CN107376006B - Preparation method of porous artificial skin receptor - Google Patents
Preparation method of porous artificial skin receptor Download PDFInfo
- Publication number
- CN107376006B CN107376006B CN201710626794.6A CN201710626794A CN107376006B CN 107376006 B CN107376006 B CN 107376006B CN 201710626794 A CN201710626794 A CN 201710626794A CN 107376006 B CN107376006 B CN 107376006B
- Authority
- CN
- China
- Prior art keywords
- polyester
- graphene
- solution
- artificial skin
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
-
- 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
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- 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
-
- 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
-
- 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
- A61L27/60—Materials for use in artificial skin
Abstract
The invention relates to the field of receptors, and discloses a preparation method of a porous artificial skin receptor, which comprises the following steps: (1) acidifying graphene; (2) preparing a solution; (3) dissolving polyester in concentrated sulfuric acid; (4) preparing n-hexane, deionized water, fatty alcohol-polyoxyethylene ether and PEG-400 into an inverse emulsion system; (5) adding the polyester solution into the emulsion, standing, taking the lower layer suspension, and neutralizing; (6) preparing micron-sized polyester microspheres; (7) mixing the polyester microsphere solution with graphene, coating and drying; (8) treating the graphene-polyester composite film, and then soaking the graphene-polyester composite film in a solvent to dissolve polyester; (9) the composite membrane is subjected to ammonia gas reduction; (10) and (5) silvering to obtain the porous artificial skin receptor. The porous artificial skin receptor prepared by the invention has porosity and good air permeability; meanwhile, the conductive material has excellent conductivity, electrochemical sensitivity, toughness, strength and tensile property.
Description
Technical Field
The invention relates to the field of receptors, in particular to a preparation method of a porous artificial skin receptor.
Technical Field
The artificial skin is a dressing for treating skin wound, and is mainly prepared from biological materials or synthetic materials with good biocompatibility. Artificial skin has a good effect on scalds, burns and skin damages in the medical field and can even be used as a substitute for natural skin in some cases. The artificial skin which is successfully developed and applied at present mainly plays a certain role in protecting subcutaneous tissues, provides a composite material bracket for promoting the growth of epidermal cells of a wound surface, or has some slow-release medicinal factors capable of promoting the growth of skin. Such artificial skin has good biocompatibility, physical and mechanical properties and medical properties, but is complicated to produce, high in cost and does not have the tactile sensation and signal transmission functions of natural skin.
The artificial skin receptor is a film-shaped composite material which is added with an external stimulation perception function and an electric signal transmission function on the basis of the original artificial skin. The sensors have certain sensing functions on the change and stimulation of the external environment, for example, the temperature sensors can sense the change of the skin temperature, and the touch sensors can sense the deformation of the skin under the action of external force. Graphene is often used for synthesizing artificial skin because of good electrochemical sensitivity, but the general problem of the artificial skin receptors prepared by graphene at present is that the physical and mechanical properties and air permeability do not meet the use requirements.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a porous artificial skin receptor. According to the invention, a film is prepared by using graphene with good biocompatibility, and the polyester is removed by adding the polyester microspheres and dissolving after molding, so that the porous graphene film is obtained. The porous graphene film has excellent air permeability, and the porous structure is convenient for loading other effective substances in the post-processing process. The graphene has excellent conductivity and electrochemical sensitivity, particularly after being plated with silver, the resistance can be changed under the action of external force, and the graphene has excellent strength and tensile property within a certain range. And the method of post-processing after film forming avoids the agglomeration of single-layer graphene, effectively improves the toughness and overcomes the common problems of the traditional graphene film sensors.
The specific technical scheme of the invention is as follows: a method for preparing a porous artificial skin receptor comprises the following steps:
(1) grinding and crushing graphene, adding the graphene into a nitric acid solution, boiling for 20-60 minutes, and centrifuging and washing.
(2) And (3) drying and weighing part of the centrifuged graphene to determine the concentration, and then adding deionized water into the rest graphene according to the determined concentration to prepare a solution.
