CN107096069A - Nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain and preparation method thereof - Google Patents
Nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain, the composite is using silver nano-grain as core, to coat the dopamine coating of silver nano-grain as inner casing, to coat the hydroxyapatite coating layer of inner casing as the nuclear-shell structured nano-composite material of shell.Present invention also offers the preparation method of above-mentioned material：C is first prepared respectively4H11NO3HCl cushioning liquid, calcium salt soln, phosphate solution, are then dispersed in C by silver nano-grain4H11NO3In HCl cushioning liquid, make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, be redispersed in calcium salt soln, make one layer of hydroxyapatite coating layer of silver nano-grain Surface coating.The material has excellent biocompatibility, relatively low cytotoxicity and lasting anti-microbial property, available for the coating of medical implant surface, and Bone Defect Repari implantation material and the external of antibacterial auxiliary material use.
Description
Technical field
The present invention relates to technical field of biological materials, and in particular to a kind of hydroxyapatite for Bone Defect Repari is answered with silver
Condensation material and preparation method thereof.
Background technology
Bone Defect Repari substitutes operation typically wound than larger operation, and rehabilitation course is long, in surgical procedure and rehabilitation
The unavoidable bacterium infection of process, in order to avoid prevention bacterium infection, need to generally prevent thin using some antibiotic for a long time
Bacterium infects, and reduces inflammation odds.In recent decades, the antibiotic such as penicillin, streptomysin, TMP and tetracycline is big
The big morbidity and mortality for reducing pathogenic bacteria infectious disease, clinically with extensive use.However, with antibiosis
The excessive of element is used and abused, and pathogen is improved constantly to the resistance to the action of a drug of antibiotic, gently then causes pathogenic infection disease to be controlled long
It is not cured, reduces therapeutic effect, deterioration that is heavy then causing conditions of patients is even dead.With the development of nanometer technology, inorganic nano
Material due to its excellent physics, chemistry and biology property and be widely used in biomedical sector.Particularly silver nanoparticle
Particle (can suppress Gram-positive, negative bacteria, fungi even due to the antibacterial range with excellent anti-microbial property and wide spectrum
Virus), available for substitute antibiotics, to solve pathogen drug resistance problems, therefore have broad application prospects.It is exposed to material
The silver nano-grain on surface is expected because its size is small, and specific surface area is big, is easily oxidized, so as to produce substantial amounts of silver ion.Silver
Nano particle anti-microbial property and cytotoxicity depend primarily on from its meet material in the concentration of silver ion that discharges.Discharge
Silver ion not only cause physical damnification to cell membrane, and can the ATP of interference cell produce and DNA replication dna so that suppress or
Kill cell.Although therefore silver nano-grain is with very strong sterilizing ability, due to the direct haptoreaction of people's cell and table
Reveal extremely strong cytotoxicity.On the other hand, due to lacking good biological characteristics, such as biocompatibility and blood compatibility
Property, limit application of the silver nano-grain in technical field of biological material.Therefore silver nano-grain is modified to widen it in life
The application of thing Material Field is significant.
Hydroxyapatite (Ca5(PO4)3(OH) it is) to constitute one of important component of skeleton, with good osteoacusis
Property, bioactivity and biocompatibility.Hydroxyapatite can induce the bone of human body in itself as bone renovating material after being implanted into human body
Bone grows, and is preferable implantation generally acknowledged at present.But hydroxyapatite does not have anti-microbial property, Bing Renxu in itself
Infected by taking antibiotic prophylaxis pathogenic bacteria.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art with present situation, there is provided a kind of Coated With Hydroxyapatite silver nanoparticle
The nuclear-shell structured nano-composite material of particle, with obtain it is a kind of have excellent biocompatibility, relatively low cytotoxicity and hold
The biomaterial of the Coated With Hydroxyapatite silver nano-grain of long anti-microbial property.Second object of the present invention is to provide above-mentioned
The preparation method of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain, in the way of a kind of cheap and simple
Obtain the material.
The nucleocapsid knot of the Coated With Hydroxyapatite silver nano-grain provided for the foregoing invention purpose of the present invention, the present invention
Structure nano composite material, the composite be using silver nano-grain as core, to coat the DOPA amine layer of silver nano-grain as inner casing,
To coat the hydroxyapatite layer of inner casing as the nuclear-shell structured nano-composite material of shell.
