CN114471728B - Nano enzyme compounded by copper nano particles and iron porphyrin nano sheets, preparation and application thereof - Google Patents
Nano enzyme compounded by copper nano particles and iron porphyrin nano sheets, preparation and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 60
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 49
- 239000010949 copper Substances 0.000 title claims abstract description 49
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 claims abstract description 49
- 239000008103 glucose Substances 0.000 claims abstract description 49
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 36
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 239000001044 red dye Substances 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 229940088598 enzyme Drugs 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 68
- 239000007864 aqueous solution Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000002835 absorbance Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000004366 Glucose oxidase Substances 0.000 claims description 20
- 229940116332 glucose oxidase Drugs 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007853 buffer solution Substances 0.000 claims description 16
- 239000002073 nanorod Substances 0.000 claims description 13
- XDIYNQZUNSSENW-UUBOPVPUSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-UUBOPVPUSA-N 0.000 claims description 10
- 108010015776 Glucose oxidase Proteins 0.000 claims description 10
- 235000019420 glucose oxidase Nutrition 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000005750 Copper hydroxide Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- 238000004042 decolorization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 240000003291 Armoracia rusticana Species 0.000 abstract description 4
- 238000004445 quantitative analysis Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002064 nanoplatelet Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- -1 copper-tetracarboxyl phenyl iron porphyrin Chemical compound 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- B01J35/20—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
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- B01J35/33—Electric or magnetic properties
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets and a preparation method thereof, which can solve the problem that the prior art is limited to preparing enzyme-like composite nano materials by noble metals. The technical scheme includes that the composite nano-enzyme is formed by in-situ growth of non-noble metal copper nano-particles on the surface of an iron porphyrin nano-sheet, and the nano-enzyme has horseradish peroxidase-like activity. The prepared nano enzyme is utilized to realize the degradation of Congo red dye and the detection of glucose. The invention can be used in the aspects of enzyme imitation catalysis and quantitative analysis in the fields of chemical industry, environment and biotechnology.
Description
Technical Field
The invention belongs to the field of enzyme-like catalysis, and particularly relates to a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets, a preparation method and application thereof.
Background
The natural enzyme has high catalytic efficiency and mild reaction conditions, but the natural enzyme has poor stability, is easy to inactivate and store, has high cost and limits the application of the natural enzyme. It is therefore a research hotspot to find a material with both enzymatic activity and high stability. The nano-enzyme is a nano-material with simulated enzyme activity, and the discovery and research of the nano-enzyme fills the defect of the natural enzyme. Among the existing materials for simulating enzyme activity, ferriporphyrin Metal Organic Frameworks (MOFs), particularly ferriporphyrin MOFs nanosheets with two-dimensional structures, are very promising enzyme-simulating catalysts (CN 202010342037.8).
In order to further improve the catalytic performance of the ferriporphyrin nanoplatelets, some composite nanomaterials are attracting attention. Qia et al prepared Pd/Cu-TCPP (Fe) hybrid nanomaterial with Pd nanoparticles grown on the surface of ferriporphyrin MOFs nanosheets, which showed catalytic activity mimicking enzymes, and was applicable to explosive residue detection of organic peroxides (2D Materials,2019,6 (3): 035008). Ling et al found that Pt@PMOF (Fe) showed excellent catalase activity against hydrogen peroxide (H) 2 O 2 ) And O 2 Has high electrocatalytic activity and can be applied to the fields of fuel cells and the like (ACS Applied Materials And Interfaces,2020, 12 (15): 17185). However, these techniques are based on the growth of noble metal materials on two-dimensional MOFs to form composite materials that increase their catalytic activity, increasing the cost of the mimic enzymes. Therefore, the nano enzyme compounded by the non-noble metal nano material and the ferriporphyrin MOFs nano sheet is prepared, and is applied to the related fields of enzyme imitation catalysis, and has important application and research values.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a nano-enzyme compounded by copper nano-particles and iron porphyrin nano-sheets and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
synthesizing copper-tetracarboxyl phenyl iron porphyrin (Cu-FeTCPP) two-dimensional MOFs nano-sheet by a surfactant auxiliary solvothermal method, and then growing copper nano-particles on the surface of the iron porphyrin nano-sheet in situ, wherein the method specifically comprises the following steps:
(1) Synthesizing Cu-FeTCPP nano-sheets by adopting a surfactant-assisted solvothermal method, dispersing the Cu-FeTCPP nano-sheets in water, wherein the concentration of the nano-sheets is 0.3mg/mL, and obtaining a dispersion liquid;
(2) Adding the dispersion liquid into a copper chloride aqueous solution with the concentration of 0.12M, uniformly mixing, then dropwise adding an ammonia water solution with the mass fraction of 0.1%, wherein the volume ratio of the dispersion liquid to the copper chloride aqueous solution is 10:0.1-0.3, the volume ratio of the dispersion liquid to the ammonia water solution is 10:1-2, and obtaining a product solution after reaction, wherein the reaction temperature is 20-30 ℃ and the reaction time is 1 min-15 h;
(3) And sequentially carrying out centrifugal precipitation and pure water washing on the product solution to obtain the nano enzyme.
