CN110624509A - Preparation method of porous composite material based on graphene oxide and chitosan - Google Patents
Preparation method of porous composite material based on graphene oxide and chitosan Download PDFInfo
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- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
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- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
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- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0036—Porous materials, e.g. foams or sponges
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- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
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- A—HUMAN NECESSITIES
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- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/08—Polysaccharides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/23—Carbohydrates
- A61L2300/236—Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The invention provides a preparation method of a porous composite material based on graphene oxide and chitosan, which comprises the following steps: (1) uniformly mixing the graphene oxide aqueous solution and a chitosan aqueous solution containing glacial acetic acid to obtain a mixed solution; (2) and immediately pre-freezing the mixed solution, and then carrying out vacuum freeze drying on the mixed solution to obtain the porous composite material of the graphene oxide and the chitosan. The composite material provided by the invention has higher porosity, and the increase of the porosity of the composite material leads the adsorption performance of chitosan to be improved, thereby enhancing the application effect of the composite material in biomedicine aspects such as hemostatic sponge and the like; in addition, the composite material provided by the invention also has excellent mechanical properties and mechanical properties.
Description
Technical Field
The invention relates to a preparation method of a porous composite material based on graphene oxide and chitosan, belonging to the technical field of composite materials and preparation thereof.
Background
Chitosan, which is a product of chitin after partial deacetylation, is a natural polymer widely present in the wings or shells of arthropods, cell walls of fungi and algae, and organic acids, antibiotics and brewing byproducts of enzymes, is the most abundant natural organic product on earth after cellulose, is the only natural basic polysaccharide in nature, and is one of the few natural products with positive charges.
After the effect of chitin on human trauma was first reported by Muzzarelli in 1977, the hemostatic effect of chitin and chitosan became one of the research hotspots for the activity development. Okamoto et al demonstrated that chitosan significantly shortened blood clotting time and that this effect was dose-dependent. The Janvikul et al study showed that chitosan significantly reduced whole blood clotting time. The chitosan sponge prepared by Gu et al has better hemostatic effect than gelatin sponge and oxidized cellulose in acute and chronic in vivo hemorrhage models of heparinized rats. The Yang et al found that the effect of chitosan acetic acid solution on the aggregation and deformation of erythrocytes is more remarkable due to the reduction of the Degree of Deacetylation (DD), but the molecular weight (Mw) is not significantly affected in the range of 105-106, while the chitosan solid cannot aggregate and deform erythrocytes. However, Wu et al found that solid chitosan with low DD had a stronger hemostatic ability because it absorbed more platelets. The hemostasis mechanism is that positive charge molecules in the chitosan are combined with visible components such as red blood cells, white blood cells and platelets with negative charges in blood to form a cell embolus or a blood coagulation embolus to generate blood coagulation, and meanwhile, glycosaminoglycan such as hyaluronic acid can be promoted to secrete, so that the wound healing is accelerated, and the mechanical properties of materials can be improved. Animal experiments and clinical application show that the hemostatic sponge and hemostatic powder prepared from chitosan have good hemostatic effect. However, for the wound surface with extensive bleeding, the hemostatic effect of chitosan is limited, so the method of compounding other hemostatic agents is often adopted to make up for the limitation of chitosan hemostasis. Yi gang et al prepared chitosan powder through formulation modification and structure change, and added with calcium and zinc preparations to develop a novel chitosan styptic powder, and experiments prove that the novel chitosan styptic powder has good application effect in a rat liver lobe excision hemorrhage model. Bin and the like are used for large-area bleeding wound surfaces of rat livers by preparing a chitosan/sodium alginate-Yunnan white drug powder composite film, and as a result, the composite film has the advantages of rapid hemostasis, good adhesion with the wound surfaces and the like. Through further research and improvement, the chitosan/sodium alginate-Yunnan white drug powder composite film can be used as a future medical hemostatic material for large wound surfaces in vivo, and is expected to be widely applied to surgical operations. The special feature of the hemostatic activity of the chitosan makes the chitosan have great development value. However, the research on the chitosan hemostatic material is still in the initial stage, and the problems of limited hemostatic effect, non-ideal hemostatic effect on the extensive bleeding wound surface, high price and the like are not yet solved, so that the further wide use of the chitosan hemostatic material is limited. Therefore, the research on chitosan hemostatic materials, especially composite chitosan hemostatic sponges, is a focus of attention. In summary, the development of novel and efficient hemostatic materials is a research hotspot in the scientific research community and even the industrial community of all countries at present, and has important social significance and economic benefit.
