CN105536050A - Graphene oxide modified bone cement as well as preparation method and application thereof - Google Patents
Graphene oxide modified bone cement as well as preparation method and application thereof Download PDFInfo
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- CN105536050A CN105536050A CN201610082371.8A CN201610082371A CN105536050A CN 105536050 A CN105536050 A CN 105536050A CN 201610082371 A CN201610082371 A CN 201610082371A CN 105536050 A CN105536050 A CN 105536050A
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- graphene oxide
- bone cement
- hydroxyapatite
- oxide modified
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 182
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000002639 bone cement Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical class [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 142
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 109
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 75
- 239000000843 powder Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000004048 modification Effects 0.000 claims abstract description 37
- 238000012986 modification Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 230000007547 defect Effects 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000001506 calcium phosphate Substances 0.000 claims description 25
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 25
- 235000011010 calcium phosphates Nutrition 0.000 claims description 25
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910052586 apatite Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 7
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical class [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 208000006670 Multiple fractures Diseases 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 3
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 3
- 238000009418 renovation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 210000000988 bone and bone Anatomy 0.000 abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- -1 Graphene modified hydroxylapatite Chemical class 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
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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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- 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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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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
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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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
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- 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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- 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 graphene oxide modified bone cement as well as a preparation method and application thereof. The bone cement is composed of powder and liquid, wherein the powder comprises 1-50% of graphene oxide modified hydroxyapatite and 50-99% of calcium sulfate, and the main component of the liquid is graphene oxide aqueous solution or water. The graphene oxide modified bone cement provided by the invention is applied to multiple filling and repairing materials for fracture fixation and bone defect. Graphene oxide and hydroxyapatite are directly combined and modified so as to prevent impurities from entering during modification by graphene oxide in a hydroxyapatite preparation process. Hydroxyl groups in graphene oxide and hydroxyl groups in hydroxyapatite form hydrogen bonding so as to ensure that when the bone cement is operated, no dross or powder falls off or peels off, and no solid-liquid separation phenomenon exists; and by providing graphene oxide for modifying hydroxyapatite, the bone cement has favorable antibacterial property, water scattering resistance and biocompatibility. The graphene oxide modified bone cement provided by the invention is simple and convenient in process and is widely used for biological materials.
Description
Technical field
The present invention relates to a kind of graphene oxide modification bone cement and preparation method and application, be mainly used in bone material field.
Background technology
Traditional artificial bone carries out Bone Defect Repari through Operation human body after need being prefabricated into definite shape in vitro, and this operation wound is larger.Injection type artificial bone repairing bone defect wound is little, is applied to the with the obvious advantage of shallow, cystic and vertebral body position bone defect healing, just day by day draws attention, become the developing direction of following artificial bone.Conventional injectable materials has injection type calcium sulfate, calcium phosphate and compound formulation, organic material etc.
Calcium sulfate is as a kind of traditional bone renovating material, have a good application prospect in Bone Defect Repari with its good biocompatibility, syringeability, bone conductibility etc., the MIIG bone cement of Wright company of U.S. development and production, not only clinical efficacy and biological property are more definite, stable, and provide a kind of effective way for minimally-invasive treatment Cranial defect; But, calcium sulfate bone cement also exist simultaneously the injectable time shorter, lack the shortcomings such as bone-inducting active.
Calcium phosphate material has good injectivity, wherein hydroxyapatite has good biological activity and biocompatibility, osteogenesis can be conducted, progressively be absorbed by tissue and produce osteanagenesis effect, but hydroxyapatite meet water easily defeated and dispersed, reduce the shortcomings such as mechanical strength, degradation speed be slow and limit its application to a certain extent.
Therefore hydroxyapatite is carried out to the mechanical property of modification reinforcing material, water resistant collapsibility etc., graphene oxide is single atomic layer, be regarded as a kind of flexible material of non-traditional form, there is polymer, colloid, thin film, and amphiphilic characteristic, and have the functional group that higher specific surface area and surface are enriched, as hydroxyl, carboxyl etc., there is outstanding mechanical property and biocompatibility, can be combined with hydroxyapatite and improve hydroxyapatite performance, if (CN102569749B) such as Yang little Fei by adding graphene oxide as presoma in the preparation process of hydroxyapatite, aminoacid prepares graphene oxide/nano hydroxyapatite composite material as structure regulating agent, the present invention is under the effect of dispersant, directly by graphene oxide and the modification of hydroxyapatite hydro-thermal reaction, improve the water collapsibility of hydroxyapatite, mechanical property and antibiotic property, modified hydroxyapatite is combined with calcium sulfate, prepare graphene oxide modification bone cement, the research of related content in the present invention be have not been reported.
