CN105688285A - Method for preparing chitosan three-dimensional scaffold coated by graphene material - Google Patents

Method for preparing chitosan three-dimensional scaffold coated by graphene material Download PDF

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CN105688285A
CN105688285A CN201610051206.6A CN201610051206A CN105688285A CN 105688285 A CN105688285 A CN 105688285A CN 201610051206 A CN201610051206 A CN 201610051206A CN 105688285 A CN105688285 A CN 105688285A
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chitosan
graphene oxide
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material coating
grapheme material
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CN105688285B (en
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王欣
文少林
王赞
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Jilin University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/20Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/303Carbon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials

Abstract

The invention provides a method for preparing a chitosan three-dimensional scaffold having graphene oxide coatings of different reducing degrees. The method specifically comprises the following steps: preparing a chitosan scaffold material having a porous structure by a freeze drying method; then soaking the chitosan scaffold material in graphene oxide dispersion fluids of different concentrations; adsorbing graphene oxide sheets to pore walls of chitosan through the electrostatic interaction and the hydrogen-bond interaction; drying, and finally carrying out gradient heating and reducing to obtain the chitosan scaffold which has greatly improved mechanical strength and has graphene oxide coatings of different reducing degrees. The chitosan scaffold has a good application prospect in the aspect of neural tissue engineering. The method provided by the invention is simple to operate and can be used for preparing a great amount of desired product.

Description

A kind of preparation method of grapheme material coating chitosan three-dimensional support
Technical field:
A kind of method that the present invention relates to Graphene coating chitosan stent prepared and there is different reducing degree, the present invention utilizes electrostatic between graphene oxide sheet self assembly principle and oxygen-containing functional group and chitosan stent material and hydrogen bond action, achieve graphene oxide coating on chitosan stent, finally given the composite material bracket of redox graphene and the chitosan with organizational project application prospect by thermal reduction method。
Background technology:
Life and reengineer, including the mankind future realize handling nervous system, the ability of biological cell and organizer official rank is considered as one of subject involved by science and the 6th scientific and technological revolution of industrial quarters。Wherein regeneration techniques is as the important technology of fourth industrial revolution, becomes the advanced layout in various countries, seizes strategic high ground, thus winning initiative, grasping the target that core patent is fallen over each other to chase。
The concept of " organizational project " the earliest by National Science Foundation in formal definition in 1987, be the principle of application cell biology, biomaterial and engineering, research and development are for repairing a science of human body lesion。Its research field has related to materialogy, engineering and life sciences。In recent years, the research and development of tissue engineering material are always up the focus of attention of researchers, and as biomaterial, they must are fulfilled for these conditions following:
(1) good biocompatibility: avirulence, do not cause inflammation reaction, meanwhile, to be also conducive to seed cell to adhere to, propagation and differentiation;
(2) there is three-dimensional porous structure and higher specific surface area, roomy surface area and space and the ability of nutrient substance and gas exchange can be provided for cell;
(3) suitable mechanical strength;
(4) Modulatory character of surface microenvironment;
(5) easily sterilize;
(6) excellent biodegradability。
And the material of one-component tends not to meet all conditions above, so urgently research and development can meet the biomaterial of above-mentioned condition。
Graphene, as a kind of novel nano-material, has potential using value extremely widely at biomedical sector, such as: biosensor, bio-imaging, photo-thermal physical therapy, medicament transport, organizational project aspect etc.。It has the extremely mechanics of excellence, electric property and biocompatibility, and unique physicochemical properties can provide the extracellular matrix condition of Growth of Cells, and this is its very big advantage as tissue engineering bracket material。At present, grapheme material (intrinsic Graphene, few layer graphene film, graphene oxide etc.) research in organizational project is concentrated mainly on two-dimensional film, graphene nanometer sheet is as performance enhancement additive and adopts chemical vapour deposition technique to prepare Graphene three-dimensional foam etc.。Using graphene film as surface modifying material, prepare very few based on the research of the complex three-dimensional stent material of Graphene coating。
