CN108434515A - A kind of preparation method of high bioactivity timbering material - Google Patents
A kind of preparation method of high bioactivity timbering material Download PDFInfo
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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
- A61L27/56—Porous materials, e.g. foams or sponges
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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
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
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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
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
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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
- A61L27/58—Materials at least partially resorbable by the body
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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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
Abstract
The present invention relates to the preparing technical fields of inorganic non-metallic material and the artificial bone renovating material of field of biomedical materials, and in particular to a kind of preparation method of high bioactivity timbering material.Titanium-based titanate nanowire matrix is made by material of titanium sheet in the present invention, self-control solid oxide graphene is configured to suspension, sodium hydroxide is added in ultrasonic disperse, equal substances obtain graphene nanometer sheet suspension after monoxone, electrophoretic deposition is carried out to titanium-based titanate nanowire matrix using deposition liquid and obtains high bioactivity timbering material, by graphene oxide deposition modification in matrix surface, improve the biocompatibility and bioactivity of timbering material, coating liquid used is fibroin albumen stoste and casein, degradation property is good and does not generate any harmful toxic matter, pass through monoxone, 1, the hydroxyl to graphene oxide such as 3 propane diamine, amino, the functionalization of carboxyl further improves the timbering material self-bone grafting ability of non-functionalization, it has a extensive future.
Description
Technical field
The present invention relates to the technologies of preparing of inorganic non-metallic material and the artificial bone renovating material of field of biomedical materials
A kind of field, and in particular to preparation method of high bioactivity timbering material.
Background technology
Disease, wound, aging of population and natural calamity etc. can cause body bone tissue to damage, clinically to Bone Defect Repari
Materials demand is huge.And as the operation of the autologous bone transplanting of Golden Rule since its source is limited and to patient's second operation pain
It is set much to cannot be satisfied present situation.There is also bio-safety potential problems for allogenic bone transplantation operation, may be left to patient throughout one's life
Immunological rejection and bring unidentified illness.Therefore, it manually prepares bone renovating material and clinically receives more and more passes
Note.
The process of regeneration and restoration is porous by seeding cells into the biodegradable with certain bioactivity
On timbering material, after carrying out culture a period of time in vitro, obtained cell-scaffold compound is implanted into and is organized in patient body
Defect, cell Proliferation simultaneously break up, become and be similar to natural tissue, and timbering material is degradable, gradually by newly-generated group
Replacement is knitted, to repair or replace the tissue of patient itself lesion or defect.Therefore, the core of organizational project is living cells and can
The timbering material for carrying out vital movement for cell and mutual total use between them.
Timbering material is the most basic framework of engineered tissue, is provided for cell and obtains nutrition, gas exchanges, row
The place of waste and growth metabolism is let out, and forms the material base of the new tissue with form and function, organ.Group weaver
Requirement of the journey to timbering material mainly has the following：（1）Biological safety is good, no sensitization nontoxic to human body and without carcinogenic
Property；（2）Biocompatibility is good, has no adverse reaction to human body, tissue, Hemic and immune system；（3）There should be good cell
Adhesive capacity can simulate suitable cell growth, hyperplasia, the physiological environment of differentiation as far as possible；（4）Must be biodegradable, degradation
Product is answered nontoxic, can should be matched with agglutination and regenerative process by organism metabolism or removing, degradation time, is had suitable for operation
Mechanical characteristic, mechanical characteristic after degradation, which changes, to be matched with healing or regeneration event；（5）Holder will have certain flexible
Property, it can organically be closely linked with body.
However, the research and application of bone tissue engineering scaffold are still faced with many problems at present, such as：1, degradation in material bodies
Uncontrollable, cell proliferation efficiency is low, and catabolite causes inflammatory reaction, cell de-differentiation etc..Especially in terms of mechanical property,
Single has that intensity is weak or brittleness is big using polymer or ceramic material as timbering material, all cannot be satisfied load
The requirement of Bone Defect Repari；2, molding is difficult, poor plasticity；3, poor biocompatibility；4, easy fragmentation, degradation are slower etc. when dry.
Therefore, there is an urgent need for develop a kind of timbering material that can be solved the above problems to be highly desirable.
