CN114887644A - Nitrogen-doped iron carbide/carbon nanoenzyme and preparation method and application thereof - Google Patents
Nitrogen-doped iron carbide/carbon nanoenzyme and preparation method and application thereof Download PDFInfo
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- CN114887644A CN114887644A CN202210593040.6A CN202210593040A CN114887644A CN 114887644 A CN114887644 A CN 114887644A CN 202210593040 A CN202210593040 A CN 202210593040A CN 114887644 A CN114887644 A CN 114887644A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 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
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- 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
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- 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
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Abstract
The invention discloses a nitrogen-doped iron carbide/carbon nanoenzyme and a preparation method and application thereof, belonging to the technical field of analytical chemistry. The technical scheme is as follows: 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 nanoenzyme. The synthetic 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 nanoenzyme and a preparation method and application thereof.
Background
The nano enzyme has the advantages of both nano material and natural enzyme, has the characteristics of high catalytic activity and stable chemical property, and can be widely applied to the fields of medicine, chemical industry, food, environment and the like. Nanoenzymes typically exhibit both peroxidase-like and oxidase-like activity. When the peroxidase is used for analysis and detection, H is required 2 O 2 H2O2 not only has adverse effects on the environment, but also limits the application of detection methods. The development of oxidase-like enzymes has thus been subject toThere is a wide concern.
L-cysteine plays an important role in the activity of a living body, and plays an important role in the metabolism of substances such as coenzyme A, heparin, biotin, and lipoid. In addition, L-cysteine (L-Cys) is an important marker for many diseases in the living body, and its concentration is related to chronic diseases such as rheumatoid arthritis, uremia and Alzheimer's disease, and poor pregnancy. Therefore, the rapid detection of the concentration is of great significance to the health of the organism. At present, the cysteine detection methods mainly comprise plasma atomic emission spectroscopy, high performance liquid chromatography, electrochemical measurement methods, capillary electrophoresis methods and the like, and the methods have the defects of expensive instruments, high detection cost and the like, so that the cysteine detection is limited.
The colorimetric method is based on the selective absorption of color developing agent to light, and has the characteristics of relatively timely response, high sensitivity and strong anti-interference capability. Developing a oxidase-like nano enzyme for colorimetric detection, and having great significance for detecting the concentration of L-cysteine quickly and efficiently at low cost.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the nitrogen-doped iron carbide/carbon nanoenzyme and the preparation method and the application thereof are provided, and the synthetic method is simple, efficient and 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 nanoenzyme, 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 nanoenzyme.
Preferably, the iron salt is one or more of ferric chloride, ferric nitrate, ferric stearate, potassium ferricyanide, ferric acetylacetonate, ferric amine citrate, ferric oleate, ferric sodium ethylene diamine tetraacetate, ferric amine hexacyanoferrate and ferric acrylate.
Preferably, the molar ratio of the m-phenylenediamine to the iron ions in the iron 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 0.1-100 h; preferably, the stirring time is 0.2-5 h.
Preferably, the calcination temperature is 500 ℃ to 1000 ℃; preferably, the calcining temperature is 600 ℃ to 900 ℃; the calcination time is 1-20 h; preferably, the calcination time is 1-10 h.
In a second aspect, the present invention provides a nitrogen-doped iron carbide/carbon nanoenzyme prepared by the above method.
In a third aspect, the invention provides an application of the nitrogen-doped iron carbide/carbon nanoenzyme in detecting the concentration of L-cysteine, which comprises the following steps:
(1) mixing nitrogen-doped iron carbide/carbon nanoenzyme with L-cysteine solutions with different concentrations and buffer solutions with pH of 2-4, adding TMB solution, standing at 30-60 ℃, obtaining absorbance change by using an ultraviolet visible spectrometer, and calculating a linear equation of the absorbance and the L-cysteine concentration;
(2) mixing nitrogen-doped iron carbide/carbon nanoenzyme with L-cysteine to be detected and a buffer solution with the pH value of 4, adding a TMB solution, standing at the temperature of 30-60 ℃, and determining the concentration of the L-cysteine to be detected by using the absorbance obtained by an ultraviolet-visible spectrometer in combination with the linear equation in the step (1).
Preferably, in step (1), the linear equation is Δ a ═ 0.01026C L-Cys +0.02323 wherein Δ A represents the absorbance change value, C L-Cys Represents the concentration of L-cysteine.
Preferably, the concentration of L-cysteine is detected in the range of 0.1-10. mu.M, with a detection limit of 0.056. mu.M.
According to the invention, 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 the defect sites and improve the catalytic activity of the carbon material.