Chitosan is as a kind of Natural polycations biological polyoses, it is present in a large number in nature, there is good biocompatibility and biodegradability, still in the ascendant about its research in organizational project, but face two subject matters as having bioactive support: and (1) relatively low mechanical property is often difficult to the growth of carrying tissue and organ;(2) not easily it is modified, faces the challenge in cell controllable growth。
At present, researcher has been had to achieve phosphors coating lime stone on chitosan stent, collagen scaffold is coated with graphene oxide, they all have good biocompatibility, also scientist is had to prepare the chitosan stent adding stannic oxide/graphene nano sheet, not only mechanical strength is improved, and has good biocompatibility。But there is presently no in conjunction with simple and easy to do infusion process, chemical oxidization method, low temperature step heat reduction method, traditional polymer chitosan three-dimensional support realizes the report with the coating of different reducing degree graphene film。This research has great importance for improving the biological activity of chitosan three-dimensional support, mechanical property and electric property。
Summary of the invention:
The invention provides a kind of using chitosan stent as matrix, graphene oxide realizes self assembly on matrix, forms coating, again through the way of thermal reduction, finally gives the Graphene coating Chitosan Composite Scaffold Materials with different reducing degree。The present invention is simple to operate, it is possible to realize large-scale production。
The present invention specifically comprises the following steps that
A kind of preparation method of grapheme material coating chitosan three-dimensional support, step is as follows:
1) being dissolved in aqueous acetic acid by Chitosan powder, preparation has certain density chitosan solution;
2) by step 1) in chitosan solution inject in 24 orifice plate moulds, freeze forming, then dry with vacuum freeze drier, it is thus achieved that there is the chitosan stent of loose structure;
3) by step 2) in porous support be immersed in aqueous slkali, neutralize remaining acetic acid, then clean to neutral with deionized water;In this lyophilization;
4) utilize the Hummers method of improvement to prepare graphene oxide, it is mixed with ethanol, supersound process, obtain the graphene oxide dispersion with variable concentrations;
5) step 3) chitosan stent that obtains immerses step 4) in the graphene oxide dispersion that obtains, finally dry in atmosphere, obtain compound rest;
6) step 5) medium-height trestle carries out staged heating in vacuum environment, obtains the chitosan stent with the graphite oxide ene coatings of different reducing degree。
Step 1) described in chitosan solution concentration be 1~4%。
Step 1) in used by state aqueous acetic acid concentration be 2% (v/v)。
Step 2) in 24 orifice plate mold materials used be polystyrene;Described cryogenic temperature is-20 DEG C, and lyophilization temperature is-60 DEG C。
Step 3) in alkali used be sodium hydroxide solution, concentration is 0.5mg/ml。
Step 4) in graphite powder used be the 325 order natural graphite scales that Alpha Co., Ltd produces;Sonification power is 350w, and ultrasonic time is 1h, and graphene oxide concentration is 0~1mg/ml。
Step 6) in heating-up temperature be 60,120,150 DEG C respectively, each temperature section retention time is 12 hours。
It is a feature of the present invention that, solve chitosan stent coagulation problem in graphene oxide aqueous dispersions, the porosity of prepared sample substantially remains in 92%, product is observed by scanning electron microscope (SEM), find that support aperture is comparatively uniform, hole ordered orientation degree is high, illustrates that ladder heats prepared coating to chitosan multi-porous structure substantially without impact。The compound rest of graphene oxide coating, hole wall has fold to occur, illustrates to define Graphene coating on hole wall。X-ray diffraction (XRD) and FTIR technique (FTIR) test result also indicate that, within the scope of 150 DEG C, heating is little on phase structure and functional group's impact of chitosan。X-ray photoelectron power spectrum (XPS) illustrates, under different reduction temperatures, obtains the graphite oxide ene coatings with different reducing degree。And, the compressive strength of compound rest is greatly improved。
Accompanying drawing illustrates:
Fig. 1 be in embodiment chitosan stent and chitosan/oxidized Graphene compound rest heat at different temperatures after optical photograph, support is diameter 1.3cm, the cylinder of height 9mm, order from left to right is: CS-60 DEG C, CS-120 DEG C, CS-150 DEG C, (through chitosan/Graphene compound rest that the graphene oxide dispersion that concentration is 1mg/ml is soaked) CS-GO-60 DEG C, CS-GO-120 DEG C, CS-GO-150 DEG C。
Fig. 2 is the porosity test result in case study on implementation。
Fig. 3 is in case study on implementation, and coating graphene oxide membrane (GO) on the glass sheet heats the X-ray diffraction analysis figure of afterproduct at different temperatures。
