means in the prior art. To achieve sufficient protective properties, the coating must be uniform, dense, and have good adhesion to the substrate. Moreover, as a functional material, medical magnesium alloy is particularly required to be designed into a novel coating with excellent corrosion resistance, good biocompatibility and excellent bacteriostatic ability from a way of integrating the structure and the function of the coating. To date, various surface modification coatings and surface modification techniques have been developed, and numerous products have been developed. However, the magnesium alloy products with modified surfaces manufactured by the prior art have many defects, which mainly show that the comprehensive performance indexes such as corrosion resistance, biocompatibility, binding force, durability and the like are not sufficient, and the actual using effect is not particularly ideal.
Sodium Copper Chlorophyllin (SCC), a water-soluble sodium copper chlorophyllin extracted from chlorophyll, has good biocompatibility, and has been used as a food dye and a wound healing promoter for decades. In recent years, squamous cell carcinoma has been receiving attention in the field of nano-biomaterials due to its good effect in PDT or PTT therapy. On the other hand, the role of copper ions in the SCC structural center cannot be underestimated, and copper ions are indispensable micronutrients for human health, play an important role in human enzymes, and promote cellular respiration, neurotransmitter, and peptide hormone production. Copper ions also have good antibacterial properties, and by triggering the decomposition of S-nitrosothiols in the body, NO is produced, and reacts with free radical superoxide to form reaction byproducts (peroxynitrite and dinitrogen trioxide), which cause membrane destruction and cell dysfunction of bacteria, such as influenza A virus, staphylococcus aureus, escherichia coli, and the like. In addition, the copper ions can regulate the effects of various cytokines and growth factors, stimulate angiogenesis and collagen deposition and effectively promote wound healing. The application research of the sodium copper chlorophyllin in the surface modification of magnesium/magnesium alloy/zinc alloy has bright prospect. Through the successful application of copper chlorophyll, the metalloporphyrin of the same system as the copper chlorophyll also has wide prospect in the surface modification of magnesium alloy.
The surface of the magnesium/magnesium alloy/zinc alloy is modified by sodium copper chlorophyllin, so that the biocompatibility can be improved, and more characteristics can be endowed to the magnesium/magnesium alloy/zinc alloy by constructing a composite coating.
Disclosure of Invention
The invention aims to provide a multilayer composite coating material with good corrosion resistance, good binding force, high density, good biocompatibility and excellent antibacterial effect, and a photo-thermal, photodynamic and metal ion synergistic antibacterial material which is used for biomedical and takes magnesium/magnesium alloy/zinc alloy as a matrix and a preparation method thereof.
The technical scheme adopted for realizing the purpose is as follows:
the photo-thermal, photodynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as a matrix is characterized in that the material has a layered structure and sequentially comprises the magnesium/magnesium alloy/zinc alloy matrix, a corrosion product film of the matrix and a calcium-phosphorus-metalloporphyrin coating from inside to outside;
the calcium-phosphorus-metal porphyrin coating is 5-10 layers, all the layers are sequentially stacked, and the next layer is coated on the previous layer;
each layer is formed by mutually attaching and assembling calcium-phosphorus coatings induced by metalloporphyrin;
the calcium phosphorus-metal porphyrin coating is a crystalline coating.
Preferably, the calcium phosphorus-metal porphyrin coating is 10 layers, and the total thickness is 9.94 mu m;
preferably, the metalloporphyrin is any one of copper chlorophyll, heme, ruthenium porphyrin, cobalt porphyrin and zinc protoporphyrin trihydrate.
Preferably, the metalloporphyrin is copper chlorophyll.
