CN105688285B - A kind of preparation method of grapheme material coating chitosan three-dimensional bracket - Google Patents
A kind of preparation method of grapheme material coating chitosan three-dimensional bracket Download PDFInfo
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- CN105688285B CN105688285B CN201610051206.6A CN201610051206A CN105688285B CN 105688285 B CN105688285 B CN 105688285B CN 201610051206 A CN201610051206 A CN 201610051206A CN 105688285 B CN105688285 B CN 105688285B
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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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/303—Carbon
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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
Abstract
The present invention provides a kind of preparation methods of chitosan stent with different reducing degree graphite oxide ene coatings.Specifically include the chitosan stent material that there is porous structure by freeze-drying preparation, it is immersed in the graphene oxide dispersion of various concentration again, graphene oxide sheet is adsorbed on chitosan hole wall by electrostatic interaction and hydrogen bond action, it is dry, finally carry out ladder heating reduction, it obtains mechanical strength to be greatly improved, the chitosan stent with different reducing degree graphite ene coatings has a good application prospect in terms of neural tissue engineering.Method of the invention is easy to operate, can largely prepare required product.
Description
Technical field:
The present invention relates to a kind of method of graphene coating chitosan stent prepared with different reducing degrees, the present invention
It is to utilize the electrostatic and hydrogen bond between graphene oxide sheet self assembly principle and oxygen-containing functional group and chitosan stent material
Effect, realizes coating of the graphene oxide on chitosan stent, is finally obtained by thermal reduction method with organizational project
The redox graphene of application prospect and the composite material bracket of chitosan.
Background technique:
Life and reengineer manipulate nervous system, biological cell and organizer official rank in following realize including the mankind
Ability is considered as one of subject involved in science and the 6th scientific and technological revolution of industry.Wherein regeneration techniques are as the 4th time
The important technology of Industrial Revolution becomes various countries and is laid out in advance, seizes strategic high ground, to win initiative, grasp core patent
Fall over each other the target chased.
It is using thin in formal definition in 1987 that the concept of " organizational project ", which is by National Science Foundation earliest,
The principle of born of the same parents' biology, biomaterial and engineering science researchs and develops a science for repairing human body lesion.It is studied
Field has been related to materialogy, engineering science and life science.In recent years, the research and development of tissue engineering material are always scientific research
The focus of attention of workers, as biomaterial, they must satisfy these following conditions:
(1) good biocompatibility: nontoxicity does not cause inflammatory reaction, meanwhile, it is viscous to be also conducive to seed cell
Attached, proliferation and differentiation；
(2) there is three-dimensional porous structure and higher specific surface area, roomy surface area and space can be provided for cell, with
And the ability of nutriment and gas exchanges；
(3) suitable mechanical strength；
(4) Modulatory character of surface microenvironment；
(5) easily disinfection；
(6) excellent biodegradability.
And the material of one-component tends not to meet all conditions above, so urgently research and development are able to satisfy above-mentioned item
The biomaterial of part.
Graphene has extremely extensive potential using value as a kind of novel nano-material, in field of biomedicine,
Such as: biosensor, bio-imaging, photo-thermal physical therapy, medicament transport, organizational project aspect etc..It has extremely excellent
Mechanics, electric property and biocompatibility, unique physicochemical properties are capable of providing the extracellular matrix item of cell growth
Part, this is its one very big advantage as tissue engineering bracket material.Currently, grapheme material (intrinsic graphene, few layer stone
Black alkene film, graphene oxide etc.) in terms of organizational project research be concentrated mainly on two-dimensional film, graphene nanometer sheet as performance
Enhance additive and graphene three-dimensional foam etc. is prepared using chemical vapour deposition technique.Change graphene film as surface
Property material, prepare the compound three-dimensional stent material based on graphite ene coatings research it is very few.
Chitosan is largely present in nature as a kind of Natural polycations biological polyoses, has good biology
Compatibility and biodegradability, it is still in the ascendant about its research in terms of organizational project, but it is biological living as having
The bracket of property faces two main problems: (1) lower mechanical property is often difficult to carry the growth of tissue and organ；(2) no
It is easily modified, faces the challenge in terms of cell controllable growth.
