CN113351220A - CuNi/CoMoO serving as multifunctional laccase-like enzyme4Preparation method and application of - Google Patents
CuNi/CoMoO serving as multifunctional laccase-like enzyme4Preparation method and application of Download PDFInfo
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- CN113351220A CN113351220A CN202110544866.9A CN202110544866A CN113351220A CN 113351220 A CN113351220 A CN 113351220A CN 202110544866 A CN202110544866 A CN 202110544866A CN 113351220 A CN113351220 A CN 113351220A
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- laccase
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- 229910003336 CuNi Inorganic materials 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 120
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 88
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 44
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 44
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 44
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 29
- 102000004190 Enzymes Human genes 0.000 claims abstract description 25
- 108090000790 Enzymes Proteins 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 12
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 claims description 56
- 229930182837 (R)-adrenaline Natural products 0.000 claims description 49
- 229960005139 epinephrine Drugs 0.000 claims description 49
- 238000001514 detection method Methods 0.000 claims description 45
- 108010029541 Laccase Proteins 0.000 claims description 32
- UCTWMZQNUQWSLP-UHFFFAOYSA-N adrenaline Chemical compound CNCC(O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-UHFFFAOYSA-N 0.000 claims description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002835 absorbance Methods 0.000 claims description 20
- 239000003344 environmental pollutant Substances 0.000 claims description 20
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000007853 buffer solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 231100000719 pollutant Toxicity 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- MIIIXQJBDGSIKL-UHFFFAOYSA-N 2-morpholin-4-ylethanesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)CCN1CCOCC1 MIIIXQJBDGSIKL-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 230000000007 visual effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 10
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- 239000002243 precursor Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 238000011088 calibration curve Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 claims description 4
- 229960003887 dichlorophen Drugs 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229940090668 parachlorophenol Drugs 0.000 claims description 4
- 229960003742 phenol Drugs 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003556 assay Methods 0.000 claims description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 26
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 238000005470 impregnation Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 229940088598 enzyme Drugs 0.000 description 22
- 235000013824 polyphenols Nutrition 0.000 description 21
- 239000010949 copper Substances 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 230000037361 pathway Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000027756 respiratory electron transport chain Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910002476 CuII Inorganic materials 0.000 description 4
- LVNMAAGSAUGNIC-BQBZGAKWSA-N Cys-His Chemical compound SC[C@H](N)C(=O)N[C@H](C(O)=O)CC1=CNC=N1 LVNMAAGSAUGNIC-BQBZGAKWSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007987 MES buffer Substances 0.000 description 3
- 229940102884 adrenalin Drugs 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
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- 108010016626 Dipeptides Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
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- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
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- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
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- 125000003636 chemical group Chemical group 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- 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
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- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
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- 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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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- C02F2101/40—Organic compounds containing sulfur
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention relates to CuNi/CoMoO serving as a multifunctional laccase-like enzyme4Preparation method and application of (1), bagThe method comprises the following steps: s1: CoMoO4Preparation of (a) and S2: CuNi/CoMoO4And (4) preparing. The invention adopts a method combining hydrothermal treatment, calcination and impregnation to prepare CuNi/CoMoO4Is favorable for adsorbing reactants to participate in enzyme catalytic reaction and shows better catalytic activity. Using CuNi/CoMoO4The ascorbic acid colorimetric sensor is established by the laccase-like activity, a portable intelligent terminal platform combined with a chrominance signal is established, and efficient degradation of acid fuchsin is realized.
Description
Technical Field
The invention relates to a chemical substance preparation and determination technology, in particular to CuNi/CoMoO serving as a multifunctional laccase-like enzyme4The preparation method and the application thereof.
Background
The nano material with the biological enzyme-like activity is called nano enzyme, and because the nano material can overcome the defects of long fermentation time, low yield, poor stability and the like inherent in natural enzyme, the nano material draws great attention and interest in various fields. At present, a plurality of nano enzymes are proved to have properties like peroxidase, oxidase, catalase, superoxide dismutase and laccase, and have wide application prospects in the aspects of biosensing, pollutant degradation, environmental remediation and the like. For example, MMoO has been successfully prepared4(M ═ Co, Ni) nanoflower having peroxidase-like activity and useful for copper ion (Cu)2+) Selective detection of (2). Metal Organic Framework (MOF) derived Co has also been prepared3O4The @ Co-Fe oxide double-shell nanocage is used as a multifunctional specific peroxidase-like nanoenzyme catalyst, a multifunctional platform for detecting acetylcholinesterase is constructed, the activity of Peroxymonosulfate (PMS) can be well activated, and after 10 cycles, the degradation efficiency of Acid Fuchsin (AF) is still kept at 92.3%.