Summary of the invention
The object of the present invention is to provide a kind of graphene oxide modification bone cement, containing a large amount of hydrophilic carboxyl, hydroxyl in graphene oxide, hydrogen bonded is formed by the hydroxyl of hydroxyl and hydroxyapatite in aqueous, the hydroxy combining of carboxyl and hydroxyapatite generates ester group, improves the mechanical property of hydroxyapatite, anti-microbial property and water resistant collapsibility performance.Graphene oxide modified hydroxylapatite is combined with calcium sulfate, adjustment mass ratio, control the inject time of bone cement, it is made to meet the needs of Operation, control the degradation rate of bone cement, degradation rate and skeletonization speed are matched, and the modification of graphene oxide can improve the mechanical property of bone cement, water resistant collapsibility performance, can give the antibiotic property that bone cement is certain.
Object of the present invention is achieved by following technical proposals:
A kind of graphene oxide modification bone cement, is made up of powder body and liquid two parts, composition and mass percentage as follows:
Powder body:
Graphene oxide modified hydroxylapatite 1 ~ 50%;
Calcium sulfate 50 ~ 99%;
Liquid: mass percentage be 0.5 ~ 2% graphene oxide water solution, 0.05 ~ 3% sodium alginate aqueous solution, 0.05 ~ 3% chitosan aqueous solution, 0.05 ~ 3% aqueous solution of sodium hyaluronate, 0.01 ~ 1% polyvinyl alcohol water solution, the Aqueous Solutions of Polyethylene Glycol of 0.01 ~ 1%, the cellulose aqueous solution of 0.01 ~ 5% or water.
In bone cement powder body, preferential oxidation Graphene modified hydroxylapatite mass percentage is 1 ~ 20%, and preferably calcium sulfate mass percentage is 80 ~ 99%;
Wherein in graphene oxide modified hydroxylapatite, graphene oxide mass percentage is 0.5 ~ 3%, and hydroxyapatite mass percentage is 97 ~ 99.5%.
In bone cement powder body of the present invention, part calcium sulfate is substituted by calcium phosphate, and wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 5 ~ 30%.
Mass ratio 1 ~ the 3:1 of powder body and liquid.
Preferred hydroxyapatite is of a size of 10 ~ 1000nm; Preferential oxidation Graphene particle size is 1 ~ 200nm; Preferably calcium sulfate is of a size of 0.2 ~ 50 μm.
Graphene oxide modified hydroxylapatite preparation method of the present invention is as follows:
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b: graphene oxide granule is added to the water, adopt ultrasonator ultrasonic disperse even, obtain graphene oxide water solution a, wherein the mass percentage of graphene oxide is 0.25 ~ 1.55%;
Taking hydroxyapatite joins in ethanol water, and the mass ratio of hydroxyapatite and solution entirety is 1:1; Stirring obtains hydroxyapatite suspension b;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
The mass ratio selecting solution a and suspension b is 1:1, joins in suspension b by solution a control rate 1 ~ 10ml/min, reacts 3 ~ 8h, obtain the suspension of graphene oxide modified hydroxylapatite in the environment of 120 ~ 150 DEG C; Sucking filtration, drying obtain graphene oxide modified hydroxylapatite powder body.
In described ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite.
The preparation method of bone cement of the present invention, step is as follows:
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, graphene oxide modified hydroxylapatite mass percentage is 1 ~ 50%, and calcium sulfate is 50 ~ 99%;
(2) according to powder liquid mass ratio 1 ~ 3:1, powder body is added liquid mixing, stirs, solidify to form graphene oxide modification bone cement.
The filling renovation material being applied to the fixing of multiple fracture and Cranial defect of graphene oxide modification bone cement of the present invention.
