CN107537063B - A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof - Google Patents
A kind of complex stephanoporate bracket of carbon nanotubes and preparation method thereof Download PDFInfo
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses complex stephanoporate brackets of a kind of carbon nanotubes and preparation method thereof.Chitosan, gelatin, hydroxyapatite are dissolved in acetic acid solution, add different amounts of carbon nanotube, bracket is prepared using desivac, and be crosslinked in the ethanol solution of n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, obtain the more stable complex stephanoporate bracket of structure.The bracket of this method preparation has many advantages, such as that porosity is high and hole is connected to, good biocompatibility, osteoinductive activity, mechanical performance are strong, stable structure, and good biology performance is shown to important seed cell-fat stem cell of bone tissue engineer, it can be used as the excellent bio-medical material of one kind and be applied to bone tissue engineer clinical transplantation and reparation.
Description
Technical field
The invention belongs to tissue engineering material fields, in particular to a kind of to be received by chitosan, gelatin, hydroxyapatite, carbon
The method that four kinds of Material claddings of mitron, crosslinking prepare compound rest.
Background technique
Bone defect caused by the reasons such as infection, congenital malformation, wound, tumour is clinically very common, and treats hardly possible
Degree is big.The quick healing for how promoting bone defect position is always field of orthopaedics difficult medical problem urgently to be resolved.Traditional treatment
Method include autologous bone transplanting, homogeneous allogenic bone transplantation and artificial bone substitution etc., but autologous bone transplanting limited source and
Wound can be brought to patient, allogenic bone transplantation is easy to produce immunological rejection, and there are bone formation performances not to know for artificial bone
Defect.With the rise of Tissue Engineering Study, the treatment of bone defect is carried out using tissue engineering technique with very wide
Application prospect.Most important three elements are seed cell, timbering material and Biological somatomedin in organizational project, wherein propping up
Frame material is the most key factor.
The timbering material synthesized with property combination by multiple material according to different ratios is compound support frame material, can be effective
The shortcomings that overcoming homogenous material component and having a single function is prepared and more coincide with bone tissue natural formation, has good life
The bone tissue engineering scaffold of object compatibility, osteoconductive and osteoinductive.Bone tissue engineer compound rest mainly by chitosan,
The two kinds or three kinds compound preparations of progress naturally or in synthetic material such as gelatin, collagen, hydroxyapatite.Chitosan
(Chitosan is abbreviated CS) chitin extraction can obtain from the shell of shellfish by deacetylated, possess good
Biocompatibility, degradability, it can promote absorption, proliferation, the differentiation of biological tissue cell, apply in bone tissue engineer
Extensively.Gelatin (Gelatin is abbreviated Gel) is class protein, it can hydrolyze to obtain by collagenous portion, have excellent
Biocompatibility, bioactivity and biodegradability are commonly utilized in clinical medicine, in medical industry.Hydroxyapatite
(Hydroxyapatite is abbreviated HAP) is to constitute Human osteoblast to organize main inorganic composition, is had between tissue other
The incomparable compatibility of material, and be very easy to form synostosis with bone tissue, but there is that brittleness is big, inductivity
The problems such as poor.Often biocompatibility is preferable for this few class natural material, is easier to combine with organism, and decomposition product is also easy quilt
Organism is absorbed.But the mechanical performance of natural material is poor, and there are certain defects.
