CN103751850A - Three-dimensional graphene/hydroxyapatite hydrogel material - Google Patents
Three-dimensional graphene/hydroxyapatite hydrogel material Download PDFInfo
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Abstract
The invention provides a three-dimensional graphene/hydroxyapatite hydrogel material. The material is prepared in the following steps: mixing a graphene oxide solution with concentration of 6-10mg/ml and hydroxyapatite size, sufficiently and uniformly stirring to obtain a mixed solution, wherein the mass ratio of the graphene oxide to hydroxyapatite in the mixed solution is 1:(0.5-5); transferring the mixed solution into a hydrothermal reaction kettle, insulating for 0.5-24 hours at 160-200 DEG C to react; cooling to room temperature, and absorbing free water on the surface of the product to obtain the three-dimensional graphene/hydroxyapatite hydrogel material. The material is hydrogel with a network structure, is high in porosity, large in specific surface area and excellent in mechanical performance, can be directly used as bone tissue repairing materials and drug carriers with good treatment and repair effect and excellent drug-loading and drug-release effects.
Description
Technical field
The present invention relates to a kind of three-dimensional grapheme/hydroxyapatite hydrogel material, belong to nano composite material and biomaterial.
Background technology
Hydroxyapatite (Hydroxyapatite, HA) be a kind of typical biomaterial, being the main inorganic composition of body bone tissue and tooth, having good biocompatibility and osteogenic activity, is that the good bone of generally acknowledging in bone reparation replacement field is replaced biomaterial.But hydroxyapatite, as a kind of bone renovating material, also exists the shortcomings such as different application requirement that fragility is large, poor to load carrying, can not adapt to well clinical bone reparation simultaneously.For addressing this problem, hydroxyapatite is normal to carry out compound to reach the object of enhancing mechanical property with other materials.
Graphene (Graphene or Reduced-Graphene Oxide, RGO) as a kind of material of emerging nanoscale, there is excellent electricity, mechanics, optics and thermal property, also there is specific surface area large simultaneously, the features such as quality is light, make it in fields such as electronic device, composite, reinforcers, have broad application prospects.It is bio-safety that a series of cell compatibility evaluation experimentals of at present Graphene being carried out demonstrate Graphene, does not have virose (Small.2010,6:537-544 and Nano Res2008,1:203-212).Therefore; by the even compound and composite that obtains of Graphene and hydroxyapatite; both there is the biological activity that hydroxyapatite is good; there is again the performances such as the superpower mechanical property of Graphene, electricity and optics, Graphene/hydroxyapatite composite material is had a wide range of applications in fields such as biomedicine and the energy, electronic device, environmental conservation.Graphene/hydroxyapatite composite material can be used for the reparation replacement of human body hard tissue, aspects such as the external naturopathy of orthopaedic disease, slow releasing carrier of medication material and sewage disposals.
The Graphene of usining is at present prepared Graphene/hydroxyapatite composite material research as hydroxyapatite wild phase seldom.The existing research report of preparing about Graphene/hydroxyapatite composite material is on a small quantity that the situation that is based upon multiple reducing agent interpolation gets off to realize mostly.Hongyan Liu etc. utilizes dopamine redox graphene, obtain the Graphene presoma of dopamine load, and through rinsing the dopamine remove not with graphite oxide alkene reaction, again by method synthesizing graphite alkene/hydroxyapatite composite material (J.Phys.Chem.C2012 of biomineralization, 116,3334 – 3341).The shortcoming of this method is to guarantee to reduce dopaminergic used removal completely under rinse stage, therefore can cause potential toxic and side effects.Simultaneously poor owing to being dispersed in the hydroxyapatite crystal crystallinity and the mechanical property that obtain by biomineralization method forming core on graphene sheet layer, this structure cannot reach the object that desirable Graphene strengthens hydroxyapatite mechanical property.Gururaj M etc. utilizes ethylenediamine redox graphene to obtain Graphene presoma, and by flushing remove unnecessary not with the ethylenediamine of graphite oxide alkene reaction, obtain the graphene solution of ethylenediamine reduction, then by coprecipitation, under graphene aqueous solution system, obtain Graphene/hydroxyapatite composite material (J.Materials Research Bulletin. (2010) .08.077).This method ethylenediamine used is that a kind of to the healthy material that causes murder by poisoning, its interpolation can reduce the biocompatibility of hydroxyapatite, causes composite to have the possibility of bio-toxicity.And above two kinds of methods all need first graphene oxide is processed early stage, obtain grapheme material or Graphene presoma, and then form hydroxyapatite thereon and obtain Graphene/hydroxyapatite composite material, increase like this reaction time and increase production cost, being unfavorable for large-scale production.Chinese patent CN201210055981.0 using graphene oxide as presoma, aminoacid as structure regulating agent, adopt hydro-thermal method to prepare graphene/hydroxyapatite nano composite, but this method is added aminoacid as structure regulating agent, increase preparation cost, and the response time is long, the having little significance of large-scale production.