Therefore, the chitosan has excellent performances of biocompatibility and blood compatibility, safety, microbial degradability and the like, and can be applied to aspects of biomedicine and the like. The graphene oxide has a large number of hydroxyl groups, carboxyl groups and epoxy groups, and the functional groups provide reaction sites for chemical modification and functionalization of the graphene oxide. By preparing the composite material of the chitosan and the graphene oxide, the functionalized chitosan with certain mechanical strength can be obtained, so the composite material of the graphene oxide and the chitosan is concerned. The existing graphene oxide and chitosan are mostly prepared into composite materials by adopting a method of drying a mixed solution by heating. In addition, the traditional graphene oxide material with a planar structure limits the working area of chitosan to some extent, and the mechanical properties of the obtained composite material are still to be improved.
Therefore, providing a novel preparation method of a porous composite material based on graphene oxide and chitosan has become a technical problem to be solved urgently in the field.
Disclosure of Invention
In order to solve the above disadvantages and shortcomings, the present invention aims to provide a method for preparing a porous composite material based on graphene oxide and chitosan.
The invention also aims to provide the porous composite material based on graphene oxide and chitosan, which is prepared by the preparation method of the porous composite material based on graphene oxide and chitosan.
The invention also aims to provide a hemostatic material prepared from the porous composite material based on graphene oxide and chitosan.
The invention also aims to provide application of the porous composite material based on the graphene oxide and the chitosan in preparation of hemostatic materials and drug release.
In order to achieve the above object, in one aspect, the present invention provides a preparation method of a porous composite material based on graphene oxide and chitosan, wherein the preparation method comprises the following steps:
(1) uniformly mixing the graphene oxide aqueous solution and a chitosan aqueous solution containing glacial acetic acid to obtain a mixed solution;
(2) and immediately pre-freezing the mixed solution, and then carrying out vacuum freeze drying on the mixed solution to obtain the porous composite material of the graphene oxide and the chitosan.
According to the preparation method, the graphene oxide is a substance which is conventional in the field and can be prepared by a Hummers method existing in the field.
According to the preparation method of the present invention, preferably, the concentration of the graphene oxide aqueous solution is 1-10mg/mL (calculated based on the total volume of the graphene oxide aqueous solution).
According to the preparation method, the adding sequence of the graphene oxide aqueous solution and the glacial acetic acid-containing chitosan aqueous solution in the step (1) is not particularly required.
According to the preparation method of the present invention, preferably, the concentration of chitosan in the aqueous solution of chitosan containing glacial acetic acid is 1-20mg/mL (calculated based on the total volume of the aqueous solution of chitosan containing glacial acetic acid);
also preferably, the volume concentration of the glacial acetic acid in the chitosan aqueous solution containing glacial acetic acid is 1-2% (calculated by taking the total volume of the chitosan aqueous solution containing glacial acetic acid as a reference).
According to the preparation method provided by the invention, preferably, the mass ratio of the chitosan to the graphene oxide is 20-100: 1.
According to the preparation method provided by the invention, in the step (2), the graphene oxide aqueous solution and the glacial acetic acid-containing chitosan aqueous solution are directly mixed to obtain the mixed solution, the mixed solution is pre-frozen, so that the uniform state of the mixed solution can be maintained, and then the pre-frozen sample is subjected to vacuum freeze drying. The method for preparing the porous composite material based on the graphene oxide and the chitosan by directly freezing and drying the mixed solution in vacuum is convenient, and the composite material with higher porosity can be obtained.
