CN115920890A - Preparation method of iron monoatomic-doped fluorescent carbon dot nanoenzyme - Google Patents
Preparation method of iron monoatomic-doped fluorescent carbon dot nanoenzyme Download PDFInfo
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- CN115920890A CN115920890A CN202211634035.1A CN202211634035A CN115920890A CN 115920890 A CN115920890 A CN 115920890A CN 202211634035 A CN202211634035 A CN 202211634035A CN 115920890 A CN115920890 A CN 115920890A
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Abstract
The invention discloses a preparation method of iron monatomic doped fluorescent carbon dot nanoenzyme, which comprises the steps of taking chitosan, glutamic acid and ferrous sulfate heptahydrate as reaction precursors, synthesizing an iron monatomic doped carbon dot nanoenzyme base solution with fluorescence characteristics by one step through a hydrothermal method, and dialyzing, cooling and drying to obtain the final iron monatomic doped fluorescent carbon dot nanoenzyme solid. The method for synthesizing the iron monatomic carbon dot nanoenzyme is simple to operate, can realize the iron monatomic doped fluorescent carbon dot nanoenzyme without strict equipment such as ultrahigh-temperature pyrolysis and complex reaction steps, and can effectively avoid the problem of metal load reduction under the ultrahigh-temperature condition. The synthesized iron monatomic fluorescent carbon dot nanoenzyme has good water solubility, photoluminescence performance and excellent peroxidase characteristics, and has higher stability, adjustable catalytic activity and feasibility of large-scale preparation compared with natural enzyme.
Description
Technical Field
The invention belongs to the technical field of synthesis of monatomic nanoenzymes, and relates to a preparation method of a fluorescent carbon dot nanoenzyme doped with iron monatomic.
Background
The monatomic nanoenzyme is a nanoenzyme with ultrahigh catalytic activity, generally, the metal-doped carbon-point nanoenzyme needs expensive reaction equipment and special conditions, and the metal loading capacity can be reduced due to the ultrahigh synthesis temperature, so that the catalytic activity of the finally obtained product is reduced. The currently reported monatomic nanoenzymes are mainly a prerequisite for decomposing iron coordination by selecting a pyrolysis mode, and the monatomic iron nanoenzymes are prepared (Boosting Fenton-Like Reactions via Single Atom Fe Catalysis, environmental Science & Technology,2019,53 (19) -11391-11400). Therefore, it is of great significance to explore a method for synthesizing the monatomic nanoenzyme conveniently, greenly and at low cost.
Composite materials with enzyme activity such as metal, metal compound, metal organic framework and the like are still a challenge in terms of affinity and specificity compared with traditional enzymes, while carbon-based nanoenzyme has good biocompatibility, but the catalytic activity of pure carbon-based nanoenzyme is not high and does not necessarily have stronger luminescence property, and metal-doped carbon-based nanoenzyme can sometimes improve the catalytic activity of nanoenzyme (bioadsiable hydrogel with phenolic carbon dot supported Pd nanoparticles as a localized immobilized enzyme for cancer catalytic immunization, DOI:10.1016/j. Biological materials 2021.121272). Therefore, the development of the single-atom fluorescent carbon dot nanoenzyme with ultrahigh peroxidase activity, good biocompatibility and excellent fluorescence characteristics has innovative significance.
Disclosure of Invention
The invention aims to provide a preparation method of iron monoatomic-doped fluorescent carbon dot nanoenzyme. The method comprises the steps of taking chitosan, glutamic acid and ferrous sulfate heptahydrate as raw materials, obtaining basic reaction liquid through one-step hydrothermal reaction, removing precipitates through centrifugation, dialyzing, freezing and drying to obtain the iron monatomic fluorescent carbon dot nano-enzyme, wherein the product has excellent peroxidase activity.
The invention adopts the following technical scheme to solve the technical problems, and the preparation method of the fluorescent carbon dot nanoenzyme doped with the iron monoatomic atom is characterized by comprising the following specific steps of:
step S1: dissolving chitosan in 1% (v/v) acetic acid aqueous solution, performing ultrasonic treatment to form uniform solution, adding glutamic acid and ferrous sulfate heptahydrate powder into the dispersed chitosan solution, stirring uniformly, finally dropwise adding ethylenediamine solution, transferring the solution into a reaction kettle, and reacting in a high-temperature oven.
Step S2: and (3) centrifuging the reaction liquid obtained in the step (S1) to remove precipitates, dialyzing, collecting the liquid, and freeze-drying the liquid to obtain a brownish black powder solid product.