The nuclear-shell structured nano-composite material for the Coated With Hydroxyapatite silver nano-grain that the present invention is provided, can by including
It is prepared by the method for following processing step：
(1) it is 9~10mmol/L to prepare trishydroxymethylaminomethane concentration with deionized water, and pH is 7~10
C4H11NO3- HCl cushioning liquid；
(2) with the calcium salt soln of deionized water and soluble calcium salt compound concentration for 0.1~1mol/L；
(3) with the phosphate solution of deionized water and soluble phosphate compound concentration for 0.1~1mol/L；
(4) silver nano-grain is dispersed in C4H11NO3In-HCl cushioning liquid, C4H11NO3The amount of-HCl cushioning liquid
Satisfaction can make silver nano-grain dispersed wherein, add dopamine according at least 2mg/mL concentration, stir at least 2 hours,
Make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, then stand at least half an hour, be separated off using after liquid phase
Deionized water is washed, and obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver nano-grain I；
(5) silver nano-grain I is scattered in calcium salt soln, the amount of calcium salt soln, which is met, can make silver nano-grain I uniform
It is scattered wherein to stir 12~24 hours at room temperature, make poly-dopamine and calcium ion and the abundant chelant of calcium ion, then stand at least
Half an hour, it is separated off being washed with deionized after liquid phase into deionized water after washing after adding phosphate solution and does not produce
Raw precipitation, obtains silver nano-grain II；
(6) silver nano-grain II is dispersed in phosphate solution, the amount of phosphate solution, which is met, can make silver nanoparticle
Particle II is dispersed wherein, and it is (0.50 to meet phosphate solution with phosphorus calcium (element) mol ratio in step (2) calcium salt soln
~0.65):1, pH to 9~10 is adjusted with ammoniacal liquor, at least stirring reaction 6~12 hours at temperature 60 C~95 DEG C makes Yin Na
Rice grain II Surface coating, one layer of hydroxyapatite layer, then at least stands half an hour, is separated off after liquid phase using deionized water
Washing, obtains the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain after drying.
In the above-mentioned technical proposal of the present invention, the soluble calcium salt prioritizing selection calcium nitrate or calcium chloride.
In the above-mentioned technical proposal of the present invention, the soluble phosphate is potassium phosphate, sodium phosphate, ammonium phosphate, phosphoric acid
One kind in one hydrogen potassium, disodium-hydrogen, potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium di-hydrogen phosphate and DAP.
In the above-mentioned technical proposal of the present invention, step (2) preferably adds when adding dopamine according to 2~5mg/mL concentration
Enter dopamine.
The amount of phosphate solution, which is met, in the above-mentioned technical proposal of the present invention, in step (6) can make silver nano-grain II
It is dispersed wherein, and it is 0.6 to meet phosphorus calcium (element) mol ratio in phosphate solution and step (2) calcium salt soln:1.
In the above-mentioned technical proposal of the present invention, the temperature of stirring reaction is preferably controlled as 75~85 DEG C in step (6).
Compared with prior art, the present invention has below due to effect：
1. new biomaterial --- the Coated With Hydroxyapatite silver nanoparticle replaced for Bone Defect Repari the invention provides in
The nuclear-shell structured nano-composite material of particle, can be used for the coating of medical implant surface, can be implanted into material as Bone Defect Repari
External with antibacterial auxiliary material uses.
2. in the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain of the present invention, poly-dopamine
Coating is greatly improved the hydrophily of material, biocompatibility and to Gram-positive, the antibiotic property of negative bacteria, silver nanoparticle
Particle can efficiently control silver ion rate of release after dopamine and hydroxyapatite modified, so as to significantly decrease material
In cytotoxicity, cytotoxicity experiment, the corresponding cell survival rate of silver nano-grain of hydroxyapatite has been wrapped up up to 92%, and
The corresponding cell survival rate of silver is 61%, and assigns the lasting anti-microbial property of material and excellent biocompatibility, and the material exists
Bone Defect Repari replacement has important application value in field.
3. the nuclear-shell structured nano-composite material preparation method letter of Coated With Hydroxyapatite silver nano-grain of the present invention
It is single, it is with low cost.
Brief description of the drawings
Fig. 1 is the IR of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain prepared by embodiment 1
Spectrogram.
Fig. 2 is the silver of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain prepared by embodiment 1
Plasma diffusing W,Mo curve.
Fig. 3 is the uniform curve of experiment 1 and experiment 2 in bacteriostatic experiment, wherein, (a) is each material to Staphylococcus aureus
The Bactericidal curves of bacterium, (b) is Bactericidal curves of each material to Escherichia coli.