Fig. 4 is in case study on implementation, chitosan stent and be that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the X-ray diffraction analysis figure of afterproduct at different temperatures through concentration。
Fig. 5 is in case study on implementation, coating graphene oxide membrane (GO) on the glass sheet, chitosan (CS) support and through concentration be the FTIR technique figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats afterproduct at different temperatures。
Fig. 6 is in case study on implementation, and chitosan (CS) support heats the xps energy spectrum figure of the C1s core level of afterproduct at 150 DEG C。
Fig. 7 is in case study on implementation, and chitosan (CS) support heats the xps energy spectrum figure of the N1s core level of afterproduct at 150 DEG C。
Fig. 8 is in case study on implementation, and graphene oxide membrane (GO) heats the xps energy spectrum figure of the C1s core level of afterproduct at 60 DEG C。
Fig. 9 is in case study on implementation, and graphene oxide membrane (GO) heats the xps energy spectrum figure of the C1s core level of afterproduct at 120 DEG C。
Figure 10 is in case study on implementation, and graphene oxide membrane (GO) heats the xps energy spectrum figure of the C1s core level of afterproduct at 150 DEG C。
Figure 11 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the C1s core level of afterproduct at 60 DEG C through concentration。
Figure 12 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the N1s core level of afterproduct at 60 DEG C through concentration。
Figure 13 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the C1s core level of afterproduct at 120 DEG C through concentration。
Figure 14 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the N1s core level of afterproduct at 120 DEG C through concentration。
Figure 15 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the C1s core level of afterproduct at 150 DEG C through concentration。
Figure 16 is in case study on implementation, is the xps energy spectrum figure that chitosan/oxidized Graphene (CS/GO) compound rest that 1mg/ml graphene oxide dispersion is soaked heats the N1s core level of afterproduct at 150 DEG C through concentration。
Figure 17 is in case study on implementation, and chitosan stent heats 70 times of scanning electron microscope (SEM) images of afterproduct at 60 DEG C, and in figure it can be seen that aperture is comparatively uniform, and the degree of order is high。
Figure 18 is in case study on implementation, and chitosan stent heats 1000 times of scanning electron microscope (SEM) images of afterproduct at 60 DEG C, hole wall does not find fold exists。
Figure 19 is in case study on implementation, it is 1000 times of scanning electron microscope (SEM) images that the compound rest that 0.02mg/ml graphene oxide dispersion is soaked heats afterproduct at 60 DEG C through concentration, it can be seen that hole wall occurs fold spline structure (as shown by arrows)。
Figure 20 is in case study on implementation, is 1000 times of scanning electron microscope (SEM) images that the compound rest that 1mg/ml graphene oxide dispersion is soaked heats afterproduct at 60 DEG C through concentration, it has been found that occur obvious fold (as shown by arrows) on hole wall。
Figure 21 is in case study on implementation, is 1000 times of scanning electron microscope (SEM) images that the compound rest that 1mg/ml graphene oxide dispersion is soaked heats afterproduct at 150 DEG C through concentration, and on hole wall, fold becomes apparent from。
Figure 22 is in case study on implementation, is 15000 times of scanning electron microscope (SEM) images that the compound rest that 1mg/ml graphene oxide dispersion is soaked heats afterproduct at 150 DEG C through concentration, and surface layer is redox graphene film。
Figure 23 is the compressive strength test comparison table in case study on implementation。
Detailed description of the invention
Particular content and the embodiment thereof of the present invention is further illustrated below in conjunction with example。
Embodiment:
Preparation has the Graphene coating of different reducing degree and the composite of chitosan three-dimensional support, and specific experiment condition is as follows:
1) Chitosan powder is dissolved in the glacial acetic acid solution that volumetric concentration is 2%, stirs 2h, be made into the chitosan solution that concentration is 4% (w/v), supersound process 1h, stand, remove bubble。
2) chitosan solution in step (1) is injected in mould, 4 DEG C of environment stand 12h, be then transferred in the environment of-20 DEG C freezing processing 24h, place into lyophilization 48h in freezer dryer。
3) porous support in step (2) is immersed in 0.5% sodium hydroxide solution, neutralizes remaining acetic acid, then soak with deionized water, clean to neutral;Lyophilization again。
4) the Hummers method of improvement is utilized to prepare graphite oxide:
1. 1.5g sodium nitrate is dissolved in 69ml concentrated sulphuric acid, adds 2g graphite, stir。
2. put in ice-water bath, be slowly added to potassium permanganate 9g。
3. ice-water bath keeps 12 hours。
4. it is warming up to 40 degrees Celsius, keeps 1 hour。
5. it is warming up to 60 degrees Celsius, keeps 18h。
6. it is cooled to room temperature, adds 200ml frozen water。
