CN112086218A - Preparation method of cellulose-based bionic skin with amphipathy and capable of rapidly capturing biological signals - Google Patents
Preparation method of cellulose-based bionic skin with amphipathy and capable of rapidly capturing biological signals Download PDFInfo
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- CN112086218A CN112086218A CN202010729309.XA CN202010729309A CN112086218A CN 112086218 A CN112086218 A CN 112086218A CN 202010729309 A CN202010729309 A CN 202010729309A CN 112086218 A CN112086218 A CN 112086218A
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- cellulose
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 33
- 239000001913 cellulose Substances 0.000 title claims abstract description 33
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000502 dialysis Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- 230000003592 biomimetic effect Effects 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 206010020751 Hypersensitivity Diseases 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 229910002567 K2S2O8 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/102—Different kinds of radiation or particles beta or electrons
Abstract
The invention provides a preparation method of cellulose-based bionic skin with amphipathy and capable of rapidly capturing biological signals. The material has excellent conductivity, amphipathy and hypersensitive biological signal capture, has low resistivity, shows different hydrophilicities on two sides of the material, and can rapidly capture signals of temperature, illumination, gas and human body deformation; the bionic skin material has extremely quick catching capacity on various biological signals, is simple to prepare, has mild reaction conditions, and has wide application prospect in the field of bionic skin.
Description
Technical Field
The invention relates to a preparation method of cellulose-based bionic skin, in particular to a preparation method of cellulose-based bionic skin which is amphiphilic and can quickly capture biological signals.
Background
With the advent of the 5G information age, the intelligence degree in human life is continuously improved, and the wearable artificial intelligence electronic skin (e-skin) is widely used in human life. Electronic skin, which generates electrical signals in response to external stimuli (pressure, temperature and humidity), can mimic the mechanical and sensory properties of skin. Due to good flexibility, excellent electrical conductivity, high strength, long-term stability and lightness, electronic skin has been widely used in the fields of health monitoring, robotic systems, human-computer interaction and biomedicine.
At present, the bionic skin mostly uses petrochemical materials with poor biocompatibility as substrate materials. A Wearable, health, and additive epidemic sensitive Assembled from Mussel-intensive synthetic Hydrogel Framework article (Adv.Funct.Mater.2017,1703852) published by Meihong Liao et al in journal Advanced Functional Materials describes the preparation of polyacrylamide Hydrogel biomimetic skin and its application in human-computer interaction and medical care monitoring. But the polyacrylamide has poor biocompatibility and the hydrogel is easy to dehydrate, so that the development of the polyacrylamide in the fields of artificial intelligent sensing, flexible capacitors and the like is restricted.
Therefore, the invention takes the commercialized cellulose dialysis bag as the raw material, and a layer of conductive polymer is polymerized on the surface of the dialysis bag through interfacial polymerization. The preparation is simple and efficient, and the composite material has more sensitive signal capture capability and better biocompatibility.
Disclosure of Invention
The invention aims to provide a preparation method of cellulose-based bionic skin with amphipathy and rapid biological signal capture, which is simple to prepare, simple and convenient to operate, green and pollution-free and is convenient for large-scale production.
The cellulose-based bionic skin capable of rapidly capturing multiple biological signals is prepared by taking a commercialized cellulose dialysis bag as a raw material and performing interfacial polymerization.
A preparation method of cellulose-based bionic skin with amphipathy and rapid biological signal capture comprises the following specific steps:
1) putting the cellulose dialysis bag into a water bath kettle with a proper temperature, and heating for a period of time to obtain a pre-dialysis bag;
2) adding a conductive polymer monomer dilute acid solution with a proper concentration into the preliminary dialysis bag obtained in the step 1), sealing and placing a beaker filled with an oxidant dilute acid solution with a proper concentration, placing the beaker in a low-temperature ultrasonic cleaning instrument, performing ultrasonic treatment for a proper time, and placing the beaker in a vacuum oven at the temperature of 25-30 ℃ for drying for 3-5 hours to obtain the cellulose-based bionic skin.
The proper temperature in the step 1) is 65-95 ℃, and the period of time is 10-60 min.