Currently, had researcher to realize coats apatite on chitosan stent, in collagen scaffold
Graphene oxide is coated, they all have good biocompatibility, also have scientist to prepare addition graphene oxide and receive
The chitosan stent of rice piece, not only mechanical strength is improved, but also has good biocompatibility.But do not have also at present
Have in conjunction with easy-to-use infusion process, chemical oxidization method, low temperature step heating restoring method, in traditional polymer chitosan three-dimensional
The report with the coating of different reducing degree graphene films is realized on bracket.This research is for improving chitosan three-dimensional bracket
Bioactivity, mechanical property and electric property have great importance.
Summary of the invention:
The present invention provides one kind using chitosan stent as matrix, and graphene oxide realizes self assembly, shape on matrix
At coating, then by the method for thermal reduction, the graphene coating chitosan compound rest with different reducing degrees is finally obtained
Material.Operation of the present invention is simple, can be realized large-scale production.
Specific step is as follows by the present invention:
A kind of preparation method of grapheme material coating chitosan three-dimensional bracket, steps are as follows:
1) Chitosan powder is dissolved in aqueous acetic acid, preparation has certain density chitosan solution；
2) chitosan solution in step 1) is injected in 24 hole board molds, then freeze forming uses vacuum freeze drying
Machine is dry, obtains the chitosan stent with porous structure；
3) porous support in step 2) is immersed in aqueous slkali, neutralizes remaining acetic acid, then with deionized water clean to
It is neutral；It is freeze-dried herein；
4) graphene oxide is prepared using the Hummers method of improvement, it is mixed with alcohol, be ultrasonically treated, had
The graphene oxide dispersion of various concentration；
5) chitosan stent that step 3) obtains is immersed in the graphene oxide dispersion that step 4) obtains, finally in sky
It is dry in gas, obtain compound rest；
6) bracket in step 5) is carried out in vacuum environment staged heating, obtains the oxidation with different reducing degrees
The chitosan stent of graphite ene coatings.
Chitosan solution concentration described in step 1) is 1~4%.
It is 2% (v/v) that aqueous acetic acid concentration is stated used in step 1).
24 orifice plate mold materials used in step 2) are polystyrene；The cryogenic temperature is -20 DEG C, is freeze-dried temperature
It is -60 DEG C.
Alkali used is sodium hydroxide solution, concentration 0.5mg/ml in step 3).
Graphite powder used is 325 mesh natural graphite scales of Alpha Co., Ltd's production in step 4)；Sonification power is
350w, ultrasonic time 1h, graphene oxide concentration are 0~1mg/ml.
Heating temperature is 60,120,150 DEG C respectively in step 6), and each temperature section retention time is 12 hours.
It is a feature of the present invention that solving the problems, such as coagulation of the chitosan stent in graphene oxide aqueous dispersions, institute
The porosity for preparing sample substantially remains in 92%, and product is observed by scanning electron microscope (SEM), discovery bracket aperture compared with
To be uniform, hole ordered orientation degree is high, illustrates the prepared coating of ladder heating on chitosan multi-porous structure substantially without influence.Oxygen
The compound rest of graphite alkene coating, hole wall have fold appearance, illustrate to form graphite ene coatings on hole wall.X-ray diffraction
(XRD) and FTIR technique (FTIR) test result also indicates that, heating is to chitosan within the scope of 150 DEG C
Phase structure and functional group influence little.X-ray photoelectron spectroscopy (XPS) illustrates, under different reduction temperatures, has obtained having not
With the graphite oxide ene coatings of reducing degree.Moreover, the compressive strength of compound rest is greatly improved.
Detailed description of the invention:
Fig. 1 is that chitosan stent and chitosan/oxidized graphene compound rest add at different temperatures in embodiment
Optical photograph after heat, bracket are diameter 1.3cm, and the cylindrical body of height 9mm, sequence from left to right is: CS-60 DEG C, CS-
120 DEG C, CS-150 DEG C, (chitosan/graphene compound rest impregnated through the graphene oxide dispersion that concentration is 1mg/ml)
CS-GO-60℃、CS-GO-120℃、CS-GO-150℃。
Fig. 2 is the porosity test result in case study on implementation.