It is nanometer scale that carbon nanotube (Carbon nanotube, be abbreviated CNT), which is a kind of radial dimension, and axial dimension is
Micron dimension, pipe both ends have special mechanical property, electrochemistry by the new one-dimensional quantum material of hemispherical end cap closure
Performance and high-specific surface area.It is 100 times of steel such as 100~150GPa of tensile strength, but density only has the 1/6 of steel；The body of CNT
Conductivity is 1000S/cm, is far longer than carbon black 100S/cm；The specific surface area of CNT is about 150~300m2/g.CNT conduct
A kind of nano-scale carbon material, research has shown that also having excellent biocompatibility.Therefore, based on CNT special mechanical property,
Chemical property, high-specific surface area and biocompatibility, can be used as a kind of supporting material and conductive material is applied in bone tissue
In engineering, for increasing the mechanical performance and electric conductivity of compound support frame material, to prepare high tenacity, high-intensitive composite support
Frame.Patent CN103877612A " a kind of the cytoskeleton of carbon nanotubes and preparation method thereof ", the invention is with polylactic acid-glycolic base
The hexafluoroisopropanol solution of acetate multipolymer and the hexafluoroisopropanol suspension mixing of carbon nanotube obtain electrostatic spinning liquid, use
Electrostatic spinning technique is prepared for three-dimensional cell bracket, and what which selected is that poly lactide-glycolide acid is that bracket is main
Base material.Patent CN106668946A " a kind of Carbon Nanotubes/Chitosan/collagen compound support frame material and its preparation ",
This method prepares three-dimensional porous rack using desivac, but not compound using chitosan, collagen, carbon nanotube mixing
It constitutes Human osteoblast and organizes main inorganic composition-hydroxyapatite, crosslinking agent used is glutaraldehyde, Carbodiimides or epoxy
Alkyls, and lack the research for carrying Porcine HGF.
Based on the studies above status, the present invention basis compound in natural biologic material chitosan, gelatin, hydroxyapatite
On introduce carbon nanotube, compound rest is prepared using freeze-drying, and natural with bone tissue by chemical crosslinking preparation
Construction and the more identical compound rest of performance regulate and control the porosity of compound rest, water absorption rate by the additional amount of carbon nanotube
And mechanical performance, the mechanical property and electrology characteristic of compound rest are enhanced, the fat stem cell that can promote to be inoculated with thereon carries out
Tissue differentiation.
Summary of the invention
The purpose of the present invention is for conventional composite bracket bio-compatible difference, mechanical performance is lower, stability is poor etc. asks
Topic, invents a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes.The porous support materials that this method produces have
The advantages that good biocompatibility, porosity height, high mechanical strength, osteoinductive activity, stable structure.
In order to achieve the above object, the technical solution of the present invention is as follows:
A kind of preparation method of the complex stephanoporate bracket of carbon nanotubes, the preparation method is with chitosan, gelatin, hydroxyl phosphorus
Lime stone is main material, adds the carbon nanotube of different proportion, prepares compound rest using freeze-drying, is specifically included following
Step:
(1) by certain hydroxyl apatite HAP dispersion, be dissolved in secondary distilled water, stirring 30~50min to solution at
Emulsus obtains HAP milky solution, wherein HAP content is 1~2g/100mL.
(2) appropriate chitosan CS and gelatin Gel is added into HAP milky solution, adds glacial acetic acid and obtains mixed solution；
Mixed solution heats at 40~60 DEG C, 60~120min of magnetic agitation obtains CS/Gel/HAP after each substance is evenly dispersed
Mixed solution A.Wherein, CS content is 2~5g/100mL, and Gel content is 1~3g/100mL, and HAP content is 1~2g/
100mL；The volume fraction of acetic acid is 1~5% in mixed solution A.
(3) it disperses a certain amount of carbon nanotube CNT in secondary distilled water, is added appropriate glacial acetic acid, ultrasonic treatment 30~
100~150min of magnetic agitation after 50min obtains CNT acetic acid solution.Wherein, CNT content is 0.5~3g/100mL；CNT second
The volume fraction of acetic acid is 1~3% in acid solution.
The carbon nanotube CNT is multi-walled carbon nanotube, and diameter is 7~9nm, and length is 5~20 μm.
(4) the CNT acetic acid solution that step (3) is prepared the CS/Gel/HAP that step (2) is prepared is added to mix
It closes in solution A, is heated at 40~60 DEG C, stirs 50~100min to being uniformly mixed, obtain the mixing of CS/Gel/HAP/CNT
Solution B.
