CN107096069B - Core-shell structure nano composite material of silver nano particles coated with hydroxyapatite and preparation method thereof - Google Patents
Core-shell structure nano composite material of silver nano particles coated with hydroxyapatite and preparation method thereof Download PDFInfo
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Abstract
The invention provides a core-shell structure nano composite material of silver nano particles coated by hydroxyapatite, which is a core-shell structure nano composite material taking the silver nano particles as a core, a dopamine coating coated by the silver nano particles as an inner shell and a hydroxyapatite coating coated by the inner shell as an outer shell. The invention also provides a preparation method of the material, which comprises the following steps: first, prepare C separately4H11NO3-HCl buffer solution, calcium salt solution, phosphate solution, then uniformly dispersing silver nanoparticles in C4H11NO3-HCl buffer solutionCoating a layer of uniform polydopamine film on the surface of the silver nano particles, and dispersing the polydopamine film in a calcium salt solution to coat a layer of hydroxyapatite coating on the surface of the silver nano particles. The material has excellent biocompatibility, lower cytotoxicity and durable antibacterial performance, and can be used for coating on the surface of a medical implant, bone repair implant materials, in-vitro use of antibacterial auxiliary materials and the like.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a hydroxyapatite and silver composite material for bone repair and a preparation method thereof.
Background
The bone repair and replacement surgery is usually a surgery with a large wound, the recovery process is long, bacterial infection is difficult to avoid in the surgery process and the recovery process, in order to avoid bacterial infection, antibiotics are usually used for a long time to prevent bacterial infection, and the occurrence rate of inflammation is reduced. In recent decades, antibiotics such as penicillin, streptomycin, trimethoprim and tetracycline greatly reduce the morbidity and mortality of pathogenic bacterial infection diseases, and are widely applied clinically. However, with the overuse and abuse of antibiotics, the resistance of pathogens to antibiotics is increasing, which may lead to the persistent and intractable infection of pathogens, decrease of treatment effect, and even to the worsening and death of patients. With the development of nanotechnology, inorganic nanomaterials are widely used in the biomedical field due to their excellent physical, chemical and biological properties. Particularly, the silver nanoparticles have excellent antibacterial performance and a broad antibacterial range (can inhibit gram-positive bacteria, negative bacteria, fungi and even viruses), can be used for replacing antibiotics to solve the problem of pathogen resistance, and therefore have wide application prospects. The silver nanoparticles exposed on the surface of the material are easy to be oxidized due to small size and large specific surface area, so that a large amount of silver ions are generated. The antibacterial properties and cytotoxicity of silver nanoparticles depend largely on the concentration of silver ions released from their composite materials. The released silver ions not only cause physical damage to cell membranes, but also can interfere with ATP production and DNA replication of cells, thereby inhibiting or killing the cells. Therefore, the silver nanoparticles have strong bactericidal ability, but show strong cytotoxicity due to direct contact reaction with human cells. On the other hand, the application of silver nanoparticles in the field of biomaterials is limited due to the lack of good biological properties, such as biocompatibility and hemocompatibility. Therefore, the modification of the silver nanoparticles to broaden the application of the silver nanoparticles in the field of biological materials is of great significance.
Hydroxyapatite (Ca)5(PO4)3(OH)) is one of the important components constituting human bones, and has good osteoconductivity, bioactivity and biocompatibility. The hydroxyapatite is taken as a bone repair material, can induce the growth of the bone of a human body after being implanted into the human body, and is an ideal bone repair substitute material which is generally accepted at present. However, hydroxyapatite itself does not have antibacterial properties and patients need to take antibiotics to prevent pathogenic bacterial infections.
Disclosure of Invention
The invention aims to provide a core-shell structure nano composite material of silver nano particles coated by hydroxyapatite aiming at the defects and the current situation of the prior art so as to obtain a biological material of silver nano particles coated by hydroxyapatite, which has excellent biocompatibility, lower cytotoxicity and lasting antibacterial performance. A second object of the present invention is to provide a method for preparing the above-mentioned core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite, which can be obtained in a simple and inexpensive manner.
Aiming at the aim of the invention, the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite provided by the invention is a core-shell structure nanocomposite taking silver nanoparticles as a core, a dopamine layer coated with the silver nanoparticles as an inner shell and a hydroxyapatite layer coated with the inner shell as an outer shell.
