CN108273496A - A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose - Google Patents
A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose Download PDFInfo
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- CN108273496A CN108273496A CN201810218925.1A CN201810218925A CN108273496A CN 108273496 A CN108273496 A CN 108273496A CN 201810218925 A CN201810218925 A CN 201810218925A CN 108273496 A CN108273496 A CN 108273496A
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- bacteria cellulose
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- 241000894006 Bacteria Species 0.000 title claims abstract description 49
- 229920002678 cellulose Polymers 0.000 title claims abstract description 48
- 239000001913 cellulose Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 19
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 19
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000002086 nanomaterial Substances 0.000 claims abstract description 29
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000017 hydrogel Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000001580 bacterial effect Effects 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000002255 enzymatic effect Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- -1 manganese oxide compound Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention discloses a kind of preparation method and applications of the bionic enzyme based on bacteria cellulose.It is characterized in that synthesizing carbon fiber using bacteria cellulose high temperature cabonization, and using the porous structure of bacteria cellulose and high moisture holding capacity, the liquor potassic permanganate of high concentration is loaded in bacteria cellulose by the function of exchange of water.Bacteria cellulose/potassium permanganate aeroge is formed using freeze-drying.Then make bacteria cellulose be carbonized to form carbon fiber using high-temperature calcination, while potassium permanganate generates manganese oxide nano granule by pyrolytic.Carbon fiber/manganese oxide composite nano materials prepared by this method have preferable bionical enzymatic activity, can be catalyzed the disproportionated reaction of superoxide anion, are applied to the preparation of superoxide anion sensor, have higher application value in biology and medical domain.And this method is at low cost, easy to operate, is convenient for mass production and marketing application.
Description
Technical field
The present invention relates to a kind of preparation methods of the bionic enzyme of bacteria cellulose, and Gao Meng is loaded using natural bacteria cellulose
Sour potassium forms carbon fiber/manganese oxide composite nano-fiber material by high-temperature calcination, belongs to polymer-based functional composite material
Technology.
Background technology
Carbon fiber is a kind of novel c-based nanomaterial, has fabulous mechanical strength, prodigious volume mass ratio, porous
Network structure.Carbon fiber has the diameter of nano-scale, the general performance with nano material, the boundary site of carbon fiber surface
Surface electronic can be promoted to shift, be used for electrochemistry instrument or electrochemical analysis.There are many method for preparing carbon fiber, wherein most often
Electrical spinning method, can utilize polymer solution or fusant synthesize several nanometers to several micron diameters nanofiber.
In recent years, brainstrust has developed some particularly simple method prepares carbon nano-fiber.Some is fine using some natural plants
Dimension, such as:The materials such as cotton, leaf, bacteria cellulose handle synthesis carbon fiber through chemically or physically method and are used for the energy and sensing
Field.
Bacteria cellulose be one kind by specific bacterium such asAcetobacter、AgrobacteriumEtc. outputs it is organic poly-
Close object material.Compared with common plant cellulose, bacteria cellulose has small purity height, diameter, high mechanical strength, retentiveness
The advantages that good is the ideal carrier for synthesizing other nano materials.For example, using bacteria cellulose as template, silver can be synthesized
The composite nano fiber of nano particle doping;Synthesis bacterial fibers/CdTe quantum composite material is used to prepare pH and glucose
Sensor;Or utilize the metal ions such as method synthesis carbon fiber Wesy detection Cd (II), the Pb (II) of high-temperature calcination.But it utilizes
The composite material research that bacteria cellulose synthesizes carbon fiber-based is less, is ground to the correlation of carbon fiber/manganese oxide composite nano materials
Study carefully and has not been reported.
This patent is provided prepares carbon fiber/manganese oxide composite nano materials using bacteria cellulose and potassium permanganate as raw material
Preparation method and its application in superoxide anion detection.