The prepared iron porphyrin nanosheets in the nano enzyme have ultrathin two-dimensional lamellar structures, and the thickness is 3-10 nm; the copper nano particles comprise copper hydroxide and copper oxide, the morphology of the copper nano particles comprises the morphology of nano particles, nano needles and nano rods, the particle size of the nano particles is 10-50 nm, the diameter of the nano needles is 20-40 nm, the length of the nano needles is 100-300 nm, the diameter of the nano rods is 50-70 nm, and the length of the nano rods is 200-300 nm; the copper nano particles are uniformly distributed on the surface of the ferriporphyrin nano sheet, and the mass ratio of the copper nano particles to the ferriporphyrin nano sheet is 0.35:1-0.8:1.
The nano enzyme compounded by the copper nano particles and the iron porphyrin nano sheets has horseradish peroxidase-like catalytic activity and can catalyze H 2 O 2 Oxidizing 3,3', 5' -tetramethyl benzidine (TMB) to make it develop color, and making the copper series nano particles and iron porphyrin nano sheets have synergistic action, and the catalytic activity of the composite nano enzyme is higher than that of copper series nano particles, iron porphyrin nano sheets and their mixture, and reaction substrate H 2 O 2 And TMB has good affinity, and the Mie constant is lower than that of the iron porphyrin nanosheets serving as catalysts under the same condition.
The nano-enzyme compounded by the copper nano-particles and the iron porphyrin nano-sheets can be used as horseradish-like peroxidase and applied to enzyme-like catalysis.
Preferably, the nano enzyme compounded by the copper nano particles and the iron porphyrin nano sheets is applied to catalyzing Congo red dye degradation, and is reacted for 20min under the optimized condition, wherein the Congo red dye decoloring rate is more than 90%, the degradation efficiency is high, and the method for catalyzing the Congo red dye comprises the following steps:
(1) Adding Tris buffer solution with the concentration of 0.1 to M, pH of 6.8 to 8 into Congo red water solution; wherein, the volume ratio of the Congo red water solution to the Tris buffer solution is 1:1-5;
(2) Adding the aqueous solution of the nano-enzyme and H into the solution in the step (1) 2 O 2 Obtaining an initial mixed solution by using the aqueous solution, and finishing the degradation of Congo red dye after reacting for 0.5-6 h; wherein the concentration of the nano enzyme in the initial mixed solution is 10-100 mg/L, and the H is 2 O 2 The concentration of Congo red is 10-100 mM, and the concentration of Congo red is 10-200 mu M.
Preferably, the nano enzyme compounded by the copper nano particles and the iron porphyrin nano sheets is applied to glucose detection, the minimum detection limit of the glucose detection is 12 mu M, the detection sensitivity is high, and the detection method comprises the following steps:
(1) Preparing at least three standard aqueous solutions with glucose concentration, respectively adding glucose oxidase phosphate buffer solution into each standard aqueous solution to obtain glucose-glucose oxidase mixed solution, reacting at 50 ℃ for 1h, sequentially adding acetic acid buffer solution with 1-5 times of the volume of the glucose-glucose oxidase mixed solution, aqueous solution of nano enzyme and TMB aqueous solution to obtain initial reaction solution, reacting the initial reaction solution at 20-30 ℃ for 2-5 h to obtain detection solution, and respectively detecting each detection solution by an ultraviolet spectrophotometer to obtain absorbance corresponding to each standard aqueous solution;
wherein, in the initial reaction solution, the concentration of the glucose is 0.05-1.5 mM, the concentration of the glucose oxidase is 0.5-2 mg/mL, the pH of the acetic acid buffer solution is 3.5-4.2, the concentration of the nano enzyme is 0.1M, the concentration of the nano enzyme is 5-20 mg/mL, and the concentration of the TMB is 0.05-0.2 mM; the detection wavelength of the ultraviolet spectrophotometer is 650nm;
(2) Fitting a standard curve equation according to the concentration of glucose in each standard aqueous solution and the corresponding absorbance;
(3) And (3) testing the glucose aqueous solution to be detected by adopting the method of the step (1), obtaining the absorbance of the glucose aqueous solution to be detected, and calculating the concentration of the glucose aqueous solution to be detected according to the standard curve equation obtained in the step (2).