Invention content
Present invention mainly solves the technical issues of, uncontrollable for degrading in current material bodies, catabolite easily causes inflammation
Property reaction, single use polymer or ceramic material as timbering material, and poor plasticity, bioactivity are low, and cell Proliferation is fast
Rate is slow, cannot be satisfied the defect of load Bone Defect Repari requirement, provides a kind of preparation method of high bioactivity timbering material.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of high bioactivity timbering material, it is characterised in that specifically preparation process is：
（1）Titanium sheet is placed in supersonic cleaning machine, is cleaned successively with absolute ethyl alcohol and acetone, the titanium sheet after cleaning is put into baking oven
It is transferred to after middle drying in the autoclave equipped with 10~15mL sodium hydroxide solutions, heat temperature raising, insulation reaction obtains titanium
Base titanate nanowire matrix；
（2）0.2~0.3g graphite powders and 0.12~0.13g sodium nitrate are added to the beaker equipped with 10~12mL concentrated sulfuric acid solutions
In, beaker is placed in ice-water bath, is stirred to react, removes and is stirred to react under ice-water bath room temperature, 10~15mL is added into beaker
Deionized water and 20~25mL hydrogen peroxide continue to be stirred to react until bubble-free generates；
（3）It continues up to state and 20~25mL sulfuric acid solutions and 10~15mL hydrogen peroxide is added in beaker, be stirred to react rear vacuum and take out
It filters out filtrate and obtains filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, the filter cake after flushing is put
Enter drying in baking oven, obtains solid oxide graphene；
（4）The solid oxide graphene of above-mentioned preparation is placed in ultrasonic disperse machine, distilled water ultrasonic disperse is added, is aoxidized
Graphene suspension takes 10mL graphene oxide suspensions, and 1.2g sodium hydroxides and 1.0g monoxone ultrasounds point are added thereto
It dissipates, obtains carboxylated graphene oxide colloid；
（5）1~2g trishydroxymethylaminomethanes are added in above-mentioned carboxylated graphene oxide colloid, mixed liquor is obtained, to mixed
It closes in liquid and continuously adds 2~3g1-（3- dimethylamino-propyls）- 3- ethyl-carbodiimide hydrochlorides and 3~4g1,3- propane diamine,
Graphene nanometer sheet suspension is obtained by the reaction；
（6）Fibroin albumen stoste, casein are mixed to get coating liquid, hang graphene nanometer sheet in two electrode cell reaction tanks
Supernatant liquid is as deposition liquid, and using titanium-based titanate nanowire matrix as working electrode, platinum plate electrode is used as to electrode, carries out electrophoresis
Deposition obtains biomimetic scaffolds, then using coating liquid as new deposition liquid, electrophoretic deposition is carried out to biomimetic scaffolds, and it is living to obtain high biology
Property timbering material.
Step（1）The absolute ethyl alcohol and acetone scavenging period be 10~15min, control supersonic frequency be 30~
35kHz, baking oven set temperature are 70~80 DEG C, and drying time is 4~5h, and the mass fraction of sodium hydroxide solution is 40%, high pressure
Temperature is 200~240 DEG C after reaction kettle heating, and the insulation reaction time is 7~8h.
Step（2）The mass fraction of the concentrated sulfuric acid solution is 85%, and it is 30~45min to be stirred to react the time, removes ice
It is 1~2h to be stirred to react the time after water-bath under room temperature, and hydrogen peroxide mass fraction is 10%.
Step（3）The sulfuric acid solution mass fraction is 8%, and hydrogen peroxide mass fraction is 5%, and it is 45 to be stirred to react the time
~50min, oven temperature be 60~70 DEG C, drying time be 20~for 24 hours.
Step（4）The addition distilled water ultrasonic disperse time is 10~15min, obtained graphene oxide suspension
Mass concentration is 2~3mg/L, and the ultrasonic disperse time is 1~2h after monoxone is added, and control supersonic frequency is 30~33kHz.
Step（5）The ultrasonic disperse time is 30~35min, and the reaction time is 3~4h.