Fig. 3 is to produce in case study on implementation after the graphene oxide membrane (GO) for coating on the glass sheet heats at different temperatures
The X-ray diffraction analysis figure of object.
Fig. 4 is chitosan stent and the shell impregnated through concentration for 1mg/ml graphene oxide dispersion in case study on implementation
The X-ray diffraction analysis figure of product after glycan/graphene oxide (CS/GO) compound rest heats at different temperatures.
Fig. 5 is to coat graphene oxide membrane (GO) on the glass sheet, chitosan (CS) bracket and warp in case study on implementation
Concentration is chitosan/oxidized graphene (CS/GO) compound rest of 1mg/ml graphene oxide dispersion immersion in different temperatures
The FTIR technique figure of product after lower heating.
Fig. 6 is the xps energy spectrum of the C1s core level of product after chitosan (CS) bracket heats at 150 DEG C in case study on implementation
Figure.
Fig. 7 is the xps energy spectrum of the N1s core level of product after chitosan (CS) bracket heats at 150 DEG C in case study on implementation
Figure.
Fig. 8 is the XPS energy of the C1s core level of product after graphene oxide membrane (GO) heats at 60 DEG C in case study on implementation
Spectrogram.
Fig. 9 is the XPS energy of the C1s core level of product after graphene oxide membrane (GO) heats at 120 DEG C in case study on implementation
Spectrogram.
Figure 10 is the XPS of the C1s core level of product after graphene oxide membrane (GO) heats at 150 DEG C in case study on implementation
Energy spectrum diagram.
Figure 11 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the C1s core level of product after alkene (CS/GO) compound rest heats at 60 DEG C.
Figure 12 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the N1s core level of product after alkene (CS/GO) compound rest heats at 60 DEG C.
Figure 13 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the C1s core level of product after alkene (CS/GO) compound rest heats at 120 DEG C.
Figure 14 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the N1s core level of product after alkene (CS/GO) compound rest heats at 120 DEG C.
Figure 15 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the C1s core level of product after alkene (CS/GO) compound rest heats at 150 DEG C.
Figure 16 is in case study on implementation, is the chitosan/oxidized graphite that 1mg/ml graphene oxide dispersion is impregnated through concentration
The xps energy spectrum figure of the N1s core level of product after alkene (CS/GO) compound rest heats at 150 DEG C.
Figure 17 is 70 times of scanning electron microscope (SEM) images of product after chitosan stent heats at 60 DEG C in case study on implementation,
In figure it can be seen that aperture is more uniform, and the degree of order is high.
Figure 18 is 1000 times of scanning electron microscope (SEM) figures of product after chitosan stent heats at 60 DEG C in case study on implementation
Picture does not find that fold exists on hole wall.
Figure 19 is in case study on implementation, is the compound rest that impregnates of 0.02mg/ml graphene oxide dispersion 60 through concentration
1000 times of scanning electron microscope (SEM) images of product after being heated at DEG C, it can be seen that occur fold spline structure (such as arrow on hole wall
It is shown).
Figure 20 is in case study on implementation, is the compound rest that impregnates of 1mg/ml graphene oxide dispersion at 60 DEG C through concentration
1000 times of scanning electron microscope (SEM) images of product after heating find obvious fold (as shown by arrows) occur on hole wall.
Figure 21 is in case study on implementation, is the compound rest that impregnates of 1mg/ml graphene oxide dispersion at 150 DEG C through concentration
1000 times of scanning electron microscope (SEM) images of product after lower heating, fold is more obvious on hole wall.
Figure 22 is in case study on implementation, is the compound rest that impregnates of 1mg/ml graphene oxide dispersion at 150 DEG C through concentration
15000 times of scanning electron microscope (SEM) images of product after lower heating, superficial layer are redox graphene film.
Figure 23 is the compressive strength test table of comparisons in case study on implementation.
Specific embodiment
Particular content and embodiments thereof of the invention are further illustrated below with reference to example.
Embodiment:
Prepare the composite material of the graphite ene coatings and chitosan three-dimensional bracket with different reducing degrees, specific experiment item
Part is as follows:
1) Chitosan powder is dissolved in the glacial acetic acid solution that volumetric concentration is 2%, stirs 2h, being made into concentration is 4%
(w/v) chitosan solution is ultrasonically treated 1h, stands, and removes bubble.