(5) the mixed solution B that step (4) is prepared is moved on in plastics orifice plate, and by plastics orifice plate -20~-30
Pre-freeze is carried out under the conditions of DEG C and handles 20~30h, is carried out freeze-drying process after pre-freeze processing and is obtained compound rest pre-product.
The temperature of the freeze-drying is -40~-60 DEG C, and the time is 20~30h.
(6) one layer of fine and close substance for removing compound rest pre-product surface, under normal temperature condition, by compound rest pre-product
It is immersed in after being chemically crosslinked 20~30h in crosslinking agent, is cleaned, is dried, can be obtained the carbon containing nanometer of stable structure
The bone tissue engineer compound rest of pipe.
The crosslinking agent is n-hydroxysuccinimide, ethanesulfonic acid, two Asia of 1- (3- dimethylamino-propyl) -3- ethyl carbon
Mixed solution of the amine hydrochlorate in 65% ethanol solution.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino
Propyl) concentration of -3- ethyl-carbodiimide hydrochloride is 50mmol/L.Dosage of crosslinking agent is 15~20mL/g bracket.
The cleaning process is 4~6h to be rinsed using disodium hydrogen phosphate, then rinse 6~8h using secondary distilled water.
The drying temperature is 60~80 DEG C, and drying time is 20~30h.
Chitosan, gelatin, hydroxyapatite three in the complex stephanoporate bracket for the carbon nanotubes that above-mentioned preparation method obtains
The mass ratio of kind substance is 1:(0.2~1): (0.2~1)；It is porous structure, hole inside the complex stephanoporate bracket of carbon nanotubes
Gap rate is in 69.51%~84.35% range, and water absorption rate is in 667.32%~946.82% range.
Chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest prepared by the present invention, to bone tissue engineer typical case
Seed cell-fat stem cell shows good biology performance, is suitable for bone tissue engineer field.
The present invention compared with the existing technology, has the following advantages and beneficial effects: the compound of the method for the invention preparation
Bracket has gathered chitosan, gelatin, hydroxyapatite, the advantage of four kinds of materials of carbon nanotube respectively, has both excellent biological
Energy and mechanical property；By chemical crosslinking, the more stable compound rest of structure is obtained；By adjusting in compound support frame material
Content of carbon nanotubes, to regulate and control porosity, water absorption rate and the mechanical performance of compound rest；Obtain porosity height, water absorption rate
Height, good biocompatibility, stable structure chitosan/gelatin/hydroxylapatite/carbon nanotube compound support frame material；Scanning electricity
Mirror, hydrophilicity experiment and cell compatibility experiment detection all demonstrate the timbering material and can satisfy bone tissue engineer for bracket
The demand of material.
Detailed description of the invention
Fig. 1 is chitosan/gelatin/hydroxyapatite compound rest scanning of content of carbon nanotubes 0% prepared by the present invention
Electron microscope；
Fig. 2 is that chitosan/gelatin/hydroxylapatite/carbon nanotube of content of carbon nanotubes 5.0% prepared by the present invention is multiple
Close bracket scanning electron microscope (SEM) photograph；
Fig. 3 is chitosan/gelatin/hydroxylapatite/carbon nanotube of content of carbon nanotubes 10.0% prepared by the present invention
Compound rest scanning electron microscope (SEM) photograph；
Fig. 4 is chitosan/gelatin/hydroxylapatite/carbon nanotube of content of carbon nanotubes 15.0% prepared by the present invention
Compound rest scanning electron microscope (SEM) photograph.
Specific embodiment
The present invention is illustrated with following embodiment, but the present invention is not limited to the following embodiments, is not departing from the front and back ancestor
In the range of purport, all modifications and variation based on basic thought of the present invention belong to the claimed technical scope of the present invention
It is interior.