The preparation method of the photo-thermal, photodynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as a matrix is characterized by comprising the following steps of:
(a) Pretreatment: grinding a magnesium/magnesium alloy/zinc alloy substrate by using p1500 abrasive paper until the surface has no obvious scratch, cleaning the magnesium/magnesium alloy/zinc alloy substrate by using deionized water, drying the magnesium/magnesium alloy/zinc alloy substrate at the constant temperature of between 60 and 80 ℃ for 30 to 60 minutes, and taking the magnesium/magnesium alloy/zinc alloy substrate out;
(b) Carrying out hydroxylation treatment on the sample by adopting a sodium hydroxide solution;
(c) Preparation of calcium-phosphorus coating induced by copper chlorophyll: soaking the hydroxylated magnesium/magnesium alloy/zinc alloy matrix in a copper chlorophyll solution, placing the solution in a heat collection type constant-temperature heating magnetic stirrer for constant-temperature stirring, taking out the solution after 10min, washing the solution with deionized water, and drying the solution; then soaking the materials into a calcium-phosphorus solution, stirring the materials under the same conditions at a constant temperature, taking the materials out after 10min, washing the materials clean by deionized water, and drying the materials by wind, wherein the wind temperature is 25-60 ℃;
(d) Repeating the soaking sequence in the step (c) for 5-10 times to obtain a sample, and drying the sample in a drying oven at the constant temperature of 60-80 ℃ for 30min to obtain the magnesium/magnesium alloy/zinc alloy material with the photo-thermal antibacterial corrosion-resistant composite coating.
Preferably, in the step (b), when the hydroxylation treatment is performed by using a sodium hydroxide solution, the pretreated sample is soaked in a 1M sodium hydroxide solution to prepare a hydroxylation sample, and the hydroxylation sample is taken out after being kept for 20min in a heat collection type constant-temperature heating magnetic stirrer; then placing the mixture in an oven at the temperature of between 60 and 80 ℃ and drying the mixture for 40min at constant temperature.
Preferably, in the step (c), the constant-temperature stirring temperature range in the heat collection type constant-temperature heating magnetic stirrer is 25-100 ℃, and the concentration range of the copper chlorophyll solution is 0.1-1 g/L.
Preferably, the constant-temperature stirring temperature in the heat collection type constant-temperature heating magnetic stirrer is 37 ℃, and the concentration of the copper chlorophyll solution is 1g/L.
Preferably, in the step (c), the calcium phosphate solution is prepared by adding calcium nitrate tetrahydrate and sodium dihydrogen phosphate into 100mL of deionized water, or adding calcium nitrate tetrahydrate and potassium dihydrogen phosphate into 100mL of deionized water, wherein the concentration of the calcium nitrate tetrahydrate is in the range of 0.1M to 0.2M, and the concentration of the sodium dihydrogen phosphate or the potassium dihydrogen phosphate is in the range of 0.05M to 0.15M. Sodium dihydrogen phosphate and potassium dihydrogen phosphate are similar in nature and may be used alternatively in the present invention to prepare calcium phosphate solutions.
Preferably, the concentration of the calcium nitrate tetrahydrate solution is 0.15M, and the concentration of sodium dihydrogen phosphate or potassium dihydrogen phosphate is 0.1M.
The technical effect directly brought by the technical scheme is that the process is simple, the reaction time is short, and the obtained magnesium/magnesium alloy/zinc alloy surface coating has compact structure, strong corrosion resistance, good biocompatibility, high antibacterial performance and excellent photo-thermal and photo-dynamic performance.
In order to better understand the above technical scheme, the reaction principle is briefly explained:
in the technical scheme, metalloporphyrin is used as an inducer of the calcium-phosphorus coating.
The components in the solution have the following functions: calcium nitrate tetrahydrate and sodium dihydrogen phosphate ionize calcium ions, hydrogen phosphate ions and phosphate ions in an aqueous solution to provide ions required for forming a calcium-phosphorus coating.