However, few laccase-like active nanoenzymes have been reported, compared to nanoenzymes with peroxidase-like activity. Natural laccase is a copper-containing polyphenol oxidase, which can directly convert O2Reduction to H2O without producing H2O2Widely distributed in bacteria, fungi and plantsIn a species. Recently, researchers have prepared a novel nano enzyme with laccase-like activity by coordination of Cu (I)/Cu (II) and cysteine (Cys) -histidine (His) dipeptide, and the nano enzyme is used for degrading and detecting phenolic pollutants by modifying active sites and electron transfer pathways.
However, the preparation of multifunctional nanoenzymes with high laccase-like activity for chemical and biological sensing, contaminant degradation, and PMS activation, etc. remains a great challenge. In recent years, mixed transition metal molybdate oxides have received increasing attention as a catalyst material with high catalytic activity. CoMoO with large specific surface area4Exhibit excellent catalytic activity in various fields such as catalysis, lithium ion batteries, high-performance supercapacitors and sensors. For example, a CoMoO having a large specific surface area is prepared by a simple hydrothermal method4Due to the synergistic effect of good oxidation-reduction property of Co element and good conductivity of Mo element, Co element shows higher peroxidase-like activity and is used for colorimetric detection of H2O2. Nickel has been extensively studied as an abundant and stable metal in the field of catalysis, and some have prepared Ni/Cu nanosheet arrays by constant current electrodeposition, showing high electrocatalytic activity against Hydrogen Evolution Reaction (HER). Some successfully prepared CuNi-NPs loaded MIL-101 nano composite materials, have high catalytic activity and are used for aminoborane hydrolysis. In previous reports, the metal Cu and Ni nanoparticles have strong synergistic effect, and can improve the catalytic activity.
However, the preparation of multifunctional nanoenzymes with high laccase-like activity and the application thereof in chemical and biological sensing, pollutant degradation and other aspects are still technical problems to be solved in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides CuNi/CoMoO as a multifunctional laccase-like enzyme4The CuNi/CoMoO is prepared by a method combining hydrothermal, calcination and impregnation4More effective active sites are provided, the specific surface area of the composite material is increased by introducing CuNi nano particles, and more active sites are exposedThe Cu (I) active center is favorable for adsorbing reactants to participate in enzyme catalytic reaction, and shows better catalytic activity. The invention also provides a CuNi/CoMoO as a multifunctional laccase-like enzyme4Using CuNi/CoMoO4The activity of the laccase-like enzyme establishes a colorimetric sensor of ascorbic acid, can effectively degrade phenolic pollutants and environmental pollutants, takes epinephrine as a model of the phenolic pollutants, establishes a portable intelligent terminal platform combined with chrominance signals, realizes convenient, visual and intuitive detection, and realizes efficient degradation of acid fuchsin.
In order to achieve the purpose, the invention adopts the main technical scheme that:
CuNi/CoMoO serving as multifunctional laccase-like enzyme4The preparation method comprises the following steps:
S1：CoMoO4preparation of
Mixing Na2MoO4·2H2O and Co (NO)3)2·6H2O is fully stirred and dissolved in deionized water, and then the mixture is reacted in a high-pressure kettle; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, and the precursor is calcined to obtain the CoMoO4；
S2：CuNi/CoMoO4Preparation of
Adding CuCl2·2H2O、NiCl2·6H2O and prepared CoMoO4Dissolving in deionized water and stirring; then adding NaHB4Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO4。
Further, in step S1:
Na2MoO4·2H2o and Co (NO)3)2·6H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1;
the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h;
the vacuum drying temperature is 75-85 ℃, the calcining temperature is 345-355 ℃, and the calcining time is 1.5-2.5 h.
Further, in step S2:
CuCl2·2H2o and NiCl2·6H2The dosage ratio of O is a molar ratio which is 1-6: 1;
stirring in deionized water for 2-4 h;
NaHB4the concentration of (A) is 9-11mgmL-1Adding NaHB4The later stirring time is 4-6 h;
the temperature of vacuum drying is 75-85 ℃.
According to a second aspect of the invention, the CuNi/CoMoO obtained4Application to the determination of ascorbic acid:
uniformly dispersing CuNi/CoMoO4Adding into tris buffer solution, adding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations, and incubating at 37 deg.C for 1.5h to obtain red sample;
then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
CuNi/CoMoO4the concentration of (3) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
Furthermore, the linear detection range of the ascorbic acid is 1-150 mu M, and the detection limit is 0.70 mu M;
wherein:
when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R2＝0.98826；
When the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R2＝0.99611；
Wherein: and X is the concentration of ascorbic acid.