The proper concentration of the dilute acid solution of the conductive polymer monomer in the step 2) is 0.01-0.3 mol/L; the conductive polymer monomer is thiophene (C)4H4S), pyrrole (C)4H5N), aniline (C)6H7N) and 3, 4-ethylenedioxythiophene (C)6H6O2S) and the like; the dilute acid solution is 0.1-30 wt% hydrochloric acid (HCl) and sulfuric acid (H)2SO4) And dilute nitric acid (HNO)3) And the like.
The proper concentration of the oxidant dilute acid solution in the step 2) is 0.01-0.3 mol/L; the oxidant is ammonium persulfate (APS, (NH)4)2S2O8) Iron chloride (FeCl)3) Potassium persulfate (K)2S2O8) One of the like; the dilute acid solution is 0.1-30 wt% hydrochloric acid (HCl) and sulfuric acid (H)2SO4) And dilute nitric acid (HNO)3) And the like.
The low temperature of the ultrasonic cleaning instrument in the step 2) is-15-0 ℃.
The ultrasound in the step 2) is carried out for 1-5 h.
Observing the morphology of the composite material by using a field emission scanning electron microscope (FF-SEM) on the cellulose-based bionic skin obtained by the method; analyzing the chemical structure of the complex using fourier infrared spectroscopy (FTIR); using a universal ammeter to test the resistance change of the water contact angle; ethanol, formaldehyde and toluene were tested for their ability to respond to gases with the following results:
(1) a field emission scanning electron microscope (FF-SEM) test shows that polyaniline on the surface of a dialysis bag in cellulose-based bionic skin is rough in appearance, and the figure 1 shows that the polyaniline is rough.
(2) Fourier infrared spectroscopy (FTIR) tests showed successful polymerization of polyaniline on dialysis bags, see fig. 2.
(3) Cellulose-based biomimetic skin has excellent gas response, see figure 3.
The cellulose-based bionic skin prepared by the method has excellent gas response capability and has wide application prospect in the aspect of electronic skin.
The invention has the beneficial effects that:
the invention utilizes the commercialized dialysis bag as the raw material to prepare the cellulose-based bionic skin, and has the advantages of commercialization, low price and the like.
Drawings
FIG. 1 is a field emission scanning electron microscope (FF-SEM) test chart of cellulose-based biomimetic skin prepared in example 1.
FIG. 2 is a Fourier Infrared Spectroscopy (FTIR) test chart of cellulose-based biomimetic skin prepared in example 1.
Fig. 3 is a gas response graph of the cellulose-based biomimetic skin prepared in example 1.
Concrete experimental case
The invention is further illustrated below with reference to specific examples. These embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
Placing the cellulose dialysis bag in a water bath kettle at a proper temperature of 90 ℃, and heating for 20 min; 0.2mol/L C6H7N dilute sulfuric acid (10 wt%) was added to the dialysis bag; sealing the dialysis bag and putting the dialysis bag into a beaker containing 0.1mol/L APS dilute sulfuric acid solution (10 wt%); placing the beaker in an ultrasonic cleaning instrument at the temperature of-5 ℃; after ultrasonic treatment for 2 hours, placing the mixture in a vacuum oven at 25 ℃ for drying for 3 hours; the gas response was tested using ethanol.
Example 2
Placing cellulose dialysis bag in water bath at 95 deg.C, and heating for 60 min; 0.3mol/L C4H5N diluted hydrochloric acid (30 wt%) was added to the dialysis bag; the dialysis bag is sealed and filled with 0.3mol/L FeCl3Diluted hydrochloric acid (30 wt%) in a beaker; placing the beaker in an ultrasonic cleaning instrument at 0 ℃; after ultrasonic treatment for 5h, placing the mixture in a vacuum oven at 30 ℃ for drying for 5 h; the gas response was tested using ethanol.
Example 3
Placing cellulose dialysis bag in water bath at 65 deg.C, and heating for 10 min; 0.01mol/L C6H6O2S dilute sulfuric acid (0.1 wt%) was added to the dialysis bag; the dialysis bag is sealed and put into the bag with 0.01mol/L K2S2O8Dilute sulfuric acid (0.1 wt%) in a beaker; placing the beaker in an ultrasonic cleaning instrument at-15 ℃; after ultrasonic treatment for 3 hours, placing the mixture in a vacuum oven at 27 ℃ for drying for 3 hours; the gas response was tested using ethanol.