Metalloporphyrin promotes the nucleation of calcium-phosphorus structures through electron conjugation and electrostatic attraction. Namely, the core technical idea of the above technical solution is as follows: the hydroxylated matrix is used for attaching metalloporphyrin on the surface, and the metalloporphyrin promotes the nucleation of a calcium-phosphorus structure through the electron conjugation effect and the electrostatic attraction effect. The film layer is compact by a layer-by-layer assembly method, the corrosion resistance of the coating is improved, and the introduction of the metalloporphyrin obviously improves the photo-thermal and photo-dynamic properties of the coating.
Meanwhile, due to the existence of calcium and phosphorus components in the coating, the coating has good biocompatibility and biodegradability.
In the above technical solution, the main chemical reaction is concentrated in the beaker for the following reasons: the reaction is carried out in a water bath kettle, so that crystals growing under a relatively low thermal stress condition can be effectively ensured; in the above technical solution, another reason for introducing the copper chlorophyll component is that: the metalloporphyrin is nontoxic and has stable structure. The metal elements are one of the trace elements necessary for human body, and most of the trace elements are necessary for human body. Copper is an important component of human enzymes, has a promoting effect on cellular respiration, neurotransmitter and peptide hormones, and can also promote the production of human blood vessels by stimulating the production of vascular endothelial growth factor, fibroblast growth factor and angiogenin. In short, the introduction of metalloporphyrin components into the magnesium/magnesium alloy/zinc alloy coating can greatly improve biocompatibility.
The beneficial effects of the invention are as follows:
(1) The magnesium/magnesium alloy zinc/zinc alloy surface coating prepared by the invention is a calcium-phosphorus coating and a photo-thermal/photo-dynamic/metal ion synergistic antibacterial material, has compact and uniform structure, not only has excellent corrosion resistance, but also has good biocompatibility and photo-thermal antibacterial property;
(2) The preparation method of the magnesium/magnesium alloy/zinc alloy surface coating provided by the invention has the advantages of simple process and easily controlled conditions, and can solve the problems of high production cost, large brittleness, poor corrosion resistance, poor biocompatibility and the like of amorphous magnesium alloy.
Drawings
In order to clearly illustrate the embodiments or technical solutions of the present invention in the prior art, the drawings used in the description of the embodiments or prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Fig. 1 is a scanning electron micrograph of the surface and cross-section of an AZ31 magnesium alloy material having a 10-layer composite coating layer prepared in example 1;
fig. 2 is a surface scanning electron micrograph of an AZ31 magnesium alloy material having a calcium-phosphorus coating layer prepared in comparative example 1;
fig. 3 is a scanning electron micrograph of the surface and cross-section of an AZ31 magnesium alloy material having a 5-layer composite coating layer produced in example 12;
fig. 4 is a scanning electron micrograph of the surface and cross-section of an AZ31 magnesium alloy material having a 7-layer composite coating layer obtained in example 13;
fig. 5 is XRD patterns of the AZ31 magnesium alloy material having a calcium-phosphorus coating layer prepared in comparative example 1 and the AZ31 magnesium alloy material having a composite coating layer prepared in example 1;
fig. 6 is a potentiodynamic polarization plot of an AZ31 magnesium alloy substrate, an AZ31 magnesium alloy material with a calcium-phosphorus coating prepared in comparative example 1, and an AZ31 magnesium alloy material with a composite coating prepared in example 1;
the left graph in fig. 7 is an impedance curve of the AZ31 magnesium alloy substrate and the AZ31 magnesium alloy material with the calcium-phosphorus coating and the photothermal photodynamic metal ion synergistic antibacterial coating prepared in the comparative example 1;
fig. 8 is a temperature rise curve of the AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material with a calcium-phosphorus coating layer produced in example 1 of the present invention, and the AZ31 magnesium alloy material with a composite coating layer produced in example 1 in the air;
fig. 9 is temperature rise curves of the AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material with a calcium-phosphorus coating prepared in comparative example 1, and the AZ31 magnesium alloy material with a composite coating prepared in example 1 in a simulated body fluid;
FIG. 10 is a cyclic photothermal curve of the AZ31 magnesium alloy material with a composite coating prepared in example 1 excited by near infrared light of 808nm in air;
FIG. 11 is a cyclic photothermal curve of the AZ31 magnesium alloy material with a composite coating prepared in example 1 in a solution under the excitation of near infrared light of 808 nm;
FIG. 12 is a graph showing the photodynamic activity of the AZ31 magnesium alloy material with a composite coating layer obtained in example 1 when excited by near infrared light of 808 nm;
fig. 13 shows the results of the antibacterial performance test of the AZ31 magnesium alloy substrate and the AZ31 magnesium alloy material with the calcium-phosphorus coating prepared in comparative example 1 under the conditions of no illumination, visible light illumination and 808nm near-infrared light excitation.