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, non-noble metal copper nano particles are adopted to be compounded with iron porphyrin nano sheets to prepare nano enzyme, so that the nano enzyme has enhanced horseradish-like peroxidase activity;
2. according to the invention, the nano enzyme compounded by the copper nano particles and the iron porphyrin nano sheets is applied to the degradation of Congo red dye, so that the high-efficiency decolorization of Congo red under the preferable condition is realized;
3. the invention applies the nano enzyme compounded by the copper nano particles and the iron porphyrin nano sheets to the detection of glucose, and establishes a high-sensitivity detection method for glucose based on the catalysis of the compound nano enzyme.
Drawings
FIG. 1. Ultraviolet absorption spectra of different types of catalysts for catalyzing TMB (catalysts: a, iron porphyrin nanoplatelets in comparative example 1; b, copper-based nanoparticles in comparative example 2; c, a mixture of copper-based nanoparticles and iron porphyrin nanoplatelets in comparative example 3; d, nanoenzyme of copper-based nanoparticle and iron porphyrin nanoplatelets complex in example 1), respectively);
FIG. 2 is a transmission electron microscope image of a nano-enzyme compounded by copper-based nano-particles and iron porphyrin nano-sheets in example 1;
FIG. 3 shows the change in Congo red dye discoloration rate over time in example 1;
FIG. 4 is a graph showing the relationship between the color of the solution and the concentration of glucose in example 1;
FIG. 5 is a transmission electron microscope image of a nanoenzyme in which copper-based nanoparticles and iron porphyrin nanoplates are compounded in example 2;
FIG. 6 is a transmission electron microscope image of a nanoenzyme in which copper-based nanoparticles and iron porphyrin nanoplates were combined in example 3.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
The invention relates to a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets, and preparation and application thereof. Specifically, non-noble metal copper nano particles are adopted to be compounded with the iron porphyrin nano sheet in an in-situ growth mode to prepare nano enzyme, so that the catalytic activity of the iron porphyrin nano sheet is improved, and the problem that the preparation of the enzyme-like material by the noble metal nano particles is limited in the prior art is solved. The present invention will be further described with reference to examples, but the present invention is not limited to the examples.
Comparative example 1: preparation and catalysis of copper-tetracarboxyl phenyl iron porphyrin (Cu-FeTCPP) two-dimensional MOFs nano-sheet
Dissolving 0.01mmol of copper nitrate and 10.0mg of polyvinylpyrrolidone in 12mL of a mixed solution of N, N-dimethylformamide and absolute ethyl alcohol in a volume ratio of 3:1, and marking the mixed solution as a solution a; dissolving 0.005mmol of tetracarboxyphenyl ferriporphyrin (FeTCPP) in 4mL of a mixed solution of N, N-dimethylformamide and absolute ethyl alcohol in a volume ratio of 3:1, and marking the mixed solution as a solution b; solution b was added dropwise to solution a, followed by 20 μl of trifluoroacetic acid (1.0M), mixed well by sonication and reacted at 80 ℃ for 3h; after the reaction, adding a proper amount of absolute ethyl alcohol, washing and centrifuging for 10min at the temperature of 8000r.p.m, repeating for 3 times, and dispersing in water for standby.
The prepared Cu-FeTCPP iron porphyrin nanosheets are used as catalysts for catalytic color development of TMB, and experimental conditions are as follows: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb chromogenic absorbance at 650nm wavelength of 0.28 as shown in fig. 1 a.