And, synthetic Graphene/the hydroxyapatite composite material of above method is powder, is used in when biological bone is repaired field, to carry out again compressingly, prepares that loose structure is wasted time and energy, cost is high, its regulation process is complicated simultaneously, and degree of repeatability has much room for improvement; During as slow releasing carrier of medication material, owing to not forming three dimensional network structure, its porosity is not high enough, its medicine carrying, release effect have much room for improvement.
Summary of the invention
The object of this invention is to provide a kind of three-dimensional grapheme/hydroxyapatite hydrogel material, this kind of hydrogel that material is network structure, porosity is high, and specific surface area is large, good mechanical performance; Can directly make osseous tissue renovating material and pharmaceutical carrier and use, its treatment repairing effect is good, and medicine carrying, release effect are good.
It is that a kind of three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods that the present invention realizes the technical scheme that its goal of the invention adopts:
The graphene oxide solution that is 6-10mg/ml by concentration mixes with hydroxyapatite slurry, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:0.5～5; Again mixed solution is proceeded in hydrothermal reaction kettle, at 160-200 ℃, be incubated 0.5-24 hour and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
Reaction mechanism in the preparation process of material of the present invention is:
The hydroxyapatite of employing pulp-like of the present invention mixes with graphene oxide, both guaranteed the two mix homogeneously, make again the graphene oxide concentration in mixed solution enough high, thereby in the hydro-thermal stage, after graphene oxide is reduced, the graphene sheet layer of assembling is by π-π active force, Van der Waals force, and the electrostatic repulsion forces of the residual oxygen-containing functional group of graphene sheet layer interacts and is stacked to the hydrogel of three-dimensional grid structure shape; While hydroxyapatite slurry recrystallize in water-heat process, form the high hydroapatite particles of crystallinity, and with Graphene on the residual effective combination of oxygen-containing functional group, finally form evenly Graphene/hydroxyapatite hydrogel of the three dimensional network structure shape of parcel hydroxyapatite.
Compared with prior art, the invention has the beneficial effects as follows:
One, the composite making is Graphene/hydroxyapatite hydrogel of three dimensional network structure shape, but not powder is without again compressing, easy to use while being used in biological bone reparation field.
Two, the hydrogel of three dimensional network trellis, is beneficial to osteoblast growth therein as osseous tissue renovating material and sticks, and treatment repairing effect is good;
Three, the hydrogel of three dimensional network trellis is as slow releasing carrier of medication material, and its porosity is higher, medicine carrying, release better effects if.
Calcium salt and phosphate that above-mentioned hydroxyapatite slurry is is 1.67 by Ca/P mol ratio are synthesized into by wet method.
The synthetic method of wet method of above-mentioned hydroxyapatite slurry is chemical coprecipitation, hydro-thermal method, solvent-thermal method or microemulsion method.
The method synthetic by these wet methods can directly obtain hydroxyapatite slurry, and the hydroxyapatite that sintering process obtains is solid, need be milled into powder, then can obtain slurry through disperseing to overcome reunion.Thereby preparation cost and the operating procedure of material of the present invention have been reduced.
The concentration of above-mentioned hydroxyapatite slurry is 50～200mg/ml.
The hydroxyapatite slurry of concentration can better make the graphene oxide concentration in mixed solution high like this, in the hydro-thermal stage, after graphene oxide is reduced, is more conducive to graphene sheet layer and assembles, and reaction forms the Graphene hydrogel of three-dimensional grid structure shape.
Above-mentioned calcium salt is lime nitrate, calcium chloride, calcium acetate, calcium hydroxide or calcium carbonate.
Above-mentioned phosphate is sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate, diammonium phosphate, tetrasodium pyrophosphate or sodium tripolyphosphate.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the optical photograph of three-dimensional grapheme/hydroxyapatite hydrogel of embodiment mono-.
Fig. 2 is the X-ray diffractogram of three-dimensional grapheme/hydroxyapatite hydrogel of embodiment mono-.
Fig. 3 is the scanning electron microscope diagram of three-dimensional grapheme/hydroxyapatite of embodiment mono-.