The method adjusts the solvent and the precursor, so that the prepared nitrogen-doped iron carbide/carbon material has a sheet structure. Literature reports (Sensors & actors: B.chemical 333(2021)129549) show that sheet-like structures can expose more catalytic sites, reduce mass transfer distances, and increase catalytic activity. In addition, the introduction of carbon helps to improve the conductivity of the iron carbide. The invention directly realizes the preparation of the nitrogen-doped iron carbide/carbon material with a sheet structure, the method is simple, and the obtained nano enzyme has uniqueness and good effect. It is noted that the detection limit of the present invention is lower than that reported in many literatures (0.15 μ M (Dalton trans.2017,46, 8942-.
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 a precursor, 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 large-scale production. The nitrogen-doped iron carbide/carbon nanoenzyme has low detection limit on L-cysteine, has good anti-interference performance on alanine, lysine, tyrosine, glutamic acid and inorganic ions, and has high application value.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Fig. 1 is a transmission electron microscope 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 the NFeC nanoenzyme prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of NFeC nanoenzyme prepared in example 1 of the present invention.
FIG. 4 is a graph showing the change in absorbance of NFeC nanoenzymes prepared in example 1 of the present invention when L-cysteine solutions of different concentrations were added.
FIG. 5 is a linear relationship graph of the absorbance and L-cysteine concentration of the NFeC nanoenzyme prepared in example 1 of the present invention after adding L-cysteine solutions of different concentrations.
FIG. 6 is a graph comparing the selectivity of NFeC nanoenzyme prepared in example 1 of the present invention for L-cysteine detection.
Fig. 7 is a transmission electron micrograph of nitrogen-doped iron carbide/carbon nanoenzyme (NFeC) prepared in example 2 of the present invention.
FIG. 8 is an X-ray diffraction pattern of NFeC nanoenzyme prepared in example 2 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the nitrogen-doped iron carbide/carbon nanoenzyme (NFeC) of this example includes the following steps: 1g of m-phenylenediamine, 0.19g of ferric nitrate (FeNO) 3 .9H 2 O) is dispersed in ethanol, stirred for 30min, and the reaction liquid is centrifuged to obtain solid substance, namely the poly (m-phenylenediamine) doped with iron; the obtained iron-doped poly (m-phenylenediamine) is added in N 2 Calcining for 2h at 700 ℃ in the atmosphere to obtain the nitrogen-doped iron carbide/carbon nanoRice enzyme.
FIG. 1 is a Transmission Electron Microscope (TEM) image of the synthesized NFeC nanoenzyme, and it can be seen from FIG. 1 that the prepared nanoenzyme is a sheet-like structure with a size of about 100 nm.
Fig. 2 shows X-ray photoelectron spectroscopy (XPS) of the synthesized NFeC nanoenzyme, which has Fe, N, and C elements as shown in fig. 2.
FIG. 3 shows the X-ray diffraction pattern (XRD) of the synthesized NFeC nanoenzyme, which is Fe in FIG. 3 3 C. With reference to fig. 2, the present example illustrates the successful preparation of nitrogen-doped iron carbide/carbon nanosheet nanoenzyme.
Example 2
The preparation method of the nitrogen-doped iron carbide/carbon nanoenzyme (NFeC) of this example includes the following steps: 1g of m-phenylenediamine, 1.8g of ferric nitrate (FeNO) 3 .9H 2 O) is dispersed in ethanol, stirred for 30min, and the reaction liquid is centrifuged to obtain solid substance, namely the poly (m-phenylenediamine) doped with iron; the obtained iron-doped poly (m-phenylenediamine) is added in N 2 Calcining for 2h at 800 ℃ in the atmosphere to obtain the nitrogen-doped iron carbide/carbon nanoenzyme.
FIG. 7 is a Transmission Electron Micrograph (TEM) of the synthesized NFeC nanoenzyme, and from FIG. 7, it can be seen that the nanoenzyme prepared is a sheet-like structure with a larger size, probably due to the increased amount of reactants.
FIG. 8 shows the X-ray diffraction pattern (XRD) of the synthesized NFeC nanoenzyme, which is Fe in FIG. 8 3 C. With reference to fig. 7, the present example illustrates the successful preparation of nitrogen-doped iron carbide/carbon nanosheet nanoenzyme.