Comparative example 2: preparation and catalysis of copper nanoparticles
Adding 0.1mL of 0.12M copper chloride aqueous solution into 10mL of water, uniformly mixing, and then dropwise adding 1mL of 0.1% ammonia water solution for reaction for 1min; the product was then subjected to centrifugal precipitation and washed 3 times with pure water.
The prepared copper nano-particlesAs a catalyst, for catalytic color development of TMB, experimental conditions: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb chromogenic absorbance at 650nm wavelength of 0.07 as shown in fig. 1 b.
Comparative example 3: preparation and catalysis of mixture of copper nano particles and Cu-FeTCPP nano sheets
The Cu-FeTCPP nano-sheet prepared in comparative example 1 and the copper-based nano-particle prepared in comparative example 2 are mixed in a mass ratio of 1:0.35 and used as a catalyst for catalytic color development of TMB, and experimental conditions are as follows: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb chromogenic absorbance at 650nm wavelength of 0.35 as shown in fig. 1 c.
Example 1:
preparing a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets:
(1) Dispersing the Cu-FeTCPP nano-sheets prepared in comparative example 1 in water to make the concentration of the Cu-FeTCPP nano-sheets be 0.3mg/mL;
(2) Taking 10mL of the solution in the step (1), adding 0.1mL of 0.12M copper chloride aqueous solution, uniformly mixing, and then dropwise adding 1mL of 0.1% ammonia water solution for reaction for 1min at 20 ℃;
(3) And (3) centrifugally precipitating the product, and washing the product with pure water for 3 times to obtain the nano enzyme.
The copper-based nano particles mainly comprise copper hydroxide and copper oxide, and are in the shape of nano particles, nano needles and nano rods as shown in figure 2, wherein the nano particles and the nano needles are mainly used, the particle size of the nano particles is 10-50 nm, the diameter of the nano needles is 20-40 nm, the length of the nano needles is 100-300 nm, and the nano needles are uniformly distributed on the surface of the nano sheet; the mass ratio of the copper nano-particles to the iron porphyrin nano-sheets is 0.35:1.
The nano-enzyme is used as a catalyst for the catalytic color development of TMB, and the experimental conditions are as follows: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb developed absorbance at 650nm wavelength of 0.48 (as shown in fig. 1 d), with horseradish-like peroxidase-like activity, and comparativeThe TMB color development absorbance is high in the proportion of 1 to 3, and the enzyme-like activity is higher.
The nano-enzyme is applied to degradation of Congo red dye:
(1) Adding 3 times volume of Tris buffer solution with the concentration of 0.1M and the pH of 7 into the Congo red dye solution;
(2) Adding nano enzyme water solution and H into the solution in the step (1) 2 O 2 An aqueous solution, wherein the Congo red concentration is 80 mu M, the nano enzyme concentration is 100mg/L, H 2 O 2 The concentration was 100mM; after the initial mixed solution is reacted for 4 hours, the decoloring rate is 95 percent, and the Congo red dye degradation is completed.
As the reaction proceeded, congo red concentration gradually decreased, and the decolorization rate reached 91% at 20min of the reaction, as shown in FIG. 3.
The nano-enzyme is applied to glucose detection:
(1) Preparing 9 standard aqueous solutions with glucose concentration, respectively adding glucose oxidase phosphate buffer solution into each standard aqueous solution to obtain glucose-glucose oxidase mixed solution, reacting at 50 ℃ for 1h, sequentially adding acetic acid buffer solution with 3 times of volume of the glucose-glucose oxidase mixed solution, aqueous solution of nano enzyme and aqueous solution of TMB to obtain initial reaction solution, reacting the initial reaction solution at 25 ℃ for 3h to obtain detection solutions, and respectively detecting the 9 detection solutions by an ultraviolet spectrophotometer to obtain absorbance of each standard aqueous solution at 650nm;
wherein, in the initial reaction solution, the concentration of glucose is 0.05-1.5 mM, the concentration of glucose oxidase is 1mg/mL, the pH of the acetic acid buffer solution is 3.6, the concentration is 0.1M, the concentration of nano enzyme is 10mg/mL, and the concentration of TMB is 0.1mM;
(2) Fitting a standard curve equation according to the concentration of glucose in each standard aqueous solution and the corresponding absorbance;
(3) And (3) testing the glucose aqueous solution to be detected by adopting the method of the step (1), obtaining the absorbance of the glucose aqueous solution to be detected, and calculating the concentration of the glucose aqueous solution to be detected according to the standard curve equation obtained in the step (2).
