CN110628427A - Double-peak emission carbon quantum dot and preparation method and application thereof - Google Patents
Double-peak emission carbon quantum dot and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorescent materials, and particularly relates to a double-peak emission carbon quantum dot and a preparation method and application thereof. The carbon quantum provided by the invention comprises, by mass, 20-22% of N, 27-28% of O, 1.2-1.5% of Cu and the balance of C. The invention dopes N and Cu to obtain the carbon quantum dots with high fluorescence intensity and bimodal emission. The embodiment result shows that after the carbon quantum dot provided by the invention is excited by ultraviolet light with the wavelength of 340nm, fluorescence emission exists at 400-450 nm and 460-500 nm, namely violet light and blue light respectively, and the carbon quantum dot is a typical double-peak emission carbon quantum dot.
Description
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to a double-peak emission carbon quantum dot and a preparation method and application thereof.
Background
Carbon quantum dots, as an emerging "zero-dimensional" carbon nanomaterial, are considered a new star in the luminescent material community. The carbon quantum dots have excellent water solubility, chemical inertness, low toxicity, easy functionalization, photobleaching resistance and adjustable optical characteristics, so that the carbon quantum dots have application prospects in the fields of analysis and detection, photocatalysis, light-emitting diodes, living body imaging, cell marking and the like, and therefore, the carbon quantum dots are widely concerned by researchers.
The preparation of carbon quantum dots has been developed more and more mature, for example, chinese patents CN201710977580.3, CN201810440595.0 and CN201811599749.7 disclose carbon quantum dots and corresponding preparation methods, respectively, but all obtained by the above methods are single-peak emission fluorescent materials; the carbon quantum dots of the double-peak emission are less, and only CN201610757716.5 is publicly reported. Therefore, it is still of great significance to develop more carbon quantum dots with bimodal emission properties.
Disclosure of Invention
The carbon quantum dot provided by the invention has fluorescence emission at 400-450 nm and 460-500 nm after being excited by ultraviolet light of 340nm, and is a typical double-peak emission carbon quantum dot.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a double-peak emission carbon quantum dot which comprises, by mass, 20-22% of N, 27-28% of O, 1.2-1.5% of Cu and the balance of C.
Preferably, the chemical bond in the bimodal emitting carbon quantum dot comprises C N, C-N-C, N- (C)3、H-N-(C)2And N-Cu-N.
Preferably, the bimodal emission carbon quantum dots are quasi-spherical, and the particle size is 1.5-4.0 nm.
Preferably, after the double-peak emission carbon quantum dots are irradiated by ultraviolet light, fluorescence emission exists at 400-450 nm and 460-500 nm.
The invention provides a preparation method of the double-peak emission carbon quantum dot in the technical scheme, which comprises the following steps:
mixing a nitrogen-containing carbon source, copper salt and a solvent to obtain a reaction mixed solution;
carrying out solvothermal reaction on the reaction mixed solution to obtain a reaction crude product;
and sequentially filtering, removing the solvent, dispersing in water and dialyzing the reaction crude product to obtain the double-peak emission carbon quantum dots.
Preferably, the nitrogen-containing carbon source comprises one or more of glycine, polyethyleneimine, urea, glucosamine, o-phenylenediamine, dopamine, folic acid, glutamic acid and phenylalanine;
the copper salt comprises one or more of copper acetate, copper nitrate, copper sulfate and copper chloride.
Preferably, the mass ratio of the nitrogen-containing carbon source to the copper salt is (0.01-5) to (0.01-5).
Preferably, the temperature of the solvothermal reaction is 100-280 ℃ and the time is 0.5-48 h.
Preferably, the cut-off molecular weight of the dialysis membrane for dialysis is 500-12000 Da, and the dialysis time is 6-72 h.
The invention provides application of the bimodal carbon quantum dot in the technical scheme or the bimodal carbon quantum dot prepared by the preparation method in the technical scheme in the field of ascorbic acid fluorescence sensors or cell imaging.
The double-peak emission carbon quantum dot comprises, by mass, 20-22% of N, 27-28% of O, 1.2-1.5% of Cu and the balance of C. The invention dopes N and Cu to obtain the carbon quantum dots with high fluorescence intensity and bimodal emission. The embodiment result shows that the carbon quantum dots provided by the invention have fluorescence emission at 400-450 nm and 460-500 nm after being excited by ultraviolet light of 340nm, and are typical double-peak emission carbon quantum dots.
The invention provides a preparation method of a double-peak emission carbon quantum dot, which takes common nitrogen-containing organic molecules as raw materials, does not need to additionally add a nitrogen source, is cheap and easy to obtain, effectively reduces the production cost, and has simple reaction process operation and good reproducibility.
Drawings
FIG. 1 is a transmission electron micrograph of the carbon quantum dots obtained in example 1;
FIG. 2 is a particle size distribution diagram of the carbon quantum dots obtained in example 1;
FIG. 3 is a FT-IR spectrum of the carbon quantum dots obtained in example 2;
FIG. 4 is an XPS spectrum of the carbon quantum dots obtained in example 2;
FIG. 5 is a graph of fluorescence excitation, emission and UV absorption spectra of carbon quantum dots obtained in example 2;
FIG. 6 is an optical photograph of the carbon quantum dots obtained in example 3 under natural light and ultraviolet light;
FIG. 7 is a cytotoxicity monitoring chart of the carbon quantum dots obtained in example 1;
FIG. 8 is a diagram of fluorescence imaging of carbon quantum dot laser confocal cells obtained in example 1;
FIG. 9 is a fluorescence detection spectrum of ascorbic acid by the carbon quantum dots obtained in example 2.