The invention has the advantages that: adopt ethanol as dispersant, the suspension of hydroxyapatite is made to keep stable, directly by graphene oxide with hydroxyapatite in conjunction with modification, to avoid in hydroxyapatite preparation process graphene oxide to the introducing of impurity during its modification.Hydroxyl in graphene oxide and the hydroxyl in hydroxyapatite form hydrogen bonded, ensure that bone cement is when operating, without dregs, the dropping or peeling off of powder, also without solid-liquid separation phenomenon, introduce graphene oxide to hydroxyapatite modified, give anti-microbial property, water resistant collapsibility that bone cement is good, injectivity, biocompatibility, compared with simple calcium sulfate bone cement, graphene oxide and hydroxyapatite add the mechanical property that can strengthen bone cement.Present invention process is easy, can be widely used in biomaterial.
Accompanying drawing explanation
Fig. 1: the SEM figure of graphene oxide modified hydroxylapatite;
In figure, 1-A is hydroxyapatite pattern before modified, and 1-B is the graphene oxide modified hydroxylapatite pattern of modified preparation;
Fig. 2: the XRD figure of graphene oxide modified hydroxylapatite;
Fig. 3: the mechanical property comparison diagram of remodeling bone cement and pure calcium sulfate bone cement;
In figure, C, D, E, F, G represent the mean compressive strength of embodiment 1 ~ 5 respectively;
Fig. 4: the mechanical property figure of graphene oxide modified hydroxylapatite sulfate composite calcium, calcium phosphate;
In figure, H, I, J represent the mean compressive strength of embodiment 6 ~ 8 respectively.
Detailed description of the invention
Below in conjunction with embodiment, content of the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
A kind of graphene oxide modification bone cement, bone cement is made up of powder body and liquid two parts, powder constituents is graphene oxide modified hydroxylapatite and calcium sulfate, graphene oxide modified hydroxylapatite mass percentage is 1 ~ 50%, calcium sulfate is 50 ~ 99%, preferential oxidation Graphene modified hydroxylapatite mass percentage is 1 ~ 20%, and preferably calcium sulfate is 80 ~ 99%.
Wherein, in graphene oxide modified hydroxylapatite, graphene oxide mass percentage is 0.5 ~ 3%, and hydroxyapatite mass percentage is 97 ~ 99.5%;
Preferred hydroxyapatite is of a size of 10 ~ 1000nm; Preferential oxidation Graphene particle size is 1 ~ 200nm; Preferably calcium sulfate is of a size of 0.2 ~ 50 μm.
Liquid is made up of water or aqueous solution, can to be mass percentage be 0.5 ~ 2% graphene oxide water solution, 0.05 ~ 3% sodium alginate aqueous solution, 0.05 ~ 3% chitosan aqueous solution, 0.05 ~ 3% aqueous solution of sodium hyaluronate, 0.01 ~ 1% polyvinyl alcohol water solution, the Aqueous Solutions of Polyethylene Glycol of 0.01 ~ 1%, the cellulose aqueous solution of 0.01 ~ 5% or water, the preferably graphene oxide water solution of 0.5 ~ 2%.
Mass ratio 1 ~ the 3:1 of powder body and liquid.
Graphene oxide modified hydroxylapatite, prepare as follows:
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Be added to the water by graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain solution a, wherein the mass percentage of graphene oxide is 0.25 ~ 1.55%;
Taking hydroxyapatite joins in ethanol water, and the mass ratio of hydroxyapatite and solution entirety is 1:1; Keep agitation obtains suspension b; Wherein in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
The mass ratio selecting solution a and suspension b is 1:1, joins in suspension b by solution a control rate 1 ~ 10ml/min, reacts 3 ~ 8h, obtain the suspension of graphene oxide modified hydroxylapatite in the environment of 120 ~ 150 DEG C; Sucking filtration, drying obtain graphene oxide modified hydroxylapatite powder body.In the graphene oxide modified hydroxylapatite of preparation, graphene oxide mass percentage is 0.5 ~ 3%, and hydroxyapatite mass percentage is 97 ~ 99.5%.
The preparation method of graphene oxide modification bone cement, prepare according to following steps:
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, graphene oxide modified hydroxylapatite mass percentage is 1 ~ 50%, and calcium sulfate is 50 ~ 99%;
(2) according to powder liquid mass ratio 1 ~ 3:1, powder body is added liquid mixing, stirs, solidify to form graphene oxide modification bone cement.