According to the preparation method of the present invention, preferably, the pre-freezing is to freeze and crystallize the mixed solution to a solid state;
more preferably, the pre-freezing temperature is less than or equal to-15 ℃, and the pre-freezing time is more than or equal to 5 hours.
According to the preparation method of the invention, the temperature of the vacuum freeze drying is preferably-70 to-90 ℃ and the time is 10 to 15 hours.
On the other hand, the invention also provides the porous composite material based on the graphene oxide and the chitosan, which is prepared by the preparation method of the porous composite material based on the graphene oxide and the chitosan.
According to the composite material, the porosity of the composite material is more than or equal to 93%, the water absorption rate reaches 50-70 times, and the 25% indentation hardness of the composite material with the specification of 20mm multiplied by 20mm reaches 10-15N.
In another aspect, the invention also provides a hemostatic material prepared from the porous composite material based on graphene oxide and chitosan.
The hemostatic material according to the present invention is preferably a hemostatic sponge.
On the other hand, the invention also provides application of the porous composite material based on the graphene oxide and the chitosan in preparation of hemostatic materials and drug release.
The preparation method of the porous composite material based on graphene oxide and chitosan provided by the invention has the advantages of less chitosan amount, low cost and suitability for large-scale production.
The porous composite material based on the graphene oxide and the chitosan provided by the invention has higher porosity, and the increase of the porosity of the composite material leads the adsorption performance of the chitosan to be improved, thereby enhancing the application effect of the composite material in biomedicine aspects such as hemostatic sponge and the like; in addition, the composite material provided by the invention also has excellent mechanical properties and mechanical properties.
Drawings
Fig. 1 is a process flow diagram of a preparation method of a porous composite material based on graphene oxide and chitosan provided in an embodiment of the present invention;
fig. 2 is a scanning electron microscope image of the porous composite material based on graphene oxide and chitosan obtained in example 2 of the present invention;
FIG. 3 is a pressure strain curve diagram of the porous composite material based on graphene oxide and chitosan obtained in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the graphene oxide and chitosan composite film obtained in the comparative example of the present invention.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
The embodiment provides a preparation method of a porous composite material based on graphene oxide and chitosan, wherein a process flow diagram of the preparation method is shown in fig. 1, and the preparation method comprises the following steps:
adding 100 mu L of glacial acetic acid into 4mL of deionized water, weighing 50mg of chitosan powder, adding the chitosan powder, uniformly stirring until the chitosan powder is dissolved, finally adding a small amount of deionized water, and fixing the volume to 5mL to prepare a chitosan aqueous solution;
taking 0.1mL of graphene oxide aqueous solution with the concentration of 5mg/mL, mixing and stirring the graphene oxide aqueous solution with the obtained chitosan aqueous solution, and carrying out ultrasonic treatment for 2 hours to obtain a mixed solution;
pouring the mixed solution into a mold, immediately putting the mold into a refrigerator for freezing and crystallizing to a solid state, putting the pre-frozen sample (with the temperature of-20 ℃) into a freeze drying device, carrying out vacuum freeze drying for 15h at the temperature of-85 ℃, and taking out the sample to obtain the porous composite material based on the graphene oxide and the chitosan.