Preferably, the feeding mass ratio of the glutamic acid to the ferrous sulfate heptahydrate in the step S1 is 1:1.
Preferably, the centrifugation time in the step S2 is 8-14min, and the dialysis time is 10-14h.
The invention relates to a convenient, green and low-cost novel monatomic nanoenzyme preparation method, which takes chitosan, glutamic acid and ferrous sulfate heptahydrate as raw materials and prepares the fluorescent carbon dot nanoenzyme doped with the iron monatomic through one-step hydrothermal reaction.
Compared with the prior art, the invention has the following advantages:
1. the invention has low cost, including material cost and reaction equipment cost, and simple preparation method and reaction post-treatment;
2. compared with other synthesis methods, the temperature of the prepared iron monatomic fluorescent carbon dot nanoenzyme is low, and the reaction conditions are mild;
3. the iron monatomic fluorescent carbon dot nanoenzyme prepared by the method has good water solubility, has excellent peroxidase activity under the loading of the iron monatomic, retains the excellent fluorescence property of the carbon dot, has higher fluorescence quantum yield, and has potential application value in various fields of enzyme catalysis.
The iron monatomic fluorescent carbon dot nanoenzyme prepared by the invention has the performance of peroxide mimic enzyme and can catalyze hydrogen (H) oxide 2 O 2 ) Hydroxyl radicals (. OH) are generated, so that the chromogenic substrates 3,3',5,5' -Tetramethylbenzidine (TMB) and o-phenylenediamine (OPD) are oxidized to oxidized 3,3',5,5' -tetramethylbenzidine (OxTMB) and 2,3-Diaminophenazine (DAP), respectively, and have UV-visible response. The iron monatomic fluorescent carbon dot nanoenzyme obtained by enzyme steady-state kinetic experiment has a low Michaelis constant (K) m ) Indicating strong enzyme catalytic activity.
Drawings
FIG. 1 is a schematic diagram of the synthesis steps of the iron monatomic fluorescent carbon dot nanoenzyme prepared in example 2.
FIG. 2 is a TEM image of the iron monatomic fluorescent carbon dot nanoenzyme prepared in example 2.
FIG. 3 is a spherical aberration electron microscope image of the iron monatomic fluorescent carbon dot nanoenzyme prepared in example 2.
FIG. 4 is a HAADF-STEM diagram of the iron monatomic fluorescent carbon dot nanoenzyme prepared in example 2.
Fig. 5 shows the emission spectra obtained by excitation with a fluorescence spectrometer at different excitation wavelengths.
FIG. 6 is a graph showing the ultraviolet absorption of the iron monatomic fluorescent carbon dot nanoenzyme measured in a wavelength range of 200 to 800nm by an ultraviolet spectrophotometer.
FIG. 7 is an XPS map of the iron monatomic fluorescent carbon dot nanoenzyme prepared in example 2.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: dissolving 0.1g of chitosan in 10mL of 1% (v/v) acetic acid aqueous solution, performing ultrasonic treatment in an ultrasonic cleaning machine for 30min, adding 0.05g of glutamic acid, fully stirring to dissolve solid powder, adding 100 mu L of ethylenediamine, transferring to a high-temperature reaction kettle, sealing and preserving heat at 180 ℃ for 6h.
Step S2: and (3) cooling the reaction kettle reacted in the step (S1) to room temperature, taking out black liquid obtained by the reaction, centrifuging to remove solid impurities, dialyzing for 12h by using a dialysis bag (MW = 500-1000), and collecting the liquid in the dialysis bag to freeze-dry the liquid into brownish black powder, namely the fluorescent carbon dot powder.
Example 2
Step S1: dissolving 0.1g of chitosan in 10mL of 1% (v/v) acetic acid aqueous solution, carrying out ultrasonic treatment in an ultrasonic cleaning machine for 30min, then adding 0.05g of ferrous sulfate heptahydrate and 0.05g of glutamic acid, fully stirring to dissolve solid powder, adding 100 mu L of ethylenediamine, transferring to a high-temperature reaction kettle, sealing and keeping the temperature at 180 ℃ for 6h.
Step S2: and (2) cooling the reaction kettle reacted in the step (S1) to room temperature, taking out black liquid obtained by the reaction, centrifuging to remove solid impurities, dialyzing for 12 hours by using a dialysis bag (MW = 500-1000), collecting liquid in the dialysis bag, and freeze-drying the liquid to form brownish black powder, namely the iron monatomic fluorescent carbon dot nano-enzyme powder.