The fungistatic effect photo of experiment 3 in Fig. 4 bacteriostatic experiments, wherein (a), the corresponding material of (d) they are hydroxyapatite,
(b), (e) corresponding material is silver nano-grain, and (c), (f) material are the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material；(a) the corresponding bacteriums of~(c) are Escherichia coli, and the corresponding bacteriums of (d)~(f) are Staphylococcus aureus
Bacterium.
Fig. 5 is the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain prepared by embodiment 1 to big
The antibacterial ring size that enterobacteria and staphylococcus aureus produce；Wherein, (a) is staphylococcus aureus, and (b) is Escherichia coli.
Fig. 6 is the preparation of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain of the present invention
Journey schematic diagram.
The TEM figures of the nuclear-shell structured nano-composite material of Fig. 7 Coated With Hydroxyapatite silver nano-grains of the present invention.
Embodiment
The core shell structure of Coated With Hydroxyapatite silver nano-grain of the present invention is received below by embodiment
Nano composite material and preparation method thereof is described further, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
(1) it is 9mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 8 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium nitrate solution for being 0.5mol/L with deionized water and calcium nitrate compound concentration；
(3) the diammonium hydrogen phosphate solution for being 0.3mol/L with deionized water and diammonium hydrogen phosphate compound concentration；
(4) by 12mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 240mL, add
480mg dopamines, stir 2 hours, make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, then stand at room temperature
30 minutes, supernatant liquid is outwelled, is washed with deionized at least 3 times, obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver
Nano particle I；
(5) silver nano-grain I is dispersed in 60mL calcium nitrate solutions, stirred 24 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after diammonium hydrogen phosphate solution, outwell supernatant, obtain
To silver nano-grain II；
(6) silver nano-grain II is dispersed in 60mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 6 hours at 80 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material, its IR spectrogram is shown in Fig. 1.
Embodiment 2
(1) it is 10mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 10 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium nitrate solution for being 0.1mol/L with deionized water and calcium nitrate compound concentration；
(3) the diammonium hydrogen phosphate solution for being 0.1mol/L with deionized water and diammonium hydrogen phosphate compound concentration；
(4) by 120mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 400mL, add
800mg dopamines, stir 2 hours, make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, then stand at room temperature
30 minutes, supernatant liquid is outwelled, is washed with deionized at least 3 times, obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver
Nano particle I；
(5) silver nano-grain I is dispersed in 500mL calcium nitrate solutions, stirred 12 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after diammonium hydrogen phosphate solution, outwell supernatant, obtain
To silver nano-grain II；
(6) silver nano-grain II is dispersed in 300mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 11 hours at 70 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material.
Embodiment 3
(1) it is 9.5mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 9.5 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium nitrate solution for being 1mol/L with deionized water and calcium nitrate compound concentration；
(3) the diammonium hydrogen phosphate solution for being 0.6mol/L with deionized water and diammonium hydrogen phosphate compound concentration；
(4) by 12mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 240mL, add
720mg dopamines, stir 2 hours, make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, then stand at room temperature
30 minutes, supernatant liquid is outwelled, is washed with deionized at least 3 times, obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver
Nano particle I；
(5) silver nano-grain I is dispersed in 60mL calcium nitrate solutions, stirred 24 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after diammonium hydrogen phosphate solution, outwell supernatant, obtain
To silver nano-grain II；
(6) silver nano-grain II is dispersed in 60mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 8 hours at 60 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material.
Embodiment 4
(1) it is 9mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 8 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium nitrate solution for being 1mol/L with deionized water and calcium nitrate compound concentration；
(3) the diammonium hydrogen phosphate solution for being 1mol/L with deionized water and diammonium hydrogen phosphate compound concentration；
(4) by 120mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 400mL, add
1216mg dopamines, stir 2 hours, make one layer of silver nano-grain Surface coating uniform poly-dopamine film, Ran Houjing at room temperature
Put 30 minutes, outwell supernatant liquid, be washed with deionized at least 3 times, obtain, through the amine-modified silver nano-grain of DOPA, being designated as
Silver nano-grain I；
(5) silver nano-grain I is dispersed in 100mL calcium nitrate solutions, stirred 16 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after diammonium hydrogen phosphate solution, outwell supernatant, obtain
To silver nano-grain II；
(6) silver nano-grain II is dispersed in 60mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 8 hours at 60 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material.