The core-shell structure nano composite material of silver nano particles coated by hydroxyapatite can be prepared by a method comprising the following process steps:
(1) deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9-10 mmol/L and the pH of 7-104H11NO3-a HCl buffer solution;
(2) preparing a calcium salt solution with the concentration of 0.1-1 mol/L by using deionized water and soluble calcium salt;
(3) preparing a phosphate solution with the concentration of 0.1-1 mol/L by using deionized water and soluble phosphate;
(4) uniformly dispersing silver nanoparticles in C4H11NO3-HCl buffer solution, C4H11NO3The amount of HCl buffer solution is enough to enable silver nanoparticles to be uniformly dispersed in the HCl buffer solution, dopamine is added according to the concentration of at least 2mg/mL, stirring is carried out for at least 2 hours, a layer of uniform polydopamine membrane is coated on the surfaces of the silver nanoparticles, then standing is carried out for at least half an hour, and the silver nanoparticles are washed by deionized water after liquid phase is separated and removed, so that the silver nanoparticles modified by dopamine are obtained and marked as silver nanoparticles I;
(5) dispersing silver nanoparticles I in a calcium salt solution, wherein the amount of the calcium salt solution is enough to enable the silver nanoparticles I to be uniformly dispersed in the calcium salt solution, stirring at room temperature for 12-24 hours to fully chelate polydopamine with calcium ions and calcium ions, then standing for at least half an hour, separating to remove a liquid phase, washing with deionized water until no precipitate is generated after the phosphate solution is added into the washed deionized water, and obtaining silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in a phosphate solution, wherein the amount of the phosphate solution is enough to uniformly disperse the silver nanoparticles II, the molar ratio of the phosphate solution to phosphorus and calcium (elements) in the calcium salt solution in the step (2) is (0.50-0.65): 1, adjusting the pH value to 9-10 by using ammonia water, stirring and reacting at least for 6-12 hours at the temperature of 60-95 ℃, coating a hydroxyapatite layer on the surfaces of the silver nanoparticles II, standing for at least half an hour, separating and removing a liquid phase, washing with deionized water, and drying to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
In the above technical solution of the present invention, the soluble calcium salt is preferably calcium nitrate or calcium chloride.
In the above technical solution of the present invention, the soluble phosphate is one of potassium phosphate, sodium phosphate, ammonium phosphate, potassium monohydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate and ammonium dihydrogen phosphate.
In the technical scheme of the invention, when the dopamine is added in the step (2), the dopamine is preferably added according to the concentration of 2-5 mg/mL.
In the technical scheme of the invention, the amount of the phosphate solution in the step (6) is enough to uniformly disperse the silver nanoparticles II therein, and the molar ratio of the phosphate solution to the phosphorus and calcium (element) in the calcium salt solution in the step (2) is 0.6: 1.
In the technical scheme of the invention, the stirring reaction temperature in the step (6) is preferably controlled to be 75-85 ℃.
Compared with the prior art, the invention has the following effects:
1. the invention provides a novel biological material for bone repair and replacement, namely a core-shell structure nano composite material of hydroxyapatite-coated silver nanoparticles, which can be used for a coating on the surface of a medical implant, and can be used as a bone repair implant material and an antibacterial auxiliary material for in vitro use and the like.
2. In the core-shell structure nano composite material of silver nano particles coated by hydroxyapatite, the poly-dopamine coating can greatly improve the hydrophilicity and biocompatibility of the material and the antibacterial property to gram-positive and gram-negative bacteria, the silver nano particles can effectively control the release speed of silver ions after being modified by dopamine and hydroxyapatite, so that the cytotoxicity of the material is remarkably reduced, the cell survival rate corresponding to the silver nano particles coated by the hydroxyapatite reaches 92 percent and the cell survival rate corresponding to the silver reaches 61 percent in a cytotoxicity experiment, the material is endowed with lasting antibacterial performance and excellent biocompatibility, and the material has important application value in the field of bone repair and replacement.
3. The preparation method of the core-shell structure nano composite material of silver nano particles coated by hydroxyapatite is simple and has low cost.