Example 4
Placing cellulose dialysis bag in water bath at 75 deg.C, and heating for 30 min; 0.1mol/L C4H4S dilute nitric acid (20 wt%) is added into the dialysis bag; the dialysis bag is sealed and put into the bag with 0.1mol/L K2S2O8Diluted nitric acid (20 wt%) in a beaker; placing the beaker in an ultrasonic cleaning instrument at-10 ℃; after ultrasonic treatment for 4 hours, placing the mixture in a vacuum oven at 28 ℃ for drying for 4 hours; the gas response was tested using ethanol.
Example 5
Placing cellulose dialysis bag in water bath at 85 deg.CHeating in a pan for 40 min; 0.15mol/L C6H6O2S dilute nitric acid (25 wt%) was added to the dialysis bag; the dialysis bag is sealed and put into the bag with 0.15mol/L K2S2O8In a beaker of dilute nitric acid (25 wt%); placing the beaker in an ultrasonic cleaning instrument at-12 ℃; after ultrasonic treatment for 1h, placing the mixture in a vacuum oven at 29 ℃ for drying for 3.5 h; the gas response was tested using ethanol.
Claims (6)
1. A preparation method of cellulose-based bionic skin with amphipathy and rapid biological signal capture is characterized by comprising the following steps:
1) putting the cellulose dialysis bag into a water bath kettle with a proper temperature, and heating for a period of time to obtain a pre-dialysis bag;
2) adding a conductive polymer monomer dilute acid solution with a proper concentration into the preliminary dialysis bag obtained in the step 1), sealing and placing a beaker filled with an oxidant dilute acid solution with a proper concentration, placing the beaker in a low-temperature ultrasonic cleaning instrument, performing ultrasonic treatment for a proper time, and placing the beaker in a vacuum oven at the temperature of 25-30 ℃ for drying for 3-5 hours to obtain the cellulose-based bionic skin.
2. The method for preparing cellulose-based biomimetic skin with amphipathy and rapid biological signal capturing functions as claimed in claim 1, wherein: the proper temperature in the step 1) is 65-95 ℃, and the period of time is 10-60 min.
3. The method for preparing cellulose-based biomimetic skin with amphipathy and rapid biological signal capturing functions as claimed in claim 1, wherein: the proper concentration of the dilute acid solution of the conductive polymer monomer in the step 2) is 0.01-0.3 mol/L; the conductive polymer monomer is thiophene (C)4H4S), pyrrole (C)4H5N), aniline (C)6H7N) and 3, 4-ethylenedioxythiophene (C)6H6O2S) is selected; the dilute acid solution is 0.1-30 wt% hydrochloric acid (HCl) and sulfuric acid (H)2SO4) And dilute nitric acid (HNO)3) One kind of (1).
4. The method for preparing cellulose-based biomimetic skin with amphipathy and rapid biological signal capturing functions as claimed in claim 1, wherein: the proper concentration of the oxidant dilute acid solution in the step 2) is 0.01-0.3 mol/L; the oxidant is ammonium persulfate (APS, (NH)4)2S2O8) Iron chloride (FeCl)3) Potassium persulfate (K)2S2O8) One of (1); the dilute acid solution is 0.1-30 wt% hydrochloric acid (HCl) and sulfuric acid (H)2SO4) And dilute nitric acid (HNO)3) One kind of (1).
5. The method for preparing cellulose-based biomimetic skin with amphipathy and rapid biological signal capturing functions as claimed in claim 1, wherein: the low temperature of the ultrasonic cleaning instrument in the step 2) is-15-0 ℃.
6. The method for preparing cellulose-based biomimetic skin with amphipathy and rapid biological signal capturing functions as claimed in claim 1, wherein: the ultrasound in the step 2) is carried out for 1-5 h.
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| CN107660146A (en) * | 2015-04-23 | 2018-02-02 | 拜奥希医药公司 | The homogeneous chitosan aqueous solution of the pH close to the injectable of physiological pH |
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| CN108517050A (en) * | 2018-04-28 | 2018-09-11 | 万玉梅 | A kind of preparation method of high strength fibre element conductive film |
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2020
- 2020-07-27 CN CN202010729309.XA patent/CN112086218A/en active Pending
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| KR20000017827U (en) * | 1999-03-05 | 2000-10-05 | 윤종용 | Kimch'i storehouse |
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Application publication date: 20201215 |