Step（6）The fibroin albumen stock solution quality score is 20%, fibroin albumen stoste and casein mixing quality ratio
It is 5:1, the pH of control deposition liquid is 7.00~8.50 in deposition process, and deposition voltage is 1.0~1.3V, sedimentation time is 5~
10min。
The beneficial effects of the invention are as follows：
（1）Titanium-based titanate nanowire matrix is made by material of titanium sheet in the present invention, by graphite powder, sodium nitrate in ice-water bath condition
Under sequentially add sulfuric acid solution, hydrogen peroxide, be filtered by vacuum after being stirred to react, obtain filter cake, solid-state is obtained after washing is dry
Solid oxide graphene is configured to suspension by graphene oxide, and ultrasonic disperse obtains carboxyl after sodium hydroxide, monoxone is added
Change graphene oxide colloid, trishydroxymethylaminomethane is mixed into ultrasonic disperse in carboxylated graphene oxide colloid, continues to add
Enter 1-（3- dimethylamino-propyls）It is outstanding that graphene nanometer sheet is obtained by the reaction in -3- ethyl-carbodiimide hydrochlorides and 1,3- propane diamine
Fibroin albumen stoste and casein are hybridly prepared into coating liquid, are received successively with graphene by two electrode cell reaction tanks by supernatant liquid
Rice piece suspension, coating liquid carry out electrophoretic deposition to titanium-based titanate nanowire matrix and obtain high bioactivity as deposition liquid
Timbering material, titanium-based titanate nanowire matrix chemical reactivity used in the present invention is high, can deposit graphene oxide and modify
On its surface, the biocompatibility and bioactivity of timbering material are not only increased, it can also be by the electrophoretic deposition time to holder
Material carries out moulding regulation and control, and coating liquid used is fibroin albumen stoste and casein, they all have high-biocompatibility, fibroin
Albumen can slowly degrade in human body, and casein can be absorbed in acidic environment by stomach, and degradation property is good and does not generate
Any harmful toxic matter；
（2）The present invention prepares the titanium-based titanate nanowire matrix with latticed microcellular structure, gained with hydrothermal synthesis method
Titanium-based titanate nanowire matrix micropore be 2 ~ 10 μm, pattern rule and be evenly distributed, can be provided for the growth of osteocyte
Place using stannic oxide/graphene nano piece is deposit to titanium by electrophoretic deposition to improve its biocompatibility, bioactivity
Silicate nanometer line matrix carries out regular, uniform modification, and using the titanate nanowire film of porous structure as substrate, spreads out outward
It is raw, three-dimensional graphene oxide pore space structure is formed, the roughness of timbering material and the contact point of cell are not only increased,
The mechanical strength of material is improved, a good environment is provided for the adherency of cell, growth, proliferation and new growing into for bone,
Oxidation stone is further improved to the functionalization of the hydroxyl of graphene oxide, amino, carboxyl by monoxone, 1,3- propane diamine etc.
The ALP activity of the titanate nanowire timbering material of black alkene modification, improves the timbering material self-bone grafting ability of non-functionalization, and
In casein institute's calcic, P elements for osteocyte breeding provide early period abundance nutriment, have a extensive future.
Specific implementation mode
Titanium sheet is placed in supersonic cleaning machine, cleans 10~15min with absolute ethyl alcohol and acetone successively, controls supersonic frequency
For 30~35kHz, the titanium sheet after cleaning is put into set temperature and is equipped with to be transferred to after dry 4~5h in 70~80 DEG C of baking oven
In the autoclave for the sodium hydroxide solution that 10~15mL mass fractions are 40%, 200~240 DEG C are heated to, heat preservation is anti-
7~8h is answered, titanium-based titanate nanowire matrix is obtained；0.2~0.3g graphite powders and 0.12~0.13g sodium nitrate are added to dress
Have in the beaker that 10~12mL mass fractions are 85% concentrated sulfuric acid solution, beaker is placed in ice-water bath, it is stirred to react 30~
45min is removed and is stirred to react 1~2h under ice-water bath room temperature, and 10~15mL deionized waters and 20~25mL matter are added into beaker
The hydrogen peroxide that score is 10% is measured, continues to be stirred to react until bubble-free generates；It continues up and states addition 20~25mL matter in beaker
