CN105497986A - Synthesis method of graphene-hydroxyapatite composite material - Google Patents
Synthesis method of graphene-hydroxyapatite composite material Download PDFInfo
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- CN105497986A CN105497986A CN201510916271.6A CN201510916271A CN105497986A CN 105497986 A CN105497986 A CN 105497986A CN 201510916271 A CN201510916271 A CN 201510916271A CN 105497986 A CN105497986 A CN 105497986A
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- graphene
- composite material
- hydroxyapatite
- synthetic method
- hydroxyapatite composite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention relates to the technical field of inorganic nonmetallic materials, in particular to a synthesis method of graphene-hydroxyapatite composite material. The synthesis method of the graphene-hydroxyapatite composite material comprises the steps of preparing tris (hydroxymethyl) aminomethane buffer solution, preparing dopamine solution, reducing and modifying graphene oxide, preparing simulated body fluid and mineralizing hydroxyapatite. According to the synthesis method, the graphene-hydroxyapatite composite material is synthesized in the environment of simulating human body fluid; the obtained composite material has good stability and biocompatibility, and can be applied to the field of biological medicines.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, be specifically related to a kind of synthetic method of Graphene-hydroxyapatite composite material.
Background technology
One of development important research direction having become current field of novel of biocompatible materials, hydroxyapatite (HA) is the key component of organism sclerous tissues, there is good biocompatibility, be widely used in Bone Defect Repari and bone shaping.But the hydroxyapatite of synthetic has the shortcomings such as resisting expansion strength low and fracture toughness difference, thus limit its effect in Bone Defect Repari.In order to head it off, many materials such as high molecular polymer, silicon materials, titanium alloy are used to hydroxyapatite compound to improve its mechanical performance, but there is the second-phase added, effectively can not realize the object that the mechanics ability of composite biological material and biological activity all improve.Such as add CNT (CNT) although the mechanical property of HA can be increased substantially, but because CNT is originally unfavorable for adhesion and the propagation of cell as tubular column structure, but desirable reinforcement material does not affect its biocompatibility improving its mechanical performance while.
Research shows that Graphene has good biocompatibility, and the two-dimension plane structure of Graphene is conducive to adhesion and the propagation of cell, and has very high mechanical strength.This makes Graphene become the reinforcement material of ideal hydroxyapatite.
CN102569749A patent discloses a kind of Graphene-Hydroxyapatite Nanocomposites and preparation method thereof, aminoacid hydro-thermal method is adopted to prepare Graphene-Hydroxyapatite Nanocomposites, this patent of invention preparation condition is harsh, and high to equipment requirements, energy consumption is also high.CN104415399A discloses a kind of method that wet chemistry method prepares hydroxyapatite-graphene nano composite powder, ammonia is adopted to regulate mixed liquor to obtain hydroxyapatite-Graphene precursor pulp in the basic conditions, then by after precursor pulp ripening, form composite, still be compounded to form in the basic conditions although the preparation condition of this invention is simple, and the pH of human body fluid is about 7.5, be difficult to ensure the mechanical performance of this composite in human body and biocompatibility.
At present, find a kind of simple and reliable, mix homogeneously can be obtained, combine good and Graphene-hydroxyapatite composite material the synthetic method with good biocompatibility is one of important research content of osseous tissue Material Field.
Summary of the invention
In order to simple, controlled synthesizing graphite alkene and hydroxyapatite composite material can be realized, ensure that composite has good biocompatibility simultaneously, the invention provides a kind of synthetic method of Graphene-hydroxyapatite composite material.
Concrete steps of the present invention are as follows:
(1) preparation of Tris (Tris) buffer
Accurately take 2.42g Tris (Tris), dissolve with distilled water, be settled to 2000mL, then adjust pH to 8.5 with the hydrochloric acid of 0.01mol/L, be mixed with the buffer of the Tris of 10mM.