Embodiment 5
(1) it is 9.5mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 7.5 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium chloride solution for being 0.5mol/L with deionized water and calcium chloride compound concentration；
(3) potassium phosphate solution for being 0.5mol/L with deionized water and potassium phosphate compound concentration；
(4) by 12mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 240mL, add
480mg dopamines, stir 2 hours, make the uniform poly-dopamine film of one layer of silver nano-grain Surface coating, then stand at room temperature
30 minutes, supernatant liquid is outwelled, is washed with deionized at least 3 times, obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver
Nano particle I；
(5) silver nano-grain I is dispersed in 100mL calcium nitrate solutions, stirred 16 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after potassium phosphate solution, outwell supernatant, obtain silver
Nano particle II；
(6) silver nano-grain II is dispersed in 60mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 9 hours at 60 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material.
Embodiment 6
(1) it is 9mmol/L that trishydroxymethylaminomethane concentration is prepared with deionized water, and pH is 8 C4H11NO3-HCl
(Tris-HCl cushioning liquid) cushioning liquid；
(2) calcium chloride solution for being 0.5mol/L with deionized water and calcium chloride compound concentration；
(3) the diammonium hydrogen phosphate solution for being 0.3mol/L with deionized water and diammonium hydrogen phosphate compound concentration；
(4) by 120mg silver nano-grains ultrasonic disperse in the Tris-HCl cushioning liquid of the above-mentioned preparations of 400mL, add
1216mg dopamines, stir 2 hours, make one layer of silver nano-grain Surface coating uniform poly-dopamine film, Ran Houjing at room temperature
Put 30 minutes, outwell supernatant liquid, be washed with deionized at least 3 times, obtain, through the amine-modified silver nano-grain of DOPA, being designated as
Silver nano-grain I；
(5) silver nano-grain I is dispersed in 200mL calcium chloride solutions, stirred 15 hours at room temperature, stand 30 points
Clock, makes poly-dopamine and the abundant chelant of calcium ion, and question response terminates to outwell supernatant liquor, uses deionized water cyclic washing, until
Added in the supernatant that last time washing is taken out untill not producing precipitation after diammonium hydrogen phosphate solution, outwell supernatant, obtain
To silver nano-grain II；
(6) silver nano-grain II is dispersed in 200mL diammonium hydrogen phosphate solution, pH is adjusted to 9~10 with ammoniacal liquor,
Stirred 7 hours at 80 DEG C, make silver nano-grain II Surface coating, one layer of hydroxyapatite coating layer, then stand 30 minutes, fallen
Fall supernatant liquor, be washed with deionized and be dried in vacuo afterwards for several times, obtain the nucleocapsid knot of Coated With Hydroxyapatite silver nano-grain
Structure nano composite material.
Silver ion release experiment
The nuclear shell structure nano of silver nano-grain and the Coated With Hydroxyapatite silver nano-grain of the preparation of embodiment 1 is taken respectively
Composite 3mg is separately added into the PBS that 15mL pH are 7.4, cultivated at 37 DEG C, every 24 in 25mL test tube
3mL supernatants are taken out hour from test tube, for inductance coupled plasma optical emission spectrometer measurement concentration of silver ions, every time
Take out after supernatant, be supplemented the fresh PBSs of 3mL.Co-culture 7 days, survey concentration of silver ions 7 times, by the survey measured silver
Ion concentration data are depicted as concentration time curve, see Fig. 2.Symbol and material corresponds in Fig. 2：Ag-silver nano-grain,
The nuclear-shell structured nano-composite material of Ag@pDA@HA-Coated With Hydroxyapatite silver nano-grain.
As can be seen from Figure 2, the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain can be controlled effectively
Silver ion discharges, and the concentration of the silver ion of silver nano-grain release is more than the core shell structure of Coated With Hydroxyapatite silver nano-grain
The concentration of the silver ion of nano composite material release, therefore the material that the present invention is provided can realize durable antibiotic, while can also subtract
Cellule toxicity.
Bacteriostatic experiment
Experiment 1：The hydroxyapatite for taking 1mg silver nano-grains, hydroxyapatite nanoparticle, embodiment 1 to prepare respectively
The nuclear-shell structured nano-composite material of cladding silver nano-grain takes a test tube to be not added with any sample in 3 sterile test tubes, separately
As blank group, 10mL fluid nutrient mediums and 100 μ L staphylococcus aureuses are added into every test tube, 3 groups of parallel realities are set up
Test group.Each group is cultivated in 37 DEG C of constant-temperature tables, optical density (OD) value is surveyed within every 3 hours.The data measured are depicted as
Each material is shown in Fig. 3 (a) to the Bactericidal curves of staphylococcus aureus.