Embodiment 1 not carbon nanotubes chitosan/gelatin/hydroxyapatite compound rest preparation
Accurate weighing 1.00g hydroxyapatite, is added in flask, and the secondary distilled water of 98mL is then added, and magnetic force stirs
After mixing about 30min, solution is at emulsus.2.50g chitosan and 1.50g gelatin are added into milky solution, then adds 2mL ice
Acetic acid.Then the solution is placed in 40 DEG C of water-bath after heating, magnetic agitation about 120min, is dispersed in each substance
In solution, flask can be taken out.The flask of taking-up is placed in ultrasonic wave or static a period of time removes the gas in solution
Bubble.After bubble removing, the solution in flask is moved on in plastics orifice plate using rubber head dropper.The modeling of mixed solution will be filled
Material orifice plate, which is placed in -20 DEG C of refrigerator, refrigerates 25h progress pre-freeze, is subsequently placed in -40 DEG C of freeze-drying 30h in freeze drier, obtains
Compound support frame material pre-product.One layer of fine and close substance for scraping off the compound support frame material pre-product surface prepared, is soaked
Bubble (n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt in 75mL crosslinking agent
Mixed solution of the hydrochlorate in 65% ethanol solution.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino third
Base) concentration of -3- ethyl-carbodiimide hydrochloride is respectively 50mmol/L), after room temperature stands crosslinking 20h, take out bracket phosphorus
Sour disodium hydrogen rinses 4h, reuses secondary distilled water and rinses 6h, chitosan/gelatin/hydroxyapatite compound rest can be completed
Crosslinking.At 60 DEG C after dry 6h, gained compound rest porosity 84.35%, water absorption rate 775.08%.
Chitosan/gelatin of 2 content of carbon nanotubes 0.5% of embodiment/hydroxylapatite/carbon nanotube compound rest preparation
Accurate weighing 1.00g hydroxyapatite, is added in flask, and the secondary distilled water of 98mL is then added, and magnetic force stirs
After mixing about 30min, solution is at emulsus.2.50g chitosan and 1.50g gelatin are added into milky solution, then adds 2mL's
Glacial acetic acid.Then the solution is placed in heating, magnetic agitation 120min in 40 DEG C of water-bath.Load weighted 0.025g carbon is received
Mitron is added in another flask, and the secondary distilled water of 5mL and the glacial acetic acid of 100 μ L are added in flask, is first ultrasonically treated
30min, subsequent magnetic agitation about 100min, carbon nanotube acetic acid solution is added to chitosan/gelatin for having stirred evenly/
In hydroxyapatite mixed solution, then remaining carbon nanotube is rinsed well with the secondary distilled water of 5mL.Continue at 40 DEG C
Lower heating stirring 100min waits for that new mixing is uniform again, and it is molten to obtain chitosan/gelatin/hydroxylapatite/carbon nanotube mixing
Liquid.The solution in flask is moved on in plastics orifice plate using rubber head dropper, the plastics orifice plate for filling mixed solution is placed in -25 DEG C
Refrigerator in refrigeration 28h carry out pre-freeze, be subsequently placed in -40 DEG C of freeze-drying 30h in freeze drier, obtain compound support frame material and produce in advance
Object.One layer of fine and close substance for scraping off the compound support frame material pre-product surface prepared, is immersed in 100mL crosslinking agent
(n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride are molten in 65% ethyl alcohol
Mixed solution in liquid.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide
The concentration of hydrochloride is respectively 50mmol/L), after room temperature stands crosslinking 22h, bracket is taken out with disodium hydrogen phosphate and rinses 4h, then is made
6h is rinsed with secondary distilled water, the crosslinking of chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest can be completed.In 60
At DEG C after dry 7h, gained compound rest porosity 83.39%, water absorption rate 786.92%.