The specific embodiment
Embodiment mono-
Three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods:
The hydroxyapatite slurry that the graphene oxide solution that is 6mg/ml by concentration is 50mg/ml with concentration mixes, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:1.7; Again mixed solution is proceeded in hydrothermal reaction kettle, at 160 ℃, be incubated 1 hour and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
Calcium salt and phosphate that the hydroxyapatite slurry that this example is used is is 1.67 by Ca/P mol ratio are synthesized into by coprecipitation.Its concrete building-up process is:
By calcium salt---lime nitrate is mixed with the solution (calcium nitrate solution) of 1mol/L, simultaneously by phosphate---sodium hydrogen phosphate is mixed with the solution (disodium phosphate soln) of 1mol/L, and the disodium phosphate soln that is 1.67 times of calcium nitrate solutions by volume is slowly added drop-wise in calcium nitrate solution, and regulate reaction system pH to make it maintain 10～11 with ammonia, after treating titration, the standing processing overnight of hydroxyapatite suspension that reaction is obtained; Rear sucking filtration, washing, the hydroxyapatite slurry of making.
Fig. 1 is the optical photograph of this routine three-dimensional grapheme/hydroxyapatite hydrogel.Fig. 1 can find out, this routine three-dimensional grapheme/hydroxyapatite hydrogel is really gelatinous solid (its highly approximately 2 centimetres, 1.5 centimetres of diameters).
Fig. 2 is the X ray diffracting spectrum of this routine three-dimensional grapheme/hydroxyapatite hydrogel, and three-dimensional grapheme/hydroxyapatite hydrogel of this Tu Biaomingben example is really the complex of Graphene and hydroxyapatite, and the good crystallinity of hydroxyapatite.
Fig. 3 is the scanning electron microscope diagram of this routine three-dimensional grapheme/hydroxyapatite hydrogel, and as can be seen from the figure the porosity of material is high, and Graphene is combined well with hydroxyapatite, and hydroxyapatite is wrapped by Graphene equably.
Embodiment bis-
This example is basic identical with the operation of embodiment mono-, different only: the concentration of hydroxyapatite slurry is 55mg/ml, the concentration of graphene oxide solution is 7.5mg/ml, and the temperature retention time of the mixed solution of graphene oxide and hydroxyapatite in hydrothermal reaction kettle is that 24 hours, holding temperature are 180 ℃; During synthesizing hydroxylapatite slurry, calcium salt is that calcium chloride, phosphate are dipotassium hydrogen phosphate.
Embodiment tri-
This example is basic identical with the operation of embodiment mono-; different only: the concentration of hydroxyapatite slurry is 180mg/ml; the concentration of graphene oxide solution is 10mg/ml, and the temperature retention time of the mixed solution of graphene oxide and hydroxyapatite in hydrothermal reaction kettle is that 10 hours, holding temperature are 170 ℃; During synthesizing hydroxylapatite slurry, calcium salt is that calcium acetate, phosphate are tetrasodium pyrophosphate.
Embodiment tetra-
Three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods:
The hydroxyapatite slurry that the graphene oxide solution that is 9mg/ml by concentration is 50mg/ml with concentration mixes, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:2.2; Again mixed solution is proceeded in hydrothermal reaction kettle, at 200 ℃, be incubated 3 hours and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
The calcium salt soln that the hydroxyapatite slurry that this example is used is is 1.67 by Ca/P mol ratio and phosphate solution adopt hydro-thermal method to be synthesized into.Its concrete building-up process is:
By calcium salt---calcium chloride is mixed with the calcium salt soln (calcium chloride solution) of 1mol/L, simultaneously by phosphate---sodium dihydrogen phosphate is mixed with the phosphate solution (sodium dihydrogen phosphate) of 1mol/L, and the sodium dihydrogen phosphate that is 1.67 times of calcium chloride solutions by volume is slowly added drop-wise in calcium nitrate solution, and regulate reaction system pH to make it maintain 12～13 with ammonia, obtain mixed liquor.Mixed liquor is transferred in reactor inner bag, is placed in stainless steel outer sleeve, sealing is incubated 2 hours and carries out hydrothermal treatment consists at 180 ℃, obtains hydroxyapatite slurry.
Embodiment five
This example is basic identical with the operation of embodiment tetra-, different only: the concentration of hydroxyapatite slurry is 140mg/ml, the concentration of graphene oxide solution is 7mg/ml, and the temperature retention time of the mixed solution of graphene oxide and hydroxyapatite in hydrothermal reaction kettle is that 2 hours, holding temperature are 180 ℃; During synthesizing hydroxylapatite slurry, calcium salt is that calcium carbonate (calcium salt soln is calcium carbonate suspension), phosphate are potassium dihydrogen phosphate.
Embodiment six
The operation of this example and embodiment tetra-is basic identical, different only: during synthesizing hydroxylapatite slurry, calcium salt is that calcium hydroxide (calcium salt soln is calcium hydroxide suspension), phosphate are sodium tripolyphosphate.
