CN113318733B - Preparation method and application of high-entropy nanoenzyme - Google Patents
Preparation method and application of high-entropy nanoenzyme Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 102000004190 Enzymes Human genes 0.000 claims abstract description 35
- 108090000790 Enzymes Proteins 0.000 claims abstract description 35
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002086 nanomaterial Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 97
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000004094 surface-active agent Substances 0.000 claims description 26
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 18
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 18
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 claims description 18
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 3
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 claims description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 16
- 229910045601 alloy Inorganic materials 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000003013 cytotoxicity Effects 0.000 abstract description 3
- 231100000135 cytotoxicity Toxicity 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- PSLMOSLVUSXMDQ-UHFFFAOYSA-N iridium;pentane-2,4-dione Chemical compound [Ir].CC(=O)CC(C)=O PSLMOSLVUSXMDQ-UHFFFAOYSA-N 0.000 abstract 1
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 abstract 1
- GJYLBGHKIMDUIH-UHFFFAOYSA-N pentane-2,4-dione;rhodium Chemical compound [Rh].CC(=O)CC(C)=O GJYLBGHKIMDUIH-UHFFFAOYSA-N 0.000 abstract 1
- RFYYQFJZJJCJNT-UHFFFAOYSA-N pentane-2,4-dione;ruthenium Chemical compound [Ru].CC(=O)CC(C)=O RFYYQFJZJJCJNT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/243—Platinum; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- B01J35/23—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method and application of high-entropy nanoenzyme. The method takes acetylacetone ruthenium, acetylacetone rhodium, acetylacetone palladium, acetylacetone platinum, acetylacetone iridium and acetylacetone as raw materials. In a strong alkaline solvent, generating a polymer precursor through intermolecular polymerization, and obtaining the high-entropy nano enzyme by utilizing a calcination method. The method has the advantages of simple method, small and uniform size of the nano particles, adjustable density of the nano particles and the like, and the reaction system is not added with redundant solvent, thereby meeting the requirement of environmental protection. The preparation method of the high-entropy nano material provided by the invention can promote the further development of related researches of nano enzyme and high-entropy alloy. The high-entropy nano material prepared by the method has excellent peroxidase-like activity, can catalyze hydrogen peroxide to generate hydroxyl radicals with strong cytotoxicity, and therefore has good medical application prospects.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method and application of high-entropy nanoenzyme.
Background
Metal alloy materials are ubiquitous in everyday life and play an extremely important role in the development of mankind. In recent years, a brand new alloy design concept breaks through the traditional thought, and researchers mix five or more elements in (near) equal atomic ratio to obtain single-phase solid solution alloy with simple crystal structure. It is considered that the maximized configuration entropy is realized by component regulation in a multi-element system to play an important role in stabilizing the novel alloy structure, so researchers name the novel alloy as a high-entropy alloy. High-entropy alloys (High-entropy alloys) are referred to as HEAs and are defined as alloys formed from five or more equal or approximately equal amounts of metals. I.e. all elements in the high entropy alloy are close to equal proportions. Recent studies have shown that the concentration of each element is between 5 and 35 atomic percent. High entropy alloys have attracted great attention in academia due to their properties of extremely high strength, toughness, corrosion resistance, wear resistance and oxidation resistance. As a nano material with catalytic activity similar to that of natural enzymes, the preparation of the high-entropy nano enzyme based on the high-entropy alloy has not been reported so far. The development of a new method for preparing the high-entropy nano enzyme has important value on the preparation of the high-entropy alloy and also has important effect on the development of the nano enzyme subject.
Disclosure of Invention
The invention aims to provide a method for preparing high-entropy nano enzyme. The high-entropy nano material is obtained by performing polymerization reaction on five metal complexes of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate in a strongly alkaline acetylacetone solution and calcining a generated polymer precursor, so that the prepared high-entropy nano material has peroxidase-like activity.
The preparation method of the high-entropy nano enzyme provided by the invention comprises the following steps:
(1) pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the mixed solution is as follows: ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, iridium acetylacetonate, 1, (0.02-0.001); treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 10-30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compounds in the reaction solution are fully dissolved to obtain a first solution;
(2) adding a surfactant into the first solution, treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring the mixed solution for 10 to 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 1.5-10 g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30-60 minutes to ensure that the mass concentration of the sodium hydroxide in the solution is as follows: 0.05-0.5 g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. And (3) drying the polymer precursor in a 60 ℃ oven for 12 hours, transferring the polymer precursor into a tubular furnace, heating the polymer precursor to 400-800 ℃ at the rate of 5 ℃ per minute for 3 hours, washing the calcined product with deionized water, and transferring the calcined product into the 60 ℃ oven for drying for 12 hours to obtain the high-entropy nano enzyme. .
The preparation method and the application of the high-entropy nano enzyme provided by the invention have the advantages that:
the preparation method of the high-entropy nano material of the invention prepares uniform high-entropy nano enzyme for the first time. The high-entropy nano enzyme prepared by the method has the advantages of simple method, nano particles with the size of only 1-2nm, adjustable density of nano alloy and the like, and a reaction system is not added with redundant solvent, so that the requirement of environmental protection is met. The preparation method can promote the further development of the related research of the nano enzyme and the high-entropy alloy. The high-entropy nano material prepared by the method has excellent peroxidase-like activity and can catalyze hydrogen peroxide to generate hydroxyl radicals with strong cytotoxicity. The high-entropy nanoenzyme prepared by the invention can be used for treating tumors, so that the high-entropy nanoenzyme has a good medical application prospect.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the high-entropy nanoenzyme prepared by the method of the present invention.
FIG. 2 is a scanning-transmission electron microscope (STEM) image of the high-entropy nanoenzyme prepared by the method of the present invention.
FIG. 3 is an X-ray energy spectrum analysis (EDS) diagram of the high-entropy nanoenzyme prepared by the method of the present invention.
FIG. 4 is a peroxidase-like enzyme activity study of the high-entropy nanoenzymes prepared by the method of the present invention.
Detailed Description
The preparation method of the high-entropy nano enzyme provided by the invention comprises the following steps:
(1) pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the mixed solution is as follows: ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate, 1 (0.02-0.001), (0.02-0.001); treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 10-30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compounds in the reaction solution are fully dissolved to obtain a first solution;
(2) adding a surfactant into the first solution, treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring the mixed solution for 10 to 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 1.5-10 g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30-60 minutes to ensure that the mass concentration of the sodium hydroxide in the solution is as follows: 0.05-0.5 g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. And (3) drying the polymer precursor in an oven at 60 ℃ for 12 hours, transferring the polymer precursor into a tubular furnace, heating the polymer precursor to 400-800 ℃ at a rate of 5 ℃ per minute, calcining the polymer precursor for 3 hours, washing the calcined product with deionized water, and transferring the calcined product into the oven at 60 ℃ for drying for 12 hours to obtain the high-entropy nano enzyme.
The surfactant in the preparation method can be cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate or sodium octadecyl sulfate.
The high-entropy nano material prepared by the preparation method can be used for catalyzing hydrogen peroxide, the high-entropy nano enzyme can simulate the property of natural enzyme, has high-efficiency peroxidase-like activity, can catalyze the hydrogen peroxide to generate hydroxyl radicals with strong cytotoxicity, and can be used as a nano medicament for treating tumors.
The application process comprises the following steps:
(1) dispersing the high-entropy nano enzyme into ultrapure water to enable the mass volume concentration of the high-entropy nano enzyme to be 0.1mg/mL, and performing ultrasonic treatment with the ultrasonic power of 250W for 10-30 minutes to obtain a fourth solution;
(2) adding 20 mu L of 3,3',5,5' -Tetramethylbenzidine (TMB) solution with the mass concentration of 5mg/mL into acetic acid-sodium acetate (HAc-NaAc) buffer solution with the pH value of 4.5, adding 5-25 mu L of fourth solution, and then adding 20 mu L of hydrogen peroxide. Then, the ultraviolet absorption change of the reaction solution is measured by using an ultraviolet spectrophotometer, and the enzymatic activity of the reaction solution is measured.
The method of the invention uses ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, iridium acetylacetonate and acetylacetone as raw materials, generates a polymer precursor through intermolecular polymerization reaction in a strong alkaline solvent, and obtains a TEM picture of the high-entropy nanoenzyme by means of calcination as shown in figure 1 and a STEM picture as shown in figure 2. The size of the high entropy nanoenzyme is shown in FIGS. 1 and 2 as 1-2 nm. As shown in FIG. 3, ESD characterization shows that the high-entropy nanoenzyme contains five elements of ruthenium, rhodium, palladium, platinum and iridium.
The nano enzyme prepared by the method has high-efficiency catalytic activity of peroxidase-like enzyme, and can quickly catalyze hydrogen peroxide and generate hydroxyl radicals. FIG. 4 is a UV absorption spectrum of a peroxidase-like enzyme tested for its activity.
The following describes embodiments of the method of the invention:
example 1:
(1) five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate are poured into the acetylacetone solution, and the mass ratio of the mixed solution is acetylacetone to ruthenium acetylacetonate to rhodium acetylacetonate to palladium acetylacetonate to platinum acetylacetonate to iridium acetylacetonate is 1:0.02:0.02:0.02:0.02: 0.02. Treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 10 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compound in the reaction solution is fully dissolved to obtain a first solution;
(2) adding a surface active agent cetyl trimethyl ammonium chloride into the first solution, treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 10 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surface active agent in the reaction solution is fully dissolved so that the mass concentration of the surface active agent is as follows: 1.5g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30 minutes, wherein the mass concentration of the sodium hydroxide in the solution is as follows: 0.05g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. After drying the polymer precursor in an oven at 60 ℃ for 12 hours, it was transferred to a tube furnace and calcined at a rate of 5 ℃ per minute to 800 ℃ for 3 hours. And washing the calcined product with deionized water, and transferring the calcined product to a 60-DEG C oven for drying for 12 hours to obtain the high-entropy nano enzyme.
Example 2:
(1) pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the acetylacetone to the ruthenium acetylacetonate to the rhodium acetylacetonate to the palladium acetylacetonate to the platinum acetylacetonate to the iridium acetylacetonate is 1:0.001:0.001:0.001: 0.001. Treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 10 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compound in the reaction solution is fully dissolved to obtain a first solution;
(2) adding a surfactant cetyl trimethyl ammonium chloride into the first solution, treating the mixed solution for 10 minutes by using ultrasonic with the power of 250W, and stirring for 10 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 1.5g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30 minutes, wherein the mass concentration of the sodium hydroxide in the solution is as follows: 0.05g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. After drying the polymer precursor in an oven at 60 ℃ for 12 hours, it was transferred to a tube furnace and calcined at a rate of 5 ℃ per minute to 400 ℃ for 3 hours. And washing the calcined product with deionized water, and transferring the calcined product to a 60-DEG C oven for drying for 12 hours to obtain the high-entropy nano enzyme.
Example 3:
(1) the method comprises the steps of pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the mixed solution is acetylacetone to ruthenium acetylacetonate to rhodium acetylacetonate to palladium acetylacetonate to platinum acetylacetonate to iridium acetylacetonate to 1:0.01:0.01:0.01: 0.01. Treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compound in the reaction solution is fully dissolved to obtain a first solution;
(2) adding cetyl trimethyl ammonium bromide serving as a surfactant into the first solution, treating the mixed solution for 10 minutes by using ultrasonic with the power of 250W, and stirring for 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 10g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 60 minutes, wherein the mass concentration of the sodium hydroxide in the solution is as follows: 0.5g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. After drying the polymer precursor in an oven at 60 ℃ for 12 hours, it was transferred to a tube furnace and calcined at a rate of 5 ℃ per minute to 800 ℃ for 3 hours. And washing the calcined product with deionized water, and transferring the calcined product to a 60-DEG C oven for drying for 12 hours to obtain the high-entropy nano enzyme.
Example 4:
(1) the method comprises the steps of pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the mixed solution is that ruthenium acetylacetonate to rhodium acetylacetonate to palladium acetylacetonate to platinum acetylacetonate to iridium acetylacetonate is 1:0.005:0.005:0.005:0.005: 0.005. Treating the mixed solution by using ultrasonic with the power of 250W for 30 minutes, and stirring the mixed solution for 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compound in the reaction solution is fully dissolved to obtain a first solution;
(2) adding sodium dodecyl benzene sulfonate serving as a surfactant into the first solution, treating the mixed solution for 10 minutes by using ultrasonic with the power of 250W, and stirring the mixed solution for 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 10g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 60 minutes, wherein the mass concentration of the sodium hydroxide in the solution is as follows: 0.05g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. After drying the polymer precursor in an oven at 60 ℃ for 12 hours, it was transferred to a tube furnace and calcined at a rate of 5 ℃ per minute to 800 ℃ for 3 hours. And washing the calcined product with deionized water, and transferring the calcined product to a 60-DEG C oven for drying for 12 hours to obtain the high-entropy nano enzyme.
Example 5:
(1) five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate are poured into the acetylacetone solution, and the mass ratio of the mixed solution is acetylacetone to ruthenium acetylacetonate to rhodium acetylacetonate to palladium acetylacetonate to platinum acetylacetonate to iridium acetylacetonate is 1:0.02:0.02:0.02:0.02: 0.02. Treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring for 20 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the compound in the reaction solution is fully dissolved to obtain a first solution;
(2) adding sodium stearyl sulfate serving as a surfactant into the first solution, treating the mixed solution by using ultrasonic waves with the power of 250W for 10 minutes, and stirring the mixed solution for 30 minutes by using a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 10g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30-60 minutes, wherein the mass concentration of the sodium hydroxide in the solution is as follows: 0.15g/mL to obtain a third reaction solution;
(4) and placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor. After drying the polymer precursor in an oven at 60 ℃ for 12 hours, it was transferred to a tube furnace and calcined at a rate of 5 ℃ per minute to 800 ℃ for 3 hours. And washing the calcined product with deionized water, and transferring the calcined product to a 60-DEG C oven for drying for 12 hours to obtain the high-entropy nano enzyme.
Application example 1:
(1) dispersing the high-entropy nano enzyme into ultrapure water to ensure that the mass volume concentration of the high-entropy nano enzyme is 0.1mg/mL, and carrying out ultrasonic treatment for 10 minutes with the ultrasonic power of 250W to obtain a fourth solution;
(2) 20 μ L of TMB solution with a mass concentration of 5mg/mL was added to HAc-NaAc buffer solution with a pH of 4.5, 5 μ L of the fourth solution was added, 20 μ L of hydrogen peroxide was added, and the change in the ultraviolet absorption of the reaction solution was measured using an ultraviolet spectrophotometer to measure the enzymatic activity thereof.
Application example 2:
(1) dispersing the high-entropy nano enzyme into ultrapure water to ensure that the mass volume concentration of the high-entropy nano enzyme is 0.1mg/mL, and carrying out ultrasonic treatment for 30 minutes with the ultrasonic power of 250W to obtain a fourth solution;
(2) 20. mu.L of TMB solution with a mass concentration of 5mg/mL was added to HAc-NaAc buffer solution with a pH of 4.5, 25. mu.L of the fourth solution was added, 20. mu.L of hydrogen peroxide was added, and the change in the ultraviolet absorption of the reaction solution was measured using an ultraviolet spectrophotometer to measure the enzymatic activity thereof.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of high-entropy nanoenzyme is characterized by comprising the following steps:
(1) pouring five compounds of ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate and iridium acetylacetonate into an acetylacetone solution, wherein the mass ratio of the mixed solution is as follows: ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, iridium acetylacetonate =1 (0.02-0.001), (0.02-0.001); treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and after the compound in the reaction solution is fully dissolved, stirring for 10-30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute to obtain a first solution;
(2) adding a surfactant into the first solution, treating the mixed solution by using ultrasonic with the power of 250W for 10 minutes, and stirring the mixed solution for 10 to 30 minutes in a magnetic stirrer with the stirring speed of 600 revolutions per minute after the surfactant in the reaction solution is fully dissolved so that the mass concentration of the surfactant is as follows: 1.5-10 g/L to obtain a second solution;
(3) adding sodium hydroxide into the second solution, and then stirring the mixed solution in a magnetic stirrer with the stirring speed of 600 revolutions per minute for 30-60 minutes to ensure that the mass concentration of the sodium hydroxide in the solution is as follows: 0.05-0.5 g/mL to obtain a third reaction solution;
(4) and (3) placing the third solution at room temperature for reaction for two weeks to obtain a solidified polymer precursor, drying the polymer precursor in a 60 ℃ drying oven for 12 hours, transferring to a tubular furnace, heating to 400-800 ℃ at the rate of 5 ℃ per minute for calcining for 3 hours, washing the calcined product with deionized water, and transferring to the 60 ℃ drying oven for drying for 12 hours to obtain the high-entropy nano enzyme.
2. The method according to claim 1, wherein the surfactant in step (2) is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate or sodium octadecylsulfate.
3. Use of a high-entropy nanomaterial prepared by the preparation method according to claim 1, wherein the high-entropy nanomaterial is used for catalyzing hydrogen peroxide, and comprises the following steps:
(1) dispersing the high-entropy nano enzyme into ultrapure water to enable the mass volume concentration of the high-entropy nano enzyme to be 0.1mg/mL, and performing ultrasonic treatment with the ultrasonic power of 250W for 10-30 minutes to obtain a fourth solution;
(2) adding 20 mu L of 3,3',5,5' -Tetramethylbenzidine (TMB) solution with the mass concentration of 5mg/mL into acetic acid-sodium acetate (HAc-NaAc) buffer solution with the pH value of 4.5, adding 5-25 mu L of fourth solution, and then adding 20 mu L of hydrogen peroxide.
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| CN108526481A (en) * | 2018-03-28 | 2018-09-14 | 华侨大学 | A kind of preparation method of racemosus shape Nanoalloy elctro-catalyst |
| CN112475315A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Method for universally preparing high-entropy alloy nanoparticles |
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| CN108526481A (en) * | 2018-03-28 | 2018-09-14 | 华侨大学 | A kind of preparation method of racemosus shape Nanoalloy elctro-catalyst |
| CN112475315A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Method for universally preparing high-entropy alloy nanoparticles |
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