7. dripping hydrogen peroxide, produce to bubble-free, solution becomes glassy yellow。
8. hydrochloric acid eccentric cleaning is used, then by deionized water eccentric cleaning to supernatant close to neutral。
The graphite oxide stock solution obtained is mixed with dehydrated alcohol, 350w supersound process 1h, configuration concentration respectively 0,0.02,0.1,1mg/ml graphene oxide dispersion。
5) chitosan stent step (3) obtained immerses in the graphene oxide dispersion that step (4) obtains, and keeps 48h, with washes of absolute alcohol for several times, finally dries in atmosphere, obtain compound rest;
6) step (5) medium-height trestle is carried out staged heating in vacuum environment: 12h at 60 DEG C, 12h at 120 DEG C, 12h at 150 DEG C, obtain the chitosan stent with the graphite oxide ene coatings of different reducing degree。
7) compound rest being carried out XRD test, porosity is tested, and FTIR tests, and SEM tests, and XPS tests, and compressive strength is tested。
According to the method that foregoing invention is lifted, it is possible to preparing the chitosan three-dimensional support of grapheme material coating, its feature is as follows:
1) it can be seen that the pure chitosan support of graphene oxide dispersion immersion on macroscopic view optics picture, along with the rising of temperature, chitosan surface color turns yellow;After being coated with graphene oxide, chitosan surface color overstrike, along with the rising of heating-up temperature, gradually become black。
2) adopt ethanol substitution method that made sample is carried out analysis of porosity, it is shown that all supports (before and after coating) porosity is held at about 92%。Along with the increase of the graphene oxide concentration used, porosity presents the trend slightly reduced。
3) X-ray diffraction analysis shows, all supports all have the typical diffractive peak of chitosan: 2 θ=14.9 ° and 2 θ=20.4 °, illustrates that the chitosan that graphene oxide is coated with heats through ladder, and the phase structure of chitosan is substantially free of and changes;Compared to base case polysaccharide, graphene oxide content is little, thus fails to (reduction) the graphene oxide diffraction maximum substantially observing in compound rest。Other condition is identical, coating graphite oxide ene coatings on the glass sheet, raising along with heating-up temperature, it can be seen that, when diffracted primary peak is by 60 DEG C 12.04 ° move to 13.65 ° (being warming up to 120 DEG C) and 23.52 ° (heating-up temperatures of 150 DEG C), illustrate that graphene oxide is being reduced gradually。
4) made sample is carried out FTIR technique analysis, it has been found that all supports all present chitosan typical absorption peak: 1085cm-1Place is the feature C-O stretching vibration absworption peak of saccharide, 1583cm-1Place is amide I peak band, 1384cm-1Place is amide II peak band, 2861cm-1Place is the C-H stretching vibration peak of chitosan alkyl, 3458cm-1Place is-OH stretching vibration peak。Not finding obvious graphene oxide absworption peak, this is that absworption peak relative intensity is low owing to graphene oxide content is considerably less relative to chitosan。Coating graphene oxide membrane on the glass sheet then presents the characteristic absorption peak of graphene oxide: 1035,1225,1627,1739cm-1Correspond respectively to the C-O absworption peak of epoxy radicals, C-OH absworption peak, the C-O absworption peak of C=C absworption peak and COOH, 3455cm-1Then corresponding O-H absworption peak。Along with heating-up temperature raises, absorption peak strength corresponding to graphene oxide membrane is all declining, and also illustrates that graphene oxide is being reduced gradually。
5) in order to further determine that composition and bonding state, the sample of preparation has been carried out X-ray photoelectron spectroscopic analysis by us。It is shown that chitosan stent is respectively through after 60 DEG C, 120 DEG C, 150 DEG C treatment of different temperature, C1s and N1s combines energy peak position and peak shape is substantially free of and changes, and illustrates that low-temperature heat does not change structure and the composition of chitosan。Wherein in the xps energy spectrum of C element, 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。To after the XPS spectrum figure deconvolution processing of the sample C1s after graphene oxide colloid heat reduction it is shown 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。Contrast and can be seen that through the C1s of the sample of 60 DEG C, 120 DEG C, 150 DEG C heat reductions process, higher than 120 DEG C of heat treated, epoxy-functional on graphene film there occurs decomposition deoxidation effect, can effectively remove the oxygen content in sample higher than 150 DEG C of thermal reductions, obtain the Graphene coating with different reducing degree。It is consistent that XPS analysis result analyzes result with FTIR。The XPS spectrum figure of the C1s of the chitosan sample of graphene coated layer can obtain 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)。The existing carbon core level power spectrum come from Graphene of C1s from the XPS spectrum figure of C1s it can be seen that in sample, has again the contribution result of C element in chitosan, it can be said that Graphene has effectively been coated in chitosan stent surface。The chemical environment of the N element in the graphene coated chitosan sample obtained under 60 DEG C of reduction temperatures is pyridine nitrogen and graphite nitrogen, N core level in the sample of 120 DEG C of reduction is 399.2eV (pyridine nitrogen) and 400.5eV (graphite nitrogen, graphitic-N1Or pyrroles's nitrogen, N-H), the XPS spectrum figure of the N1s testing to obtain after 150 DEG C of reduction is corresponding to pyridine nitrogen (399.4eV)。