According to a third aspect of the invention, the CuNi/CoMoO obtained4The method is applied to the catalytic degradation of phenolic pollutants:
uniformly dispersing CuNi/CoMoO4Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates at 510nm by using an ultraviolet-visible spectrophotometer;
the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol;
wherein the content of the first and second substances,
CuNi/CoMoO4the concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
According to a fourth aspect of the invention, the CuNi/CoMoO obtained4Application to the catalytic degradation of acid fuchsin:
preparation of CuNi/CoMoO containing acid fuchsin solution and peroxymonosulfate4Uniformly dispersing the mixed solution of the suspension by using ultrasonic waves, and measuring the absorbance of the suspension at 545nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
the pH of the acid fuchsin solution is 3.0-6.0, and the CuNi/CoMoO4Has a concentration of 1.5mg/mL and a concentration of peroxymonosulfate of 2mg/mL-1。
According to a fifth aspect of the invention, the CuNi/CoMoO is prepared4Application to the catalytic oxidation of epinephrine:
different concentrations of epinephrine are injected into a solution containing CuNi/CoMoO4In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer;
wherein:
CuNi/CoMoO4the concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM;
the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R20.99745 for adrenalineThe linear detection range of the concentration and the adrenalin is 5-50 mu g/mL.
According to the sixth aspect of the invention, the prepared CuNi/CoMoO is detected based on the visual detection platform of the portable intelligent terminal4Visual assay applied to epinephrine:
different concentrations of epinephrine were mixed with CuNi/CoMoO4Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO4Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp;
then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen;
wherein:
CuNi/CoMoO4the concentration of (3) was 1.0mg/mL, and the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer was 7.0 and the concentration was 50 mM.
Further, the curve fitted with epinephrine is Y ═ 0.7561+0.0344X, R2And (3) 0.9937, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
The invention has the beneficial effects that:
(1) the CuNi/CoMoO is prepared by a method combining hydrothermal treatment, calcination and impregnation4The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity even under extreme pH, temperature, long-term storage and high salt concentration4Also shows higher activity.
(2) Using CuNi/CoMoO4The laccase-like enzyme activity establishes a colorimetric sensor of ascorbic acid, the linear range of the colorimetric sensor is 1-150 mu M, the detection limit is 0.70 mu M, the detection limit and the linear range of the colorimetric sensor are equivalent to those of methods obtained by other sensors, even the colorimetric sensor is obtained by other sensorsAnd more preferably.
(3) Can effectively degrade phenolic pollutants and environmental pollutants, CuNi/CoMoO4Not only can catalyze the oxidation of phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, and the catalytic activity shows that CuNi/CoMoO4The nano enzyme has good substrate universality.
(4) A portable intelligent terminal platform combined with a chrominance signal is constructed by taking epinephrine as a model of phenolic pollutants, and a visual, visual and convenient epinephrine instant detection method is established without expensive equipment.
(5)CuNi/CoMoO4Due to the catalytic generation of SO4 ·-And OH, realizing efficient degradation of acid fuchsin.
Drawings
FIG. 1 shows CuNi/CoMoO4Schematic representation of laccase-like nanoenzyme catalysis mechanism.
FIG. 2 shows CuNi/CoMoO4Schematic synthesis of (a).
FIG. 3 is a CoMoO4Scanning Electron Microscope (SEM) images of (a).
FIG. 4 is a schematic representation of CuNi/CoMoO4Scanning Electron Microscope (SEM) images of (a).
FIG. 5 is a schematic representation of CuNi/CoMoO4Transmission Electron Microscope (TEM) images of (a).
FIG. 6 is a schematic representation of CuNi/CoMoO4The ultraviolet absorption spectrum of (1) with or without Ascorbic Acid (AA).
FIG. 7 is a calibration curve for Ascorbic Acid (AA).
Fig. 8 is a graph of Total Antioxidant Capacity (TAC) measured in a commercial beverage using ascorbic acid as a model.
FIG. 9 is a schematic representation of CuNi/CoMoO4Comparing the catalytic effect of natural laccase on different phenolic substrates (n ═ 3), wherein a1 is CuNi/CoMoO4Catalyzing the absorbance of different phenolic substrates, and a2 is the absorbance of the natural laccase catalyzing different phenolic substrates.
FIG. 10 shows 2- (N-morpholino) ethanesulfonic acid monohydrate (PMS), CuNi/CoMoO4And CuNi/CoMoO4The effect of PMS system on Acid Fuchsin (AF) degradation is shown.
Figure 11 is the effect of initial pH on AF degradation.
FIG. 12 shows the reaction rate constants (k) for AF solutions at different pH values.
FIG. 13 is a schematic representation of CuNi/CoMoO4The method is applied to the relation between different concentrations of adrenalin (n-3) and absorbance.
FIG. 14 is a CuNi/CoMoO-based alloy4Schematic diagram of applying to visual analysis determination APP colorimetric signal quantitative determination adrenaline of adrenaline.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The technical scheme of the invention is summarized as follows: the invention provides a CuNi/CoMoO serving as a multifunctional laccase-like enzyme4The CuNi/CoMoO is prepared by a method combining hydrothermal, calcination and impregnation4The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity. The invention also provides a CuNi/CoMoO as a multifunctional laccase-like enzyme4Using CuNi/CoMoO4The activity of the laccase-like enzyme establishes a colorimetric sensor of ascorbic acid, can effectively degrade phenolic pollutants and environmental pollutants, takes epinephrine as a model of the phenolic pollutants, establishes a portable intelligent terminal platform combined with chrominance signals, realizes convenient, visual and intuitive detection, and realizes efficient degradation of acid fuchsin. CuNi/CoMoO of the invention4The laccase-like nanoenzyme catalysis mechanism is shown in fig. 1.