In bone cement powder body, part calcium sulfate can be substituted by calcium phosphate, for improving curing performance and the degradation property of bone cement, meets the needs of different situations defect, and graphene oxide modification bone cement can be used for the filling reparation of the fixing of multiple fracture and Cranial defect.It is 1 ~ 50% that bone cement powder body consists of graphene oxide modified hydroxylapatite mass percentage; Calcium sulfate and calcium phosphate mass percentage are 50 ~ 99%, and wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 5 ~ 30%.
Embodiment 1
The preparation of graphene oxide modified hydroxylapatite in accordance with the following methods
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Join in 19.69g water by 0.31g graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain 20ga, wherein the mass percentage of graphene oxide is 1.55%;
Take 10g hydroxyapatite and join (mass ratio of hydroxyapatite and ethanol water is 1:1) in 10g ethanol water, Keep agitation obtains 20gb; Wherein in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
20ga control rate 3ml/min is joined (mass ratio of a and b is 1:1) in 20gb, in the environment of 120 DEG C, react 8h, obtain the suspension of graphene oxide modified hydroxylapatite; Sucking filtration, drying obtain 10.31g graphene oxide modified hydroxylapatite powder body; In the graphene oxide modified hydroxylapatite of preparation, graphene oxide mass percentage is 3%, and hydroxyapatite mass percentage is 97%, and the hydroxyapatite of selection is of a size of 500nm; Graphene oxide particle size is 100nm.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, 3g graphene oxide modified hydroxylapatite (50%) and 3g calcium sulfate (50%) is taken; Calcium sulfate is selected to be of a size of 50 μm;
(2) according to powder liquid mass ratio 1:1, powder body being joined mass percentage is in the 6g graphene oxide water solution of 0.5%, and be uniformly mixed 2min, the injectable time is 7min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
To the graphene oxide modified hydroxylapatite morphology observation of preparation, as shown in Figure 1, the pattern of known hydroxyapatite is before modified lamellar structure, and modified is irregular particle shape.
XRD sign is carried out to the graphene oxide modified hydroxylapatite of preparation, as shown in Figure 2, known with the contrast of hydroxyapatite before modified, the diffraction maximum of hydroxyapatite offsets to low angle, and halfwidth becomes large, peak area increases, and degree of crystallinity weakens, and illustrates that graphene oxide and hydroxyapatite esterification may occur.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 7.64Mpa (as shown in C in accompanying drawing 3).
Embodiment 2
The preparation of graphene oxide modified hydroxylapatite in accordance with the following methods
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Join in 19.796g water by 0.204g graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain 20ga, wherein the mass percentage of graphene oxide is 1.02%;
Take 10g hydroxyapatite and join (mass ratio of hydroxyapatite and ethanol water is 1:1) in 10g ethanol water, Keep agitation obtains 20gb; Wherein in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
20ga control rate 10ml/min is joined (mass ratio of a and b is 1:1) in 20gb, in the environment of 135 DEG C, react 6h, obtain the suspension of graphene oxide modified hydroxylapatite; Sucking filtration, drying obtain 10.204g graphene oxide modified hydroxylapatite powder body; In the graphene oxide modified hydroxylapatite of preparation, graphene oxide mass percentage is 2%, and hydroxyapatite mass percentage is 98%, and the hydroxyapatite of selection is of a size of 1000nm; Graphene oxide particle size is 200nm.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, 2.4g graphene oxide modified hydroxylapatite (40%) and 3.6g calcium sulfate (60%) is taken; Calcium sulfate is selected to be of a size of 20 μm;
(2) according to powder liquid mass ratio 1.334:1, powder body being joined mass percentage is in the 4.5g graphene oxide water solution of 1%, and be uniformly mixed 2min, the injectable time is 10min, solidify to form graphene oxide modification bone cement, complete the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 9.79Mpa (as shown in D in accompanying drawing 3).