In the step (2), the graphene cannot be dried, but the concentration of a graphene sample is obtained by sampling and measuring, and then a solution with a certain concentration is prepared. Therefore, the agglomeration of graphene can be reduced, and the transparency of the finished product is improved.
(3) And 2-5g of polyester granules are dissolved in 90-110mL of concentrated sulfuric acid, and the mixture is kept stand in a dark place until the polyester is completely dissolved.
(4) 150-250mL of normal hexane, 100-200mL of deionized water, 5-10mL of fatty alcohol-polyoxyethylene ether and 2-4mL of PEG-400 are added into a three-neck flask and rapidly stirred to prepare an inverse emulsion system.
(5) And (3) dripping the prepared polyester solution into the emulsion under the stirring condition, stopping stirring after the prepared polyester solution is completely added, standing, taking the lower-layer suspension, and adding sodium hydroxide for neutralization.
(6) And adding deionized water into the neutralized suspension, centrifuging and washing for 3-5 times until no sulfate ions exist in the supernatant, adding water into the lower-layer precipitate, and freeze-drying to obtain the micron-sized polyester microspheres.
The precipitate is freeze-dried after adding a certain amount of water, and the freeze-drying can prevent the polyester microspheres from agglomerating.
(7) Preparing the polyester microspheres into 0.1-0.5 g/L solution, mixing the graphene and the polyester microsphere solution, performing ultrasonic dispersion, forming a graphene-polyester composite film by using a spin coating method, using the graphene-polyester composite film as a conductive layer, and drying.
(8) Treating the graphene-polyester composite membrane for 10-20 minutes by using 20-50mL of 0.1-1mol/L HCl solution, and then immersing the composite membrane in a phenol-tetrachloroethane solvent with the volume ratio of 0.8-1.2:1 for standing to dissolve the polyester;
(9) and introducing hydrazine gas into the dried film at the temperature of 110-130 ℃, and reducing the graphene in the film into reduced graphene.
(10) And plating a silver film on the reduced graphene film by using a vapor deposition method to obtain the porous artificial skin receptor.
The nano silver has good electrochemical sensitivity and can improve the sensitivity of the artificial skin receptor.
According to the invention, the porous artificial skin membrane is obtained by preparing the artificial skin from graphene and polyester and carrying out reduction treatment after membrane formation. Compared with the prior art, the method has the advantages of small environmental pollution and simple preparation method. The prepared artificial skin receptor has good electrical conductivity and air permeability, and has good external force response and physical and mechanical properties.
Preferably, in the step (1), the solid-to-liquid ratio of the graphene to the nitric acid solution is 0.1g to 100mL-0.5g to 100mL, and the concentration of the nitric acid solution is 0.1-1 mol/L.
The conductivity of the graphene after the nitric acid acidification treatment is improved, and meanwhile, the light transmittance of the graphene film cannot be changed.
Preferably, in the step (3), the concentration of the concentrated sulfuric acid is 98wt%, and the dissolution concentration of the polyester is less than 5 g/L; the dissolution time is 3-4 days. Under the condition of the parameters, the polyester can be ensured to be completely dissolved. Compared with the existing polyester solvent, the concentrated sulfuric acid has no pungent smell and good solubility.
Preferably, in the step (4), the volume ratio of the n-hexane, the deionized water, the fatty alcohol-polyoxyethylene ether and the PEG-40 is 65-85:40-60:1.5-2.5: 1.
Preferably, in step (5), the polyester solution is slowly added into the emulsion under ice-bath conditions, the stirring rate is controlled at 2000-3000r/min, and the dropping rate of the polyester solution is 0.25-0.50 mL/s.
The polyester solution needs to be slowly added into the emulsion under ice bath conditions to prevent the temperature of the system from being too high due to the addition of concentrated sulfuric acid. The dropping rate of the polyester solution needs to be strictly controlled to ensure that micron-sized polyester microspheres are produced.
Preferably, in the step (7), the mass ratio of the graphene to the polyester is 15:1-25:1, the ultrasonic dispersion time is 20-30min, and the drying temperature is 30-60 ℃.