The hydrogen peroxide for measuring sulfuric acid solution and 10~15mL mass fractions 5% that score is 8%, is filtered by vacuum after being stirred to react 45~50min
It removes filtrate and obtains filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, the filter cake after flushing is put into
Dry 20 in the baking oven that set temperature is 60~70 DEG C~for 24 hours, obtain solid oxide graphene；By the solid oxide of above-mentioned preparation
Graphene is placed in ultrasonic disperse machine, and distilled water ultrasonic disperse 10~15min is added, so as to get graphene oxide suspension matter
A concentration of 2~3mg/L is measured, 10mL graphene oxide suspensions are taken, 1.2g sodium hydroxides are added thereto and 1.0g monoxones are super
Sound disperses 1~2h, obtains carboxylated graphene oxide colloid, and control supersonic frequency is 30~33kHz；By 1~2g trihydroxy methyls
Aminomethane is added in above-mentioned carboxylated graphene oxide colloid, and 30~35min of ultrasonic disperse obtains mixed liquor, to mixed liquor
In continuously add 2~3g1-（3- dimethylamino-propyls）- 3- ethyl-carbodiimide hydrochlorides and 3~4g1,3- propane diamine, reaction 3
~4h obtains graphene nanometer sheet suspension；It is 5 in mass ratio by fibroin albumen stoste that mass fraction is 20%, casein:1
It is mixed to get coating liquid, using graphene nanometer sheet suspension as deposition liquid in two electrode cell reaction tanks, with titanium-based titanate
As working electrode, platinum plate electrode is used as to electrode nano wire matrix, carries out electrophoretic deposition, obtains biomimetic scaffolds, then by coating
For liquid as new deposition liquid, the pH of control deposition liquid is 7.00~8.50, and deposition voltage is 1.0~1.3V, sedimentation time is 5~
10min carries out electrophoretic deposition to biomimetic scaffolds, obtains high bioactivity timbering material.
Example 1
Titanium sheet is placed in supersonic cleaning machine, cleans 15min with absolute ethyl alcohol and acetone successively, control supersonic frequency is 35kHz,
Titanium sheet after cleaning is put into the baking oven that set temperature is 80 DEG C to be transferred to equipped with 15mL mass fractions after dry 5h be 40%
In the autoclave of sodium hydroxide solution, 240 DEG C, insulation reaction 8h are heated to, obtains titanium-based titanate nanowire base
Body；0.3g graphite powders and 0.13g sodium nitrate are added in the beaker for the concentrated sulfuric acid solution for being 85% equipped with 12mL mass fractions,
Beaker is placed in ice-water bath, 45min is stirred to react, removes and is stirred to react 2h under ice-water bath room temperature, 15mL is added into beaker
The hydrogen peroxide that deionized water and 25mL mass fractions are 10% continues to be stirred to react until bubble-free generates；It continues up and states beaker
The middle hydrogen peroxide that sulfuric acid solution and 15mL mass fractions 5% that 25mL mass fractions are 8% is added, is stirred to react vacuum after 50min
It filters removing filtrate and obtains filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, by the filter cake after flushing
It is put into drying in the baking oven that set temperature is 70 DEG C and for 24 hours, obtains solid oxide graphene；By the solid oxide graphite of above-mentioned preparation
Alkene is placed in ultrasonic disperse machine, and distilled water ultrasonic disperse 15min is added, so as to get graphene oxide suspension mass concentration be
3mg/L takes 10mL graphene oxide suspensions, and 1.2g sodium hydroxides and 1.0g monoxone ultrasonic disperse 2h are added thereto, obtains
To carboxylated graphene oxide colloid, control supersonic frequency is 33kHz；Above-mentioned carboxylated is added in 2g trishydroxymethylaminomethanes
In graphene oxide colloid, ultrasonic disperse 35min obtains mixed liquor, 3g1- is continuously added into mixed liquor（3- dimethylaminos third
Base）- 3- ethyl-carbodiimide hydrochlorides and 4g1,3- propane diamine react 4h, obtain graphene nanometer sheet suspension；By quality point
Count the fibroin albumen stoste for 20%, casein is 5 in mass ratio:1 is mixed to get coating liquid, will in two electrode cell reaction tanks
Graphene nanometer sheet suspension is as deposition liquid, using titanium-based titanate nanowire matrix as working electrode, platinum plate electrode conduct
To electrode, electrophoretic deposition is carried out, obtains biomimetic scaffolds, then using coating liquid as new deposition liquid, the pH of control deposition liquid is 8.50,
Deposition voltage is 1.3V, sedimentation time 10min, carries out electrophoretic deposition to biomimetic scaffolds, obtains high bioactivity timbering material.