Detailed Description
The drawings are for illustration purposes only and are not to be construed as limiting the invention; for a better understanding of the present embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; some well-known structures in the drawings and descriptions thereof may be omitted for those skilled in the art.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below.
Example 1
The photo-thermal, photo-dynamic and metal ion synergistic antibacterial material with the AZ31 magnesium alloy material as the matrix and the preparation method thereof provided by the embodiment specifically comprise the following steps:
(a) Pretreatment of
Firstly, polishing an AZ31 magnesium alloy substrate by using p1500 abrasive paper until the surface has no obvious scratch, cleaning the substrate by using absolute ethyl alcohol or deionized water, drying the substrate by using wind, then placing the substrate in a drying oven, and drying the substrate at the constant temperature of 70 ℃ for 60min and then taking the substrate out;
(b) Hydroxylation treatment of sample by sodium hydroxide solution
Soaking the pretreated sample in 1M sodium hydroxide solution to prepare a hydroxylated sample, and preserving the temperature in a heat collection type constant temperature heating magnetic stirrer at 60 ℃ for 20min and then taking out; then placing the mixture in a drying oven at the temperature of between 60 and 80 ℃ and drying the mixture for 40min at constant temperature;
(c) Preparation of calcium-phosphorus coating induced by copper chlorophyll
Firstly, soaking a hydroxylated AZ31 magnesium alloy matrix in a copper chlorophyll solution, placing the solution in a heat collection type constant temperature heating magnetic stirrer at 37 ℃ for constant temperature stirring, taking out the solution after 10min, washing the solution with deionized water, and drying the solution; then soaking in calcium phosphorus solution, stirring under the same conditions at constant temperature, taking out after 10min, washing with deionized water, and blow-drying;
(d) Repeating the soaking sequence in the step (c) for 10 times to obtain a sample, and drying the sample in a drying oven at the constant temperature of 60-80 ℃ for 30min to obtain the magnesium/magnesium alloy/zinc alloy material with the photo-thermal antibacterial corrosion-resistant composite coating;
the above-mentioned copper chlorophyll solution is sodium copper chlorophyll solution with concentration of 1g/L;
the calcium phosphate solution is prepared by adding 0.1M sodium dihydrogen phosphate into 0.15M calcium nitrate tetrahydrate solution prepared in 100ml deionized water.
The average thickness of the composite coating prepared by the method is about 9.94 mu m, and the calcium phosphorus-copper chlorophyll coating is a crystalline coating.