The NFeC nanoenzyme synthesized in example 1 was applied to the L-cysteine assay, as follows:
(1) l-cysteine with different concentrations of 0.1mL and buffer solution HAc-NaAc, NFeC nanoenzyme (20 μ L, 3 mgL) with pH 4 of 3mL -1 ) After mixing, addition of TMB solution (40. mu.L, 20mM), incubation at 40 ℃ for 4min, the change in absorbance at 652nm was recorded and the data plotted (as shown in FIG. 4). A linear relationship between absorbance and L-cysteine concentration was obtained in the range of 0.1 to 10. mu.M (as shown in FIG. 5), and the linear relationship was expressedIs Δ A ═ 0.01026C L-Cys +0.02323(R 2 =0.999)。
(2) Serum samples were centrifuged at 12000rpm for 15min to remove insoluble pellet. 400 μ L of human serum samples were mixed with 3mL of buffer solution of pH 4 and NFeC nanoenzyme (20 μ L, 3 mgL) -1 ) After mixing, TMB solution (40. mu.L, 20mM) was added and incubation at 40 ℃ for 4min, the change in absorbance at 652nm was recorded. Furthermore, 5. mu.M and 10. mu.M L-Cys was added to the serum sample, and the change in absorbance at 652nm was recorded according to the same experimental procedure. And substituting the change value of the light absorption intensity into the linear relational expression to respectively determine the concentration value of L-Cys. The results are shown in Table 1, which illustrate that the method of the present invention can be advantageously used for the detection of the concentration of L-Cys in a sample.
TABLE 1 human serum sample L-Cys content determination and sample recovery test by the method of the present invention
Selectivity test
The NFeC nanoenzyme synthesized in example 1 (20. mu.L, 3 mgL) -1 ) After mixing with 3mL of a buffer solution having a pH of 4 and a TMB solution (40. mu.L, 20mM), and incubating at 40 ℃ for 4min, 3mM of alanine (Ala), lysine (Lys), tyrosine (Tyr), glutamic acid (Glu), an inorganic ion, and L-cysteine (L-Cys) were added thereto, and the change in absorbance at 652nm before and after the addition was recorded.
FIG. 6 shows the result of the selectivity experiment, and it can be seen from FIG. 6 that the absorbance change value of the system with L-Cys added is much higher than that of the control group, indicating that the selectivity of the nanoenzyme to L-Cys is good.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. 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 nanoenzyme is characterized in that m-phenylenediamine and iron salt are dispersed in 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 nanoenzyme.
2. The method of claim 1, wherein the iron salt is one or more of ferric chloride, ferric nitrate, ferric stearate, potassium ferricyanide, ferric acetylacetonate, ferric amine citrate, ferric oleate, ferric sodium edetate, ferric amine hexacyanoferrate and ferric acrylate.
3. The method for preparing nitrogen-doped iron carbide/carbon nanoenzyme according to claim 1, wherein the molar ratio of the m-phenylenediamine to the iron ions in the iron salt is 2-20: 1.
4. the method of claim 1, wherein 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.
5. The method for preparing nitrogen-doped iron carbide/carbon nanoenzyme according to claim 1, wherein the stirring time is 0.1-100 h; preferably, the stirring time is 0.2-5 h.
6. The method of preparing nitrogen-doped iron carbide/carbon nanoenzyme according to claim 1, wherein the calcination temperature is 500 to 1000 ℃; preferably, the calcining temperature is 600 ℃ to 900 ℃; the calcination time is 1-20 h; preferably, the calcination time is 1-10 h.
7. The nitrogen-doped iron carbide/carbon nanoenzyme prepared by the preparation method according to any one of claims 1 to 6.
8. The application of the nitrogen-doped iron carbide/carbon nanoenzyme prepared by the preparation method of any one of claims 1 to 6 in detecting the concentration of L-cysteine comprises the following steps:
(1) mixing nitrogen-doped iron carbide/carbon nanoenzyme with L-cysteine solutions with different concentrations and buffer solutions with pH of 2-4, adding TMB solution, standing at 30-60 ℃, obtaining absorbance change by using an ultraviolet visible spectrometer, and calculating a linear equation of the absorbance and the L-cysteine concentration;
(2) mixing nitrogen-doped iron carbide/carbon nanoenzyme with L-cysteine to be detected and a buffer solution with the pH value of 4, adding a TMB solution, standing at the temperature of 30-60 ℃, and determining the concentration of the L-cysteine to be detected by using the absorbance obtained by an ultraviolet-visible spectrometer in combination with the linear equation in the step (1).
9. The use of claim 8, wherein in step (1), the linear equation is Δ a-0.01026C L-Cys +0.02323。
10. The use according to claim 8, wherein the concentration of L-cysteine is detected in the range of 0.1 to 10 μ M with a limit of detection of 0.056 μ M.
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