Invention content
The object of the present invention is to provide a kind of preparation methods of the bionic enzyme based on bacteria cellulose, simple and effective can make
It is standby go out carbon fiber/manganese oxide composite nano-fiber material.The composite nano materials have the catalytic activity of bionic enzyme, to super oxygen the moon
The disproportionated reaction of ion has stronger catalytic action, can be used for biomedical research and the preparation of biosensor.
The preparation method of bionic enzyme based on bacteria cellulose, including following preparation process:
(1) a kind of natural bacteria cellulose is provided;
(2) under magnetic stirring by natural bacteria cellulose, it is impregnated with 10% ethanol water and then is impregnated with deionized water
And deionized water is replaced, to remove the organic solvent contained and other impurity;
(3) the bacteria cellulose leaching material that step (2) obtains is impregnated in liquor potassic permanganate, is reacted 1 day under magnetic stirring,
Potassium permanganate is loaded, the bacteria cellulose after reaction is cleaned into flushing 3-5 times with deionized water, removes excessive potassium permanganate,
Obtain bacteria cellulose/potassium permanganate hydrogel;
(4) step (3) is obtained bacteria cellulose/potassium permanganate hydrogel to be put into liquid nitrogen and freeze, places into freeze drying box
(- 80 DEG C, 0.021 Mpa)Bacterial fibers/potassium permanganate aeroge is made in middle freeze-drying;
(5) bacteria cellulose for obtaining step (4)/potassium permanganate aeroge high-temperature calcination under nitrogen protection in tube furnace,
Carbon fiber/manganese oxide composite nano materials are formed to get to the bionic enzyme based on bacteria cellulose.
Further, the time that 10% ethanol water of use of the step (2) impregnates is 1 hour, is impregnated in deionized water
Time is 3 days, and the number for replacing deionized water is 3-6 times.
Further, a concentration of 1~40 mM of the liquor potassic permanganate of the step (3) impregnates in liquor potassic permanganate
Time is 12~24 hours.
Preferably, a concentration of 20mM of the liquor potassic permanganate of the step (3).
Further, the time of the step (4) freezed in liquid nitrogen is 30 minutes, and sublimation drying is 12~24 small
When.
Preferably, the process of the high-temperature calcination of the step (5) is that heating rate is 2 oC/ minutes, is protected in 250 oC
It holds 1 hour, is then kept for 1 hour in 450 oC, finally kept for 2 hours in 800 oC.
The carbon fiber obtained according to above-mentioned preparation method/manganese oxide composite nano materials, the activity in bionic enzyme and catalysis
The biology of the disproportionated reaction of superoxide anion and the application of medicine.
The beneficial effects of the invention are as follows:
(1) carbon fiber provided by the invention/manganese oxide composite nano materials are the bacteriums loaded by high-temperature process potassium permanganate
What cellulose was formed, synthesis cost is low to be conducive to promote and apply.
(2) diameter of carbon fiber is about 10 ~ 30nm in carbon fiber/manganese oxide composite nano materials that the present invention obtains.
(3) carbon fiber/manganese oxide composite nano materials that the present invention obtains are obtained as a concentration of 20mM of potassium permanganate
Composite material in manganese oxide mass fraction when being 1.6 ~ 3.5%, the granular size of manganese oxide is 30 ~ 70nm.
(4) carbon fiber/manganese oxide composite nano materials for obtaining of the present invention to the disproportionated reaction of superoxide anion have compared with
Strong catalytic performance has prodigious application value for the preparation of biomedical research and biosensor.
(5) preparation simple possible provided by the invention, it is easily operated, widen answering for bacteria cellulose and nano manganese oxide
With field, the new application field of bacteria cellulose is imparted, the composite material of preparation has very high economic value.
Description of the drawings
In order to keep the purpose of the present invention and technical solution advantageous effect clearer, the present invention provides following attached drawing:
Fig. 1 is the synthetic method of carbon fiber/manganese oxide composite nano materials of embodiment 1.
Fig. 2 is the scanning electron microscope microscopic appearance figure of carbon fiber/manganese oxide composite nano materials of embodiment 1.
Fig. 3 is the transmission electron microscope microscopic appearance figure of carbon fiber/manganese oxide composite nano materials of embodiment 1.
Fig. 4 is the powder diffraction spectrum of carbon fiber/manganese oxide composite nano materials of embodiment 1.
Fig. 5 is electrochemical response figure of the carbon fiber/manganese oxide composite nano materials to superoxide anion of embodiment 1.
Fig. 6 is examination criteria curve of the carbon fiber/manganese oxide composite nano materials to superoxide anion of embodiment 1.
Specific implementation mode
The present invention is described in detail With reference to embodiment.
Embodiment 1
Synthesis step schematic diagram is as shown in Figure 1, be specially:
(1)Bacteria cellulose raw material is cut into 3cm × 3cm × 0.5cm fritters, is first impregnated 1 hour in 10% ethanol water,
Then it impregnates 3 days in deionized water, to remove the organic solvent contained and other impurities.
(2)Under magnetic agitation effect, bacteria cellulose is impregnated 1 day in 20mM liquor potassic permanganates.It then takes out
It is used in combination deionized water cleaning to rinse 3-5 times, removes excessive potassium permanganate, obtain bacterial fibers/potassium permanganate hydrogel.
(3)Bacteria cellulose/potassium permanganate hydrogel is freezed 30 minutes in liquid nitrogen, is subsequently placed in freeze drying box
(- 80 DEG C, 0.021 Mpa)Bacterial fibers/potassium permanganate aeroge is made in freeze-drying 24 hours.
(4)By bacteria cellulose/potassium permanganate aeroge in tube furnace(Under nitrogen protection), with 800 oC high-temperature calcinations
2 hours.Then room temperature is naturally cooled to get to carbon fiber/manganese oxide composite nano materials.
It can see by the powder diffraction spectrum of the scanning electron microscope diagram of Fig. 2, the transmission electron microscope picture of Fig. 3 and Fig. 4
The microscopic appearance and characteristic peak of carbon fiber/manganese oxide composite nano materials illustrate successfully to have prepared carbon fiber/manganese oxide compound
Nano material.
Then carbon fiber/manganese oxide composite nano materials of 1mg synthesis and 50 μ L nafion are added to 450 μ L second
Then ultrasonic disperse in alcohol takes 5 μ L mixed solutions to drip to the glassy carbon electrode surface of milled, dry 2 hours at room temperature.Then to
The constant potential of 0.64 V carries out the experiment of electrochemical response and the detection to superoxide anion.Fig. 5 is carbon fiber/manganese oxide
For composite nano materials to the electrochemical response figure of superoxide anion, Fig. 6 is that carbon fiber/manganese oxide composite nano materials are negative to super oxygen
The examination criteria curve of ion can prove that carbon fiber/manganese oxide composite nano materials can detect very well by Fig. 5 and Fig. 6
The super oxygen root anion that tumour cell discharges in biosystem, so carbon fiber/manganese oxide composite nano materials have bionical
The biology of the disproportionated reaction of enzyme and catalysis superoxide anion and the application of medicine.
Claims (7)
1. a kind of preparation method of the bionic enzyme based on bacteria cellulose, including following preparation process:
(1) a kind of natural bacteria cellulose is provided;
(2) under magnetic stirring by natural bacteria cellulose, it is impregnated with 10% ethanol water and then is impregnated with deionized water
And deionized water is replaced, to remove the organic solvent contained and other impurity;
(3) the bacteria cellulose leaching material that step (2) obtains is impregnated in liquor potassic permanganate, is reacted 1 day under magnetic stirring,
Potassium permanganate is loaded, the bacteria cellulose after reaction is cleaned into flushing 3-5 times with deionized water, removes excessive potassium permanganate,
Obtain bacteria cellulose/potassium permanganate hydrogel;
(4) step (3) is obtained bacteria cellulose/potassium permanganate hydrogel to be put into liquid nitrogen and freeze, places into freeze drying box
(- 80 DEG C, 0.021 Mpa)Bacterial fibers/potassium permanganate aeroge is made in middle freeze-drying;
(5) bacteria cellulose for obtaining step (4)/potassium permanganate aeroge high-temperature calcination under nitrogen protection in tube furnace,
Carbon fiber/manganese oxide composite nano materials are formed to get to the bionic enzyme based on bacteria cellulose.