Embodiment 3
The preparation of graphene oxide modified hydroxylapatite in accordance with the following methods
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Join in 19.899g water by 0.101g graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain 20ga, wherein the mass percentage of graphene oxide is 0.505%;
Take 10g hydroxyapatite and join (mass ratio of hydroxyapatite and ethanol water is 1:1) in 10g ethanol water, Keep agitation obtains 20gb; Wherein in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
20ga control rate 1ml/min is joined (mass ratio of a and b is 1:1) in 20gb, in the environment of 150 DEG C, react 3h, obtain the suspension of graphene oxide modified hydroxylapatite; Sucking filtration, drying obtain 10.101g graphene oxide modified hydroxylapatite powder body; In the graphene oxide modified hydroxylapatite of preparation, graphene oxide mass percentage is 1%, and hydroxyapatite mass percentage is 99%, and the hydroxyapatite of selection is of a size of 10nm; Graphene oxide particle size is 1nm.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, 1.8g graphene oxide modified hydroxylapatite (30%) and 4.2g calcium sulfate (70%) is taken; Calcium sulfate is selected to be of a size of 0.2 μm;
(2) according to powder liquid mass ratio 1.5:1, powder body being joined mass percentage is in the 4g graphene oxide water solution of 2%, and be uniformly mixed 1.5min, the injectable time is 9min, solidify to form graphene oxide modification bone cement, complete the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 11.45Mpa (as shown in E in accompanying drawing 3).
Embodiment 4
The preparation of graphene oxide modified hydroxylapatite in accordance with the following methods
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Join in 19.95g water by 0.05g graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain 20ga, wherein the mass percentage of graphene oxide is 0.25%;
Take 10g hydroxyapatite and join (mass ratio of hydroxyapatite and ethanol water is 1:1) in 10g ethanol water, Keep agitation obtains 20gb; Wherein in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
20ga control rate 10ml/min is joined (mass ratio of a and b is 1:1) in 20gb, in the environment of 150 DEG C, react 3h, obtain the suspension of graphene oxide modified hydroxylapatite; Sucking filtration, drying obtain 10.05g graphene oxide modified hydroxylapatite powder body; In the graphene oxide modified hydroxylapatite of preparation, graphene oxide mass percentage is 0.5%, and hydroxyapatite mass percentage is 99.5%, and the hydroxyapatite of selection is of a size of 300nm; Graphene oxide particle size is 30nm.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, 1.2g graphene oxide modified hydroxylapatite (20%) and 4.8g calcium sulfate (80%) is taken; Calcium sulfate is selected to be of a size of 35 μm;
(2) according to powder liquid mass ratio 2:1, powder body being joined mass percentage is in the 3g graphene oxide water solution of 2%, and be uniformly mixed 1min, the injectable time is 8min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 17.91Mpa (as shown in F in accompanying drawing 3).
Embodiment 5
Adopt graphene oxide modified hydroxylapatite (graphene oxide mass percentage is 2%, and hydroxyapatite is 98%) prepared by embodiment 2
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite and calcium sulfate powder body, 0.06g graphene oxide modified hydroxylapatite (1%) and 5.94g calcium sulfate (99%) is taken; Calcium sulfate is selected to be of a size of 25 μm;
(2) according to powder liquid mass ratio 3:1, powder body being joined mass percentage is in the 2g graphene oxide water solution of 2%, and be uniformly mixed 1min, the injectable time is 5min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 16.10Mpa (as shown in G in accompanying drawing 3).
Embodiment 6
Adopt graphene oxide modified hydroxylapatite (graphene oxide mass percentage is 3%, and hydroxyapatite is 97%) prepared by embodiment 1.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite, calcium sulfate and calcium phosphate powder body, 0.06g graphene oxide modified hydroxylapatite (1%), 5.94g calcium sulfate and calcium phosphate (99%) powder body is taken; Wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 5%, selects calcium sulfate to be of a size of 10 μm;
(2) according to powder liquid mass ratio 3:1, powder body being joined mass percentage is in the 2g graphene oxide water solution of 2%, and be uniformly mixed 1min, the injectable time is 8min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 16.7Mpa (as shown in H in accompanying drawing 4).
Embodiment 7
Adopt graphene oxide modified hydroxylapatite (graphene oxide mass percentage is 2%, and hydroxyapatite is 98%) prepared by embodiment 2
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite, calcium sulfate and calcium phosphate powder body, 0.6g graphene oxide modified hydroxylapatite (10%), 5.4g calcium sulfate and calcium phosphate (90%) is taken; Wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 15%, selects calcium sulfate to be of a size of 5 μm;
(2) according to powder liquid mass ratio 2:1, powder body being joined mass percentage is in the 3g graphene oxide water solution of 1%, and be uniformly mixed 1min, the injectable time is 7min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 15.3Mpa (as shown in I in accompanying drawing 4).
Embodiment 8
Adopt graphene oxide modified hydroxylapatite (graphene oxide mass percentage is 0.5%, and hydroxyapatite is 99.5%) prepared by embodiment 4.