Preferably, in the step (9), the hydrazine gas is introduced for 8 to 12 hours.
The introduction of hydrazine gas can reduce the graphene which is well combined on the membrane into reduced graphene with better conductivity. Meanwhile, after the artificial skin membrane is subjected to reduction treatment after membrane formation, the agglomeration phenomenon of graphene can be effectively prevented, and the transparency of the membrane is improved.
Preferably, in step (4), the stirring speed is 2000-3000 r/min.
Preferably, in the step (8), the composite membrane is left to stand in a phenol-tetrachloroethane solvent for 20 to 28 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method, the porous graphene is obtained by mixing the graphene and the polyester microspheres to form the film and then removing the polyester, so that the product is high in porosity and excellent in air permeability.
(2) According to the invention, a reduction treatment method is adopted after graphene film forming, and the product has excellent transparency, good external force response performance and good physical and mechanical properties.
(3) The method utilizes the simultaneous action of the graphene and the silver, and has sensitive electrochemical performance.
(4) The method uses less chemicals, and the experimental process is green and environment-friendly.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a porous artificial skin receptor comprises the following steps:
(1) 0.5g of graphene is ground and crushed, then added into 0.1mol/L nitric acid solution for boiling treatment for 60 minutes, and then centrifuged and washed.
(2) Taking a proper amount of centrifuged graphene, drying, weighing, measuring the concentration, and adding deionized water to prepare a solution with the concentration of 4 mg/mL.
(3) 2g of the polyester pellets were dissolved in 50mL of 98wt% concentrated sulfuric acid, and left to stand in a dark place for 2 days until the polyester was completely dissolved.
(4) 150mL of n-hexane, 100mL of deionized water, 5mL of fatty alcohol-polyoxyethylene ether and 2mL of PEG-400 are added into a three-neck flask and rapidly stirred (2500 r/min) to prepare an inverse emulsion system.
(5) Slowly adding the prepared polyester solution into the emulsion at the speed of 1 drop/second, stopping stirring after the polyester solution is completely added, standing, taking the lower layer suspension, and adding 0.1mol/L sodium hydroxide for neutralization. Wherein the stirring speed is controlled at 2500r/min, and the dropping speed of the polyester solution is 0.40 mL/s.
(6) And adding deionized water into the neutralized suspension, carrying out centrifugal washing for 3-5 times until no sulfate ions exist in the supernatant, and then freeze-drying to obtain the micron-sized polyester microspheres.
(7) Preparing a certain amount of polyester microspheres into 0.1g/L solution, mixing graphene and polyester according to a certain mass ratio of 15:1, performing ultrasonic dispersion, wherein the ultrasonic dispersion time is 25min, the drying temperature is 45 ℃, forming a film by using a spin coating method, using the film as a conducting layer, and drying at room temperature.
(8) The graphene-polyester composite membrane is treated with 20mL of 0.1mol/LHCl solution for 10 minutes, and then the composite membrane is immersed in a phenol-tetrachloroethane 1:1 solvent and is kept stand for 24 hours to dissolve the polyester.
(9) And introducing hydrazine gas into the cleaned and dried film for 8 hours at the temperature of 120 ℃, and reducing the graphene in the film into reduced graphene.
(10) And plating a silver film on the reduced graphene film by using a vapor deposition method to obtain the porous artificial skin receptor.
Example 2
A preparation method of a porous artificial skin receptor comprises the following steps:
(1) 0.75g of graphene is ground and crushed, then added into 0.5mol/L nitric acid solution for boiling treatment for 70 minutes, and then centrifuged and washed.
(2) Taking a proper amount of centrifuged graphene, drying, weighing, measuring the concentration, and adding deionized water to prepare a solution with the concentration of 3 mg/mL.
(3) 3g of polyester pellets were dissolved in 75mL of 98wt% concentrated sulfuric acid, and the mixture was left standing in a dark place for 2 days until the polyester was completely dissolved.