And (3) detecting the activity of the peroxidase: the iron monatomic fluorescent carbon dot nanoenzyme can catalyze hydrogen peroxide (H) 2 O 2 ) Generating OH oxidized chromogenic substrate 3,3',5,5' -Tetramethylbenzidine (TMB) to form blue oxidized 3,3',5,5' -tetramethylbenzidine (OxTMB), the chromogenic substrate having a maximum absorption peak at 652 nm; in the same principle, the monatomic nanoenzyme catalyzes hydrogen peroxide (H) 2 O 2 ) Generating hydroxyl radicals (. OH) to oxidize o-phenylenediamine (OPD) to 2,3-Diaminophenazine (DAP) in yellow with a maximum absorption at 420 nm; the material can degrade Methylene Blue (MB) by hydrogen peroxideMethylene blue becomes pale in color with an absorption maximum at 665 nm.
In comparison with example 2, the fluorescent carbon dots without metallic iron doping in example 1 had no catalase-like activity.
Compared with the prior art, the prior method (biological injectable hydrogel with phenolic carbon quaternary ammonium dot supported Pd single atom microorganisms as a localized immobilized immunological catalysis for cancer catalytic catalysis, DOI:10.1016/j. Biological materials 2021.121272) obtains carbon dots by using raw materials through hydrothermal synthesis at 180 ℃ for 6 hours, and then dialyzes and freeze-dries the carbon dots into solid, and the dried solid is redissolved and Na 2 PdCl 4 The solution is stirred to synthesize the palladium monoatomic nanoenzyme supported by the carbon points, the synthesis method needs two steps of reaction, the consumed time is long, and the Mie constant (K) of the TMB is m ) 569.4mM is higher than the iron single-atom fluorescent carbon dot nanoenzyme (Mie's constant (K) of the invention m )＝0.139mM)。
The reaction conditions in example 2 of the present invention are mild, but the existing synthesis method (Boosting Fenton-Like Reactions via Single Atom Fe Catalysis, environmental Science)&Technology,2019,53 (19) -11391-11400 by calcining the material in a tube furnace at 500 deg.C for 5h, then adding Fe (NO) 3 ) 3 ·9H 2 After grinding, the O is continuously calcined at 500 ℃ for 5h, the synthesis method is complicated and the temperature is very high, and the metal load is obviously reduced due to the high temperature.
The synthesis method and the catalytic activity of the material of the present invention are described in the above examples, and it should be understood by those skilled in the art that the present invention is not limited by the above examples, and the above examples and descriptions are only illustrative of the synthesis method of the present invention, and various changes and modifications can be made without departing from the scope of the synthesis method of the present invention, and the changes and modifications are within the protection scope of the present invention.
Claims (4)
1. The preparation method of the iron monoatomic-doped fluorescent carbon dot nanoenzyme is characterized by comprising the following specific steps of:
step S1: dissolving chitosan in 1% (v/v) acetic acid aqueous solution, fully dissolving by ultrasonic, adding ferrous sulfate heptahydrate and glutamic acid into the uniform chitosan solution, fully stirring to dissolve solid powder, finally dropwise adding ethylenediamine solution into the mixed solution, uniformly stirring, transferring the mixed solution into a high-temperature reaction kettle, and reacting for 6 hours at 180 ℃;
step S2: and S1, carrying out centrifugal filtration on the obtained reaction liquid to remove solid impurities, dialyzing by using a dialysis bag, and further carrying out freeze drying on the purified liquid to obtain black-brown solid powder which is the iron monoatomic fluorescent carbon dot nanoenzyme.
2. The method for preparing the iron monoatomic-doped fluorescent carbon dot nanoenzyme according to claim 1, wherein: in the step S1, the chitosan is dissolved in 1% (v/v) acetic acid water solution for 30min by ultrasonic treatment, and the feeding mass ratio of the ferrous hexahydrate to the glutamic acid is 1:1.
3. The method for preparing the iron monoatomic-doped fluorescent carbon dot nanoenzyme according to claim 1, wherein: the apparatus used for the high temperature reaction in step S1 is a common constant temperature drying oven.
4. The method for preparing the iron monoatomic-doped fluorescent carbon dot nanoenzyme according to claim 1, wherein: in the step S2, the centrifugation time is 8-14min, and the dialysis time is 10-14h.
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| CN116726926A (en) * | 2023-06-08 | 2023-09-12 | 合肥工业大学 | Method for detecting methyl mercaptan in Fe & Cu@CDs nano-enzyme dual mode |
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| CN116735580A (en) * | 2023-08-15 | 2023-09-12 | 中国农业科学院农产品加工研究所 | Meat freshness detection sensor based on bimodal monoatomic nano enzyme and preparation method thereof |
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