The preparation of graphene oxide modification bone cement in accordance with the following methods
(1) according to powder quality percentage composition allotment graphene oxide modified hydroxylapatite, calcium sulfate and calcium phosphate powder body, 3g graphene oxide modified hydroxylapatite (50%), 3g calcium sulfate and calcium phosphate (90%) is taken; Wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 30%, selects calcium sulfate to be of a size of 15 μm;
(2) according to powder liquid mass ratio 1:1, powder body being joined mass percentage is in the 6g graphene oxide water solution of 0.5%, and be uniformly mixed 1min, the injectable time is 5min, solidify to form graphene oxide modification bone cement, completes the reparation of Cranial defect.
Carry out intensity test to the bone cement sample of solidification 24h, intensity test sample is cylindric (Φ 6mm × 12mm), and comprcssive strength meansigma methods is 13.9Mpa (as shown in J in accompanying drawing 4).
Open and a kind of graphene oxide modification bone cement that proposes of the present invention and preparation method and application, those skilled in the art are by using for reference present disclosure, the links such as suitable change condition route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (9)
1. a graphene oxide modification bone cement, is made up of powder body and liquid two parts, it is characterized in that, composition and mass percentage as follows:
Powder body:
Graphene oxide modified hydroxylapatite 1 ~ 50%;
Calcium sulfate 50 ~ 99%;
Liquid: mass percentage be 0.5 ~ 2% graphene oxide water solution, 0.05 ~ 3% sodium alginate aqueous solution, 0.05 ~ 3% chitosan aqueous solution, 0.05 ~ 3% aqueous solution of sodium hyaluronate, 0.01 ~ 1% polyvinyl alcohol water solution, the Aqueous Solutions of Polyethylene Glycol of 0.01 ~ 1%, the cellulose aqueous solution of 0.01 ~ 5% or water.
2. bone cement as claimed in claim 1, it is characterized in that in bone cement powder body, graphene oxide modified hydroxylapatite mass percentage is 1 ~ 20%; Calcium sulfate mass percentage is 80 ~ 99%.
3. as a kind of graphene oxide modification bone cement of claim 1 or 2, it is characterized in that in bone cement powder body, part calcium sulfate is substituted by calcium phosphate, wherein calcium phosphate accounts for the percentage composition of calcium sulfate and calcium phosphate gross mass is 5 ~ 30%.
4. bone cement as claimed in claim 1 or 2, it is characterized in that in graphene oxide modified hydroxylapatite, graphene oxide mass percentage is 0.5 ~ 3%, and hydroxyapatite mass percentage is 97 ~ 99.5%.
5. bone cement as claimed in claim 1, is characterized in that the mass ratio 1 ~ 3:1 of powder body and liquid.
6. bone cement as claimed in claim 1, is characterized in that hydroxyapatite is of a size of 10 ~ 1000nm; Graphene oxide particle size is 1 ~ 200nm; Calcium sulfate is of a size of 0.2 ~ 50 μm.
7. the bone cement as described in claim 1 or 3, is characterized in that graphene oxide modified hydroxylapatite preparation method is as follows:
(1) preparation of graphene oxide water solution a and hydroxyapatite suspension b:
Be added to the water by graphene oxide granule, adopt ultrasonator ultrasonic disperse even, obtain graphene oxide water solution a, wherein the mass percentage of graphene oxide is 0.25 ~ 1.55%;
Taking hydroxyapatite joins in ethanol water, and the mass ratio of hydroxyapatite and solution entirety is 1:1; Stirring obtains hydroxyapatite suspension b;
(2) preparation of graphene oxide modified hydroxylapatite powder body:
The mass ratio selecting solution a and suspension b is 1:1, joins in suspension b by solution a control rate 1 ~ 10ml/min, reacts 3 ~ 8h, obtain the suspension of graphene oxide modified hydroxylapatite in the environment of 120 ~ 150 DEG C; Sucking filtration, drying obtain graphene oxide modified hydroxylapatite powder body.
8. bone cement as claimed in claim 7, it is characterized in that in ethanol water, ethanol mass percentage is 10%, and ethanol is as the dispersant of hydroxyapatite.
9. the filling renovation material being applied to the fixing of multiple fracture and Cranial defect of graphene oxide modification bone cement.
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