2) by the chitosan solution injection mold in step (1), 12h is stood in 4 DEG C of environment, is then transferred to -20 DEG C
Environment in freezing processing for 24 hours, place into and be freeze-dried 48h in freeze drier.
3) porous support in step (2) is immersed in 0.5% sodium hydroxide solution, neutralizes remaining acetic acid, then spend
Ionized water is impregnated, is cleaned to neutrality；It is freeze-dried again.
4) graphite oxide is prepared using the Hummers method of improvement:
1. 1.5g sodium nitrate is dissolved in the 69ml concentrated sulfuric acid, 2g graphite is added, stirs evenly.
2. being put into ice-water bath, it is slowly added to potassium permanganate 9g.
3. ice-water bath is kept for 12 hours.
4. being warming up to 40 degrees Celsius, kept for 1 hour.
5. being warming up to 60 degrees Celsius, 18h is kept.
6. being cooled to room temperature, 200ml ice water is added.
7. hydrogen peroxide is added dropwise, until bubble-free generates, solution becomes glassy yellow.
8. close neutral to supernatant with hydrochloric acid eccentric cleaning, then with deionized water eccentric cleaning.
Obtained graphite oxide stoste is mixed with dehydrated alcohol, 350w is ultrasonically treated 1h, and configuration concentration is respectively 0,
0.02,0.1,1mg/ml graphene oxide dispersion.
5) chitosan stent that step (3) obtains is immersed in the graphene oxide dispersion that step (4) obtain, is kept
48h for several times with washes of absolute alcohol is finally dried in air, obtains compound rest；
6) bracket in step (5) is carried out staged heating: 12h at 60 DEG C in vacuum environment, 12h at 120 DEG C, 150
12h at DEG C obtains the chitosan stent of the graphite oxide ene coatings with different reducing degrees.
7) XRD test, porosity test, FTIR test, SEM test, XPS test, compressive strength are carried out to compound rest
Test.
The method lifted according to foregoing invention can prepare the chitosan three-dimensional bracket of grapheme material coating, special
It levies as follows:
1) macroscopical optical picture on piece can be seen that the pure chitosan bracket of graphene oxide dispersion immersion, with temperature
Raising, chitosan surface color turn yellow；After being coated with graphene oxide, chitosan surface color becomes brown, with heating
The raising of temperature, has gradually become black.
2) analysis of porosity is carried out to made sample using alcohol method of substitution, the results showed that, all brackets (coating front and back)
Porosity is held at 92% or so.With the increase of the graphene oxide concentration used, becoming for slightly reduction is presented in porosity
Gesture.
3) X-ray diffraction analysis is shown, all brackets all have a typical diffractive peak of chitosan: 2 θ=14.9 ° and 2 θ=
20.4 °, illustrate that the chitosan of graphene oxide coating is heated by ladder, there is no variations substantially for the phase structure of chitosan；
Compared to matrix chitosan, graphene oxide content is seldom, therefore fails obviously to observe that (reduction) in compound rest aoxidizes
Graphene diffraction maximum.Other conditions are identical, coat graphite oxide ene coatings on the glass sheet, with the raising of heating temperature,
It can be seen that 12.04 ° when diffracted primary peak is by 60 DEG C move to 13.65 ° (being warming up to 120 DEG C) and 23.52 ° (150 DEG C plus
Hot temperature), illustrate that graphene oxide is gradually being reduced.
4) FTIR technique analysis is carried out to made sample, it is found that all brackets all show chitosan
Typical absorption peak: 1085cm-1Place is the feature C-O stretching vibration absworption peak of carbohydrate, 1583cm-1Place is I peak band of amide,
1384cm-1Place is II peak band of amide, 2861cm-1Place is the C-H stretching vibration peak of chitosan alkyl, 3458cm-1Place is that-OH stretches
Contracting vibration peak.Apparent graphene oxide absorption peak is not found, this is because graphene oxide content is non-with respect to for chitosan
Often few, absorption peak relative intensity is low.The feature that the graphene oxide membrane of coating on the glass sheet then shows graphene oxide is inhaled
Receipts peak: 1035,1225,1627,1739cm-1Correspond respectively to the C-O absorption peak of epoxy group, C-OH absorption peak, C=C absorption peak
With the C-O absorption peak of-COOH, 3455cm-1Then correspond to O-H absorption peak.As heating temperature increases, graphene oxide membrane is corresponding
Absorption peak strength is all declining, and also illustrates that graphene oxide is gradually being reduced.