(2) preparation of dopamine solution
Dopamine is dissolved in Tris (Tris) buffer of 10mM and is prepared into 2mgmL
-1dopamine solution.
(3) reduction of graphene oxide and modification
By ultrasonic for graphene oxide 30min, make 1mgmL
-1unit for uniform suspension, get 10mL graphene oxide solution and add in 10mL dopamine solution, ultrasonic 1h, continue under room temperature to stir 12h, product Graphene-poly-dopamine (RGO-PDA), by collected by centrifugation, is dispersed in water with after distilled water wash 3 times, is made into 5mgmL
-1graphene-poly-dopamine (RGO-PDA) dispersion of materials liquid.
(4) preparation of simulated body fluid (SBF)
Configuration simulated body fluid (SBF), simulated body fluid pH7.5, wherein each ion concentration is respectively Na
+, 213.0mM; K
+, 7.5mM; Mg
2+, 2.25mM; Ca
2+, 3.75mM; Cl
-, 221.7mM; HCO
3 -, 6.3mM; HPO
4 2-, 1.5mM; SO
4 2-, 0.75mM.
(5) mineralising of hydroxyapatite (HA)
Add in the simulated body fluid of 20mL by the dispersion liquid of above-mentioned for 1mL Graphene-poly-dopamine, the water-bath being placed in 37 DEG C is cultivated 14 days.Cultured products collected by centrifugation, with distilled water wash 3 times, products therefrom is Graphene-hydroxyapatite composite material.
Described ultrasound condition is power 1000W, temperature 25 ± 2 DEG C.
Described stirring condition is 120r/min.
Described centrifugal condition is 6000r/min.
Inventive principle of the present invention: dopamine buffer has very strong reproducibility, can be reduced to Graphene by graphene oxide, and dopamine has good polymerizing power simultaneously, and the Graphene of reduction can be made to form Graphene-poly-dopamine complex; Containing Ca in standard body fluid
2+, HPO
4 2be the leading ion forming hydroxyapatite, adopt the sedimentation method to form Graphene-hydroxyapatite composite material.
Beneficial effect of the present invention is: the present invention is synthesizing graphite alkene-hydroxyapatite (RGO-HA) composite under simulated body fluid environment, and gained composite has good stability, biocompatibility, can be used for biomedicine field.
Accompanying drawing explanation
Fig. 1 is the ultra-violet absorption spectrum of graphene oxide (GO), Graphene (RGO), Graphene-poly-dopamine (RGO-PDA).
Fig. 2 is the infrared spectrum of graphene oxide (GO), Graphene-hydroxyapatite (RGO-HA).
Fig. 3 is graphene oxide (GO), Graphene-hydroxyapatite (RGO-HA) cells growth activity under variable concentrations.
Detailed description of the invention
The present invention is specifically implemented as follows:
(1) preparation of Tris (Tris) buffer
Accurately take 2.42gTris, dissolve with distilled water, be settled to 2000mL, then adjust pH to 8.5 with the hydrochloric acid of 0.01mol/L, be mixed with the buffer of the Tris of 10mM.
(2) preparation of dopamine solution
Dopamine is dissolved in Tris (Tris) buffer of 10mM and is prepared into 2mgmL
-1dopamine solution.
(3) reduction of graphene oxide and modification
By ultrasonic for graphene oxide 30min, make 1mgmL
-1unit for uniform suspension, get 10mL graphene oxide solution and add in 10mL dopamine solution, ultrasonic 1h, under room temperature continue stir 12h.Product graphene oxide-poly-dopamine, by collected by centrifugation, is dispersed in water with after distilled water wash 3 times, is mixed with 5mgmL
-1graphene-poly-dopamine dispersion of materials liquid.
(4) preparation of simulated body fluid (SBF)
Configuration simulated body fluid (SBF), the pH7.5 of simulated body fluid, wherein each ion concentration is respectively Na
+, 213.0mM; K
+, 7.5mM; Mg
2+, 2.25mM; Ca
2+, 3.75mM; Cl
-, 221.7mM; HCO
3 -, 6.3mM; HPO
4 2-, 1.5mM; SO
4 2-, 0.75mM.