Chitosan/gelatin of 3 content of carbon nanotubes 5.0% of embodiment/hydroxylapatite/carbon nanotube compound rest preparation
Accurate weighing 1.00g hydroxyapatite, is added in flask, and the secondary distilled water of 110mL is then added, and magnetic force stirs
After mixing about 40min, solution is at emulsus.3.50g chitosan and 1.50g gelatin are added into milky solution, then adds 3mL's
Glacial acetic acid.Then the solution is placed in heating, magnetic agitation 100min in 50 DEG C of water-bath.Load weighted 0.31g carbon is received
Mitron is added in another flask, and the secondary distilled water of 15mL and the glacial acetic acid of 200 μ L are added in flask, is first ultrasonically treated
40min, subsequent magnetic agitation about 100min, carbon nanotube acetic acid solution is added to chitosan/gelatin for having stirred evenly/
In hydroxyapatite mixed solution, then remaining carbon nanotube is rinsed well with the secondary distilled water of 5mL.Continue at 50 DEG C
Lower heating stirring 70min waits for that new mixing is uniform again, and it is molten to obtain chitosan/gelatin/hydroxylapatite/carbon nanotube mixing
Liquid.The solution in flask is moved on in plastics orifice plate using rubber head dropper, the plastics orifice plate for filling mixed solution is placed in -25 DEG C
Refrigerator in refrigeration 30h carry out pre-freeze, be subsequently placed in -50 DEG C of freeze-drying 30h in freeze drier, obtain compound support frame material and produce in advance
Object.One layer of fine and close substance for scraping off the compound support frame material pre-product surface prepared, is immersed in 120mL crosslinking agent
(n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride are molten in 65% ethyl alcohol
Mixed solution in liquid.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide
The concentration of hydrochloride is respectively 50mmol/L), after room temperature stands crosslinking 25h, bracket is taken out with disodium hydrogen phosphate and rinses 5h, then is made
7h is rinsed with secondary distilled water, the crosslinking of chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest can be completed.In 70
At DEG C after dry 6h, gained compound rest porosity 81.39%, water absorption rate 946.82%.
Chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest system of 4 content of carbon nanotubes 10.0% of embodiment
It is standby
Accurate weighing 1.50g hydroxyapatite, is added in flask, and the secondary distilled water of 110mL is then added, and magnetic force stirs
After mixing about 50min, solution is at emulsus.3.00g chitosan and 2.00g gelatin are added into milky solution, then adds 4mL's
Glacial acetic acid.Then the solution is placed in heating, magnetic agitation 80min in 60 DEG C of water-bath.By load weighted 0.72g carbon nanometer
Pipe is added in another flask, and the secondary distilled water of 25mL and the glacial acetic acid of 500 μ L are added in flask, is first ultrasonically treated 50min,
Carbon nanotube acetic acid solution, is added to the chitosan/gelatin/hydroxyl phosphorus stirred evenly by subsequent magnetic agitation about 120min
In lime stone mixed solution, then remaining carbon nanotube is rinsed well with the secondary distilled water of 5mL.It continues at 60 DEG C and heats
Stirring 60min waits for that new mixing is uniform again, obtains chitosan/gelatin/hydroxylapatite/carbon nanotube mixed solution.It uses
Rubber head dropper moves on to the solution in flask in plastics orifice plate, and the plastics orifice plate for filling mixed solution is placed in -30 DEG C of refrigerator
Middle refrigeration 26h carries out pre-freeze, is subsequently placed in -60 DEG C of freeze-dryings in freeze drier and for 24 hours, obtains compound support frame material pre-product.It scrapes
The one layer of fine and close substance on compound support frame material pre-product surface prepared is removed, (N- hydroxyl is immersed in 130mL crosslinking agent
Base succinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride are in 65% ethanol solution
Mixed solution.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
Concentration be respectively 50mmol/L), room temperature stand crosslinking 26h after, take out bracket with disodium hydrogen phosphate rinse 5h, reuse secondary
The crosslinking of chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest can be completed in distilled water flushing 8h.It is done at 70 DEG C
After dry 8h, gained compound rest porosity 75.41%, water absorption rate 684.24%.
Chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest system of 5 content of carbon nanotubes 15.0% of embodiment
It is standby
Accurate weighing 1.50g hydroxyapatite, is added in flask, and the secondary distilled water of 100mL is then added, and magnetic force stirs
After mixing about 50min, solution is at emulsus.3.00g chitosan and 1.80g gelatin are added into milky solution, then adds 5mL's
Glacial acetic acid.Then the solution is placed in heating, magnetic agitation 120min in 50 DEG C of water-bath.Load weighted 1.11g carbon is received
Mitron is added in another flask, and the secondary distilled water of 50mL and the glacial acetic acid of 600 μ L are added in flask, is first ultrasonically treated
50min, subsequent magnetic agitation about 150min, carbon nanotube acetic acid solution is added to chitosan/gelatin for having stirred evenly/
In hydroxyapatite mixed solution, then remaining carbon nanotube is rinsed well with the secondary distilled water of 5mL.Continue at 50 DEG C
Lower heating stirring 80min waits for that new mixing is uniform again, and it is molten to obtain chitosan/gelatin/hydroxylapatite/carbon nanotube mixing
Liquid.The solution in flask is moved on in plastics orifice plate using rubber head dropper, the plastics orifice plate for filling mixed solution is placed in -30 DEG C
Refrigerator in refrigeration 30h carry out pre-freeze, be subsequently placed in -60 DEG C of freeze-drying 30h in freeze drier, obtain compound support frame material and produce in advance
Object.One layer of fine and close substance for scraping off the compound support frame material pre-product surface prepared, is immersed in 150mL crosslinking agent
(n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride are molten in 65% ethyl alcohol
Mixed solution in liquid.Wherein, n-hydroxysuccinimide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide
The concentration of hydrochloride is respectively 50mmol/L), after room temperature stands crosslinking 30h, bracket is taken out with disodium hydrogen phosphate and rinses 6h, then is made
8h is rinsed with secondary distilled water, the crosslinking of chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest can be completed.In 80
Dry 7h at DEG C, rear gained compound rest porosity 69.51%, water absorption rate 667.32%.
Chitosan/gelatin/hydroxylapatite/carbon nanotube compound rest of 6 carbon nanotube containing different proportion of embodiment is thin
The detection of cell phase capacitive
Seed cell-fat stem cell is seeded on CS/Gel/HA/CNT timbering material and carries out compound criteria, same to bracket
Life or death Fluorescent Staining Observation is carried out after cell compound criteria object culture for a period of time, discovery carbon nanotube containing different proportion is answered
Close the coloration result and no significant difference of bracket and cell compound criteria object.Large area is issued using Calcein-AM staining cell
Green fluorescence shows that cells survival is in good condition, a small amount of red fluorescence only occurs using PI dyeing and shows that dead cell is less, and makes
There is large area blue-fluorescence with Hoechst dyeing.The above experimental phenomena shows the compound rest of the carbon nanotube containing different proportion
Material is provided with preferable biocompatibility, can satisfy bone tissue engineer for the demand of timbering material.
The culture of cytoskeleton compound criteria object after a week, places it in orifice plate, with 2.5% glutaraldehyde in 4 DEG C of conditions
Lower fixation for 24 hours, then with PBS washes twice, and is successively taken off using the alcohol that concentration gradient is 50%, 70%, 90%, 100%
Water, dewatering time 30min are dried in vacuo after the completion of dehydration, use scanning electron microscopic observation CS/Gel/HA/ after the completion of dry
Cell adherence and extracellular matrix secretion situation on CNT compound rest.According to electron microscopic picture as can be seen that cell is adsorbed on branch completely
It on frame, sufficiently sprawls, upgrowth situation is good.
Claims (8)
1. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes, which is characterized in that following steps:
(1) by hydroxyapatite HAP dispersion, be dissolved in secondary distilled water, it is molten that stirring to solution at emulsus obtains HAP emulsus
Liquid, wherein HAP content is 1~2g/100mL；
(2) chitosan CS and gelatin Gel is added into HAP milky solution, adds glacial acetic acid and obtains mixed solution；Mixed solution
At 40~60 DEG C heating, magnetic agitation to each substance it is evenly dispersed after, obtain the mixed solution A of CS/Gel/HAP；
(3) it disperses carbon nanotube CNT in secondary distilled water, glacial acetic acid is added, carries out magnetic agitation after ultrasonic treatment and obtains
CNT acetic acid solution, wherein CNT content is 0.5~3g/100mL in CNT acetic acid solution, the volume fraction of acetic acid is 1~3%；
(4) the CNT acetic acid solution that step (3) is prepared is added in the mixed solution A that step (2) is prepared, 40
It heated under the conditions of~60 DEG C, stir 50~100min to being uniformly mixed, obtain the mixed solution B of CS/Gel/HAP/CNT；
(5) the mixed solution B that step (4) is prepared is moved on in plastics orifice plate, and by plastics orifice plate in -20~-30 DEG C of items
Pre-freeze is carried out under part and handles 20~30h, is carried out freeze-drying process after pre-freeze processing and is obtained compound rest pre-product；
(6) one layer of dense matter for removing compound rest pre-product surface, under normal temperature condition, compound rest pre-product is immersed in
After being chemically crosslinked 20~30h in crosslinking agent, after being cleaned with disodium hydrogen phosphate, secondary distilled water, it is dried to obtain structure
The bone tissue engineer compound rest of stable carbon nanotubes, the crosslinking agent are n-hydroxysuccinimide, ethanesulfonic acid, 1-
Mixed solution of (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride in 65% ethanol solution；Wherein, N- hydroxyl amber
Amber acid imide, ethanesulfonic acid, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride concentration be 50mmol/L.
2. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes according to claim 1, which is characterized in that institute
CS content is 2~5g/100mL in the step of stating (2) mixed solution A, Gel content is 1~3g/100mL, HAP content be 1~
2g/100mL, acetic acid volume fraction be 1~5%.
3. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes according to claim 1 or 2, feature exist
In carbon nanotube CNT is multi-walled carbon nanotube in the step (3), and diameter is 7~9nm, and length is 5~20 μm.
4. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes according to claim 1 or 2, feature exist
In sonication treatment time is 30~50min in the step (3), and the magnetic agitation time is 100~150min.
5. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes according to claim 3, which is characterized in that institute
Sonication treatment time is 30~50min in the step of stating (3), and the magnetic agitation time is 100~150min.
6. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes, feature described according to claim 1 or 2 or 5
It is, the temperature being freeze-dried in the step (5) is -40~-60 DEG C, and the time is 20~30h；In the step (6)
Drying temperature be 60~80 DEG C, drying time be 20~30h.
7. a kind of preparation method of the complex stephanoporate bracket of carbon nanotubes according to claim 3, which is characterized in that institute
The temperature being freeze-dried in the step of stating (5) is -40~-60 DEG C, and the time is 20~30h；Dry temperature in the step (6)
Degree is 60~80 DEG C, and drying time is 20~30h.
8. using the complex stephanoporate bracket for the carbon nanotubes that preparation method as claimed in claim 1 to 7 obtains, feature
It is, the complex stephanoporate bracket of the carbon nanotubes adds carbon using chitosan, gelatin, hydroxyapatite as main material
Nanotube is prepared using freeze-drying；
The mass ratio of chitosan, gelatin, hydroxyapatite in the complex stephanoporate bracket is 1:0.2~1:0.2~1；
It is porous structure inside the complex stephanoporate bracket, porosity exists in 69.51%~84.35% range, water absorption rate
667.32%~946.82% range.
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| CN108946729A (en) * | 2018-08-17 | 2018-12-07 | 江苏师范大学 | A kind of preparation method of chitosan/gelatin carbon nanotube skeleton absorbent charcoal material |
| CN109745578B (en) | 2018-08-31 | 2021-01-22 | 京东方科技集团股份有限公司 | Bone repair material and preparation method thereof |
| CN111825859A (en) * | 2020-07-23 | 2020-10-27 | 陕西科技大学 | Bionic electronic skin medical stent material with self-repairing function and preparation method thereof |
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