Embodiment seven
Three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods:
The hydroxyapatite slurry that the graphene oxide solution that is 10mg/ml by concentration is 200mg/ml with concentration mixes, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:0.5; Again mixed solution is proceeded in hydrothermal reaction kettle, at 180 ℃, be incubated 2 hours and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
The calcium salt soln that the hydroxyapatite slurry that this example is used is is 1.67 by Ca/P mol ratio and phosphate solution adopt solvent-thermal method to be synthesized into.Its concrete building-up process is:
The ratio that is 1.67 according to Ca/P mol ratio by calcium chloride powder and sodium phosphate powder is evenly mixed, put into autoclave, add anhydrous alcohol solution, at 150 ℃, carry out hydro-thermal reaction 24h, then treat that autoclave is cooled to room temperature and takes out product, with dehydrated alcohol and distilled water, wash respectively 3 times, then be mixed with hydroxyapatite slurry.
Embodiment eight
Three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods:
The hydroxyapatite slurry that the graphene oxide solution that is 8mg/ml by concentration is 150mg/ml with concentration mixes, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:5; Again mixed solution is proceeded in hydrothermal reaction kettle, at 200 ℃, be incubated 0.5 hour and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
The calcium salt that the hydroxyapatite slurry that this example is used is is 1.67 by Ca/P mol ratio and phosphate adopt microemulsion method to be synthesized into.Its concrete building-up process is:
Surfactant Dodecyl trimethyl ammonium chloride (DTAC), cosurfactant n-octyl alcohol, oil phase cyclohexane extraction, calcium nitrate aqueous solution are mixed to get to microemulsion one.Surfactant Dodecyl trimethyl ammonium chloride (DTAC), cosurfactant n-octyl alcohol, oil phase cyclohexane extraction, ammonium dibasic phosphate aqueous solution are mixed to get to microemulsion two.The mol ratio of the phosphorus in the calcium in microemulsion one and microemulsion two is 1:1.67, and the pH value of adjusting two parts of microemulsions is 11.Microemulsion two is dropwise joined in the microemulsion one in high degree of agitation, and question response, after 24 hours, has hydroxyapatite particle to separate out, ageing, and centrifugal treating, then be mixed with hydroxyapatite slurry.
Embodiment nine
The operation of this example and embodiment eight is basic identical, different only: during synthesizing hydroxylapatite slurry, calcium salt is that calcium acetate, phosphate are Ammonium biphosphate.
Claims (6)
1. three-dimensional grapheme/hydroxyapatite hydrogel material, is made by following methods:
The graphene oxide solution that is 6-10mg/ml by concentration mixes with hydroxyapatite slurry, after stirring mixed solution, and to make the mass ratio of graphene oxide and hydroxyapatite in mixed solution be 1:0.5～5; Again mixed solution is proceeded in hydrothermal reaction kettle, at 160-200 ℃, be incubated 0.5-24 hour and react, be then cooled to room temperature, with filter paper, sponge the Free water on product surface, obtain three-dimensional grapheme/hydroxyapatite hydrogel material.
2. three-dimensional grapheme/hydroxyapatite hydrogel material according to claim 1, is characterized in that: calcium salt and phosphate that described hydroxyapatite slurry is is 1.67 by Ca/P mol ratio are synthesized into by wet method.
3. three-dimensional grapheme/hydroxyapatite hydrogel material according to claim 2, is characterized in that: the synthetic method of wet method of described hydroxyapatite slurry is chemical coprecipitation, hydro-thermal method, solvent-thermal method or microemulsion method.
4. three-dimensional grapheme/hydroxyapatite hydrogel material according to claim 1, is characterized in that: the concentration of described hydroxyapatite slurry is 50～200mg/ml.
5. three-dimensional grapheme/hydroxyapatite hydrogel material according to claim 2, is characterized in that: described calcium salt is lime nitrate, calcium chloride, calcium acetate, calcium hydroxide or calcium carbonate.
6. three-dimensional grapheme/hydroxyapatite hydrogel material according to claim 2, is characterized in that: described phosphate is sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate, diammonium phosphate, tetrasodium pyrophosphate or sodium tripolyphosphate.
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| CN104740638A (en) * | 2015-02-16 | 2015-07-01 | 南京工业大学 | Hydroxyapatite and folic acid co-modified carboxylated graphene oxide as well as preparation method and application thereof |
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| CN105126160A (en) * | 2015-07-21 | 2015-12-09 | 常州大学 | Hydroxyapatite scaffold material with graphene-modified surface and preparation method of hydroxyapatite scaffold material |
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| CN108421085A (en) * | 2018-05-18 | 2018-08-21 | 青岛大学附属医院 | graphene and hydroxyapatite composite bionic bone material and preparation method thereof |
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Application publication date: 20140430 |