Experiment 2：Staphylococcus aureus is replaced with into Escherichia coli, according to above-mentioned same procedure, each material is obtained to large intestine
The Bactericidal curves of bacillus, are shown in Fig. 3 (b).
Symbol and material corresponds in Fig. 3：Ag-silver nano-grain, Ag@HA-Coated With Hydroxyapatite silver nanoparticle
The nuclear-shell structured nano-composite material of grain, HA-hydroxyapatite nanoparticle, Control-blank group.
As can be seen from Figure 3, Ag and Ag@HA can effectively suppress the growth of bacterium, and growth unrestraints of the HA to bacterium is made
With.Therefore Ag and Ag@HA are respectively provided with good fungistatic effect.
Experiment 3：From experiment 1 and experiment 2 cultivated the test tube of 24 hours in take 100 μ L bacterium solution in solid medium
In, coating is uniform, is cultivated 24 hours in 37 DEG C of constant-temperature tables, observes each material to the bactericidal effect of two kinds of bacteriums, sees Fig. 4.
In Fig. 4, (a), (d) corresponding material are hydroxyapatite, and the corresponding material of (b), (e) is silver nano-grain, (c), (f's)
Material is the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain；(a) the corresponding bacteriums of~(c) are large intestine
Bacillus, the corresponding bacteriums of (d)~(f) are staphylococcus aureus.
As can be seen from Figure 4, after cultivating 24 hours, Ag and Ag@HA sterilizing rate can reach 99.99%, and HA is without bactericidal action.
Illustrate that Ag and Ag@HA are respectively provided with good fungistatic effect.
Bacteriostasis circle test
Coated With Hydroxyapatite silver prepared by 1mg silver nano-grains, hydroxyapatite nanoparticle and embodiment 1 is taken respectively
The nuclear-shell structured nano-composite material of nano particle is on filter paper, plus 20 μ L sterilized waters make material disperse in circular filter paper piece
Uniformly, place 24 hours, be placed on after after filter paper drying containing solid medium (bacterium is uniformly coated on solid medium)
Flat board on.The size of antibacterial ring size is observed after being cultivated 24 hours at 37 DEG C.Experimental result is as shown in Figure 5.
Symbol and material corresponds in Fig. 5：Ag-NPs-silver nano-grain, Ag@pDA@HA-Coated With Hydroxyapatite
The nuclear-shell structured nano-composite material of silver nano-grain, HA-NPs-hydroxyapatite nanoparticle, Control-blank group.
As can be seen from Figure 5, there is obvious inhibition zone around the filter paper of the HA containing Ag-NPs and Ag@pDA@, and containing Ag-NPs
Filter paper around inhibition zone be significantly greater than inhibition zone around the pDA@of@containing Ag HA filter paper, and the filter paper containing HA-NPs
But without obvious inhibition zone around piece.This explanation Ag-NPs bactericidal effect is better than Ag@pDA@HA, furtherly Ag@pDA@
HA can control silver ion to discharge well, be conducive to the durable antibiotic of material.
Biological safety (cytotoxicity) evaluation experimental
MG63 human osteosarcoma cells are cultivated with the DMEM containing 10% hyclone nutrient solution.After cell attachment growth, change
Fresh culture medium, when cell reaches 80% aggregation extent, by cell with 104The density in/hole is seeded on 96 orifice plates simultaneously
Cultivate 24h.Then culture medium is replaced with the Coated With Hydroxyapatite silver nano-grain prepared containing embodiment 1 and silver nanoparticle
The similar culture medium of grain (200 μ g/ml), respectively as an experimental group, and sets up control group and blank group, each group sets up six
Individual parallel group, cultivates 24h again.Wherein, control group is the similar culture medium for being not added with nano particle, and blank group is not plus nano
The similar culture medium of grain and cell.
Cytotoxicity is detected using CCK-8 kits.Each group absorbance is measured by ELIASA under 450nm wavelength.
Versus cell survival rate (%)=(absorbance of absorbance-blank group of experimental group)/(extinction of control group
The absorbance of angle value-blank group) * 100%.