5) in order to further determine ingredient and bonding state, we have carried out x-ray photoelectron spectroscopy to the sample of preparation
Analysis.The result shows that chitosan stent is respectively through after 60 DEG C, 120 DEG C, 150 DEG C for the treatment of of different temperature, C1s and N1s combination energy
Peak position and peak shape illustrate that low-temperature heat does not change the structure and ingredient of chitosan substantially there is no variation.Wherein C element
In xps energy spectrum, the combination of 284.4eV can correspond to sp2C=C, 285.7eV, 286.5eV, 287.7eV correspond respectively to sp2N-
C,C-O,C-O-C；In the xps energy spectrum of N element, the combination of 399.1eV can correspond to pyridine nitrogen.Graphene oxide colloid is heated
After the XPS spectrum figure deconvolution processing of sample C1s after reduction the result shows that, 284.4eV, 285.4eV, 286.8eV, 287.7eV,
288.6eV and 289.2eV can be attributed to sp respectively2C=C, sp3C-C, C-OH, C-O-C, O=C-OH and C=O group.Comparison
The C1s of sample through 60 DEG C, 120 DEG C, 150 DEG C heating reduction treatments can be seen that be heated higher than 120 DEG C, graphene film
On epoxy-functional have occurred and decompose deoxidation effect, higher than 150 DEG C thermal reductions can effectively remove oxygen content in sample,
Obtain the graphite ene coatings with different reducing degrees.XPS analysis result is consistent with FTIR analysis result.Graphene coated layer
The XPS spectrum figure of the C1s of chitosan sample available following result after peak-fit processing: 284.0eV (sp2C-C)、284.4eV
(sp2C=C), 285.3eV (sp3C-C/sp2N-C), 286.7eV (C-OH), 287.8eV (C-O-C), 288.6 (O=C-OH),
(289.6eV C=O).From the existing carbon core energy in graphene of C1s that can be seen that in the XPS spectrum figure of C1s in sample
Grade power spectrum, and have the contribution of C element in chitosan as a result, it can be said that graphene has effectively been coated in chitosan stent table
Face.The chemical environment of the N element in graphene coated chitosan sample obtained under 60 DEG C of reduction temperatures be pyridine nitrogen and
Graphite nitrogen, 120 DEG C reduction samples in N core level be 399.2eV (pyridine nitrogen) and 400.5eV (graphite nitrogen, graphitic-
N1Or pyrroles's nitrogen, N-H), the XPS spectrum figure of the N1s tested after 150 DEG C of reduction corresponds to pyridine nitrogen (399.4eV).
6) using the surface topography of sample prepared by scanning electron electron microscope analysis.As can be seen that bracket aperture is more
Even, for aperture size between 150-300 μm, hole ordered orientation degree is high, is in the form of a column, illustrates graphite ene coatings and heating treatment pair
The porous structure of chitosan influences little.The compound rest of graphene oxide coating, hole wall have fold appearance, illustrate shape on hole wall
At graphite oxide ene coatings, and with the raising of heating temperature, fold degree increases, this is because graphite oxide ene coatings by
Gradually it is reduced the reason for foring typical redox graphene film.
7) compressive strength test, compression factor 25% are carried out to prepared sample.As can be seen that with chitosan stent
The increase of impregnated GO dispersion liquid concentration, the raising of heating temperature, the compressive strength of bracket are to be gradually increased.It is through concentration
The compressive strength of product is pure chitosan branch after the compound rest that 1mg/ml graphene oxide dispersion is impregnated heats at 150 DEG C
1.7 times of product after being heated at 60 DEG C of frame.This explanation, graphite oxide ene coatings can largely improve the power of chitosan stent
Learn performance.