Example 2
The photo-thermal, photo-dynamic and metal ion synergistic antibacterial material with the AZ31 magnesium alloy material as the matrix and the preparation method thereof provided by the embodiment specifically comprise the following steps:
(a) Pretreatment of
Firstly, polishing an AZ31 magnesium alloy substrate by using p1500 sand paper until no obvious scratch is formed on the surface, cleaning the substrate by using absolute ethyl alcohol or deionized water, drying the substrate by using wind, then placing the substrate in a drying oven, and drying the substrate at the constant temperature of 70 ℃ for 60min and taking the substrate out;
(b) Hydroxylating a sample by adopting a sodium hydroxide solution
Soaking the pretreated sample in 1M sodium hydroxide solution to prepare a hydroxylated sample, and preserving the temperature in a heat collection type constant temperature heating magnetic stirrer at 60 ℃ for 20min and then taking out; then placing the mixture in a drying oven at the temperature of between 60 and 80 ℃ and drying the mixture for 40min at constant temperature;
(c) Preparation of a calcium-phosphorus coating induced by Heme
Firstly, soaking a hydroxylated AZ31 magnesium alloy matrix in a heme solution, placing the solution in a heat collection type constant-temperature heating magnetic stirrer at 37 ℃ for constant-temperature stirring, taking out the solution after 10min, washing the solution with deionized water, and drying the solution; then soaking the materials in calcium-phosphorus solution, stirring under the same conditions at constant temperature, taking out after 10min, washing with deionized water, and blow-drying;
(d) Repeating the soaking sequence in the step (c) for 10 times to obtain a sample, and drying the sample in an oven at the constant temperature of 60-80 ℃ for 30min to obtain the AZ31 magnesium alloy material with the photo-thermal/photo-dynamic/metal ion synergistic antibacterial and anticorrosive composite coating;
the concentration of the heme solution is 1g/L;
the calcium phosphate solution is prepared by adding 0.1M sodium dihydrogen phosphate into 0.15M calcium nitrate tetrahydrate solution prepared in 100ml deionized water.
Example 3
The difference between this example and example 1 is that ruthenium porphyrin is used as the metalloporphyrin in this example, and the concentration of the solution is also 1g/L.
Example 4
The difference between this example 4 and example 1 is that cobalt porphyrin is used as the metalloporphyrin-based drug in this example.
Example 5
The difference between this example 5 and example 1 is that zinc protoporphyrin trihydrate is used as the metalloporphyrin drug in this example.
Example 6
Example 6 is different from example 1 in that the concentration of the copper chlorophyll solution in this example is 0.1g/L.
Example 7
Example 7 is different from example 1 in that the concentration of the copper chlorophyll solution in this example is 0.5g/L.
Example 8
This example differs from example 1 in that pure magnesium is used for the matrix.
Example 9
This example differs from example 1 in that pure zinc is used for the matrix in this example.
Example 10
The present embodiment 10 is different from embodiment 1 in that the temperature of constant temperature stirring by the heat-collecting type constant temperature heating magnetic stirrer in the present embodiment is 25 ℃.
Example 11
The present embodiment 11 is different from embodiment 1 in that the temperature of constant temperature stirring by the heat collection type constant temperature heating magnetic stirrer in the present embodiment is 100 ℃.
Example 12
This example 12 is different from example 1 in that in the step (d) of this example, the soaking was repeated 5 times in the soaking order in the step (c).
Example 13
This example 13 is different from example 1 in that in step (d) of this example, the number of times of soaking repeated in the soaking order in step (c) is 7.
Comparative example 1
This comparative example 1 differs from example 1 in that it uses only a hydroxylated AZ31 magnesium alloy substrate to induce a calcium phosphorous coating, the preparation steps being:
(a) Pretreatment of
Firstly, polishing an AZ31 magnesium alloy substrate by using p1500 sand paper until no obvious scratch is formed on the surface, cleaning the substrate by using absolute ethyl alcohol or deionized water, drying the substrate by using wind, then placing the substrate in a drying oven, and drying the substrate at the constant temperature of 70 ℃ for 60min and taking the substrate out;
(b) Hydroxylating a sample by adopting a sodium hydroxide solution
Soaking the pretreated sample in 1M sodium hydroxide solution to prepare a hydroxylated sample, and preserving the temperature in a heat collection type constant temperature heating magnetic stirrer at 60 ℃ for 20min and then taking out; then placing the mixture in a drying oven at the temperature of between 60 and 80 ℃ and drying the mixture for 40min at constant temperature;
(c) Preparing the AZ31 magnesium alloy direct induction calcium-phosphorus coating after pretreatment
Soaking the hydroxylated AZ31 magnesium alloy matrix in a calcium-phosphorus solution, placing the solution in a heat collection type constant-temperature heating magnetic stirrer at 37 ℃ for constant-temperature stirring, taking out the solution after 10min, washing the solution with deionized water, drying the solution, repeating the step for ten times, and drying the obtained sample in an oven at the constant temperature of 60-80 ℃ for 30min to obtain a comparative example coating;
(d) Repeating the soaking sequence in the step (c) for 10 times to obtain a sample, and drying the sample in a drying oven at the constant temperature of 60-80 ℃ for 30min to obtain the magnesium/magnesium alloy/zinc alloy material with the photo-thermal antibacterial corrosion-resistant composite coating;
the calcium phosphate solution is prepared by adding 0.1M sodium dihydrogen phosphate into 0.15M calcium nitrate tetrahydrate solution prepared in 100ml deionized water.
The example 1 is taken as a representative example, and the relevant performance is detected and explained.
As shown in fig. 1, wherein, in fig. 1, a and b are surface scanning electron micrographs of the AZ31 magnesium alloy material with the composite coating prepared in example 1, and c is a cross-sectional view of the composite coating, the composite coating grows in situ on the surface of the AZ31 magnesium alloy substrate, and the two coatings are tightly connected without delamination.
Fig. 2 is a scanning electron micrograph of the surface of the AZ31 magnesium alloy material having a calcium-phosphorus coating layer not induced by metalloporphyrin prepared in comparative example 1. As can be seen from fig. 1 and 2, the surface of the calcium-phosphorus coating layer not induced by metalloporphyrin is loose, has no obvious nucleation center, and is easy to cause corrosion when the solution contacts with the matrix, so that the corrosion resistance is affected, while the surface of the calcium-phosphorus composite coating layer induced by copper chlorophyllin is stacked by lamellar structures, has obvious flower-shaped nucleation center, has more compact structure, and can be used as a physical barrier to improve the corrosion resistance of the magnesium alloy matrix.
As shown in fig. 3, in a scanning electron micrograph of the surface of the AZ31 magnesium alloy material having the 5-layer composite coating prepared in example 12, a small number of lamellar and foliated calcium-phosphorus structures appeared but did not completely cover the surface of the substrate, and the exposed surface of the substrate had corrosion cracks formed by corrosion of the metalloporphyrin solution.
As shown in fig. 4, a surface scanning electron micrograph of the AZ31 magnesium alloy material having the 7-layer composite coating layer obtained in example 13 shows that a large number of lamellar and foliate calcium phosphorus structures appear but completely cover the surface of the matrix, and a small number of flower-like nucleation centers appear.
As shown in FIG. 5, in order to show XRD patterns of the AZ31 magnesium alloy material having a calcium-phosphorus coating layer not induced by metalloporphyrin prepared in comparative example 1 and the AZ31 magnesium alloy material having a composite coating layer prepared in example 1, it can be seen from FIG. 2 that the main components of the coatings prepared in example 1 and comparative example 1 are hydroxyapatite, ca 3 (PO) 2 、CaHPO 4 And Mg (OH) 2 The successful induction of a calcium-phosphorus coating on an AZ31 magnesium alloy substrate is demonstrated.
As shown in FIG. 6, showing the zeta potential polarization curves of the AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material with the calcium-phosphorus coating layer not induced by metalloporphyrin prepared in the comparative example 1 and the AZ31 magnesium alloy material with the composite coating layer prepared in the example 1, it can be seen from FIG. 3 that the AZ31 magnesium alloy material with the composite coating layer prepared in the example 1 has a reduced self-corrosion current density from 5.45X 10 -6 A/cm 2 Reduced to 1.35X 10 -7 A/cm 2 The magnesium alloy material with the composite coating has excellent corrosion resistance.