To illustrate the solution and technical advancement of the present invention, the technical solution and technical application designed now are as follows:
CuNi/CoMoO serving as multifunctional laccase-like enzyme4The preparation method comprises the following steps:
S1：CoMoO4preparation of
Mixing Na2MoO4·2H2O and Co (NO)3)2·6H2Fully stirring and dissolving O in deionized water, and then reacting in a high-pressure kettle; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, and the precursor is calcined to obtain the CoMoO4；
S2：CuNi/CoMoO4Preparation of
Adding CuCl2·2H2O、NiCl2·6H2O and prepared CoMoO4Dissolving in deionized water and stirring; then adding NaHB4Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO4。
In step S1: na (Na)2MoO4·2H2O and Co (NO)3)2·6H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1; the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h; the vacuum drying temperature is 75-85 ℃, the calcining temperature is 345-355 ℃, and the calcining time is 1.5-2.5 h.
In step S2: CuCl2·2H2O and NiCl2·6H2The dosage ratio of O is a molar ratio which is 1-6: 1; stirring in deionized water for 2-4 h; NaHB4The concentration of (A) is 9-11mg/mL, NaHB is added4The later stirring time is 4-6 h; the temperature of vacuum drying is 75-85 ℃.
The prepared CuNi/CoMoO4Application to the determination of ascorbic acid: uniformly dispersing CuNi/CoMoO4Adding into tris buffer solution, adding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations, and incubating at 37 deg.C for 1.5h to obtain red sample; then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer; wherein, CuNi/CoMoO4The concentration of (3) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
Ascorbic acid threadThe sexual detection range is 1-150 mu M, and the detection limit is 0.70 mu M; wherein: when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R20.98826; when the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R20.99611; wherein: and X is the concentration of ascorbic acid.
The prepared CuNi/CoMoO4The method is applied to the catalytic degradation of phenolic pollutants: uniformly dispersing CuNi/CoMoO4Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates by using an ultraviolet-visible spectrophotometer; the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol; wherein, CuNi/CoMoO4The concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
The prepared CuNi/CoMoO4Application to the catalytic degradation of acid fuchsin: preparation of a solution containing acid fuchsin, peroxymonosulfate and CuNi/CoMoO4Uniformly dispersing the mixed solution of the suspension by using ultrasonic waves, and measuring the absorbance of the suspension at 545nm by using an ultraviolet-visible spectrophotometer; wherein the pH of the acid fuchsin solution is 3.0-6.0, and the pH value of the acid fuchsin solution is CuNi/CoMoO4The concentration of (2) is 1.5mg/mL and the concentration of peroxysulphate is 2 mg/mL.
The prepared CuNi/CoMoO4Application to the catalytic oxidation of epinephrine: different concentrations of epinephrine are injected into a solution containing CuNi/CoMoO4In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer; wherein: CuNi/CoMoO4The concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM; the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R20.99745, X is kidneyThe concentration of the adrenaline and the linear detection range of the adrenaline are 5-50 mug/mL.
The prepared CuNi/CoMoO4Visual assay applied to epinephrine: different concentrations of epinephrine were mixed with CuNi/CoMoO4Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO4Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp; then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen; wherein: CuNi/CoMoO4The concentration of (3) was 1.0mg/mL, and the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer was 7.0 and the concentration was 50 mM.
The curve fitted for epinephrine is Y-0.7561 +0.0344X, R2And (3) 0.9937, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
Example (b):
(I) CuNi/CoMoO4Preparation example
S1：CoMoO4Preparation of
Adding 1mmol Na2MoO4·2H2O and 1mmolCo (NO)3)2·6H2O is fully stirred and dissolved in 40mL deionized water, and then the mixture reacts in a 50mL autoclave at 160 ℃ for 10 hours; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out at 80 ℃, and the precursor is calcined for 2h under the air condition of 350 ℃ to obtain the CoMoO4。
S2：CuNi/CoMoO4Preparation of
The molar ratio of the components is 3: 0.0768g of CuCl were weighed out in 12·2H2O, 0.0387g of NiCl2·6H2Ono and S1 prepared 0.04g of CoMoO4Dissolved in 20mL deionized water and stirred for 3h, then 10mL, 10mg/mL NaHB was added4Stirred for 5h, then washed with deionized water and ethanol and vacuum dried at 80 deg.CDrying, the resulting Cu/Ni molar ratio being about 3: 1 CuNi/CoMoO4。
As shown in FIGS. 1 to 4, CuNi/CoMoO is prepared by a combined hydrothermal, calcination and impregnation method4FIG. 1 shows CuNi/CoMoO4The synthesis process of (2); scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) images show the results from CoMoO4To CuNi/CoMoO4As shown in fig. 2-4. CoMoO4A rod-like structure and a smooth surface were presented (fig. 2). After CuNi nanoparticles (CuNi-NPs) are grown, in a CuNi/CoMoO4Medium, CoMoO4The rod-like structure of the body was maintained, but the surface was roughened and irregular by loading CuNi-NPs (fig. 3). The transmission electron microscope further proves that CuNi/CoMoO4A rod-like structure with a rough surface (fig. 4). The CuNi nano particles can be well dispersed in CoMoO with a rod-like structure4In addition, a more effective active site is provided for improving the laccase activity. The introduction of the CuNi nano particles increases the specific surface area of the composite material, exposes more Cu (I) active centers, is favorable for adsorbing reactants to participate in enzyme catalytic reaction, and shows better catalytic activity.
CuNi/CoMoO4The catalysis mechanism of (2) is shown in figure 1, and the copper cluster is the main active center of the natural laccase catalytic oxidation-reduction reaction. Laccase can be combined with substrate oxidation to promote O2Reduction of four electrons to H2O and can oxidize some environmental pollutants (e.g., phenol). Laccase, as a multicopper oxidase, is classified into type 1 (T1), type 2 (T2) and binuclear type 3 (T3) according to its unique spectral characteristics. The oxidation of the substrate by the natural laccase takes place in the vicinity of T1. Thereafter, electrons are transferred through the Cys-His pathway
The three-core copper cluster of T2/T3 is reached, and then redox occurs. According to previous reports, T1 is considered to be a metal-containing Electron Transfer (ET) active site, consisting of a short Cu-S (Cys) bond and two normal Cu-N (His) bonds. Cys-His is thought to be a bridge linking a remote catalytically active site to T1-Cu during electron transfer, and contains two potential electronsThe sub-transfer pathway: pathway 1(P1) passes through the protein backbone and pathway 2(P2) passes through hydrogen bonds between Cys-His. Due to Cu+/Cu0Has a redox potential higher than that of Cu2+/Cu+Thus, the electron transfer from the Cys-His pathway in native laccases is from Cu+To Cu2+。
In the presence of CuNi/CoMoO4In the catalysis of nano enzyme, 2, 4-dichlorophenol (2,4-DP) is used as a phenol substrate, CuNi/CoMoO4Possible catalytic pathways are shown in figure 1. The catalytic pathway mainly comprises four processes: (i) substrate adsorption, (ii) substrate oxidation, (iii) electron transfer and (iv) O transfer by four electrons2Reduction to H2And O. Specifically, Cu (Cu) is bonded to NiⅠ) More active, phenolic substrates 2,4-DP are coated with CuNi/CoMoO4Cu of nanoenzymeⅠAnd (4) adsorbing. Then, due to CuⅠOxidation ability of (2) is higher than that of CuIIHigh, phenolic substrates by CuⅠOxidation to phenolic hydroxyl radical with CuⅠIs reduced to Cu0. Subsequently, reduced Cu0Quilt O2Further oxidized to CuⅠ，O2As the primary acceptor site for single electron oxidation, electrons are transferred from Cu via steric interactions (saturation bonds, covalent bonds and hydrogen bonding electron transfer pathways)ⅠTransfer to CuII. After obtaining electrons, CuIIConversion to CuⅠ. Cu in the reaction system due to lack of protection of chemical groupsⅠQuilt O2Oxidation to CuIIWhile being O2Is reduced to H by four electron transfer2And O. Finally CuNi/CoMoO4The nanoenzyme is recycled.
(II) CuNi/CoMoO4Analytical determination example applied to Ascorbic Acid (AA)
First, 100. mu.L of 1.0mg/mL of uniformly dispersed CuNi/CoMoO is added4Tris-HCl buffer (1.5 mL) at pH6.5 was added to 100. mu.L of 2, 4-dichlorophenol (1 mg/mL), 100. mu.L of 4-aminoantipyrine (4-AP) at a concentration of 1mg/mL and ascorbic acid (different concentrations) and incubated at 37 ℃ for 1.5h to form a red sample. Measuring the reaction solution at 510nm with a UV-visible spectrophotometerAbsorbance.
Based on CuNi/CoMoO, as shown in FIGS. 6-84The laccase-like activity of (2) establishes a simple colorimetric chemical/biosensor for detecting AA. Under the optimal conditions, at 37 ℃, pH6.5(Tris-HCl buffer), the system reacts for 1.5h, and the mixture of 2, 4-dichlorophenol and 4-AP does not absorb at 510nm, as shown in figure 6, 2, 4-dichlorophenol, 4-AP and CuNi/CoMoO4The mixture of (2) has strong absorption at 510 nm. However, after adding AA to the mixture, the absorbance at 510nm decreased dramatically as shown in fig. 6, demonstrating the feasibility of AA detection. The linear dynamic range and limit of detection were obtained by tracking the uv-vis absorbance at 510nm for a series of mixed solutions of different AA concentrations. Within the range of 1-150 μ M, the Δ A value of ascorbic acid is linear with concentration, as shown in FIG. 7. The limit of detection (LOD) for AA is based on 3 σ/b (where σ is the standard deviation of the blank signal and b is the slope of the regression line) (S/N-3) with an ultra-low limit of detection of 0.70 μ M. As shown in table 1, the detection limit and linear range of the present invention are comparable to, and even better than, the methods obtained with other sensors.
Table 1 analytical method comparison for ascorbic acid detection.
Determination of Total Oxidation resistance (TAC)
As shown in fig. 8, the total antioxidant capacity of 5 commercial beverages was measured using ascorbic acid as an antioxidant model. In the determination of total antioxidant capacity, the conditions were the same as those for ascorbic acid detection except that the ascorbic acid was replaced with an actual sample. The concentration of the above sample was diluted to within the linear detection range of ascorbic acid. Finally, the total antioxidant capacity in the sample is expressed in ascorbic acid/liter.
Thereby further exploring the method inApplication in the analysis of actual commercial samples. Based on CuNi/CoMoO4Better laccase-like activity, and the TAC sensor is developed by taking AA as an antioxidant model. TAC is an important comprehensive index for evaluating the antioxidant capacity of an actual sample and can be used as an antioxidant biomarker for monitoring the health of organisms. Therefore, the development of a sensitive TAC detection technology is of great significance. Here, five commercial beverages were selected as the analysis targets. The test result is basically consistent with the technical indexes of the actual sample, which shows that the method can meet the test requirements of the actual sample and has certain practical significance.
(III) CuNi/CoMoO4Examples of the catalytic degradation of phenolic contaminants
To test CuNi/CoMoO4The laccase activity of (a) utilizes different laccase substrates including hydroquinone, phenol, dichlorophen, parachlorophenol, ortho-nitrophenol, and ortho-aminophenol. First, 100. mu.L of 1mg/mL of uniformly dispersed CuNi/CoMoO4Adding into 2- (N-morpholinyl) ethanesulfonic acid Monohydrate (MES) buffer solution with pH of 7.0, total volume of 1.5mL and concentration of 50mM, respectively adding 100 μ L and 1mg/mL of different laccase substrates and 100 μ L and 1mg/mL of 4-aminoantipyrine, incubating at 37 deg.C for 1.5h, and measuring absorbance of different laccase substrates at 510nm with ultraviolet-visible spectrophotometer. For comparison, 100. mu.L of 1U/mg of the natural laccase was also investigated according to the same procedure. The results are shown in FIG. 9.
Due to CuNi/CoMoO4Has laccase-like activity, and can be used for degrading 2, 4-DP. Furthermore, to evaluate CuNi/CoMoO4Substrate universality of nano-enzyme, which is mixed with different types of phenol and color developing agent (4-AP), proves that CuNi/CoMoO4Not only can catalyze the oxidation of the phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, which shows that CuNi/CoMoO4The nano enzyme has good substrate universality.
(IV) CuNi/CoMoO4Example of catalytic degradation applied to acid fuchsin
Evaluation of CuNi/CoMoO4Catalytic activity on Acid Fuchsin (AF) degradation. Preparing a simulated dye solution by adding acid fuchsin into distilled water, wherein the concentration of the acid fuchsinIt was 15 mg/L. Prior to measurement, 100. mu.L of 1.5mg/mL CuNi/CoMoO containing 10mL of an acid fuchsin solution (pH 5.0) and 400. mu.L of 2mg/mL Peroxosulfate (PMS) was prepared in a 25mL beaker4A mixed solution of the suspension, which is then uniformly dispersed with ultrasonic waves. The absorbance of the suspension at 545nm was recorded with a UV-Vis spectrophotometer for a predetermined period of time. The degradation efficiency of AF was calculated as follows:
eta: degradation efficiency;
C0: initial concentration of acid fuchsin (mol. L)-1)；
Ct: concentration of acid fuchsin at t (mol. L)-1)
The activation of AF by PMS evaluated CuNi/CoMoO4The catalytic performance of (2). PMS and H2O2Has similar O-O bonds and can be used as a strong oxidant. PMS and H2O2Standard oxidation/reduction potential (E)0) 1.82V and 1.776V, respectively. However, they have a limited ability to independently oxidize organic substances. To solve this problem, CuNi/CoMoO is used4PMS is activated to obtain SO with stronger oxidation capacity4 ·-And OH. Wherein the SO has a higher oxidation-reduction potential4 ·-The degradation capability of (2.5-3.1V) to pollutants is stronger than that of OH (1.8-2.7V). As shown in fig. 10, PMS reduced AF by only 5.80% within 40min, indicating that PMS produced almost no active radicals without catalyst. Similarly, the degradation efficiency of a single catalyst for AF was about 58.36%, indicating that CuNi/CoMoO4Has excellent specific surface adsorption AF. But when CuNi/CoMoO4When PMS and AF coexist, the degradation efficiency of AF reaches 99.45 percent, which shows that CuNi/CoMoO4The PMS can be well activated to achieve efficient degradation of AF. In addition, the CuNi/CoMoO4 can still maintain a good structure after degrading AF, which indicates that the catalyst has strong stability.