(4) 200mL of n-hexane, 150mL of deionized water, 8mL of fatty alcohol-polyoxyethylene ether and 3mL of PEG-400 are added into a three-neck flask and rapidly stirred (2000 r/min) to prepare an inverse emulsion system.
(5) And slowly adding the prepared polyester solution into the emulsion at the speed of 2 drops/second, stopping stirring after the polyester solution is completely added, standing, taking the lower layer suspension, and adding 0.2mol/L sodium hydroxide for neutralization. Wherein the stirring speed is controlled at 2000r/min, and the dropping speed of the polyester solution is 0.25 mL/s.
(6) And adding deionized water into the neutralized suspension, carrying out centrifugal washing for 3-5 times until no sulfate ions exist in the supernatant, and then freeze-drying to obtain the micron-sized polyester microspheres.
(7) Preparing a certain amount of polyester microspheres into 0.2g/L solution, mixing graphene and polyester according to a certain mass ratio of 20:1, performing ultrasonic dispersion, wherein the ultrasonic dispersion time is 20min, the drying temperature is 60 ℃, forming a film by using a spin coating method, using the film as a conducting layer, and drying at room temperature.
(8) The graphene-polyester composite membrane is treated by 30mL of 0.2mol/LHCl solution for 20 minutes, and then the composite membrane is immersed in a phenol-tetrachloroethane 1:1 solvent and is kept still for 28 hours to dissolve the polyester.
(9) And introducing hydrazine gas into the cleaned and dried film for 9 hours at the temperature of 120 ℃, and reducing the graphene in the film into reduced graphene.
(10) And plating a silver film on the reduced graphene film by using a vapor deposition method to obtain the porous artificial skin receptor.
Example 3
A method for preparing a flexible transparent artificial skin receptor comprises the following steps:
(1) grinding and crushing 1.0g of graphene, adding the crushed graphene into a 1.0mol/L nitric acid solution, boiling for 70 minutes, and centrifuging and washing.
(2) Taking a proper amount of centrifuged graphene, drying, weighing and determining the concentration, and adding deionized water to prepare a solution with the concentration of 2 mg/mL.
(3) 5g of polyester pellets were dissolved in 100mL of 98wt% concentrated sulfuric acid, and the resulting solution was left standing in a dark place for 3 days until the polyester was completely dissolved.
(4) 250mL of n-hexane, 200mL of deionized water, 8mL of fatty alcohol-polyoxyethylene ether and 4mL of PEG-400 are added into a three-neck flask and rapidly stirred (3000 r/min) to prepare an inverse emulsion system.
(5) Slowly adding the prepared polyester solution into the emulsion at the speed of 2 drops/second, stopping stirring after the polyester solution is completely added, taking the lower layer suspension after standing, and adding 0.5mol/L sodium hydroxide for neutralization. Wherein the stirring speed is controlled at 3000r/min, and the dropping speed of the polyester solution is 0.50 mL/s.
(6) And adding deionized water into the neutralized suspension, carrying out centrifugal washing for 3-5 times until no sulfate ions exist in the supernatant, and then freeze-drying to obtain the micron-sized polyester microspheres.
(7) Preparing a certain amount of polyester microspheres into 0.5g/L solution, mixing graphene and polyester according to a certain mass ratio of 25:1, performing ultrasonic dispersion, wherein the ultrasonic dispersion time is 30min, the drying temperature is 30 ℃, forming a film by using a spin coating method, using the film as a conducting layer, and drying at room temperature.
(8) The graphene-polyester composite membrane is treated with 40mL of 0.5mol/LHCl solution for 20 minutes, and then the composite membrane is immersed in a phenol-tetrachloroethane 1:1 solvent and is kept stand for 20 hours to dissolve the polyester.
(9) And introducing hydrazine gas into the cleaned and dried film for 10 hours at the temperature of 120 ℃, and reducing the graphene in the film into reduced graphene.