Example 2
Titanium sheet is placed in supersonic cleaning machine, cleans 13min with absolute ethyl alcohol and acetone successively, control supersonic frequency is 33kHz,
Titanium sheet after cleaning is put into the baking oven that set temperature is 75 DEG C to be transferred to equipped with 13mL mass fractions after dry 4.5h be 40%
Sodium hydroxide solution autoclave in, be heated to 220 DEG C, insulation reaction 7.5h, obtain titanium-based titanate nanometer
Line matrix；0.25g graphite powders and 0.12g sodium nitrate are added to the burning for the concentrated sulfuric acid solution for being 85% equipped with 11mL mass fractions
In cup, beaker is placed in ice-water bath, 38min is stirred to react, removes and is stirred to react 1.5h under ice-water bath room temperature, added into beaker
Enter 13mL deionized waters and 23mL mass fractions for 10% hydrogen peroxide, continues to be stirred to react until bubble-free generates；It continues up
The hydrogen peroxide that sulfuric acid solution and 13mL mass fractions 5% that 23mL mass fractions are 8% are added in beaker is stated, 47min is stirred to react
After filtrate be removed by suction filtration under vacuum obtain filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, after flushing
Filter cake to be put into set temperature be dry 22h in 65 DEG C of baking oven, obtain solid oxide graphene；By the solid oxygen of above-mentioned preparation
Graphite alkene is placed in ultrasonic disperse machine, and distilled water ultrasonic disperse 13min is added, so as to get graphene oxide suspension quality
A concentration of 2.5mg/L takes 10mL graphene oxide suspensions, and 1.2g sodium hydroxides and 1.0g monoxone ultrasounds point are added thereto
1.5h is dissipated, carboxylated graphene oxide colloid is obtained, control supersonic frequency is 31kHz；1.5g trishydroxymethylaminomethanes are added
Enter in above-mentioned carboxylated graphene oxide colloid, ultrasonic disperse 33min obtains mixed liquor, continuously added into mixed liquor
2.5g1-（3- dimethylamino-propyls）- 3- ethyl-carbodiimide hydrochlorides and 3.5g1,3- propane diamine react 3.5h, obtain graphite
Alkene nanometer sheet suspension；It is 5 in mass ratio by fibroin albumen stoste that mass fraction is 20%, casein:1 is mixed to get coating
Liquid is made using graphene nanometer sheet suspension as deposition liquid in two electrode cell reaction tanks with titanium-based titanate nanowire matrix
For working electrode, platinum plate electrode is used as to electrode, carries out electrophoretic deposition, obtains biomimetic scaffolds, then using coating liquid as new deposition
The pH of liquid, control deposition liquid is 7.8, deposition voltage 1.2V, sedimentation time 7min, and electrophoretic deposition is carried out to biomimetic scaffolds,
Obtain high bioactivity timbering material.