Drawings
Fig. 1 is an IR spectrum of a core-shell structure nanocomposite of hydroxyapatite-coated silver nanoparticles prepared in example 1.
Fig. 2 is a silver ion release curve of the core-shell structure nanocomposite of hydroxyapatite-coated silver nanoparticles prepared in example 1.
Fig. 3 is a uniform curve of experiment 1 and experiment 2 in the bacteriostatic experiment, wherein (a) is the bacteriostatic curve of each material against staphylococcus aureus, and (b) is the bacteriostatic curve of each material against escherichia coli.
Fig. 4 is a photograph of the bacteriostatic effect of experiment 3 in the bacteriostatic experiment, in which the corresponding materials of (a) and (d) are hydroxyapatite, (b) and (e) are silver nanoparticles, and (c) and (f) are core-shell structure nanocomposite materials of silver nanoparticles coated with hydroxyapatite; (a) the bacteria corresponding to (a) to (c) are Escherichia coli, and the bacteria corresponding to (d) to (f) are Staphylococcus aureus.
Fig. 5 shows the antibacterial ring of the core-shell structure nanocomposite of hydroxyapatite-coated silver nanoparticles prepared in example 1 against escherichia coli and staphylococcus aureus; wherein, (a) is staphylococcus aureus, and (b) is escherichia coli.
Fig. 6 is a schematic diagram of a preparation process of the core-shell structure nanocomposite material of silver nanoparticles coated with hydroxyapatite according to the present invention.
FIG. 7 is a TEM image of a core-shell structure nanocomposite material of silver nanoparticles coated with hydroxyapatite according to the present invention.
Detailed Description
The core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite and the preparation method thereof according to the present invention will be further described with reference to the following embodiments, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9mmol/L and the pH value of 84H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium nitrate solution with the concentration of 0.5mol/L by using deionized water and calcium nitrate;
(3) preparing a diammonium phosphate solution with the concentration of 0.3mol/L by using deionized water and diammonium phosphate;
(4) ultrasonically dispersing 12mg of silver nanoparticles into 240mL of the prepared Tris-HCl buffer solution, adding 480mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surface of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, and marking as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 60mL of calcium nitrate solution, stirring for 24 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after a diammonium hydrogen phosphate solution is added into the supernatant taken out after the last washing, and pouring out the supernatant to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 60mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 6 hours at 80 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite, wherein an IR spectrogram of the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite is shown in figure 1.
Example 2
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 10mmol/L and the pH value of 104H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium nitrate solution with the concentration of 0.1mol/L by using deionized water and calcium nitrate;
(3) preparing a diammonium phosphate solution with the concentration of 0.1mol/L by using deionized water and diammonium phosphate;
(4) ultrasonically dispersing 120mg of silver nanoparticles into 400mL of the prepared Tris-HCl buffer solution, adding 800mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surfaces of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, which are marked as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 500mL of calcium nitrate solution, stirring for 12 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after a diammonium hydrogen phosphate solution is added into the supernatant taken out after the last washing, and pouring out the supernatant to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 300mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 11 hours at 70 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
Example 3
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9.5mmol/L and the pH value of 9.54H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium nitrate solution with the concentration of 1mol/L by using deionized water and calcium nitrate;
(3) preparing a diammonium phosphate solution with the concentration of 0.6mol/L by using deionized water and diammonium phosphate;
(4) ultrasonically dispersing 12mg of silver nanoparticles into 240mL of the prepared Tris-HCl buffer solution, adding 720mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surface of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, which are marked as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 60mL of calcium nitrate solution, stirring for 24 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after a diammonium hydrogen phosphate solution is added into the supernatant taken out after the last washing, and pouring out the supernatant to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 60mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 8 hours at 60 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
Example 4
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9mmol/L and the pH value of 84H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium nitrate solution with the concentration of 1mol/L by using deionized water and calcium nitrate;
(3) preparing a diammonium phosphate solution with the concentration of 1mol/L by using deionized water and diammonium phosphate;
(4) ultrasonically dispersing 120mg of silver nanoparticles into 400mL of the prepared Tris-HCl buffer solution, adding 1216mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surfaces of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, and marking as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 100mL of calcium nitrate solution, stirring for 16 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after a diammonium hydrogen phosphate solution is added into the supernatant taken out after the last washing, and pouring out the supernatant to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 60mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 8 hours at 60 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
Example 5
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9.5mmol/L and the pH value of 7.54H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium chloride solution with the concentration of 0.5mol/L by using deionized water and calcium chloride;
(3) preparing a potassium phosphate solution with the concentration of 0.5mol/L by using deionized water and potassium phosphate;
(4) ultrasonically dispersing 12mg of silver nanoparticles into 240mL of the prepared Tris-HCl buffer solution, adding 480mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surface of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, and marking as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 100mL of calcium nitrate solution, stirring for 16 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant liquor after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after potassium phosphate solution is added into the supernatant liquor taken out after the last washing, and pouring out the supernatant liquor to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 60mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 9 hours at 60 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
Example 6
(1) Deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9mmol/L and the pH value of 84H11NO3-HCl (Tris-HCl buffer solution) buffer solution;
(2) preparing a calcium chloride solution with the concentration of 0.5mol/L by using deionized water and calcium chloride;
(3) preparing a diammonium phosphate solution with the concentration of 0.3mol/L by using deionized water and diammonium phosphate;
(4) ultrasonically dispersing 120mg of silver nanoparticles into 400mL of the prepared Tris-HCl buffer solution, adding 1216mg of dopamine, stirring at room temperature for 2 hours to coat a layer of uniform polydopamine membrane on the surfaces of the silver nanoparticles, standing for 30 minutes, pouring out the upper liquid, washing with deionized water for at least 3 times to obtain dopamine-modified silver nanoparticles, and marking as silver nanoparticles I;
(5) uniformly dispersing the silver nanoparticles I in 200mL of calcium chloride solution, stirring for 15 hours at room temperature, standing for 30 minutes to fully chelate polydopamine and calcium ions, pouring out supernatant after the reaction is finished, repeatedly washing with deionized water until no precipitate is generated after a diammonium hydrogen phosphate solution is added into the supernatant taken out after the last washing, and pouring out the supernatant to obtain silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in 200mL of diammonium hydrogen phosphate solution, adjusting the pH value to 9-10 by using ammonia water, stirring for 7 hours at 80 ℃ to coat a hydroxyapatite coating on the surfaces of the silver nanoparticles II, standing for 30 minutes, pouring out supernatant, washing with deionized water for several times, and then drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
Silver ion Release test
Taking 3mg of silver nanoparticles and the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite prepared in example 1, placing the silver nanoparticles and the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite in 25mL test tubes, adding 15mL of PBS buffer with pH of 7.4, culturing at 37 ℃, taking out 3mL of supernatant from the test tubes every 24 hours for measuring silver ion concentration by using an inductively coupled plasma emission spectrometer, and supplementing 3mL of fresh PBS buffer after taking out the supernatant each time. After 7 days of culture, the concentration of silver ions was measured 7 times, and the data of the measured concentration of silver ions were plotted as a concentration-time curve, as shown in FIG. 2. The symbols and material correspondence in fig. 2 are: ag-silver nano-particles, Ag @ pDA @ HA-hydroxyapatite-coated silver nano-particles.
As can be seen from fig. 2, the core-shell structure nanocomposite material of silver nanoparticles coated with hydroxyapatite can effectively control the release of silver ions, and the concentration of silver ions released by silver nanoparticles is greater than that released by the core-shell structure nanocomposite material of silver nanoparticles coated with hydroxyapatite, so that the material provided by the invention can realize lasting antibacterial property and can also reduce cytotoxicity.
Experiment for inhibiting bacteria
Experiment 1: 1mg of silver nanoparticles, 1mg of hydroxyapatite nanoparticles and the core-shell structure nanocomposite material of hydroxyapatite-coated silver nanoparticles prepared in example 1 were respectively put in 3 sterile test tubes, another test tube was taken without any sample as a blank group, 10mL of liquid medium and 100. mu.L of Staphylococcus aureus were added to each test tube, and 3 parallel experimental groups were set up. Each group was incubated at 37 ℃ on a constant temperature shaker, and the Optical Density (OD) value was measured every 3 hours. The measured data were plotted as the inhibition curves of each material against staphylococcus aureus, see fig. 3 (a).
Experiment 2: the golden grape ball was replaced with escherichia coli, and the bacteriostatic curves of the materials against escherichia coli were obtained in the same manner as described above, as shown in fig. 3 (b).
The correspondence of symbols and materials in fig. 3 is: ag-silver nanoparticles, Ag @ HA-hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite, HA-hydroxyapatite nanoparticles, Control-blank group.
As can be seen from FIG. 3, both Ag and Ag @ HA were effective in inhibiting bacterial growth, while HA had no inhibitory effect on bacterial growth. Therefore, Ag and Ag @ HA both have good bacteriostatic effects.
Experiment 3: from the test tubes cultured for 24 hours in experiment 1 and experiment 2, 100. mu.L of the bacterial liquid was taken out and put in a solid medium, and the solid medium was uniformly coated, and cultured in a shaker at a constant temperature of 37 ℃ for 24 hours, and the bactericidal effect of each material on the two kinds of bacteria was observed, as shown in FIG. 4. In fig. 4, the materials (a) and (d) are hydroxyapatite, the materials (b) and (e) are silver nanoparticles, and the materials (c) and (f) are core-shell structure nanocomposite materials of silver nanoparticles coated by hydroxyapatite; (a) the bacteria corresponding to (a) to (c) are Escherichia coli, and the bacteria corresponding to (d) to (f) are Staphylococcus aureus.
As can be seen from FIG. 4, after 24 hours of culture, the bactericidal rate of Ag and Ag @ HA was 99.99%, while HA had no bactericidal effect. The Ag and the Ag @ HA have good bacteriostatic effects.
Bacteriostatic ring test
1mg of silver nanoparticles, 1mg of hydroxyapatite nanoparticles and the core-shell structure nanocomposite material of hydroxyapatite-coated silver nanoparticles prepared in example 1 were respectively placed on a filter paper sheet, 20 μ L of sterile water was added to uniformly disperse the material on the circular filter paper sheet, the circular filter paper sheet was left to stand for 24 hours, and the filter paper sheet was placed on a plate containing a solid medium (bacteria were uniformly coated on the solid medium) after drying. The size of the zone of inhibition was observed after 24 hours of incubation at 37 ℃. The results of the experiment are shown in FIG. 5.
The correspondence of symbols and materials in fig. 5 is: Ag-NPs-silver nanoparticles, Ag @ pDA @ HA-hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite, HA-NPs-hydroxyapatite nanoparticles, Control-blank group.
As can be seen from FIG. 5, the filter paper sheets containing Ag-NPs and Ag @ pDA @ HA all have significant zones of inhibition, and the zones of inhibition around the filter paper sheets containing Ag-NPs are significantly greater than those around the filter paper sheets containing Ag @ pDA @ HA, while the zones of inhibition around the filter paper sheets containing HA-NPs are not significant. The antibacterial effect of the Ag-NPs is better than that of Ag @ pDA @ HA, and further the Ag @ pDA @ HA can well control the release of silver ions, so that the material is beneficial to lasting antibacterial property.
Evaluation test of biosafety (cytotoxicity)
Using cow containing 10% of fetusDMEM in serum medium cultured MG63 human osteosarcoma cells. After adherent growth of the cells, the medium was replaced with fresh medium and when the cells reached a degree of aggregation of 80%, the cells were added at 104Density per well was seeded on 96-well plates and cultured for 24 h. The medium was then replaced with the same type of medium containing hydroxyapatite-coated silver nanoparticles prepared in example 1 and silver nanoparticles (200. mu.g/ml) to prepare an experimental group, and a control group and a blank group were set, each group having six parallel groups, and cultured again for 24 hours. Wherein the control group is similar culture medium without nanoparticles, and the blank group is similar culture medium without nanoparticles and cells.
Cytotoxicity was detected using the CCK-8 kit. The absorbance of each set was measured by a microplate reader at a wavelength of 450 nm.
Relative cell survival (%) — (absorbance value of experimental group-absorbance value of blank)/(absorbance value of control group-absorbance value of blank) × 100%.
The experimental results are as follows: the cell survival rate of the silver nano particles coated with the hydroxyapatite reaches 92%, and the cell survival rate of the silver nano particles is 61%.
Claims (10)
1. The core-shell structure nano composite material with silver nanoparticles coated by hydroxyapatite is characterized in that the composite material is a core-shell structure material which takes the silver nanoparticles as a core, takes a polydopamine layer coated with the silver nanoparticles as an inner shell and takes the hydroxyapatite layer coated with the inner shell as an outer shell, and is prepared by dispersing the dopamine-modified silver nanoparticles fully chelated by calcium ions in a phosphate solution and stirring and reacting for 6-12 hours at 60-95 ℃.
2. A preparation method of a core-shell structure nano composite material of silver nano particles coated by hydroxyapatite is characterized by comprising the following process steps:
(1) deionized water is used for preparing C with the concentration of the trihydroxymethyl aminomethane of 9-10 mmol/L and the pH of 7-104H11NO3-a HCl buffer solution;
(2) preparing a calcium salt solution with the concentration of 0.1-1 mol/L by using deionized water and soluble calcium salt;
(3) preparing a phosphate solution with the concentration of 0.1-1 mol/L by using deionized water and soluble phosphate;
(4) uniformly dispersing silver nanoparticles in C4H11NO3-HCl buffer solution, C4H11NO3The amount of HCl buffer solution is enough to enable silver nanoparticles to be uniformly dispersed in the HCl buffer solution, dopamine is added according to the concentration of at least 2mg/mL, stirring is carried out for at least 2 hours, a layer of uniform polydopamine membrane is coated on the surfaces of the silver nanoparticles, then standing is carried out for at least half an hour, and the silver nanoparticles are washed by deionized water after liquid phase is separated and removed, so that the silver nanoparticles modified by dopamine are obtained and marked as silver nanoparticles I;
(5) dispersing silver nanoparticles I in a calcium salt solution, stirring for 12-24 hours to fully chelate polydopamine and calcium ions, standing for at least half an hour, separating to remove a liquid phase, washing with deionized water until no precipitate is generated after a washing solution is added into a phosphate solution, and obtaining silver nanoparticles II;
(6) uniformly dispersing the silver nanoparticles II in a phosphate solution, wherein the amount of the phosphate solution is enough to uniformly disperse the silver nanoparticles II in the phosphate solution, the molar ratio of phosphorus to calcium in the phosphate solution and a calcium salt solution is (0.50-0.65): 1, adjusting the pH value to 9-10 by using ammonia water, stirring and reacting at least for 6-12 hours at a temperature of 60-95 ℃, coating a hydroxyapatite coating on the surface of the silver nanoparticles II, standing for at least half an hour, separating to remove a liquid phase, washing with deionized water, and drying in vacuum to obtain the hydroxyapatite-coated silver nanoparticle core-shell structure nanocomposite.
3. The method for preparing a core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to claim 2, wherein the soluble calcium salt is calcium nitrate or calcium chloride.
4. The method for preparing a core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to claim 2, wherein the soluble phosphate is one of potassium phosphate, sodium phosphate, ammonium phosphate, potassium monohydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate and ammonium dihydrogen phosphate.
5. The method for preparing the core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to any one of claims 2 to 4, wherein the dopamine in the step (4) is added at a concentration of 2 to 5 mg/mL.
6. The method for preparing the core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to any one of claims 2 to 4, wherein the amount of the phosphate solution in the step (6) is such that the silver nanoparticles II are uniformly dispersed therein, and the molar ratio of phosphate in the phosphate solution to calcium ions in the calcium salt solution in the step (2) is 0.6: 1.
7. The method for preparing a core-shell structure nanocomposite material of silver nanoparticles coated with hydroxyapatite according to claim 5, wherein the amount of the phosphate solution in the step (6) is such that the silver nanoparticles II are uniformly dispersed therein, and the molar ratio of phosphate in the phosphate solution to calcium ions in the calcium salt solution in the step (2) is 0.6: 1.
8. The method for preparing the core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to any one of claims 2 to 4, wherein the stirring reaction temperature in the step (6) is 75 to 85 ℃.
9. The method for preparing the core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to claim 6, wherein the stirring reaction temperature in the step (6) is 75-85 ℃.
10. The method for preparing the core-shell structure nanocomposite of silver nanoparticles coated with hydroxyapatite according to claim 7, wherein the stirring reaction temperature in the step (6) is 75-85 ℃.
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