(10) And plating a silver film on the reduced graphene film by using a vapor deposition method to obtain the porous artificial skin receptor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing a porous artificial skin receptor is characterized by comprising the following steps:
(1) grinding and crushing graphene, adding the graphene into a nitric acid solution, boiling for 20-60 minutes, and centrifuging and washing;
(2) drying and weighing part of centrifuged graphene to determine the concentration, and adding deionized water into the rest graphene according to the determined concentration to prepare a solution;
(3) dissolving 2-5g of polyester granules into 90-110mL of concentrated sulfuric acid, and standing in a dark place until the polyester is completely dissolved;
(4) adding 150-250mL of normal hexane, 100-200mL of deionized water, 5-10mL of fatty alcohol-polyoxyethylene ether and 2-4mL of PEG-400 into a three-neck flask, and rapidly stirring to prepare an inverse emulsion system;
(5) dripping the prepared polyester solution into the emulsion under the stirring condition, stopping stirring after the prepared polyester solution is completely added, taking the lower layer suspension after standing, and adding sodium hydroxide for neutralization;
(6) adding deionized water into the neutralized suspension, centrifuging and washing for 3-5 times until no sulfate ion exists in the supernatant, adding water into the lower-layer precipitate, and freeze-drying to obtain micron-sized polyester microspheres;
(7) preparing a solution of 0.1-0.5 g/L of polyester microspheres from polyester microspheres, mixing the graphene and the polyester microsphere solution, performing ultrasonic dispersion, forming a graphene-polyester composite film by using a spin-coating method to serve as a conductive layer, and drying;
(8) treating the graphene-polyester composite membrane for 10-20 minutes by using 20-50mL of 0.1-1mol/L HCl solution, and then immersing the composite membrane in a phenol-tetrachloroethane solvent with the volume ratio of 0.8-1.2:1 for standing to dissolve the polyester;
(9) introducing hydrazine gas into the dried film at the temperature of 110-130 ℃, and reducing the graphene in the film into reduced graphene;
(10) and plating a silver film on the reduced graphene film by using a vapor deposition method to obtain the porous artificial skin receptor.
2. The method for preparing the porous artificial skin receptor according to claim 1, wherein in the step (1), the solid-to-liquid ratio of the graphene to the nitric acid solution is 0.1g:100mL-0.5g:100mL, and the concentration of the nitric acid solution is 0.1-1 mol/L.
3. The method of claim 1, wherein in step (3), the concentrated sulfuric acid has a concentration of 98wt%, and the polyester has a dissolution concentration of less than 5 g/L; the dissolution time is 3-4 days.
4. The method for preparing a porous artificial skin receptor according to claim 1, wherein in the step (4), the volume ratio of the n-hexane, the deionized water, the fatty alcohol-polyoxyethylene ether and the PEG-40 is 65-85:40-60:1.5-2.5: 1.
5. The method for preparing a porous artificial skin receptor according to claim 1, wherein in step (5), the polyester solution is slowly added into the emulsion under ice-bath conditions, the stirring rate is controlled at 2000-3000r/min, and the dropping rate of the polyester solution is 0.25-0.50 mL/s.
6. The method for preparing the porous artificial skin receptor according to claim 1, wherein in the step (7), the mass ratio of the graphene to the polyester is 15:1-25:1, the ultrasonic dispersion time is 20-30min, and the drying temperature is 30-60 ℃.
7. The method for preparing a porous artificial skin receptor according to claim 1, wherein in the step (9), the hydrazine gas is introduced for 8-12 h.