Example 3
Titanium sheet is placed in supersonic cleaning machine, cleans 15min with absolute ethyl alcohol and acetone successively, control supersonic frequency is 35kHz,
Titanium sheet after cleaning is put into the baking oven that set temperature is 80 DEG C to be transferred to equipped with 15mL mass fractions after dry 5h be 40%
In the autoclave of sodium hydroxide solution, 240 DEG C, insulation reaction 8h are heated to, obtains titanium-based titanate nanowire base
Body；0.3g graphite powders and 0.13g sodium nitrate are added in the beaker for the concentrated sulfuric acid solution for being 85% equipped with 12mL mass fractions,
Beaker is placed in ice-water bath, 45min is stirred to react, removes and is stirred to react 2h under ice-water bath room temperature, 15mL is added into beaker
The hydrogen peroxide that deionized water and 25mL mass fractions are 10% continues to be stirred to react until bubble-free generates；It continues up and states beaker
The middle hydrogen peroxide that sulfuric acid solution and 15mL mass fractions 5% that 25mL mass fractions are 8% is added, is stirred to react vacuum after 50min
It filters removing filtrate and obtains filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, by the filter cake after flushing
It is put into drying in the baking oven that set temperature is 70 DEG C and for 24 hours, obtains solid oxide graphene；By the solid oxide graphite of above-mentioned preparation
Alkene is placed in ultrasonic disperse machine, and distilled water ultrasonic disperse 15min is added, so as to get graphene oxide suspension mass concentration be
3mg/L takes 10mL graphene oxide suspensions, and 1.2g sodium hydroxides and 1.0g monoxone ultrasonic disperse 2h are added thereto, obtains
To carboxylated graphene oxide colloid, control supersonic frequency is 33kHz；Above-mentioned carboxylated is added in 2g trishydroxymethylaminomethanes
In graphene oxide colloid, ultrasonic disperse 35min obtains mixed liquor, 3g1- is continuously added into mixed liquor（3- dimethylaminos third
Base）- 3- ethyl-carbodiimide hydrochlorides and 4g1,3- propane diamine react 4h, obtain graphene nanometer sheet suspension；By quality point
Count the fibroin albumen stoste for 20%, casein is 5 in mass ratio:1 is mixed to get coating liquid, will in two electrode cell reaction tanks
Graphene nanometer sheet suspension is as deposition liquid, using titanium-based titanate nanowire matrix as working electrode, platinum plate electrode conduct
To electrode, electrophoretic deposition is carried out, obtains biomimetic scaffolds, then using coating liquid as new deposition liquid, the pH of control deposition liquid is 8.50,
Deposition voltage is 1.3V, sedimentation time 10min, carries out electrophoretic deposition to biomimetic scaffolds, obtains high bioactivity timbering material.
Comparative example
As a comparison case with the timbering material of Shanghai City company production
Timbering material in high bioactivity timbering material produced by the present invention and comparative example is detected, testing result such as table
Shown in 1：
The characterization of material
The macrostructure, deposition mineralising and cell that material is prepared using scanning electron microscopy Electronic Speculum observation are sprawled.Using transmission
The meso-hole structure of electron microscope observation material.The microcellular structure of material is measured using isothermal nitrogen adsorption-desorption, and is passed through
BET calculates the specific surface area and Kong Rong of material, and average pore size is calculated according to formula.Material surface is observed using laser co-focusing
Cell morphology and infiltration.Using New born formation situation at x-ray instrument detection bone defect.
Mechanics Performance Testing
10mm × 10mm × 10mm is made in timbering material in high bioactivity timbering material produced by the present invention and comparative example
Rectangle galley proof, compression test, compression speed 1mm/min are then carried out on universal testing machine.
Porosity test
The porosity of timbering material is measured according to drainage.Porosity P=（W2-W3+WS）/（W1-W3）, wherein WSFor sample quality；
W1To weigh the quality of the specific gravity bottle full of absolute ethyl alcohol；W2For sample to be put into the gross mass in specific gravity bottle；W3For sample is taken
After going out, the quality of specific gravity bottle.
Cell culture invitro
By mouse mesenchymal stem cell（rBMSCs）It is incubated at containing 10% fetal calf serum, 100U/mL penicillin, 100U/mL strepto-s
In the α-MEM culture solutions of element, in 37 DEG C, 5%CO2Secondary culture in incubator.Holder high-temperature sterilization is placed on 24 hole cell trainings
It supports in plate, rBMSCs is inoculated into material surface respectively, and culture medium is added.It is detected using MTT measuring methods after being incubated to culture
The tetramethyl azo azoles salt reagent of 100 μ L is added to every hole for cell activity and cell Proliferation, and 37 DEG C are continued after being incubated 4h, and suction is abandoned
Supernatant is added 1mLDMSO, gently shakes 20min, crystal is made to dissolve, measured at 490nm using continuous spectrum microplate reader
The absorbance value of solution.
1 performance measurement result of table
From the data in table 1, it can be seen that high bioactivity timbering material produced by the present invention, has good mechanical property, it can be well
Meet the stress support demand at Bone Defect Repari position, and porosity is high, bioactivity and good biocompatibility, macro-level and microscopic level
Pore space structure is apparent, is conducive to proliferation and the differentiation of cell, hence it is evident that is better than comparative example product.Therefore, before there is wide use
Scape.
Claims (7)
1. a kind of preparation method of high bioactivity timbering material, it is characterised in that specifically preparation process is：
（1）Titanium sheet is placed in supersonic cleaning machine, is cleaned successively with absolute ethyl alcohol and acetone, the titanium sheet after cleaning is put into baking oven
It is transferred to after middle drying in the autoclave equipped with 10~15mL sodium hydroxide solutions, heat temperature raising, insulation reaction obtains titanium
Base titanate nanowire matrix；
（2）0.2~0.3g graphite powders and 0.12~0.13g sodium nitrate are added to the beaker equipped with 10~12mL concentrated sulfuric acid solutions
In, beaker is placed in ice-water bath, is stirred to react, removes and is stirred to react under ice-water bath room temperature, 10~15mL is added into beaker
Deionized water and 20~25mL hydrogen peroxide continue to be stirred to react until bubble-free generates；
（3）It continues up to state and 20~25mL sulfuric acid solutions and 10~15mL hydrogen peroxide is added in beaker, be stirred to react rear vacuum and take out
It filters out filtrate and obtains filter cake, be used in combination deionized water to rinse gained filter cake until cleaning solution is neutral, the filter cake after flushing is put
Enter drying in baking oven, obtains solid oxide graphene；
（4）The solid oxide graphene of above-mentioned preparation is placed in ultrasonic disperse machine, distilled water ultrasonic disperse is added, is aoxidized
Graphene suspension takes 10mL graphene oxide suspensions, and 1.2g sodium hydroxides and 1.0g monoxone ultrasounds point are added thereto
It dissipates, obtains carboxylated graphene oxide colloid；
（5）1~2g trishydroxymethylaminomethanes are added in above-mentioned carboxylated graphene oxide colloid, mixed liquor is obtained, to mixed
It closes in liquid and continuously adds 2~3g1-（3- dimethylamino-propyls）- 3- ethyl-carbodiimide hydrochlorides and 3~4g1,3- propane diamine,
Graphene nanometer sheet suspension is obtained by the reaction；
（6）Fibroin albumen stoste, casein are mixed to get coating liquid, hang graphene nanometer sheet in two electrode cell reaction tanks
Supernatant liquid is as deposition liquid, and using titanium-based titanate nanowire matrix as working electrode, platinum plate electrode is used as to electrode, carries out electrophoresis
Deposition obtains biomimetic scaffolds, then using coating liquid as new deposition liquid, electrophoretic deposition is carried out to biomimetic scaffolds, and it is living to obtain high biology
Property timbering material.
2. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（1）
The absolute ethyl alcohol and acetone scavenging period is 10~15min, and control supersonic frequency is 30~35kHz, baking oven set temperature
It it is 70~80 DEG C, drying time is 4~5h, and the mass fraction of sodium hydroxide solution is 40%, and temperature is after autoclave heating
200~240 DEG C, the insulation reaction time is 7~8h.
3. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（2）
The mass fraction of the concentrated sulfuric acid solution is 85%, and it is 30~45min to be stirred to react the time, removes and is stirred under room temperature after ice-water bath
It is 1~2h to mix the reaction time, and hydrogen peroxide mass fraction is 10%.
4. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（3）
The sulfuric acid solution mass fraction is 8%, and hydrogen peroxide mass fraction is 5%, and it is 45~50min, baking oven temperature to be stirred to react the time
Degree be 60~70 DEG C, drying time be 20~for 24 hours.
5. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（4）
The addition distilled water ultrasonic disperse time be 10~15min, obtained graphene oxide suspension mass concentration be 2~
3mg/L, the ultrasonic disperse time is 1~2h after monoxone is added, and control supersonic frequency is 30~33kHz.
6. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（5）
The ultrasonic disperse time is 30~35min, and the reaction time is 3~4h.
7. a kind of preparation method of high bioactivity timbering material according to claim 1, it is characterised in that：Step（6）
The fibroin albumen stock solution quality score is 20%, and fibroin albumen stoste is 5 with casein mixing quality ratio:1, deposition process
The pH of middle control deposition liquid is 7.00~8.50, and deposition voltage is 1.0~1.3V, and sedimentation time is 5~10min.
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