(5) mineralising of hydroxyapatite (HA)
Add in the simulated body fluid of 20mL by the dispersion liquid of above-mentioned for 1mL Graphene-poly-dopamine, the water-bath being placed in 37 DEG C is cultivated 14 days, cultured products collected by centrifugation, and with distilled water wash 3 times, products therefrom is Graphene-hydroxyapatite composite material.
Described ultrasound condition is power 1000W, temperature 25 ± 2 DEG C.
Described stirring condition is 120r/min.
Described centrifugal condition is 6000r/min.
Fig. 1 is the ultra-violet absorption spectrum of graphene oxide (GO), Graphene (RGO), Graphene-poly-dopamine (RGO-PDA) composite.As shown in Figure 1, the absworption peak of graphene oxide is 230nm place, and the absworption peak at modified 230nm place disappears, and having occurred a new absworption peak at 280nm place, is the characteristic absorption of the upper bisphenol hydroxy of poly-dopamine (PDA).
For determining the existence of PDA further, after removing PDA by sodium hydroxide etch, the absorption spectrum of test product, the absworption peak at result display 280nm place disappears, and illustrates that graphenic surface has successfully modified PDA molecule.Occurred a new absworption peak at 265nm place, this shows that graphene oxide (GO) is reduced to Graphene (GRO) by the electronics produced in the oxidation polymerization process of dopamine simultaneously.
Fig. 2 is the infrared spectrum of graphene oxide (GO), Graphene-poly-dopamine (RGO-PDA) mineralization product after simulated body fluid (SBF) cultivates 14 days.As seen from Figure 2, in mineralising after 14 days, in the mineralization product of RGO-PDA composite, there is very strong PO
4 3-characteristic absorption peak, be positioned at 962cm
-1the absworption peak at place represents PO
4 3-v
1symmetrical stretching vibration, 1037cm
-1the peak at place represents PO
4 3-v
3vibration, 602 and 566cm
-1the absworption peak at place represents PO
4 3-v
4bending vibration, this illustrates that there is the generation of mineralization product hydroxyapatite (HA) on GO-PDA surface.
In order to determine that GO-PDA induces the ability of mineralising, using graphene oxide (GO) to cultivate under the same conditions simultaneously and contrasting, after 14 days, PO not detected
4 3-characteristic absorption peak.
Biocompatibility weighs the important indicator that can material be applied to biomedicine field, and Graphene-hydroxyapatite (GRO-HA) composite of synthesis is done the fibrocellular toxicity test of L929.Not commensurability GO, RGO-HA add in cell culture medium respectively, and the concentration adding rear material is 1,5,10,20 μ g/mL, observation of cell growth vigor.As shown in Figure 3, in all concentration ranges, cells growth activity and matched group are all relatively, rate of growth is greater than 95%, and cell growth rate does not have significant change with the concentration increase of added material, when concentration is greater than 10 μ g/mL, cells growth activity is greater than matched group, illustrate that Graphene-hydroxyapatite does not have cytotoxicity, there is good biocompatibility, can be used for biomedicine field.
Claims (9)
1. a synthetic method for Graphene-hydroxyapatite composite material, is characterized in that: synthetic method comprises the preparation of TRIS buffer, the preparation of dopamine solution, the reduction of graphene oxide and modification, the preparation of simulated body fluid and the mineralising of hydroxyapatite.
2. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 1, it is characterized in that: the compound method of described TRIS buffer is: accurately take 2.42g Tris, dissolve with distilled water, be settled to 2000mL, then adjust pH to 8.5 with the hydrochloric acid of 0.01mol/L, be mixed with the buffer of 10mM.
3. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 1, is characterized in that: the compound method of described dopamine solution is: be dissolved in by dopamine in the TRIS buffer of 10mM and be prepared into 2mgmL
-1dopamine solution.
4. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 1, is characterized in that: reduction and the modification of described graphene oxide are specially: by ultrasonic for graphene oxide 30min, make 1mgmL
-1unit for uniform suspension, get 10mL graphene oxide solution and add in 10mL dopamine solution, ultrasonic 1h, continue under room temperature to stir 12h, product Graphene-poly-dopamine, by collected by centrifugation, be dispersed in water with after distilled water wash 3 times, be made into 5mgmL
-1graphene-poly-dopamine dispersion of materials liquid.
5. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 1, is characterized in that: being formulated as of described simulated body fluid: body fluid is pH7.5, and wherein each ion concentration is respectively Na
+, 213.0mM; K
+, 7.5mM; Mg
2+, 2.25mM; Ca
2+, 3.75mM; Cl
-, 221.7mM; HCO
3 -, 6.3mM; HPO
4 2-, 1.5mM; SO
4 2-, 0.75mM.
6. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 1, it is characterized in that: the mineralising of described hydroxyapatite is: the dispersion liquid of above-mentioned for 1mL Graphene-poly-dopamine is added in the simulated body fluid of 20mL, the water-bath being placed in 37 DEG C is cultivated 14 days, cultured products collected by centrifugation, with distilled water wash 3 times, products therefrom is Graphene-hydroxyapatite composite material.
7. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 4, is characterized in that: described ultrasonic for power 1000W, temperature 25 ± 2 DEG C.
8. the synthetic method of a kind of Graphene-hydroxyapatite composite material according to claim 4, is characterized in that: described stirring is 120r/min.
9., according to the synthetic method of claim 4 or a kind of Graphene-hydroxyapatite composite material according to claim 6, it is characterized in that: described centrifugal condition is 6000r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510916271.6A CN105497986A (en) | 2015-12-10 | 2015-12-10 | Synthesis method of graphene-hydroxyapatite composite material |
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|---|---|---|---|
| CN201510916271.6A CN105497986A (en) | 2015-12-10 | 2015-12-10 | Synthesis method of graphene-hydroxyapatite composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999396A (en) * | 2016-05-12 | 2016-10-12 | 北京大学口腔医院 | Bone repair composite for inducing mesenchymal stem cell differentiation and preparing method of bone repair composite |
| CN107029297A (en) * | 2017-04-06 | 2017-08-11 | 福州大学 | Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation |
| CN107254076A (en) * | 2017-06-27 | 2017-10-17 | 过春明 | A kind of composite reinforced rubber and preparation method thereof |
| 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 |
| CN109440153A (en) * | 2018-11-27 | 2019-03-08 | 河北北方学院 | Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| CN104415399A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Hydroxyapatite/graphene nano-composite powder and preparation method thereof |
-
2015
- 2015-12-10 CN CN201510916271.6A patent/CN105497986A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
| CN104415399A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Hydroxyapatite/graphene nano-composite powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGYAN LIU等: "Simultaneous Reduction and Surface Functionalization of Graphene Oxide for Hydroxyapatite Mineralization", 《J. PHYS. CHEM. C》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105999396A (en) * | 2016-05-12 | 2016-10-12 | 北京大学口腔医院 | Bone repair composite for inducing mesenchymal stem cell differentiation and preparing method of bone repair composite |
| CN105999396B (en) * | 2016-05-12 | 2019-04-05 | 北京大学口腔医院 | The bone-repairing composite material and preparation method thereof of inducing mesenchymal stem cell differentiation |
| CN107029297A (en) * | 2017-04-06 | 2017-08-11 | 福州大学 | Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation |
| CN107254076A (en) * | 2017-06-27 | 2017-10-17 | 过春明 | A kind of composite reinforced rubber and preparation method thereof |
| 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 |
| CN109440153A (en) * | 2018-11-27 | 2019-03-08 | 河北北方学院 | Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating |
| CN114889175A (en) * | 2022-05-25 | 2022-08-12 | 福州大学 | Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper |
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