8. The method as claimed in claim 1, wherein in step (4), the stirring speed is 2000-3000 r/min.
9. The method of claim 1 wherein in step (8) the composite membrane is allowed to stand in a phenol-tetrachloroethane solvent for 20-28 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710626794.6A CN107376006B (en) | 2017-07-28 | 2017-07-28 | Preparation method of porous artificial skin receptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710626794.6A CN107376006B (en) | 2017-07-28 | 2017-07-28 | Preparation method of porous artificial skin receptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107376006A CN107376006A (en) | 2017-11-24 |
| CN107376006B true CN107376006B (en) | 2020-08-18 |
Family
ID=60341897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710626794.6A Active CN107376006B (en) | 2017-07-28 | 2017-07-28 | Preparation method of porous artificial skin receptor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107376006B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180463A (en) * | 2011-02-21 | 2011-09-14 | 电子科技大学 | Method for reducing sheet resistance of graphene thin film |
| CN103623817A (en) * | 2013-11-21 | 2014-03-12 | 同济大学 | High durability anode catalyst for vehicle-mounted fuel cell and preparation method of catalyst |
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
| CN106458601A (en) * | 2014-06-17 | 2017-02-22 | 埃琳娜·莫洛卡诺瓦 | Graphene and graphene-related materials for manipulation of cell membrane potential |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10761043B2 (en) * | 2011-07-22 | 2020-09-01 | The Trustees Of The University Of Pennsylvania | Graphene-based nanopore and nanostructure devices and methods for macromolecular analysis |
-
2017
- 2017-07-28 CN CN201710626794.6A patent/CN107376006B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180463A (en) * | 2011-02-21 | 2011-09-14 | 电子科技大学 | Method for reducing sheet resistance of graphene thin film |
| CN103623817A (en) * | 2013-11-21 | 2014-03-12 | 同济大学 | High durability anode catalyst for vehicle-mounted fuel cell and preparation method of catalyst |
| CN106458601A (en) * | 2014-06-17 | 2017-02-22 | 埃琳娜·莫洛卡诺瓦 | Graphene and graphene-related materials for manipulation of cell membrane potential |
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107376006A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103382225B (en) | A kind of method of modifying of Cellulose nanocrystal surface esterification | |
| CN110172161B (en) | Preparation method and application of hydrogel with triple network structure | |
| CN104226281A (en) | Composite hydrogel for adsorption of heavy metal ions and preparation method thereof | |
| CN102516443B (en) | Method for preparing super absorbent resin | |
| WO2017214741A1 (en) | Process for preparing chitosan/polyvinyl alcohol composite electrically-conductive nanofibre | |
| CN104193829B (en) | The production method of spherical cellulose acetate butyrate | |
| CN103435705A (en) | Method for preparing starch nanocrystal | |
| CN103641944A (en) | Preparation and application of molecularly imprinted hybrid material of estrogenic endocrine disrupter | |
| Mondal et al. | High lignin containing hydrogels with excellent conducting, self-healing, antibacterial, dye adsorbing, sensing, moist-induced power generating and supercapacitance properties | |
| CN107118361B (en) | Silk fibroin/carboxymethyl chitosan composite gel and preparation method thereof | |
| CN103613790A (en) | Preparation method of cellulose-based composite material | |
| Wang et al. | Preparation of cellulose based microspheres by combining spray coagulating with spray drying | |
| CN107376006B (en) | Preparation method of porous artificial skin receptor | |
| CN112195647A (en) | High-strength alginate/nano-zinc oxide composite fiber and preparation method thereof | |
| CN103102512B (en) | Chitosan-fullerene compound and preparation method | |
| CN104629098A (en) | Method for preparing porous chitosan microsphere | |
| CN110240733B (en) | Ferroferric oxide copper-loaded nano particle, preparation method thereof and application thereof in preparing root-resisting material | |
| CN107412880B (en) | Preparation method of flexible transparent artificial skin receptor | |
| CN109265758A (en) | A kind of bis- response type chitin nanofiber hydrogels of temperature/pH and preparation method thereof | |
| US11459361B2 (en) | Sericin protein particle with oxidative stress property, method for preparing the same and use thereof | |
| CN106279541A (en) | A kind of magnetic coupling hydrogel for magnetic control fixed point heating source and preparation method and application | |
| CN107927961A (en) | A kind of anlistatig scarf fabrics | |
| CN104358026A (en) | Nitrocellulose diacetate nano-fiber membrane capable of adsorbing and desorbing protein | |
| CN109400948A (en) | A kind of method that microwave process reinforcing prepares different deacetylations and degree of polymerization series chitooligosaccharide- | |
| CN110100943A (en) | A kind of raising immunity fish collagen protein powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |