CN115920935B - Sandwich-structured carbon-based nano-enzyme and preparation method and application thereof - Google Patents
Sandwich-structured carbon-based nano-enzyme and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 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 33
- 239000008103 glucose Substances 0.000 claims abstract description 33
- 108090000790 Enzymes Proteins 0.000 claims abstract description 31
- 102000004190 Enzymes Human genes 0.000 claims abstract description 31
- 229920001100 Polydextrose Polymers 0.000 claims abstract description 30
- 229940035035 polydextrose Drugs 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- -1 molybdenum salt Chemical class 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 229910017369 Fe3 C Inorganic materials 0.000 claims description 24
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- XJIPZQRDWCIXPA-UHFFFAOYSA-N [Mo+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [Mo+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] XJIPZQRDWCIXPA-UHFFFAOYSA-N 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- LXGKRVAPVVIDQW-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylbutan-1-one;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CCCC(=O)C1=CC=C[CH-]1 LXGKRVAPVVIDQW-UHFFFAOYSA-N 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 239000001259 polydextrose Substances 0.000 abstract description 5
- 235000013856 polydextrose Nutrition 0.000 abstract description 5
- 229910001567 cementite Inorganic materials 0.000 abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002077 nanosphere Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 229940088598 enzyme Drugs 0.000 description 57
- 238000003756 stirring Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 206010012601 diabetes mellitus Diseases 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 108010015776 Glucose oxidase Proteins 0.000 description 2
- 239000004366 Glucose oxidase Substances 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- 229940116332 glucose oxidase Drugs 0.000 description 2
- 235000019420 glucose oxidase Nutrition 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention belongs to the technical field of analytical chemistry, and particularly relates to a sandwich-structured carbon-based nano-enzyme, and a preparation method and application thereof. The invention realizes the increase of catalytic active sites based on rich hydroxyl on the surface of polydextrose, and firstly obtains a composite material of metal oxide, dissimilar metal carbide and carbon, and particularly, molybdenum salt is placed in polydextrose nanospheres through a hydrothermal method to obtain molybdenum salt@polydextrose, then molybdenum salt@polydextrose is blended with ferric salt, and finally, the nano-enzyme of molybdenum oxide@carbon@iron carbide is obtained through calcination. The preparation method is simple and efficient, is easy for mass production, has rich active sites, strong conductivity and excellent catalytic performance, can be used as a simulated enzyme material for colorimetric detection of biological small molecules, can rapidly and accurately detect the content of glucose, has low detection limit and has higher application value.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a sandwich-structured carbon-based nano-enzyme, and a preparation method and application thereof.
Background
The nano enzyme is a nano mimic enzyme with a catalytic function, has high catalytic activity and stable chemical property, and is widely applied to the fields of medicine, chemical industry, food, environment and the like. For example, the nano enzyme can detect the glucose content in a sample, so that the nano enzyme is applied to early screening of diabetes, has important value for prevention and control of diabetes and complications thereof, and can obviously reduce the occurrence risk of the complications of diabetes.
Nanoezymes include noble metals, metal oxides, metal carbides, carbon-based materials, and the like. The carbon-based nano enzyme has the advantages of low price, good biocompatibility and high chemical stability, but is limited by limited active sites and low in catalytic activity, so that the application of the carbon-based nano enzyme in the analysis field is restricted. It has been reported that the catalytic activity of the carbon-based nano-enzyme can be effectively enhanced by compounding the carbon-based nano-enzyme with other materials, and Chinese patent No. CN114646605A discloses a gold-graphene compounded nano-enzyme with good catalytic performance. However, the current research is mainly remained in compounding the carbon-based material with another active nano enzyme material, and the catalytic potential and application potential of the carbon-based material cannot be deeply developed, so that the technical bottleneck is caused by the fact that different types of materials need to meet different conditions during synthesis, and the generation conditions of different types of materials are difficult to meet in one system. Oxide and carbide of composite dissimilar metal in carbon-based materials have not been reported yet, and the innovation of a synthetic methodology is adopted to synthesize the carbon-based composite material of composite oxide and carbide, which is helpful for exploring the interaction among the three materials and further developing the carbon-based nano enzyme with excellent catalytic performance.