2. a kind of preparation method of bionic enzyme based on bacteria cellulose according to claim 1, which is characterized in that described
The time that 10% ethanol water of use of step (2) impregnates is 1 hour, is 3 days with soaking time in deionized water, replacement go from
The number of sub- water is 3-6 times.
3. a kind of preparation method of bionic enzyme based on bacteria cellulose according to claim 1, which is characterized in that described
A concentration of 1~40 mM of the liquor potassic permanganate of step (3), the time impregnated in liquor potassic permanganate are 12~24 hours.
4. a kind of preparation method of bionic enzyme based on bacteria cellulose according to claim 3, which is characterized in that described
A concentration of 20mM of the liquor potassic permanganate of step (3).
5. a kind of preparation method of bionic enzyme based on bacteria cellulose according to claim 1, which is characterized in that described
The time of step (4) freezed in liquid nitrogen is 30 minutes, and sublimation drying is 12~24 hours.
6. a kind of preparation method of bionic enzyme based on bacteria cellulose according to claim 1, which is characterized in that described
The process of the high-temperature calcination of step (5) is that heating rate is 2 oC/ minutes, is kept for 1 hour in 250 oC, then in 450 oC
It is kept for 1 hour, is finally kept for 2 hours in 800 oC.
7. the carbon fiber that the preparation method of the bionic enzyme based on bacteria cellulose described in claim 1~6 any one obtains/
Manganese oxide composite nano materials, in the activity of bionic enzyme and the biology of disproportionated reaction and the answering for medicine of catalysis superoxide anion
With.
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CN110143584A (en) * | 2019-05-31 | 2019-08-20 | 西南大学 | A kind of superoxide dismutase biomimetic material and its preparation method and application |
CN111569881A (en) * | 2020-05-29 | 2020-08-25 | 西南大学 | Preparation method of monatomic biomimetic enzyme, and product and application thereof |
CN111650261A (en) * | 2020-06-09 | 2020-09-11 | 苏州科技大学 | Conductive ink for electrochemical biosensor and preparation method and application thereof |
CN112834589A (en) * | 2020-12-31 | 2021-05-25 | 陕西师范大学 | AuQD @ CNFs composite material and preparation method and application thereof |
CN113694964A (en) * | 2021-08-27 | 2021-11-26 | 中国科学院化学研究所 | Bionic laccase system based on polysaccharide/dopamine composite membrane as well as preparation method and application thereof |
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CN111569881B (en) * | 2020-05-29 | 2021-11-02 | 西南大学 | Preparation method of monatomic biomimetic enzyme, and product and application thereof |
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CN111650261B (en) * | 2020-06-09 | 2022-09-20 | 苏州科技大学 | Conductive ink for electrochemical biosensor and preparation method and application thereof |
CN112834589A (en) * | 2020-12-31 | 2021-05-25 | 陕西师范大学 | AuQD @ CNFs composite material and preparation method and application thereof |
CN112834589B (en) * | 2020-12-31 | 2023-12-22 | 陕西师范大学 | AuQD@CNFs composite material and preparation method and application thereof |
CN113694964A (en) * | 2021-08-27 | 2021-11-26 | 中国科学院化学研究所 | Bionic laccase system based on polysaccharide/dopamine composite membrane as well as preparation method and application thereof |
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