Experimental result：The corresponding cell survival rate of silver nano-grain of hydroxyapatite has been wrapped up up to 92%, and silver is corresponding
Cell survival rate be 61%.
Claims (10)
1. a kind of nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain, it is characterised in that the composite
Be using silver nano-grain as core, with coat silver nano-grain poly-dopamine layer for inner casing, to coat the hydroxyapatite of inner casing
Layer is the Core-shell structure material of shell.
2. a kind of preparation method of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain, it is characterised in that
Processing step is as follows：
(1) it is 9~10mmol/L to prepare trishydroxymethylaminomethane concentration with deionized water, and pH is 7~10 C4H11NO3-HCl
Cushioning liquid；
(2) with the calcium salt soln of deionized water and soluble calcium salt compound concentration for 0.1~1mol/L；
(3) with the phosphate solution of deionized water and soluble phosphate compound concentration for 0.1~1mol/L；
(4) silver nano-grain is dispersed in C4H11NO3In-HCl cushioning liquid, C4H11NO3The amount of-HCl cushioning liquid is met
Silver nano-grain can be made dispersed wherein, dopamine is added according at least 2mg/mL concentration, stir at least 2 hours, make silver
Nano grain surface coats one layer of uniform poly-dopamine film, then stands at least half an hour, be separated off spending after liquid phase from
Sub- water washing, obtains, through the amine-modified silver nano-grain of DOPA, being designated as silver nano-grain I；
(5) silver nano-grain I is scattered in calcium salt soln, the amount of calcium salt soln, which is met, can make silver nano-grain I dispersed
Wherein, stir 12~24 hours, make poly-dopamine and the abundant chelant of calcium ion, then stand at least half an hour, be separated off liquid
It is washed with deionized after phase into deionized water after washing after adding phosphate solution and does not produce precipitation, obtains silver nanoparticle
Particle II；
(6) silver nano-grain II is dispersed in phosphate solution, the amount of phosphate solution, which is met, can make silver nano-grain
II it is dispersed wherein, and it is (0.50~0.65) to meet phosphorus calcium mol ratio in phosphate solution and step (2) calcium salt soln:1,
PH to 9~10 is adjusted with ammoniacal liquor, at least stirring reaction 6~12 hours at temperature 60 C~95 DEG C makes the table of silver nano-grain II
Bread covers one layer of hydroxyapatite layer, then at least stands half an hour, is separated off being washed with deionized after liquid phase, through vacuum
It is dried to obtain the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain.
3. the preparation side of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain according to claim 2
Method, it is characterised in that the soluble calcium salt is calcium nitrate or calcium chloride.
4. the preparation side of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain according to claim 2
Method, it is characterised in that the soluble phosphate is potassium phosphate, sodium phosphate, ammonium phosphate, potassium phosphate,monobasic, disodium-hydrogen, phosphorus
One kind in acid dihydride potassium, sodium dihydrogen phosphate, ammonium di-hydrogen phosphate and DAP.
5. the core shell structure of Coated With Hydroxyapatite silver nano-grain is received according to any claim in claim 2~4
The preparation method of nano composite material, it is characterised in that dopamine described in step (4) is added according to 2~5mg/mL concentration.
6. the core shell structure of Coated With Hydroxyapatite silver nano-grain is received according to any claim in claim 2~4
The preparation method of nano composite material, it is characterised in that the amount of phosphate solution, which is met, in step (6) can make silver nano-grain II equal
It is even to disperse wherein, and it is 0.6 to meet phosphate solution with phosphorus calcium mol ratio in step (2) calcium salt soln:1.
7. the preparation side of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain according to claim 5
Method, it is characterised in that the amount of phosphate solution, which is met, in step (6) can make silver nano-grain II dispersed wherein, and meet phosphorus
Acid salt solution is 0.6 with phosphorus calcium mol ratio in step (2) calcium salt soln:1.
8. the core shell structure of Coated With Hydroxyapatite silver nano-grain is received according to any claim in claim 2~4
The preparation method of nano composite material, it is characterised in that stirring reaction temperature is 75~85 DEG C in step (6).
9. the preparation side of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain according to claim 6
Method, it is characterised in that stirring reaction temperature is 75~85 DEG C in step (6).
10. the preparation of the nuclear-shell structured nano-composite material of Coated With Hydroxyapatite silver nano-grain according to claim 7
Method, it is characterised in that stirring reaction temperature is 75~85 DEG C in step (6).
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