According to the glucose detection method, the detection limit is calculated to be 12 mu M, the linear range is 0.05-1.25 mM, the solution is blue, and the blue is more remarkable as the glucose concentration is larger (FIG. 4).
Example 2:
preparing a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets:
(1) Dispersing the Cu-FeTCPP nano-sheets prepared in comparative example 1 in water to make the concentration of the Cu-FeTCPP nano-sheets be 0.3mg/mL;
(2) Taking 10mL of the solution in the step (1), adding 0.15mL of 0.12M copper chloride aqueous solution, uniformly mixing, and then dropwise adding 1.2mL of 0.1% ammonia water solution in mass fraction, and reacting for 3h at 25 ℃;
(3) And (3) centrifugally precipitating the product, and washing the product with pure water for 3 times to obtain the nano enzyme.
The copper-based nano particles mainly comprise copper hydroxide and copper oxide, and as shown in figure 5, the morphology of the copper-based nano particles mainly comprises nanoneedles and nanorods, the diameter of the nanoneedles is 20-40 nm, the length of the nanoneedles is 100-300 nm, the diameter of the nanorods is 50-70 nm, the length of the nanorods is 200-300 nm, and the copper-based nano particles are uniformly distributed on the surfaces of the nano sheets; the mass ratio of the copper nano-particles to the iron porphyrin nano-sheets is 0.49:1.
The nano-enzyme is used as a catalyst for the catalytic color development of TMB, and the experimental conditions are as follows: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb chromogenic absorbance at 650nm wavelength of 0.46, with horseradish peroxidase-like activity.
The nano-enzyme is applied to degradation of Congo red dye:
(1) Adding 2 times volume of Tris buffer solution with the concentration of 0.1M and the pH of 6.8 into the Congo red dye solution;
(2) Adding aqueous solution of nano enzyme and H into the solution in the step (1) 2 O 2 An aqueous solution, wherein Congo red concentration is 60 mu M, nano enzyme concentration is 80mg/L, H 2 O 2 The concentration was 70mM; after the initial mixed solution is reacted for 3 hours, the decoloring rate is 96 percent, and the Congo red dye degradation is completed.
With the progress of the reaction, the Congo red concentration gradually decreases, and the decoloring rate reaches 92% when the reaction is carried out for 20 min.
The nano-enzyme is applied to glucose detection:
(1) Preparing 5 standard aqueous solutions with glucose concentration, respectively adding glucose oxidase phosphate buffer solution into each standard aqueous solution to obtain glucose-glucose oxidase mixed solution, reacting at 50 ℃ for 1h, sequentially adding acetic acid buffer solution with 2.5 times of the volume of the glucose-glucose oxidase mixed solution, aqueous solution of nano enzyme and aqueous solution of TMB to obtain initial reaction solution, reacting the initial reaction solution at 20 ℃ for 4h to obtain detection solutions, respectively detecting the 5 detection solutions by an ultraviolet spectrophotometer to obtain absorbance of 650nm of each standard aqueous solution;
wherein, in the initial reaction solution, the concentration of the glucose is 0.07-1.2 mM, the concentration of the glucose oxidase is 1.5mg/mL, the pH of the acetic acid buffer solution is 3.9, the concentration of the nano enzyme is 0.1M, the concentration of the nano enzyme is 8mg/mL, and the concentration of the TMB is 0.15mM;
(2) Fitting a standard curve equation according to the concentration of glucose in each standard aqueous solution and the corresponding absorbance;
(3) And (3) testing the glucose aqueous solution to be detected by adopting the method of the step (1), obtaining the absorbance of the glucose aqueous solution to be detected, and calculating the concentration of the glucose aqueous solution to be detected according to the standard curve equation obtained in the step (2).
According to the glucose detection method, the detection limit is calculated to be 13 mu M, the linear range is 0.07-1.2 mM, the solution is blue, and the blue is more remarkable as the concentration of glucose is higher.