CuNi/CoMoO was studied by a series of control experiments4Degradation performance for AF. First, the effect of the initial pH of AF on the degradation efficiency was investigated. As shown in fig. 11-12, the degradation efficiency of AF was above 80% in the range of 3.0-6.0, and the reaction rate constants were calculated for AF solutions at different pH values, here the first order rate constant (k) was calculated, reaching the highest k (0.18/min) at pH 5, consistent with the AF degradation results. However, when the pH was 5 or more, the removal rate showed a tendency of slightly decreasing due to HSO5 -To be reacted with CuNi/CoMoO4The main substances of surface active center interaction, and H in PMS+And the strong hydrogen bond formed by the O-O bond inhibits the generation of free radicals. In addition, PMS undergoes self-decomposition at high pH, thereby reducing the generation of free radicals.
(V) CuNi/CoMoO4Examples of catalytic Oxidation for epinephrine
The following colorimetric reactions were performed under optimal conditions to measure epinephrine, with different concentrations of epinephrine injected into the solution containing 1mg/mLCuNi/CoMoO4Aqueous dispersion in MES buffer (50mM, pH7.0, total volume 1.5 mL). The mixture was reacted at 37 ℃ for 1.5 h. Thereafter, the epinephrine oxidation product is measured by an ultraviolet spectrophotometer at 485 nm. For comparison, a solution of the natural laccase (1U/mg, 100. mu.L) was also investigated in the same manner.
To further explore CuNi/CoMoO4The application of the nano enzyme takes epinephrine as a model molecule. Natural laccase and CuNi/CoMoO4The nano enzyme has the capability of catalyzing epinephrine to form a colored oxidation product. Epinephrine and CuNi/CoMoO4The oxidation product generated by the reaction has a characteristic absorption peak at 485nm, and can be used for detecting epinephrine. As shown in FIG. 13, the absorbance was linearly related to the concentration of epinephrine (5 to 50. mu.g/mL) and the coefficient of measurement (R)2) Is 0.997.
(VI) CuNi/CoMoO4Example of visual analysis for epinephrine
In order to conveniently measure epinephrine, a simple and inexpensive portable device based on a smart terminal was developed. Different concentrations of epinephrine were mixed with 1mg/mLCuNi/CoMoO4MES buffer at 37 ℃The reaction mixture was mixed (total volume 1.5mL) and reacted for 1.5 h. The mixed solution (CuNi/CoMoO) is then mixed4Epinephrine) were transferred to glass test tubes, placed in black boxes and illuminated with fluorescent light. The colorimetric images are collected through an intelligent terminal camera system, and a plurality of regions of the obtained photos are selected and converted into R, G, B channel values through an artificial intelligence concentration analysis application program independently developed by the inventor of the invention. A standard curve for epinephrine response was fitted with APP based on R/G (R value divided by G value). And finally, the detection results of the linear equation and the correlation coefficient are displayed on a screen, so that a foundation is laid for quick visual detection and accurate detection of epinephrine by an intelligent terminal.
In order to meet the requirements of site visualization and convenient analysis. In this research, with visual colorimetric signal and intelligent terminal platform integration, carry out RGB analysis to the image, conveniently survey adrenalin. As shown in fig. 14, when a series of concentrations of epinephrine were added to the reaction system, images were collected by the smart terminal. Then, a self-developed application program is used for selecting and recording a specific area of the image, online analysis is carried out on the obtained image, R, G, B, R/G (R divided by G), R/B (R divided by B), G/B (G divided by B) and gray values are counted, linear fitting is carried out on the R/G values and the adrenaline concentration, a fitting curve is automatically generated after the intelligent terminal platform analysis is carried out, and Y is 0.7561+0.0344X (R is 0.7561+ 0.0344X) (R is R divided by B)20.9937). Therefore, a visual, intuitive and convenient method for detecting epinephrine in real time is established without expensive equipment.
The CuNi/CoMoO serving as the multifunctional laccase-like enzyme is prepared by the method4The preparation method and the application have the following technical effects:
(1) the CuNi/CoMoO is prepared by a method combining hydrothermal treatment, calcination and impregnation4The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity even under extreme pH, temperature, long-term storage and high salt concentration4Also shows higher activity.
(2) Using CuNi/CoMoO4The laccase-like enzyme activity establishes a colorimetric sensor of ascorbic acid, the linear range of the colorimetric sensor is 1-150 mu M, the detection limit is 0.70 mu M, and the detection limit and the linear range of the colorimetric sensor are equivalent to or even better than those of methods obtained by other sensors.