Example 2
The embodiment provides a preparation method of a porous composite material based on graphene oxide and chitosan, wherein a process flow diagram of the preparation method is shown in fig. 1, and the preparation method comprises the following steps:
adding 100 mu L of glacial acetic acid into 4mL of deionized water, weighing 50mg of chitosan powder, adding the chitosan powder, uniformly stirring until the chitosan powder is dissolved, finally adding a small amount of deionized water, and fixing the volume to 5mL to prepare a chitosan aqueous solution;
taking 0.2mL of graphene oxide aqueous solution with the concentration of 5mg/mL, mixing and stirring the graphene oxide aqueous solution with the obtained chitosan aqueous solution, and carrying out ultrasonic treatment for 2 hours to obtain a mixed solution;
pouring the mixed solution into a mold, immediately putting the mold into a refrigerator for freezing and crystallizing to a solid state, putting the pre-frozen sample (with the temperature of-20 ℃) into a freeze drying device, carrying out vacuum freeze drying for 15h at the temperature of-85 ℃, and taking out the sample to obtain the porous composite material based on the graphene oxide and the chitosan.
The porous composite material based on graphene oxide and chitosan obtained in the embodiment is analyzed by a scanning electron microscope, the scanning electron microscope image of the porous composite material is shown in fig. 2, and as can be seen from fig. 2, the porous composite material prepared in the embodiment really has very high porosity, which indicates that the porous composite material has good adsorption function, the porous composite material is subjected to a water absorption test, the water absorption rate of the porous composite material is up to 50-70 times (5000% -7000%), the water absorption rate of the porous composite material is obviously higher than that of the existing adsorption material in the field, such as a high-soluble chitosan hemostatic sponge produced by Shanghai Meibao, the water absorption rate of the porous composite material is not less than 200%, and the Xinghai biological hemostatic sponge produced by Hunan Xinghai has the water absorption rate of not; therefore, the porous composite material provided by the invention can be applied to the fields of adsorption and the like.
The porous composite material obtained in the present example is prepared into a sample with the specification of 20mm × 20mm × 20mm, and then the sample is subjected to a pressure strain test (conventional test method in the art), wherein a pressure strain curve diagram of the sample is shown in fig. 3, and it can be seen from fig. 3 that the porous composite material prepared in the present example has a high indentation hardness, wherein the indentation hardness of 25% can reach about 11.8N.
Example 3
The embodiment provides a preparation method of a porous composite material based on graphene oxide and chitosan, wherein a process flow diagram of the preparation method is shown in fig. 1, and the preparation method comprises the following steps:
adding 100 mu L of glacial acetic acid into 4mL of deionized water, weighing 50mg of chitosan powder, adding the chitosan powder, uniformly stirring until the chitosan powder is dissolved, finally adding a small amount of deionized water, and fixing the volume to 5mL to prepare a chitosan aqueous solution;
taking 0.3mL of graphene oxide aqueous solution with the concentration of 5mg/mL, mixing and stirring the graphene oxide aqueous solution with the obtained chitosan aqueous solution, and carrying out ultrasonic treatment for 2 hours to obtain a mixed solution;
pouring the mixed solution into a mold, immediately putting the mold into a refrigerator for freezing and crystallizing to a solid state, putting the pre-frozen sample (with the temperature of-20 ℃) into a freeze drying device, carrying out vacuum freeze drying for 15h at the temperature of-85 ℃, and taking out the sample to obtain the porous composite material based on the graphene oxide and the chitosan.
Comparative example
The preparation method of the graphene oxide and chitosan composite film by adopting the mixed heating solution hot drying method comprises the following steps:
adding 100 mu L of glacial acetic acid into 4mL of deionized water, weighing 50mg of chitosan powder, adding the chitosan powder, uniformly stirring until the chitosan powder is dissolved, finally adding a small amount of deionized water, and fixing the volume to 5mL to prepare a chitosan aqueous solution;
taking 0.2mL of graphene oxide aqueous solution with the concentration of 5mg/mL, mixing and stirring the graphene oxide aqueous solution with the obtained chitosan aqueous solution, and carrying out ultrasonic treatment for 2 hours to obtain a mixed solution;
and pouring the mixed solution into a mold, and drying for 24 hours at 50 ℃ to obtain the graphene oxide and chitosan composite film.
Scanning electron microscope analysis is carried out on the graphene oxide and chitosan composite film obtained in the comparative example, and the scanning electron microscope image is shown in fig. 4. Comparing fig. 2 with fig. 4, it can be seen that the porous composite material based on graphene oxide and chitosan prepared by the direct freeze-drying mixed solution method provided by the present invention has higher porosity and is more advantageous in adsorption.
Claims (10)
1. A preparation method of a porous composite material based on graphene oxide and chitosan is characterized by comprising the following steps:
(1) uniformly mixing the graphene oxide aqueous solution and a chitosan aqueous solution containing glacial acetic acid to obtain a mixed solution;
preferably, the concentration of the graphene oxide aqueous solution is 1-10 mg/mL;
(2) and immediately pre-freezing the mixed solution, and then carrying out vacuum freeze drying on the mixed solution to obtain the porous composite material of the graphene oxide and the chitosan.
2. The method according to claim 1, wherein the concentration of chitosan in the aqueous solution of chitosan containing glacial acetic acid is 1-20 mg/mL;
preferably, the volume concentration of the glacial acetic acid in the chitosan aqueous solution containing the glacial acetic acid is 1-2%.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of chitosan to graphene oxide is 20-100: 1.
4. The method according to claim 1 or 2, wherein the prefreezing is a step of freeze-crystallizing the mixed solution to a solid state;
preferably, the pre-freezing temperature is less than or equal to-15 ℃, and the pre-freezing time is more than or equal to 5 hours.
5. The method of claim 1 or 2, wherein the vacuum freeze-drying is carried out at a temperature of-70 to-90 ℃ for 10 to 15 hours.
6. The porous composite material based on graphene oxide and chitosan prepared by the method for preparing the porous composite material based on graphene oxide and chitosan according to any one of claims 1 to 5.
7. The composite material of claim 6, wherein the porosity of the composite material is 93% or more, the water absorption rate is 50-70 times, and the 25% indentation hardness of the composite material with the specification of 20mm x 20mm is 10-15N.
8. A hemostatic material prepared from the graphene oxide and chitosan-based porous composite material of claim 6 or 7.
9. Hemostatic material according to claim 8, wherein the hemostatic material is a hemostatic sponge.
10. Use of the porous composite material based on graphene oxide and chitosan according to claim 6 or 7 for the preparation of hemostatic materials and for drug release.
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Cited By (4)
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| CN111408345A (en) * | 2020-03-31 | 2020-07-14 | 山东大学 | Nitrogen-doped reduced graphene oxide nanocomposite and preparation method and application thereof |
| CN112321885A (en) * | 2020-09-03 | 2021-02-05 | 方大炭素新材料科技股份有限公司 | Preparation and application of porous material assembled by graphene oxide and chitosan molecules |
| CN112516374A (en) * | 2020-11-30 | 2021-03-19 | 华南理工大学 | Chitosan/Mxene antibacterial composite sponge for hemostasis and preparation method thereof |
| CN114195660A (en) * | 2020-09-02 | 2022-03-18 | 香港城市大学深圳研究院 | Optical chromophore compound and composite material containing same |
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| CN111408345A (en) * | 2020-03-31 | 2020-07-14 | 山东大学 | Nitrogen-doped reduced graphene oxide nanocomposite and preparation method and application thereof |
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| CN114195660B (en) * | 2020-09-02 | 2023-10-31 | 香港城市大学深圳研究院 | Optical chromophore compound and composite material containing same |
| CN112321885A (en) * | 2020-09-03 | 2021-02-05 | 方大炭素新材料科技股份有限公司 | Preparation and application of porous material assembled by graphene oxide and chitosan molecules |
| CN112321885B (en) * | 2020-09-03 | 2022-08-05 | 方大炭素新材料科技股份有限公司 | Preparation and application of porous material assembled by graphene oxide and chitosan molecules |
| CN112516374A (en) * | 2020-11-30 | 2021-03-19 | 华南理工大学 | Chitosan/Mxene antibacterial composite sponge for hemostasis and preparation method thereof |
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