Example 3:
preparing a nano enzyme compounded by copper nano particles and iron porphyrin nano sheets:
(1) Dispersing the Cu-FeTCPP nano-sheets prepared in comparative example 1 in water to make the concentration of the Cu-FeTCPP nano-sheets be 0.3mg/mL;
(2) Taking 10mL of the solution in the step (1), adding 0.2mL of 0.12M copper chloride aqueous solution, uniformly mixing, and then dropwise adding 1.5mL of 0.1% ammonia water solution in mass fraction, and reacting for 6h at 25 ℃;
(3) And (3) centrifugally precipitating the product, and washing the product with pure water for 3 times to obtain the nano enzyme.
The copper-based nano particles mainly comprise copper hydroxide and copper oxide, and as shown in fig. 6, the morphology of the copper-based nano particles is mainly composed of nano needles and nano rods, the diameter of the nano needles is 20-40 nm, the length of the nano needles is 100-300 nm, the diameter of the nano rods is 50-70 nm, the length of the nano rods is 200-300 nm, and the nano needles are uniformly distributed on the surface of the nano sheets; the mass ratio of the copper nano-particles to the iron porphyrin nano-sheets is 0.64:1.
The nano-enzyme is used as a catalyst for the catalytic color development of TMB, and the experimental conditions are as follows: 9.5mg/L catalyst, 0.12mM TMB,5mM H 2 O 2 Acetic acid buffer system ph=3.6, concentration 0.1m, tmb chromogenic absorbance at 650nm wavelength of 0.44, with horseradish peroxidase-like activity.
The nano-enzyme is applied to degradation of Congo red dye:
(1) Adding 4 times volume of Tris buffer solution with the concentration of 0.1M and the pH of 8 into the Congo red dye solution;
(2) Adding aqueous solution of nano enzyme and H into the solution in the step (1) 2 O 2 An aqueous solution, wherein Congo red concentration is 40 mu M, nano enzyme concentration is 50mg/L, H 2 O 2 The concentration was 50mM; after the initial mixed solution is reacted for 2 hours, the decoloring rate is 94 percent, and the Congo red dye degradation is completed.
With the progress of the reaction, the Congo red concentration gradually decreases, and the decolorization rate reaches 93% when the reaction is carried out for 20 min.
The nano-enzyme is applied to glucose detection:
(1) Preparing 7 standard aqueous solutions with glucose concentration, respectively adding glucose oxidase phosphate buffer solution into each standard aqueous solution to obtain glucose-glucose oxidase mixed solution, reacting at 50 ℃ for 1h, sequentially adding acetic acid buffer solution with 2.5 times of the volume of the glucose-glucose oxidase mixed solution, aqueous solution of nano enzyme and aqueous solution of TMB to obtain initial reaction solution, reacting the initial reaction solution at 30 ℃ for 2h to obtain detection solutions, respectively detecting the 7 detection solutions by an ultraviolet spectrophotometer to obtain absorbance of 650nm of each standard aqueous solution;
wherein, in the initial reaction solution, the concentration of glucose is 0.08-1.5 mM, the concentration of glucose oxidase is 2mg/mL, the pH of an acetic acid buffer solution is 4.1, the concentration of nano enzyme is 0.1M, the concentration of nano enzyme is 15mg/mL, and the concentration of TMB is 0.18mM;
(2) Fitting a standard curve equation according to the concentration of glucose in each standard aqueous solution and the corresponding absorbance;
(3) And (3) testing the glucose aqueous solution to be detected by adopting the method of the step (1), obtaining the absorbance of the glucose aqueous solution to be detected, and calculating the concentration of the glucose aqueous solution to be detected according to the standard curve equation obtained in the step (2).
According to the glucose detection method, the detection limit is calculated to be 14 mu M, the linear range is 0.08-1.5 mM, the solution is blue, and the blue is more remarkable as the concentration of glucose is higher.
