CN112337466B - Nanocarbon-loaded cluster copper nanoenzyme and preparation method and application thereof - Google Patents
Nanocarbon-loaded cluster copper nanoenzyme and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 102000004190 Enzymes Human genes 0.000 claims abstract description 13
- 108090000790 Enzymes Proteins 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 3
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- 230000001580 bacterial effect Effects 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
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- 239000002113 nanodiamond Substances 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 241000894006 Bacteria Species 0.000 abstract description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000012880 LB liquid culture medium Substances 0.000 description 1
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- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
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- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Pest Control & Pesticides (AREA)
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Abstract
The invention discloses a nanocarbon-loaded cluster-state copper nanoenzyme and a preparation method and application thereof. The nano-carbon loaded copper in a cluster state is used as nano-enzyme, so that the active oxygen substance can be generated by catalyzing the decomposition of oxygen in the air at room temperature, and the sterilization purpose can be achieved by acting on bacteria. In the nano-enzyme disclosed by the invention, copper exists in the form of clusters dispersed in atomic scale, so that the enzyme catalytic activity of copper is obviously improved, and the antibacterial rate of the nano-enzyme can reach 100%. The synthesis process is simple and convenient, the reaction process is easy to control, and the prepared nano-carbon loaded cluster copper nano-enzyme has excellent catalytic antibacterial performance and has potential application in the biomedical field.
Description
Technical Field
The invention relates to the technical field of nano-enzyme catalytic antibiosis, in particular to an application of a nano-carbon-loaded atomic-level dispersed cluster copper nano-composite material as nano-enzyme catalytic antibiosis.
Background
Nanoenzyme is a nanocomposite material with enzymatic catalytic activity that has both the unique properties of nanomaterials and catalytic activity that mimics a natural enzyme. The strong and diverse enzyme catalytic activities have attracted a great deal of attention, and have potential applications in the fields of biosensors, cancer treatment, antibiosis and the like. At present, research on nano-enzymes is still in a development stage, a complete theoretical system is not established yet, and research on the field of nano-enzymes is always focused on.
With the progress and development of modern technology, more and more germs are also appeared, which seriously threatens the health of human beings. The use of a large number of antibiotics and drugs causes some germs to have drug resistance, so the search for novel antibacterial materials is not easy. Oxidative stress is an effective method of killing bacteria by allowing reactive oxygen species to act on the bacteria to destroy the metabolism within the bacterial cells, resulting in bacterial inactivation. The nano-enzyme has high-efficiency and various enzyme catalytic activities, and researches show that some nano-enzymes have the enzyme catalytic activities of simulating oxidase, peroxidase and the like, and the nano-enzyme can effectively inactivate bacteria and protect the health of people when being applied to the antibacterial field.
Disclosure of Invention
The invention aims to develop a nanocarbon supported cluster copper nanoenzyme with high-efficiency catalytic antibacterial performance, which uses nanocarbon as a carrier to support copper in an atomic-scale dispersed cluster state. The nano-enzyme is applied to the field of catalytic antibiosis, and can catalyze the decomposition of oxygen in air to generate active oxygen substances so as to completely inactivate bacteria. Has the characteristics of green, high efficiency, simplicity, practicability and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the nano carbon loaded cluster copper nano enzyme is formed by taking nano carbon as a carrier and copper in an atomic level dispersed cluster state as an active center.
Furthermore, the nano-carbon-supported cluster copper nano-enzyme has a copper loading capacity of 0.5% in terms of weight percent.
The preparation method of the nano-carbon loaded cluster copper nano-enzyme comprises the following steps: directly loading copper nano particles on nano carbon by adopting a deposition precipitation method, and carrying out H at 600 DEG C 2 Reducing for 1 hour under the condition to obtain the nano-carbon loaded cluster copper nano-enzyme.
Further, in the preparation method, the copper nanoparticles are directly loaded on the nanocarbon by adopting a deposition precipitation method, and the method comprises the following steps: dispersing nano diamond/graphene in water to obtain a suspension, regulating the pH of the system to 11, adding a copper nitrate aqueous solution into the suspension dropwise under stirring at 100 ℃, keeping stirring for 1 hour, filtering, washing and drying.
The invention provides application of nanocarbon-loaded cluster copper nanoenzyme in antibiosis.
Further, the method comprises the following steps: and adding the nano-carbon loaded cluster copper nano-enzyme into the bacterial suspension.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the nano-carbon is used as a carrier to load copper in an atomic-level dispersed cluster state as nano-enzyme, and the nano-enzyme has excellent oxidase catalytic activity. The nano-enzyme shows strong sterilization effect when applied to the field of antibiosis, and the antibiosis rate can reach 100%.
2. According to the invention, the nano-carbon is used as a carrier to load copper in an atomic-level dispersed cluster state as nano-enzyme, and the highly dispersed copper is used as an active center, so that the atomic utilization rate is improved, and the catalytic activity of the material is enhanced.
3. According to the invention, the nano-carbon is used as a carrier to load copper in an atomic-level dispersed cluster state as the nano-enzyme, and the nano-enzyme is synthesized by a deposition precipitation method, so that the preparation method is simple and the large-scale production can be realized.
4. According to the invention, the nano-carbon is used as a carrier to load copper in an atomic-level dispersed cluster state as nano-enzyme, and active oxygen substances are generated by catalyzing oxygen decomposition in air, so that the antibacterial purpose is achieved, and the method is efficient and environment-friendly.
5. The invention adopts the nano carbon as the carrier to load the copper in the atomic-level dispersed cluster state as the nano enzyme, and has very wide application prospect in the fields of chemical engineering, catalysis, biological medicine and the like.
In a word, in the nano-enzyme disclosed by the invention, copper exists in the form of clusters dispersed in atomic scale, so that the enzyme catalytic activity of copper is obviously improved, and the nano-enzyme can catalyze the decomposition of oxygen to achieve complete sterilization. The synthesis process is simple and convenient, the reaction process is easy to control, and the prepared nano-carbon loaded cluster copper nano-enzyme has excellent catalytic antibacterial performance and has potential application in the biomedical field.
Drawings
FIG. 1 is a related HAADF-STEM diagram of nanocomposite Cu-NPs/ND@G;
wherein A:100nm; b:10nm.
FIG. 2 is a schematic diagram of a nanocarbon-supported clustered copper nanoenzyme Cu 3 A related HAADF-STEM map of ND@G;
wherein A:2nm; b:1nm.
FIG. 3 is a graph of Cu-NPs/ND@G and Cu 3 Relative X-ray diffraction pattern of/ND@G (XRD pattern).
FIG. 4 is a graph of Cu-NPs/ND@G and Cu 3 TMB experimental plot of/ND@G.
Wherein A: cu-NPs/ND@G and Cu 3 Typical Michaelis-Menten curves for ND@G; b: cu (Cu) 3 ND@G at O 2 Saturation, air saturation and N 2 Ultraviolet absorption spectrum under saturation.
FIG. 5 is a graph of Cu-NPs/ND@G and Cu 3 and/ND@G.
Wherein A: blank; b: ND@G antibacterial effect diagram; c: cu-NPs/ND@G antibacterial effect diagram; d: cu (Cu) 3 and/ND@G antibacterial effect graph.
Detailed Description
For better understanding of the technical solution of the present invention, specific examples are described in further detail, but the solution is not limited thereto.
Example 1
Nanocarbon-supported clustered copper nanoenzyme (Cu 3 /ND@G)
The preparation method comprises the following steps:
1. 200mg of nano diamond/graphene (ND@G) is taken in a round-bottomed flask, 30mL of deionized water is added, the mixture is dispersed by ultrasonic treatment, and the pH value of the system is regulated to about 11, so that ND@G suspension is obtained. Then, 4mL of an aqueous copper nitrate solution (containing 0.25 mg. Multidot.mL) was stirred magnetically at 100deg.C in an oil bath -1 Cu) dropwise adding to NDIn the @ G suspension, stirring was maintained for 1 hour. And finally, naturally cooling the obtained product to room temperature, collecting solid matters, washing and drying to obtain the nanocomposite, and recording the nanocomposite as Cu-NPs/ND@G.
2. Spreading the nanocomposite Cu-NPs/ND@G obtained in step 1 in a porcelain boat, placing in a tube furnace, gradually heating to 600deg.C, and standing at H 2 Reducing for 1 hour under the condition to obtain the nano-carbon loaded cluster copper nano-enzyme which is marked as Cu 3 /ND@G). Copper loading was 0.5% by weight.
(II) detection
FIG. 1 is a related HAADF-STEM diagram of nanocomposite Cu-NPs/ND@G. From fig. 1, it can be seen that the copper nanoparticles have smaller particle size and good dispersion, and no agglomeration phenomenon occurs.
FIG. 2 shows a nanocarbon-supported clustered copper nanoenzyme Cu 3 HAADF-STEM diagram related to ND@G. As can be seen from fig. 2, copper exists in an atomically dispersed cluster state, and no agglomeration phenomenon occurs.
FIG. 3 is a graph of Cu-NPs/ND@G and Cu 3 Relative X-ray diffraction pattern of/ND@G. As can be seen from fig. 3, the loading of copper did not disrupt the structure of the carbon support, and no characteristic peaks of copper appeared in the XRD pattern, indicating that the particle size of copper was extremely small.
Example 2
Nanocarbon-supported clustered copper nanoenzyme Cu 3 Oxidase Activity Studies of ND@G
Cu-NPs/ND@G and Cu 3 TMB experiment of ND@G
Determination of Cu-NPs/ND@G and Cu by TMB experiments 3 ND@G mimics oxidase activity.
The method comprises the following steps: 10 mu L of the mixture was concentrated to 0.5 mg/mL -1 Cu-NPs/ND@G (or Cu) 3 ND@G) and 20. Mu.L of TMB (3, 3', 5' -tetramethylbenzidine) at a concentration of 20mM were added to a solution containing 970. Mu.L of sodium acetate-acetic acid buffer [100mM (pH=4.0)]Is included in the centrifuge tube. Investigation of Cu-NPs/ND@G and Cu by measuring the change in UV absorption of oxidized forms of TMB at a wavelength of 652nm 3 Catalytic oxidation of TMB by/ND@G, and further calculation of Cu-NPs/ND@G and Cu 3 Oxidase activity of ND@G.
FIG. 4 is CuNPs/ND@G and Cu 3 TMB experimental plot of/ND@G. FIG. 4A is a graph of Cu-NPs/ND@G and Cu 3 As can be seen from FIG. 4A, the typical Michaelis-Menten curve of/ND@G shows that the oxidase activity of Cu-NPs/ND@G is extremely low, cu compared with Cu-NPs/ND@G 3 ND@G exhibits excellent oxidase activity as a nanoenzyme. B in FIG. 4 is Cu 3 ND@G at O 2 Saturation, air saturation and N 2 As can be seen from the ultraviolet absorption spectrum under saturation, FIG. 4B shows, cu under different gas conditions 3 The ability of/ND@G to catalyze TMB oxidation was different, with the highest catalytic activity under oxygen conditions, and a second time in air, indicating Cu 3 the/ND@G catalytic oxygen decomposition oxidizes TMB. Verify Cu 3 The ND@G nano enzyme has excellent oxidase activity, and can catalyze the decomposition of oxygen in air to generate active oxygen substances to achieve the aim of antibiosis, so that the ND@G nano enzyme has application in the field of antibiosis.
Example 3
Nanocarbon-supported clustered copper nanoenzyme Cu 3 Application of ND@G in antibiosis
An antibacterial experiment comprises the following steps:
1) Preparation of LB medium: weighing 2.5g of sodium chloride, 2.5g of peptone, 1.25g of yeast extract powder, adding water to 250mL, and regulating the pH value of the yeast extract powder to be 7.2-7.4 by using a NaOH solution to obtain an LB liquid culture medium; adding 2% agar into LB liquid medium to obtain solid medium, sterilizing in 121 deg.C high pressure steam sterilizing pot for 30min, and refrigerating.
2) E.coli strain (E.coli ATCC 15597) is picked up by an inoculating loop, streaked on a solid culture medium, cultured for 24 hours in a 37 ℃ incubator, single colony is picked up in a liquid culture medium, and cultured for 11 hours in a constant temperature shaker at 37 ℃ to obtain bacterial suspension with an OD value of 2.162.
3) Centrifuging 5mL of the bacterial suspension on a centrifuge for 20min, washing with a phosphate buffer solution (hereinafter referred to as PBS) with pH=7.0, and adding PBS to obtain PBS bacterial suspension; stepwise diluting the bacterial suspension with phosphoric acid buffer solution to obtain final dilution concentration of 10 4 cfu·mL -1 。
4) 1mg of Cu-NPs/ND@G prepared in example 1 was weighed out separatelyCu 3 placing/ND@G into a centrifuge tube, respectively adding 4.5mL PBS, performing ultrasonic dispersion, and then respectively adding 0.5mL 10 in concentration 4 cfu·mL -1 Is fully and evenly shaken, 100 mu L of the coating plate is taken, the plate is placed in a constant temperature incubator at 37 ℃ for culturing for 24 hours, the growth condition of bacterial colonies is observed, and meanwhile, the antibacterial rate is counted and calculated.
FIG. 5 shows Cu-NPs/ND@G and Cu prepared by the method of the invention 3 and/ND@G. In the figure, A is blank; b is an ND@G antibacterial effect graph; c is Cu-NPs/ND@G antibacterial effect diagram; d is Cu 3 and/ND@G antibacterial effect graph. Cu was found by antibacterial experiments 3 The ND@G nano enzyme has more excellent antibacterial performance, and the antibacterial rate can reach 100%. This is a sufficient explanation of Cu synthesized according to the present invention 3 The ND@G nano enzyme has excellent antibacterial performance and has potential application in the field of catalytic antibacterial.
Claims (3)
1. The application of the nano-carbon loaded cluster copper nano-enzyme in the antibacterial process is characterized in that: the method comprises the following steps: adding nano-carbon loaded cluster copper nano-enzyme into the bacterial suspension; the nano-carbon-loaded cluster-state copper nano-enzyme is formed by taking nano-carbon as a carrier and taking atomic-level dispersed cluster-state copper as an active center; the preparation method of the nano-carbon loaded cluster copper nano-enzyme comprises the following steps: directly loading copper nano particles on nano carbon by adopting a deposition precipitation method, and carrying out H at 600 DEG C 2 Reducing for 1 hour under the condition to obtain the nano-carbon loaded cluster copper nano-enzyme.
2. The use according to claim 1, characterized in that: the nano carbon loaded cluster copper nano enzyme has copper loading capacity of 0.5 percent according to the weight percentage.
3. The use according to claim 1, wherein the copper nanoparticles are directly loaded onto the nanocarbons by a deposition precipitation method, comprising: dispersing nano diamond/graphene in water to obtain a suspension, regulating the pH of the system to 11, adding a copper nitrate aqueous solution into the suspension dropwise under stirring at 100 ℃, keeping stirring for 1 hour, filtering, washing and drying.
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| CN113786843B (en) * | 2021-10-09 | 2024-03-22 | 辽宁大学 | Nanometer carbon-loaded palladium-iron bimetallic cluster nano-enzyme and preparation method and application thereof |
| CN114588929B (en) * | 2022-03-16 | 2023-10-03 | 安徽大学 | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction |
| CN115121244B (en) * | 2022-06-17 | 2023-04-25 | 武汉理工大学 | Method for preparing graphene-loaded gold cluster nanocomposite by in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite |
| CN115845840A (en) * | 2022-12-23 | 2023-03-28 | 辽宁大学 | Graphene-loaded atomic-level dispersed palladium-based catalyst and preparation method and application thereof |
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| CN109806867A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院金属研究所 | Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application |
| CN111185171A (en) * | 2020-01-18 | 2020-05-22 | 中北大学 | Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme |
| CN111217401A (en) * | 2020-01-14 | 2020-06-02 | 扬州大学 | Copper-cobalt-sulfur nano enzyme material, preparation method and antibacterial application thereof |
| CN111744552A (en) * | 2020-07-17 | 2020-10-09 | 华南理工大学 | Nano-enzyme bactericide based on bimetallic organic framework and preparation method and application thereof |
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| CN109806867A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院金属研究所 | Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application |
| CN111217401A (en) * | 2020-01-14 | 2020-06-02 | 扬州大学 | Copper-cobalt-sulfur nano enzyme material, preparation method and antibacterial application thereof |
| CN111185171A (en) * | 2020-01-18 | 2020-05-22 | 中北大学 | Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme |
| CN111744552A (en) * | 2020-07-17 | 2020-10-09 | 华南理工大学 | Nano-enzyme bactericide based on bimetallic organic framework and preparation method and application thereof |
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| "纳米粒子沉积改性碳纳米管及其抗菌性能研究";陈丹;《中国优秀硕士学位论文全文数据库 工程科技I辑》(第9期);摘要 * |
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