(3) Can effectively degrade phenolic pollutants and environmental pollutants, CuNi/CoMoO4Not only can catalyze the oxidation of phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, and the catalytic activity shows that CuNi/CoMoO4The nano enzyme has good substrate universality.
(4) A portable intelligent terminal platform combined with a chrominance signal is constructed by taking epinephrine as a model of phenolic pollutants, and a visual, visual and convenient epinephrine instant detection method is established without expensive equipment.
(5)CuNi/CoMoO4Due to the catalytic generation of SO4 ·-And OH, realizing efficient degradation of acid fuchsin.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. CuNi/CoMoO serving as multifunctional laccase-like enzyme4The preparation method is characterized by comprising the following steps:
S1：CoMoO4preparation of
Mixing Na2MoO4·2H2O and Co (NO)3)2·6H2Fully stirring and dissolving O in deionized water, and then reacting in a high-pressure kettle; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, andcalcining the precursor to obtain the CoMoO4；
S2：CuNi/CoMoO4Preparation of
Adding CuCl2·2H2O、NiCl2·6H2O and prepared CoMoO4Dissolving in deionized water and stirring; then adding NaHB4Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO4。
2. The CuNi/CoMoO as a multifunctional laccase-like enzyme of claim 14The production method of (5), wherein in step S1:
Na2MoO4·2H2o and Co (NO)3)2·6H2The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1;
the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h;
the vacuum drying temperature is 75-85 ℃, the calcining temperature is 345-355 ℃, and the calcining time is 1.5-2.5 h.
3. The CuNi/CoMoO as a multifunctional laccase-like enzyme according to claim 1 or 24The production method of (5), wherein in step S2:
CuCl2·2H2o and NiCl2·6H2The dosage ratio of O is a molar ratio which is 1-6: 1;
stirring in deionized water for 2-4 h;
NaHB4the concentration of (A) is 9-11mg/mL, NaHB is added4The later stirring time is 4-6 h;
the temperature of vacuum drying is 75-85 ℃.
4. CuNi/CoMoO serving as multifunctional laccase-like enzyme4The use of CuNi/CoMoO produced according to any of claims 1 to 3, wherein4Application to the determination of ascorbic acid:
uniformly dispersing CuNi/CoMoO4Adding intoAdding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations into the buffer solution of the trihydroxymethyl aminomethane hydrochloride, and incubating for 1.5h at 37 ℃ to form a red sample;
then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
CuNi/CoMoO4the concentration of (3) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
5. The CuNi/CoMoO as a multifunctional laccase-like according to claim 44The use of (a) in the manufacture of a medicament for the treatment of,
the linear detection range of the ascorbic acid is 1-150 mu M, and the detection limit is 0.70 mu M;
wherein:
when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R2＝0.98826；
When the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R2＝0.99611；
Wherein: and X is the concentration of ascorbic acid.
6. CuNi/CoMoO serving as multifunctional laccase-like enzyme4The use of CuNi/CoMoO produced according to any of claims 1 to 3, wherein4The method is applied to the catalytic degradation of phenolic pollutants:
uniformly dispersing CuNi/CoMoO4Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates at 510nm by using an ultraviolet-visible spectrophotometer;
the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol;
wherein the content of the first and second substances,
CuNi/CoMoO4the concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
7. CuNi/CoMoO serving as multifunctional laccase-like enzyme4The use of CuNi/CoMoO produced according to any of claims 1 to 3, wherein4Application to the catalytic degradation of acid fuchsin:
preparing a mixed solution of CuNi/CoMoO4 suspension containing an acid fuchsin solution and peroxymonosulfate, uniformly dispersing the mixed solution by using ultrasonic waves, and measuring the absorbance of the suspension at 545nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
the pH of the acid fuchsin solution is 3.0-6.0, and the CuNi/CoMoO4The concentration of (2) is 1.5mg/mL and the concentration of peroxymonosulfate is 2 mg/mL.
8. CuNi/CoMoO serving as multifunctional laccase-like enzyme4The use of CuNi/CoMoO produced according to any of claims 1 to 3, wherein4Application to the catalytic oxidation of epinephrine:
different concentrations of epinephrine are injected into a solution containing CuNi/CoMoO4In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer;
wherein:
CuNi/CoMoO4the concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM;
the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R2And (3) 0.99745, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
9. CuNi/CoMoO serving as multifunctional laccase-like enzyme4Is characterized in that the CuNi/CoMoO prepared according to any one of the claims 1 to 3 is used as a visual detection platform based on a portable intelligent terminal4Visual assay applied to epinephrine:
different concentrations of epinephrine were mixed with CuNi/CoMoO4Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO4Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp;
then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen;
wherein:
CuNi/CoMoO4the concentration of (3) was 1.0mg/mL, and the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer was 7.0 and the concentration was 50 mM.
10. The CuNi/CoMoO as a multifunctional laccase-like enzyme according to claim 94The application of (2), which is characterized in that:
the curve fitted for epinephrine is Y-0.7561 +0.0344X, R2And (3) 0.9937, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
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