Claims (3)
1. a kind of preparation method of grapheme material coating chitosan three-dimensional bracket, steps are as follows:
1) Chitosan powder is dissolved in aqueous acetic acid, it is the chitosan solution of 1~4% (w/v) that preparing, which has concentration,；
2) chitosan solution in step 1) is injected in 24 hole board molds, freeze forming, it is then dry with vacuum freeze drier
It is dry, obtain the chitosan stent with porous structure；The 24 orifice plate mold material is polystyrene；The cryogenic temperature be-
20 DEG C, freeze-drying temperature is -60 DEG C；
3) porous support in step 2) is immersed in aqueous slkali, neutralizes remaining acetic acid, then cleaned to neutrality with deionized water,
It is freeze-dried again；Alkali used is NaOH, alkali concentration 0.5mg/ml；
4) graphene oxide is prepared using the Hummers method of improvement, it is mixed with dehydrated alcohol, be ultrasonically treated, had
The graphene oxide dispersion of various concentration；Sonification power is 350w, ultrasonic time 1h；Graphene oxide concentration is 0
~1mg/ml；
5) chitosan stent that step 3) obtains is immersed in the graphene oxide dispersion that step 4) obtains, finally in air
It is dry, obtain compound rest；
6) bracket in step 5) is carried out in vacuum environment staged heating, obtains the graphite oxide with different reducing degrees
The chitosan stent of ene coatings；Heating temperature is 60,120,150 DEG C respectively, and each temperature section time is 12 hours.
2. a kind of preparation method of grapheme material coating chitosan three-dimensional bracket according to claim 1, which is characterized in that
Aqueous acetic acid concentration described in step 1) is 2% (v/v).
3. a kind of preparation method of grapheme material coating chitosan three-dimensional bracket according to claim 1, which is characterized in that
Graphite powder used in step 4) is 325 mesh natural graphite scales of Alpha Co., Ltd's production.
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| CN106215234B (en) * | 2016-07-27 | 2019-09-13 | 西南科技大学 | Graphene oxide-Chitosan Composites preparation method |
| CN106581768B (en) * | 2016-11-30 | 2019-09-27 | 大连理工大学 | A kind of preparation method of the tissue engineering bracket for myocardial repair |
| CN110624509A (en) * | 2018-06-25 | 2019-12-31 | 香港城市大学深圳研究院 | Preparation method of porous composite material based on graphene oxide and chitosan |
| CN108969797A (en) * | 2018-07-23 | 2018-12-11 | 武汉理工大学 | A kind of load lipidosome gel and preparation method thereof with electro photoluminescence and the neural scar effect of inhibition |
| CN110106148B (en) * | 2019-05-16 | 2020-10-13 | 中国人民解放军军事科学院军事医学研究院 | Tissue engineering nerve tissue and construction method thereof |
| CN111028983B (en) * | 2019-12-16 | 2021-07-30 | 天新福（北京）医疗器材股份有限公司 | Conductive composite material and preparation method and application thereof |
| CN111359019A (en) * | 2020-03-16 | 2020-07-03 | 四川大学 | Preparation method of graphene and chitosan composite conductive nerve scaffold with longitudinal pore channels |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810671A (en) * | 2011-06-03 | 2012-12-05 | 株式会社半导体能源研究所 | Single-layer and multi-layer graphene and manufacture method thereof, object or electrical equipment having single-layer and multi-layer graphene |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
| CN105218871A (en) * | 2015-08-26 | 2016-01-06 | 苏州卓伟企业管理咨询有限公司 | A kind of preparation method of reduced graphene/Chitosan Composites |
-
2016
- 2016-01-26 CN CN201610051206.6A patent/CN105688285B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102810671A (en) * | 2011-06-03 | 2012-12-05 | 株式会社半导体能源研究所 | Single-layer and multi-layer graphene and manufacture method thereof, object or electrical equipment having single-layer and multi-layer graphene |
| CN102850576A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nanometer composite scaffolds assembled by adopting chitosan scaffold, preparation method and applications thereof |
| CN105218871A (en) * | 2015-08-26 | 2016-01-06 | 苏州卓伟企业管理咨询有限公司 | A kind of preparation method of reduced graphene/Chitosan Composites |
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