Disclosure of Invention
The invention aims to solve the technical problems of providing the carbon-based nano enzyme with the sandwich structure and the preparation method thereof, and the preparation method is simple, efficient and easy for mass production, and the carbon-based nano enzyme has high catalytic activity and excellent performance.
The sandwich-structured carbon-based nano enzyme provided by the invention is a composite nano enzyme comprising metal oxide, dissimilar metal carbide and carbon, wherein the dissimilar metal in the dissimilar metal carbide is different from the metal in the metal oxide.
The nanoenzyme is a composite nanoenzyme MoO 2@C@Fe3 C comprising MoO 2、FeC3 and C.
The preparation method of the sandwich structure carbon-based nano enzyme comprises the following steps:
(1) Glucose and molybdenum salt are added into water to perform hydrothermal reaction, and after the reaction is finished, molybdenum salt@polydextrose is obtained through centrifugation to obtain sediment.
(2) Adding molybdenum salt@polydextrose and ferric salt into water, mixing, evaporating to dryness, and calcining at high temperature under N 2 to obtain the nano-enzyme MoO 2@C@Fe3 C.
Preferably, the molar number of glucose: the mole number of molybdenum in the molybdenum salt is more than 1.4, and the concentration of glucose in the system is ensured to be 0.2M-0.56M.
Preferably, the molybdenum salt is one or more of phosphomolybdic acid, ammonium molybdate, ammonium phosphomolybdate, molybdenum pentachloride, molybdenum isopropoxide, molybdenum acetylacetonate and ammonium phosphomolybdate.
Preferably, the hydrothermal reaction temperature is 150-200 ℃, the hydrothermal reaction time is 6-12h, and the centrifugal rotation speed is more than 8000r/min.
Preferably, the molar number of glucose: the mole number of iron in the ferric salt is more than 1.5, and the concentration of iron ions in the system is ensured to be 0.07-1.1M.
The ferric salt is one or more of ferric nitrate, ferric chloride, ferrous chloride, sodium ferric ethylenediamine tetraacetate, potassium ferricyanide, acetyl ferrocene, ferric ammonium sulfate, benzoic acid ferrocene, ferric ammonium citrate, ferrocene, ferric acetylacetonate, butyryl ferrocene, ferric perchlorate, ferric oxalate and ferric acetate.
Preferably, the evaporating temperature is 60-100 ℃.
Preferably, the calcination temperature is 600-1000 ℃ and the calcination time is 2-5h.
The sandwich structure carbon-based nano enzyme can be applied as an enzyme-like material.
Preferably, the nano-enzyme is applied to biological small molecule colorimetric detection.
Further preferably, the nano-enzyme can be applied to the detection of glucose, wherein the detection range of the glucose content is 1-500 mu M, and the detection limit is 0.425 mu M.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the metal oxide, the dissimilar metal carbide and the carbon are firstly collected on a composite material, so that the novel nano enzyme material is obtained.
2. The preparation method is simple and efficient, and is easy for large-scale production. Molybdenum salt is placed in a polydextrose nanosphere through a hydrothermal method to obtain molybdenum salt@polydextrose, then the molybdenum salt@polydextrose is blended with ferric salt, and the nano enzyme is obtained through calcination, wherein the preparation process mainly comprises hydrothermal reaction and high-temperature calcination, and the process is simple and controllable.
3. The nano enzyme prepared by the invention has high catalytic activity and excellent performance. The invention realizes the increase of the catalytic active sites based on the rich hydroxyl on the surface of the polydextrose, not only is helpful for adsorbing more active substances, but also enhances the conductivity of the composite material, and obtains the nano-enzyme with excellent performance.
4. The nano-enzyme prepared by the invention is applied to biological micromolecular colorimetric detection, can rapidly and accurately detect the content of glucose, has low detection limit and has higher application value. The invention can carry out colorimetric detection on the glucose content, and has low cost, simplicity and convenience; the detection range of glucose is 1-500 mu M, the detection limit is 0.425 mu M, and the glucose sensor has good anti-interference performance on sucrose, galactose, fructose and maltose, and has wide application prospect in the detection of diabetes and the research and development of novel glucometers.
Drawings
FIG. 1 is a phosphomolybdic acid@polydextrose scanning electron microscope image;
FIG. 2, nanometer enzyme MoO 2@C@Fe3 C scanning electron microscope;
FIG. 3, nanometer enzyme MoO 2@C@Fe3 C transmission electron microscope;
FIG. 4, X-ray diffraction pattern of nanoenzyme MoO 2@C@Fe3 C;
FIG. 5, ultraviolet-visible absorption spectrum of nano-enzyme MoO 2@C@Fe3 C (a), absorption peak intensity under different pH conditions (b), absorption peak intensity under different temperature conditions (C);
FIG. 6 shows the absorbance change pattern (a) and the linear relationship pattern (b) after adding 1-500. Mu.M glucose solution to the nano-enzyme MoO 2@C@Fe3 C;
FIG. 7 is a graph showing the selectivity of the nano-enzyme MoO 2@C@Fe3 C for detecting glucose;
FIG. 8, X-ray diffraction diagram of molybdenum oxide @ carbon;
FIG. 9, an X-ray diffraction pattern of molybdenum oxide @ carbon @ iron oxide;
FIG. 10, X-ray diffraction pattern of molybdenum oxide @ carbon @ iron molybdate.
Detailed Description
To further illustrate the method and effect of the present invention, the present invention is further illustrated below with reference to examples. The embodiments described herein are only for the purpose of illustrating the invention and are not to be construed as limiting the invention. If specific conditions are not indicated in the examples, they are generally conventional conditions, or recommended by the reagent company; the reagents, consumables, etc. used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method of the sandwich structure carbon-based nano enzyme comprises the following steps:
(1) Adding 0.5g of glucose and 0.2g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 180 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, centrifuging for 2min at 12000r/min, and taking the precipitate to obtain phosphomolybdic acid@polydextrose.
As a result of scanning electron microscopy of phosphomolybdic acid@polydextrose, the phosphomolybdic acid@polydextrose was spherical in shape, smooth in surface, and about 500nm in diameter, as shown in FIG. 1.
(2) Mixing the obtained phosphomolybdic acid@polydextrose and 0.4g of ferric chloride in 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing in a vacuum tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 2 hours to obtain the nano-enzyme MoO 2@C@Fe3 C.
As a result of scanning electron microscopy on the nano-enzyme MoO 2@C@Fe3 C, the shape of MoO 2@C@Fe3 C is spherical, and the surface has granular feel, which proves that the coating layer of the iron carbide is successfully constructed, and the diameter is about 500 nm.
As a result of transmission electron microscopy on nano-enzyme MoO 2@C@Fe3 C, as shown in FIG. 3, moO 2@C@Fe3 C has a diameter of about 500nm, and is consistent with scanning electron microscopy data, and the particles attached to the surface are iron carbide.
The synthesis of MoO 2@C@Fe3 C was verified by X-ray diffraction analysis of the nanoenzyme MoO 2@C@Fe3 C, as shown in fig. 4.
The addition of the nano-enzyme MoO 2@C@Fe3 C to the TMB/H 2O2 system for UV-visible spectrophotometry analysis, as shown in FIG. 5a, moO 2@C@Fe3 C/TMB only produced a strong absorption peak at 650nm in the presence of H 2O2, indicating that it has peroxidase activity; meanwhile, the intensities of absorption peaks under different pH and temperature conditions were analyzed for detection, and the optimum pH was 4 (FIG. 5 b) and the optimum temperature was 40 ℃ (FIG. 5 c).
The nano-enzyme MoO 2@C@Fe3 C is applied to glucose detection, and the steps are as follows:
(1) Calculating a linear equation: 0.1mL of glucose solution with different concentrations was added to 0.5mL of buffer solution with ph=7, 0.1mL of glucose oxidase solution was added, and after incubation at 40 ℃ for 20min, TMB solution, moO 2@C@Fe3 C nano enzyme (final concentration 50 μg/mL) and buffer solution with ph=4 were added. The absorbance change at 652nm was recorded (fig. 6 a) and the data set plotted to obtain a linear plot (fig. 6 b). The linear equation is Δa=0.00139C glucose +0.0045.
(2) Measuring the glucose content: human serum samples were diluted 120-fold, 400 μl was added to 0.5mL of buffer solution with ph=7, 0.1mL of glucose oxidase solution was added, and after incubation at 40 ℃ for 20min, TMB solution, molybdenum salt @ carbon @ iron carbide nano enzyme (final concentration 50 μg/mL) and buffer solution with ph=4 were added. The absorbance at 652nm was recorded and the glucose content in the serum samples was calculated according to a linear equation.
Meanwhile, a blood glucose meter is used for detecting serum samples, three serum samples are detected in the embodiment, and comparison results are shown in table 1, so that the content of glucose detected by the nano enzyme prepared by the invention is basically consistent with the data measured by the blood glucose meter, and the relative standard deviation is smaller, so that the accuracy of detecting the content of glucose by the nano enzyme is higher. Through cost accounting, the invention only takes 0.1 yuan for detection at a time, and has low cost compared with the conventional glucometer for detecting about 0.7 yuan, and has wide application prospect in diabetes detection and research and development of novel glucometers.
Table 1 table of comparative glucose content data for serum samples
The interference resistance of the nano enzyme MoO 2@C@Fe3 C on sucrose, galactose, fructose and maltose is detected, and the result is shown in figure 7, which shows that the interference of other substances on the detection of glucose is small.
Example 2
The preparation method of the sandwich structure carbon-based nano enzyme comprises the following steps:
(1) Adding 0.5g of glucose and 0.15g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 170 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain precipitate to obtain phosphomolybdic acid@polydextrose.
(2) Mixing the obtained phosphomolybdic acid@polydextrose and 0.3g of ferric chloride in 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing in a vacuum tube furnace, heating to 750 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 2 hours to obtain the nano-enzyme MoO 2@C@Fe3 C.
Example 3
The preparation method of the sandwich structure carbon-based nano enzyme comprises the following steps:
(1) Adding 0.6g of glucose and 0.2g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 190 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain precipitate to obtain phosphomolybdic acid@polydextrose.
(2) Mixing the obtained phosphomolybdic acid@polydextrose and 0.35g of ferric chloride in 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing in a vacuum tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 3 hours to obtain the nano-enzyme MoO 2@C@Fe3 C.
Comparative example 1
The preparation method of the nano-enzyme comprises the following steps:
(1) Adding 0.5g of glucose and 0.2g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 180 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain precipitate to obtain phosphomolybdic acid@polydextrose.
(2) Adding the obtained phosphomolybdic acid@polydextrose into 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing the magnetic boat in a vacuum tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 2 hours to obtain the nano-enzyme molybdenum oxide@carbon.
The results of the X-ray diffraction of molybdenum oxide @ carbon are shown in fig. 8, and the results obtained from calcining phosphomolybdic acid @ polydextrose alone demonstrate that molybdenum phosphate is encapsulated within polydextrose spheres by a hydrothermal reaction and successfully converted to molybdenum oxide after calcination at high temperature, and finally molybdenum phosphate @ polydextrose is converted to molybdenum oxide @ carbon.
Comparative example 2
The preparation method of the nano-enzyme comprises the following steps:
(1) Adding 0.5g of glucose and 0.2g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 180 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain precipitate to obtain phosphomolybdic acid@polydextrose.
(2) Mixing the obtained phosphomolybdic acid@polydextrose and 0.6g of ferric chloride in 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing in a vacuum tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 2 hours to obtain the nano enzyme.
The result of X-ray diffraction on the nano-enzyme is shown in figure 9, wherein the nano-enzyme is molybdenum oxide @ carbon @ iron oxide, which indicates that iron oxide can be generated under the condition of excessive ferric chloride.
Comparative example 3
The preparation method of the nano-enzyme comprises the following steps:
(1) Adding 0.5g of glucose and 0.4g of phosphomolybdic acid into 10mL of water, stirring for 30min, transferring to a hydrothermal kettle after uniform mixing, placing in a constant-temperature oven at 180 ℃ for 6h, cooling to room temperature after the hydrothermal reaction is finished, and centrifuging to obtain precipitate to obtain phosphomolybdic acid@polydextrose.
(2) Mixing the obtained phosphomolybdic acid@polydextrose and 0.4g of ferric chloride in 20mL of water, continuously stirring, evaporating to dryness at 80 ℃, transferring the evaporated product to a magnetic boat, placing in a vacuum tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of N 2, and calcining for 2 hours to obtain the nano enzyme.
As a result of X-ray diffraction on the nano-enzyme, as shown in FIG. 10, the nano-enzyme was molybdenum oxide @ carbon @ iron molybdate, indicating that iron molybdate was produced under the condition of excessive phosphomolybdic acid.
Claims (6)
1. A preparation method of sandwich structure carbon-based nano-enzyme is characterized by comprising the following steps: the nano-enzyme is a composite nano-enzyme MoO 2@C@Fe3 C comprising MoO 2、FeC3 and C;
the preparation method of the sandwich structure carbon-based nano enzyme comprises the following steps:
(1) Adding glucose and molybdenum salt into water to perform a hydrothermal reaction, and obtaining molybdenum salt@polydextrose through centrifugation after the reaction is finished;
(2) Adding molybdenum salt@polydextrose and ferric salt into water, mixing, evaporating to dryness, and calcining at high temperature under N 2 to obtain the nano-enzyme MoO 2@C@Fe3 C;
glucose mole number: the mole number of molybdenum in the molybdenum salt is more than 1.4;
glucose mole number: the mole number of iron in the iron salt is >1.5.
2. The method for preparing the sandwich-structured carbon-based nano-enzyme according to claim 1, which is characterized in that: the molybdenum salt is one or more of phosphomolybdic acid, ammonium molybdate, ammonium phosphomolybdate, molybdenum pentachloride, molybdenum isopropoxide, molybdenum acetylacetonate and ammonium phosphomolybdate.
3. The method for preparing the sandwich-structured carbon-based nano-enzyme according to claim 1, which is characterized in that: the hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 6-12h.
4. The method for preparing the sandwich-structured carbon-based nano-enzyme according to claim 1, which is characterized in that: the ferric salt is one or more of ferric nitrate, ferric chloride, ferrous chloride, ferric sodium ethylenediamine tetraacetate, potassium ferricyanide, acetyl ferrocene, ferric ammonium sulfate, benzoic acid ferrocene, ferric ammonium citrate, ferrocene, ferric acetylacetonate, butyryl ferrocene, ferric perchlorate, ferric oxalate and ferric acetate.
5. The method for preparing the sandwich-structured carbon-based nano-enzyme according to claim 1, which is characterized in that: the calcination temperature is 600-1000 ℃ and the calcination time is 2-5h.
6. An application of nano-enzyme prepared by the preparation method of sandwich-structured carbon-based nano-enzyme as claimed in claim 1, which is characterized in that: the nano-enzyme is applied to enzyme-like materials.
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