6) surface topography of sample prepared by scanning electron electronic microscope photos is adopted。It can be seen that support aperture is all comparatively uniform, aperture size is between 150-300 μm, and hole ordered orientation degree is high, in column, illustrates that the loose structure of chitosan is affected little by Graphene coating and hyperthermic treatment。The compound rest of graphene oxide coating, hole wall has fold to occur, illustrates to define graphite oxide ene coatings on hole wall, and along with the rising of heating-up temperature, fold degree increases, and this is owing to graphite oxide ene coatings is reduced the reason defining typical redox graphene film gradually。
7) prepared sample being compressed strength test, compression factor is 25%。It can be seen that along with the increase of the soaked GO dispersion liquid concentration of chitosan stent, the rising of heating-up temperature, the compressive strength of support is being gradually increased。The compressive strength heating afterproduct through the compound rest that concentration is the immersion of 1mg/ml graphene oxide dispersion at 150 DEG C is 1.7 times that heat afterproduct at 60 DEG C of pure chitosan support。This illustrates, graphite oxide ene coatings can largely improve the mechanical property of chitosan stent。

Claims (7)

1. a preparation method for grapheme material coating chitosan three-dimensional support, step is as follows:
1) being dissolved in aqueous acetic acid by Chitosan powder, preparation has certain density chitosan solution;
2) by step 1) in chitosan solution inject in 24 orifice plate moulds, freeze forming, then dry with vacuum freeze drier, it is thus achieved that there is the chitosan stent of loose structure;
3) by step 2) in porous support be immersed in aqueous slkali, neutralize remaining acetic acid, then clean to neutral with deionized water, lyophilization again;
4) utilize the Hummers method of improvement to prepare graphene oxide, it is mixed with dehydrated alcohol, supersound process, obtain the graphene oxide dispersion with variable concentrations;
5) step 3) chitosan stent that obtains immerses step 4) in the graphene oxide dispersion that obtains, finally dry in atmosphere, obtain compound rest;
6) step 5) medium-height trestle carries out staged heating in vacuum environment, obtains the chitosan stent with the graphite oxide ene coatings of different reducing degree。
2. according to claim 1 a kind of grapheme material coating chitosan three-dimensional support preparation method, it is characterised in that step 1) described in chitosan solution concentration be 1~4% (w/v)。
3. the preparation method of a kind of grapheme material coating chitosan three-dimensional support according to claim 1, it is characterised in that step 1) in used by state aqueous acetic acid concentration be 2% (v/v)。
4. the preparation method of a kind of grapheme material coating chitosan three-dimensional support according to claims 1, it is characterised in that step 2) in 24 orifice plate mold materials used be polystyrene;Described cryogenic temperature is-20 DEG C, and lyophilization temperature is-60 DEG C。
5. according to claims 1 a kind of grapheme material coating chitosan three-dimensional support preparation method, it is characterised in that step 3) used by alkali be NaOH, alkali concn is 0.5mg/ml。
6. according to claims 1 a kind of grapheme material coating chitosan three-dimensional support preparation method, it is characterised in that step 4) used by graphite powder be Alpha Co., Ltd produce 325 order natural graphite scales;Sonification power is 350w, and ultrasonic time is 1h;Graphene oxide concentration is 0~1mg/ml。
7. the preparation method of a kind of grapheme material coating chitosan three-dimensional support according to claims 1, it is characterised in that in step (6), heating-up temperature is 60,120,150 DEG C respectively, and each temperature section time is 12 hours。
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106215234A (en) * 2016-07-27 2016-12-14 西南科技大学 The preparation method of graphene oxide Chitosan Composites
CN106581768A (en) * 2016-11-30 2017-04-26 大连理工大学 Preparing method of scaffold for tissue engineering used for myocardium repair
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
CN110106148A (en) * 2019-05-16 2019-08-09 中国人民解放军军事科学院军事医学研究院 A kind of tissue-engineered neural tissues and its construction method
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
CN111028983A (en) * 2019-12-16 2020-04-17 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)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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
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