Claims (4)
1. The nano enzyme compounded by copper nano particles and iron porphyrin nano sheets is characterized in that: the nano enzyme is formed by in-situ growth of copper nano particles on the surface of an iron porphyrin nano sheet;
the iron porphyrin nano-sheet is a Cu-FeTCPP nano-sheet; the Cu-FeTCPP nanosheets are two-dimensional MOFs nanosheets with tetracarboxyl phenyl ferriporphyrin as a ligand and copper ions as metal nodes;
the composition of the copper-based nanoparticles comprises copper hydroxide and copper oxide; the microscopic morphology of the copper-based nano particles comprises at least one of nano particles, nano needles and nano rods, wherein the particle size of the nano particles is 10-50 nm, the diameter of the nano needles is 20-40 nm, the length of the nano needles is 100-300 nm, and the diameter of the nano rods is 50-70 nm, and the length of the nano rods is 200-300 nm;
the copper nano particles are uniformly distributed on the surface of the iron porphyrin nano sheet, and the mass ratio of the copper nano particles to the iron porphyrin nano sheet is 0.35:1-0.8:1;
the preparation method of the nano-enzyme comprises the following steps:
(1) Synthesizing Cu-FeTCPP nano-sheets by adopting a surfactant auxiliary solvothermal method, and dispersing the Cu-FeTCPP nano-sheets in water to obtain dispersion liquid; wherein the concentration of the Cu-FeTCPP nano-sheets in the dispersion liquid is 0.3mg/mL;
(2) Adding the dispersion liquid into a copper chloride aqueous solution with the concentration of 0.12M, uniformly mixing, then dropwise adding an ammonia water solution with the mass fraction of 0.1%, wherein the volume ratio of the dispersion liquid to the copper chloride aqueous solution is 10:0.1-0.3, and the volume ratio of the dispersion liquid to the ammonia water solution is 10:1-2, and obtaining a product solution after reaction; wherein the reaction temperature of the reaction is 20-30 ℃ and the reaction time is 1 min-15 h;
(3) And sequentially carrying out centrifugal precipitation and pure water washing on the product solution to obtain the nano enzyme.
2. The application of the nano-enzyme based on the combination of the copper-based nano-particles and the iron porphyrin nano-sheets as claimed in claim 1, which is characterized by being applied to degradation of congo red dye and glucose detection.
3. The use according to claim 2, characterized in that it is applied to degrade congo red dye, for 20min, with a congo red dye decolorization ratio of more than 90%; the degradation congo red dye comprises the following steps:
(1) Adding Tris buffer solution with the concentration of 0.1 to M, pH of 6.8 to 8 into Congo red water solution; wherein, the volume ratio of the Congo red water solution to the Tris buffer solution is 1:1-5;
(2) Adding the aqueous solution of the nano-enzyme and H into the solution in the step (1) 2 O 2 Aqueous solution to obtain initial mixed solution, and making the initial mixed solution undergo the process of reactionAfter 0.5-6 h, finishing the degradation of Congo red dye; wherein the concentration of the nano enzyme in the initial mixed solution is 10-100 mg/L, and the H is 2 O 2 The concentration of Congo red is 10-100 mM, and the concentration of Congo red is 10-200 mu M.
4. The use according to claim 2, characterized in that it is applied for glucose detection with a minimum limit of detection of 12 μm; the glucose detection comprises the following steps:
(1) Preparing at least three standard aqueous solutions with glucose concentration, respectively adding glucose oxidase phosphate buffer solution into each standard aqueous solution to obtain glucose-glucose oxidase mixed solution, reacting at 50 ℃ for 1h, sequentially adding acetic acid buffer solution with 1-5 times of the volume of the glucose-glucose oxidase mixed solution, the nano enzyme and 3,3', 5' -tetramethyl benzidine to obtain initial reaction solution, reacting the initial reaction solution at 20-30 ℃ for 2-5 h to obtain detection solution, respectively detecting each detection solution by an ultraviolet spectrophotometer to obtain absorbance corresponding to each glucose standard aqueous solution;
wherein, in the initial reaction solution, the concentration of the glucose is 0.05-1.5 mM, the concentration of the glucose oxidase is 0.5-2 mg/mL, the pH of the acetic acid buffer solution is 3.5-4.2, the concentration of the nano enzyme is 0.1M, the concentration of the nano enzyme is 5-20 mg/mL, and the concentration of the 3,3', 5' -tetramethyl benzidine is 0.05-0.2 mM; the detection wavelength of the ultraviolet spectrophotometer is 650nm;
(2) Fitting a standard curve equation according to the concentration of glucose in each standard aqueous solution and the corresponding absorbance;
(3) And (3) testing the glucose aqueous solution to be detected by adopting the method of the step (1), obtaining the absorbance of the glucose aqueous solution to be detected, and calculating the concentration of the glucose aqueous solution to be detected according to the standard curve equation obtained in the step (2).
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