As shown in fig. 7, the left-hand graph is an impedance curve of the AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material with a calcium phosphorus coating layer not induced by metalloporphyrin prepared in comparative example 1, and the AZ31 magnesium alloy material with a composite coating layer prepared in example 1, and the upper left-hand corner of the graph is a partially enlarged view. As can be seen from comparison in fig. 4, the ac impedance of the AZ31 magnesium alloy material with a composite coating prepared in example 1 is significantly increased compared with that of the magnesium alloy AZ31 without a coating, and the ac impedance of the AZ31 magnesium alloy material with a composite coating prepared in example 1 is also significantly increased compared with that of the AZ31 magnesium alloy material without a metalloporphyrin-induced calcium-phosphorus coating, which indicates that the magnesium alloy material with a composite coating has excellent corrosion resistance.
As shown in fig. 8 and 9, the temperature rise curves of the AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material without the metalloporphyrin-induced calcium-phosphorus coating prepared in the comparative example 1, and the AZ31 magnesium alloy material with the composite coating prepared in the example 1 in the air and in the simulated body fluid, respectively, are shown, and it can be seen from the graphs that the magnesium alloy with the composite coating covered on the surface has excellent photo-thermal properties.
As shown in fig. 10 and 11, the cyclic photothermal curves of the AZ31 magnesium alloy material with the composite coating prepared in example 1 under the excitation of near infrared light of 808nm in air and in simulated body fluid are shown, and as can be seen from fig. 7 and 8, the composite coating has photothermal cyclability and photothermal stability.
As shown in fig. 12, which is a curve of ROS release of the AZ31 magnesium alloy material with the composite coating prepared in example 1 under the excitation of near infrared light of 808nm, it can be seen from fig. 9 that the composite coating has good photodynamic activity.
As shown in fig. 13, comparing the antibacterial performance of the AZ31 magnesium alloy substrate and the AZ31 magnesium alloy material with the composite coating prepared in example 1 under the dark condition, under the irradiation of visible light and under the excitation of near infrared light of 808nm, it can be seen from the figure that the illumination is beneficial to improving the antibacterial performance of the AZ31 magnesium alloy; in addition, compared with an AZ31 magnesium alloy substrate, the AZ31 magnesium alloy material with the composite coating has antibacterial performance under dark conditions, under visible light irradiation and under 808nm near-infrared light excitation conditions, and the antibacterial performance is best under 808nm near-infrared light excitation conditions, next under visible light irradiation conditions and worst under dark conditions. Compared with AZ31 magnesium alloy, the antibacterial property is better, and the excellent photo-thermal antibacterial property of the calcium-phosphorus coating induced by metalloporphyrin is further demonstrated.
It should be noted that the parts not described in the present invention can be realized by using or referring to the existing technology. Because sodium dihydrogen phosphate and potassium dihydrogen phosphate have similar properties, calcium phosphate solution can be used alternatively, and the examples are not repeated.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (7)
1. A preparation method of photo-thermal, photodynamic and metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as a matrix is characterized in that the material has a layered structure and sequentially comprises a magnesium/magnesium alloy/zinc alloy matrix, a corrosion product film of the matrix and a calcium-phosphorus-metalloporphyrin coating from inside to outside;
the calcium-phosphorus-metal porphyrin coating comprises 5-10 layers, all the layers are sequentially stacked, and the next layer is coated on the previous layer;
each layer is formed by mutually attaching and assembling calcium-phosphorus coatings induced by metalloporphyrin;
the calcium-phosphorus-metal porphyrin coating is a crystalline coating;
the metalloporphyrin is copper chlorophyll;
the preparation method comprises the following steps:
(a) Pretreatment: grinding a magnesium/magnesium alloy/zinc alloy substrate by using p1500 abrasive paper until the surface has no obvious scratch, cleaning the magnesium/magnesium alloy/zinc alloy substrate by using deionized water, drying the magnesium/magnesium alloy/zinc alloy substrate at the constant temperature of between 60 and 80 ℃ for 30 to 60 minutes, and taking the magnesium/magnesium alloy/zinc alloy substrate out;
(b) Carrying out hydroxylation treatment on the sample by adopting a sodium hydroxide solution;
(c) Preparation of calcium-phosphorus coating induced by copper chlorophyll: soaking the hydroxylated magnesium/magnesium alloy/zinc alloy matrix in a copper chlorophyll solution, placing the solution in a heat collection type constant-temperature heating magnetic stirrer for constant-temperature stirring, taking out the solution after 10min, washing the solution with deionized water, and drying the solution; then soaking the materials into a calcium-phosphorus solution, stirring the materials under the same conditions at a constant temperature, taking the materials out after 10min, washing the materials clean by deionized water, and drying the materials by wind, wherein the wind temperature is 25-60 ℃;
(d) Repeating the soaking sequence in the step (c) for 5-10 times to obtain a sample, and drying the sample in a drying oven at the constant temperature of 60-80 ℃ for 30min to obtain the magnesium/magnesium alloy/zinc alloy material with the photo-thermal antibacterial corrosion-resistant composite coating.
2. The preparation method of the photothermal, photodynamic, metal ion synergistic antibacterial material with the magnesium/magnesium alloy/zinc alloy as the matrix as claimed in claim 1, wherein the calcium-phosphorus-metalloporphyrin coating is 10 layers, and the total thickness is 9.94 μm.
3. The method for preparing a photothermal, photodynamic, metal ion synergistic antibacterial material with magnesium/magnesium alloy/zinc alloy as a matrix according to claim 1, wherein in the step (b), when a sodium hydroxide solution is used for hydroxylation treatment, the pretreated sample is soaked in a sodium hydroxide solution with the concentration of 1M to prepare a hydroxylated sample, and the hydroxylated sample is taken out after being kept for 20min in a heat collection type constant temperature heating magnetic stirrer; then placing the mixture in an oven at the temperature of between 60 and 80 ℃ and drying the mixture for 40min at constant temperature.
4. The preparation method of the photothermal, photodynamic, metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as the matrix according to claim 1, characterized in that the temperature range of constant-temperature stirring in a heat collection type constant-temperature heating magnetic stirrer is 25-100 ℃, and the concentration range of the copper chlorophyll solution is 0.1-1 g/L.
5. The preparation method of the photothermal, photodynamic, metal ion synergistic antibacterial material taking magnesium/magnesium alloy/zinc alloy as the matrix according to claim 1, wherein in the step (c), the constant-temperature stirring temperature in the heat collection type constant-temperature heating magnetic stirrer is 37 ℃, and the concentration of the copper chlorophyll solution is 1g/L.
6. The method for preparing a photothermal, photodynamic, metal ion synergistic antibacterial material based on magnesium/magnesium alloy/zinc alloy as claimed in claim 1, wherein in said step (c), the calcium phosphorus solution is prepared by adding calcium nitrate tetrahydrate and sodium dihydrogen phosphate or potassium dihydrogen phosphate into 100mL of deionized water, the concentration of said calcium nitrate tetrahydrate is in the range of 0.1M to 0.2M, and the concentration of said sodium dihydrogen phosphate or potassium dihydrogen phosphate is in the range of 0.05M to 0.15M.
7. The method for preparing the photothermal, photodynamic, metal ion synergistic antibacterial material based on magnesium/magnesium alloy/zinc alloy as claimed in claim 6, wherein the concentration of the calcium nitrate tetrahydrate solution is 0.15M, and the concentration of sodium dihydrogen phosphate or potassium dihydrogen phosphate is 0.1M.
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| CN111206244A (en) * | 2020-02-25 | 2020-05-29 | 山东科技大学 | Preparation method of magnesium/magnesium alloy surface biological induction calcium-phosphorus coating |
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