CN114887644B - Nitrogen-doped iron carbide/carbon nano enzyme and preparation method and application thereof - Google Patents
Nitrogen-doped iron carbide/carbon nano enzyme and preparation method and application thereof Download PDFInfo
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- CN114887644B CN114887644B CN202210593040.6A CN202210593040A CN114887644B CN 114887644 B CN114887644 B CN 114887644B CN 202210593040 A CN202210593040 A CN 202210593040A CN 114887644 B CN114887644 B CN 114887644B
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- iron carbide
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001567 cementite Inorganic materials 0.000 title claims abstract description 35
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 75
- 239000004201 L-cysteine Substances 0.000 claims abstract description 36
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 36
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002835 absorbance Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
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- 230000008859 change Effects 0.000 claims description 9
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- 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 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- -1 potassium ferricyanide Chemical compound 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229960002413 ferric citrate Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 3
- 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
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 claims description 2
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 2
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 abstract description 6
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- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- 238000013313 FeNO test Methods 0.000 description 2
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- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
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- RGJOEKWQDUBAIZ-UHFFFAOYSA-N coenzime A Natural products OC1C(OP(O)(O)=O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-UHFFFAOYSA-N 0.000 description 1
- 239000005516 coenzyme A Substances 0.000 description 1
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- KDTSHFARGAKYJN-UHFFFAOYSA-N dephosphocoenzyme A Natural products OC1C(O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 KDTSHFARGAKYJN-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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Abstract
The invention discloses nitrogen-doped iron carbide/carbon nano enzyme and a preparation method and application thereof, and belongs to the technical field of analytical chemistry. The technical proposal is as follows: and dispersing m-phenylenediamine and ferric salt into a solvent, stirring to obtain iron-doped poly-m-phenylenediamine, and calcining the poly-m-phenylenediamine in an inert atmosphere to obtain the nitrogen-doped iron carbide/carbon nano enzyme. The synthesis method is simple and efficient, and is convenient for large-scale production; the synthesized nano-enzyme has higher activity, low detection limit on L-cysteine and extremely high application value.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to nitrogen-doped iron carbide/carbon nano enzyme, and a preparation method and application thereof.
Background
The nano enzyme has the advantages of nano materials and natural enzymes, has the characteristics of high catalytic activity and stable chemical property, and has wide application in the fields of medicine, chemical industry, food, environment and the like. Nanoezymes typically exhibit peroxidase-like and oxidase-like activities. In analytical detection using peroxidase, H is required 2 O 2 H2O2 not only has a detrimental effect on the environment, but also limits the application of the detection method. The development of oxidases is therefore of great interest.
L-cysteine plays an important role in the activity of living bodies and plays an important role in the metabolism of substances such as coenzyme A, heparin, biotin, and lipoid acid. In addition, L-cysteine (L-Cys) is an important marker for many diseases in living bodies, and its concentration is associated with chronic diseases such as rheumatoid arthritis, uremia, alzheimer's disease and the like, bad pregnancy and the like. Therefore, the rapid detection of the concentration is of great importance for the health of the organism. At present, the detection method of cysteine mainly comprises a plasma atomic emission spectrum, a high performance liquid chromatography, an electrochemical measurement method, a capillary electrophoresis method and the like, and the methods have the defects of expensive instruments, high detection cost and the like, so that the detection of the cysteine is limited.
The colorimetric method is based on the selective absorption of the color reagent to light, and has the characteristics of more timely response, high sensitivity and strong anti-interference capability. Develop a kind of oxidase nanometer enzyme, carry on the colorimetric detection, it is important to the low-cost, fast, high-efficient detection L-cysteine concentration.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, provides a nitrogen-doped iron carbide/carbon nano enzyme, and a preparation method and application thereof, and has simple and efficient synthesis method, thereby being convenient for large-scale production; the synthesized nano-enzyme has higher activity, low detection limit on L-cysteine and extremely high application value.
In a first aspect, the invention provides a preparation method of nitrogen-doped iron carbide/carbon nano-enzyme, which comprises the steps of dispersing m-phenylenediamine and ferric salt into a solvent, stirring to obtain iron-doped poly-m-phenylenediamine, and then calcining the iron-doped poly-m-phenylenediamine in an inert atmosphere to obtain the nitrogen-doped iron carbide/carbon nano-enzyme.
Preferably, the iron salt is one or more of ferric chloride, ferric nitrate, ferric stearate, potassium ferricyanide, ferric acetylacetonate, ferric citrate amine, ferric citrate, ferric oleate, sodium ferric ethylenediamine tetraacetate, hexacyanoferrate, and ferric acrylate.
Preferably, the molar ratio of the m-phenylenediamine to the iron ions in the ferric salt is 2-20: 1.
preferably, the solvent is one or more of methanol, ethanol, propanol, butanol, acetonitrile, acetone, N-dimethylformamide, thionyl chloride, dichloromethane, pyridine, diethyl ether, cyclohexane, hexane, octane, pentane, ethyl acetate, cyclohexanone, methylcyclohexanone, and N-methylpyrrolidone; preferably, the solvent is one or more of methanol, ethanol, propanol and butanol.
Preferably, the stirring time is 0.1 to 100 hours; preferably, the stirring time is 0.2 to 5 hours.
Preferably, the calcination temperature is 500-1000 ℃; preferably, the calcination temperature is 600-900 ℃; the calcination time is 1-20 h; preferably, the calcination time is 1 to 10 hours.
In a second aspect, the present invention provides nitrogen doped iron carbide/carbon nanoenzymes prepared by the above method.
In a third aspect, the invention provides an application of the nitrogen-doped iron carbide/carbon nano-enzyme in detecting the concentration of L-cysteine, comprising the following steps:
(1) Mixing nitrogen-doped iron carbide/carbon nano enzyme with L-cysteine solutions with different concentrations and buffer solutions with pH=2-4, adding TMB solution, standing at 30-60 ℃, obtaining absorbance change by using an ultraviolet-visible spectrometer, and calculating a linear equation of absorbance and L-cysteine concentration;
(2) Mixing the nitrogen doped iron carbide/carbon nano enzyme with L-cysteine to be detected and a buffer solution with pH=4, adding a TMB solution, standing at 30-60 ℃, and determining the concentration of the L-cysteine to be detected by utilizing absorbance obtained by an ultraviolet visible spectrometer and combining the linear equation of the step (1).
Preferably, in step (1), the linear equation is Δa= 0.01026C L-Cys +0.02323 where ΔA represents the absorbance change, C L-Cys Represents the concentration of L-cysteine.
Preferably, the L-cysteine concentration is detected in a range of 0.1 to 10. Mu.M, and the limit of detection is 0.056. Mu.M.
According to the method, through precursor selection, nitrogen element doping is directly introduced into the iron carbide/carbon in one step, and the method is simple. The nitrogen doping can adjust the electronic structure of the carbon material, increase defect sites and improve the catalytic activity of the carbon-based material.
The invention adjusts the solvent and the precursor, so that the prepared nitrogen-doped iron carbide/carbon material is of a sheet structure. Literature reports (Sensors & detectors: B.chemical 333 (2021) 129549) indicate that the sheet structure can expose more catalytic sites, reduce the mass transfer distance and improve the catalytic activity. In addition, the introduction of carbon helps to promote conductivity of the iron carbide. The preparation method directly realizes the preparation of the nitrogen-doped iron carbide/carbon material with the lamellar structure, is simple, and the obtained nano-enzyme has uniqueness and good effect. It is notable that the detection limit of the present invention is lower than that reported in many documents (0.15. Mu.M (Dalton Trans.2017,46, 8942-8949.), 0.67. Mu.M (J. Mater. Chem. B2018,6,6207-6211.), 0.702. Mu.M (Microporous Mesoporous Mater.2018,268, 88-92.), etc.), indicating that the present invention works well.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a nano material for colorimetric detection of L-cysteine concentration, which directly realizes the combination of three elements of nitrogen, iron and carbon in the material through the selection of precursors, synthesizes a novel nano enzyme with a nano sheet structure, has the advantages of simple and reliable method, low cost, high activity of the prepared nano enzyme and easy mass production. The nitrogen-doped iron carbide/carbon nano enzyme has low detection limit on L-cysteine, has good anti-interference performance on alanine, lysine, tyrosine, glutamic acid and inorganic ions, and has higher application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a transmission electron microscopy image of nitrogen doped iron carbide/carbon nanoenzyme (NFeC) prepared in example 1 of the present invention.
FIG. 2 is an X-ray photoelectron spectrum of NFeC nanoenzyme prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern diagram of NFeC nanoenzyme prepared in example 1 of the present invention.
FIG. 4 is a graph showing the change in absorbance of a solution obtained by adding different concentrations of L-cysteine solution to NFeC nanoenzyme prepared in example 1 of the present invention.
FIG. 5 is a graph showing the linear relationship between the absorbance of a solution and the concentration of L-cysteine after adding different concentrations of L-cysteine to NFeC nanoenzymes prepared in example 1 of the present invention.
FIG. 6 is a graph showing the selectivity of NFeC nanoenzyme assay for L-cysteine prepared in example 1 of the present invention.
FIG. 7 is a transmission electron microscopy image of nitrogen doped iron carbide/carbon nanoenzyme (NFeC) prepared in example 2 of the present invention.
FIG. 8 is an X-ray diffraction pattern diagram of NFeC nanoenzyme prepared in example 2 of the present invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation method of the nitrogen-doped iron carbide/carbon nano enzyme (NFeC) of this embodiment comprises the following steps: 1g of m-phenylenediamine and 0.19g of ferric nitrate (FeNO) 3 .9H 2 O) dispersing the mixture into ethanol, stirring for 30min, and centrifuging the reaction solution to obtain a solid substance, namely the iron-doped poly (m-phenylenediamine); the obtained iron-doped poly (m-phenylenediamine) is added in N 2 Calcining for 2 hours at 700 ℃ in the atmosphere to obtain the nitrogen doped iron carbide/carbon nano enzyme.
FIG. 1 is a Transmission Electron Microscope (TEM) diagram of a synthesized NFeC nanoenzyme, and it can be seen from FIG. 1 that the nanoenzyme prepared has a sheet structure with a size of about 100 nm.
FIG. 2 is an X-ray photoelectron Spectrometry (XPS) of a synthesized NFeC nanoenzyme, which has Fe, N, C elements as can be seen from FIG. 2.
FIG. 3 is an X-ray diffraction pattern (XRD) of a synthesized NFeC nanoenzyme, as can be seen from FIG. 3, the nanoenzyme is Fe 3 C. With reference to fig. 2, this example illustrates the successful preparation of nitrogen doped iron carbide/carbon nanoplatelet nanoenzymes.
Example 2
The preparation method of the nitrogen-doped iron carbide/carbon nano enzyme (NFeC) of this embodiment comprises the following steps: 1g of m-phenylenediamine and 1.8g of ferric nitrate (FeNO) 3 .9H 2 O) dispersing the mixture into ethanol, stirring for 30min, and centrifuging the reaction solution to obtain a solid substance, namely the iron-doped poly (m-phenylenediamine); the obtained iron-doped poly (m-phenylenediamine) is added in N 2 Calcining at 800 ℃ for 2 hours under the atmosphere to obtain the nitrogen doped materialIron carbide/carbon nanoenzyme.
Fig. 7 is a Transmission Electron Microscope (TEM) image of the synthesized NFeC nanoenzyme, and as can be seen from fig. 7, the nanoenzyme prepared is a plate-like structure with a larger size, which is probably due to the increased amount of reactants.
FIG. 8 is an X-ray diffraction pattern (XRD) of a synthesized NFeC nanoenzyme, as can be seen from FIG. 8, the nanoenzyme is Fe 3 C. With reference to fig. 7, this example illustrates the successful preparation of nitrogen doped iron carbide/carbon nanoplatelet nanoenzymes.
The NFeC nanoenzyme synthesized in example 1 was applied to L-cysteine detection as follows:
(1) 0.1mL of L-cysteine was mixed with 3mL of buffer HAc-NaAc, NFeC nanoenzyme (20. Mu.L, 3mgL -1 ) After mixing, adding TMB solution (40. Mu.L, 20 mM) and incubating for 4min at 40℃the absorbance change at 652nm was recorded and the data arrangement plotted (as shown in FIG. 4). A linear relationship between absorbance and L-cysteine concentration (as shown in FIG. 5) was obtained in the range of 0.1-10. Mu.M, with a linear relationship of ΔA= 0.01026C L-Cys +0.02323(R 2 =0.999)。
(2) The serum samples were centrifuged at 12000rpm for 15min to remove insoluble sediment. 400. Mu.L of human serum sample was taken with 3mL of buffer solution at pH=4, NFeC nanoenzyme (20. Mu.L, 3 mgL) -1 ) After mixing, TMB solution (40. Mu.L, 20 mM) was added and incubated at 40℃for 4min, the absorbance change at 652nm was recorded. In addition, 5. Mu.M, 10. Mu.M L-Cys was added to the serum samples, and the absorbance change at 652nm was recorded according to the same experimental procedure. Substituting the light absorption intensity variation value into a linear relation, and respectively determining the concentration value of the L-Cys. The results are shown in Table 1, and demonstrate that the method of the present invention can be used well for the detection of L-Cys concentration in a sample.
TABLE 1 experiment for determining the content of L-Cys in human serum samples and the recovery rate of the sample by the method of the present invention
Selectivity experiment
The NFeC nanoenzyme synthesized in example 1 (20. Mu.L, 3 mgL) -1 ) After incubation with 3mL of buffer solution at ph=4 and TMB solution (40 μl,20 mM) for 4min at 40 ℃, 3mM alanine (Ala), lysine (Lys), tyrosine (Tyr), glutamine (Glu), inorganic ions, L-cysteine (L-Cys) were added thereto, respectively, and the absorbance change at 652nm before and after addition was recorded.
FIG. 6 shows the results of the selectivity test, and as can be seen from FIG. 6, the absorbance change value of the added L-Cys system is much higher than that of the control group, thus demonstrating that the nano-enzyme has good selectivity on L-Cys.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the nitrogen-doped iron carbide/carbon nano enzyme is characterized in that m-phenylenediamine and ferric salt are dispersed into a solvent and stirred to obtain iron-doped poly-m-phenylenediamine, and then the iron-doped poly-m-phenylenediamine is calcined in an inert atmosphere to obtain the nitrogen-doped iron carbide/carbon nano enzyme;
the ferric salt is one or more of ferric chloride, ferric nitrate, ferric stearate, potassium ferricyanide, ferric acetylacetonate, ferric citrate amine, ferric citrate, ferric oleate, sodium ferric ethylenediamine tetraacetate, hexacyanoferrate and ferric acrylate;
the molar ratio of the m-phenylenediamine to the iron ions in the ferric salt is 2-20: 1, a step of;
the solvent is one or more of methanol, ethanol, propanol, butanol, acetonitrile, acetone, N-dimethylformamide, thionyl chloride, dichloromethane, pyridine, diethyl ether, cyclohexane, hexane, octane, pentane, ethyl acetate, cyclohexanone, methylcyclohexanone and N-methylpyrrolidone;
the calcination temperature is 500-1000 ℃.
2. The method of preparing a nitrogen-doped iron carbide/carbon nanoenzyme according to claim 1, wherein the solvent is one or more of methanol, ethanol, propanol and butanol.
3. The method for preparing nitrogen-doped iron carbide/carbon nano enzyme according to claim 1, wherein the calcining temperature is 600 ℃ to 900 ℃; the calcination time is 1-20 h.
4. The method for preparing nitrogen-doped iron carbide/carbon nano-enzyme according to claim 3, wherein the calcination time is 1-10 hours.
5. The method for preparing nitrogen-doped iron carbide/carbon nano enzyme according to claim 1, wherein the stirring time is 0.1-100 h.
6. The method for preparing nitrogen-doped iron carbide/carbon nano-enzyme according to claim 5, wherein the stirring time is 0.2-5 h.
7. Nitrogen doped iron carbide/carbon nano-enzyme prepared by the preparation method according to any one of claims 1-6.
8. The use of nitrogen-doped iron carbide/carbon nanoenzyme prepared by the preparation method according to any one of claims 1 to 6 for detecting the concentration of L-cysteine, comprising the steps of:
(1) Mixing nitrogen-doped iron carbide/carbon nano enzyme with L-cysteine solutions with different concentrations and buffer solutions with pH=2-4, adding TMB solution, standing at 30-60 ℃, obtaining absorbance change by using an ultraviolet-visible spectrometer, and calculating a linear equation of absorbance and L-cysteine concentration;
(2) Mixing the nitrogen doped iron carbide/carbon nano enzyme with L-cysteine to be detected and a buffer solution with pH=4, adding a TMB solution, standing at 30-60 ℃, and determining the concentration of the L-cysteine to be detected by utilizing absorbance obtained by an ultraviolet visible spectrometer and combining the linear equation of the step (1).
9. The use of claim 8, wherein in step (1) the linear equation is fata= 0.01026C L-Cys +0.02323。
10. The use according to claim 8, wherein the L-cysteine concentration is detected in a range of 0.1 to 10. Mu.M and the limit of detection is 0.056. Mu.M.
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