Detailed Description
The invention provides a double-peak emission carbon quantum dot which comprises, by mass, 20-22% of N, 27-28% of O, 1.2-1.5% of Cu and the balance of C.
In the invention, the double-peak emission carbon quantum dots preferably comprise, by mass, 20.5-21.5% of N, 27.2-27.8% of O, 1.3-1.4% of Cu and the balance of C.
In the present invention, the chemical bond in the bimodal emitting carbon quantum dot preferably includes C N, C-N-C, N- (C)3、H-N-(C)2And N-Cu-N; the double-peak emission carbon quantum dots are preferably quasi-spherical, the particle size is preferably 1.5-4.0 nm, more preferably 1.7-3.7 nm, and further preferably 2.0-3.5 nm; after the double-peak emission carbon quantum dots are irradiated by ultraviolet light with the wavelength of 340nm, fluorescence emission is carried out at 400-450 nm and 460-500 nm (the emission wavelengths of the two positions are not coincident).
The invention provides a preparation method of the double-peak emission carbon quantum dot in the technical scheme, which comprises the following steps:
mixing a nitrogen-containing carbon source, copper salt and a solvent to obtain a reaction mixed solution;
carrying out solvothermal reaction on the reaction mixed solution to obtain a reaction crude product;
and sequentially filtering, removing the solvent, dispersing in water and dialyzing the reaction crude product to obtain the double-peak emission carbon quantum dots.
The method mixes nitrogen-containing carbon source, copper salt and solvent to obtain reaction mixed liquid. In the invention, the nitrogen-containing carbon source preferably comprises one or more of glycine, polyethyleneimine, urea, glucosamine, o-phenylenediamine, dopamine, folic acid, glutamic acid and phenylalanine, and more preferably glucosamine, o-phenylenediamine or folic acid; the copper salt preferably comprises one or more of copper acetate, copper nitrate, copper sulfate and copper chloride, and more preferably copper acetate, copper chloride or copper nitrate; the solvent preferably comprises one or more of water, ethanol, acetone, glycerol, N-dimethylformamide and formamide, and more preferably water, ethanol or N, N-dimethylformamide.
In the invention, the mass ratio of the nitrogen-containing carbon source to the copper salt is preferably (0.01-5) to (0.01-5), and more preferably (0.05-4): (0.05-4), preferably (0.05-3): (0.1 to 3); the dosage ratio of the nitrogen-containing carbon source to the solvent is preferably (0.01-5) g: (5-30) mL, more preferably (0.05-4) g: (5-25) mL, more preferably (0.05-3) g: (10-20) mL.
The invention has no special requirement on the mixing mode of the nitrogen-containing carbon source, the copper salt and the solvent, and can ensure that all components are uniformly dispersed. The mixing is preferably carried out for 10-15 min under the ultrasonic condition, and more preferably for 10-12 min; the invention has no special requirement on the power of the ultrasonic wave, and can fully disperse all components.
After reaction mixed liquid is obtained, the invention carries out solvent thermal reaction on the reaction mixed liquid to obtain a reaction crude product. In the invention, the temperature of the solvothermal reaction is preferably 100-280 ℃, more preferably 120-260 ℃, and further preferably 160-220 ℃; the solvothermal reaction time is preferably 0.5-48 h, more preferably 1-36 h, and still more preferably 2-24 h. In the invention, the temperature of the solvothermal reaction is preferably increased by heating, and the rate of heating from room temperature to the temperature required by the solvothermal reaction is preferably 4-6 ℃/min, more preferably 4.5-5.5 ℃/min, and most preferably 5 ℃/min. In the present invention, the solvothermal reaction is preferably carried out in a polytetrafluoroethylene autoclave and a matched homogeneous reactor.
After the solvothermal reaction, the material after the solvothermal reaction is preferably cooled to room temperature; the cooling mode is preferably natural cooling.
The invention preferably carries out the solvothermal reaction under the conditions, and can control the dehydration, polymerization, passivation and carbonization processes of the reaction precursor, thereby influencing the size distribution and the surface functional group components of the carbon quantum dots.
After a reaction crude product is obtained, the invention sequentially carries out filtration, solvent removal, water dispersion and dialysis on the reaction crude product to obtain the double-peak emission carbon quantum dot. In the present invention, the pore diameter of the filtration membrane is preferably 0.01 to 0.45. mu.m, more preferably 0.22 to 0.45. mu.m, and most preferably 0.22. mu.m.
In the invention, the solvent removal mode is preferably rotary evaporation, and the temperature of the rotary evaporation is preferably 30-90 ℃, more preferably 50-80 ℃, and most preferably 60 ℃; the rotary evaporation time is not specially limited, and complete drying can be achieved.
After the solvent is removed, the material obtained after the solvent is removed is preferably subjected to water dispersion by the invention so as to facilitate the subsequent dialysis. The invention has no special requirement on the dosage of water in the water dispersion, and can fully disperse the materials obtained after the solvent is removed to obtain uniform water dispersion.
After water dispersion, the invention dialyzes the dispersion liquid obtained by water dispersion to obtain the double-peak emission carbon quantum dots. In the invention, the cut-off molecular weight of the dialysis membrane for dialysis is preferably 500-12000 Da, more preferably 500-3500 Da, and most preferably 500 Da; the dialysis time is preferably 6-72 h, more preferably 12-48 h, and most preferably 24 h.
The invention also provides the application of the bimodal carbon quantum dot in the technical scheme or the application of the bimodal carbon quantum dot prepared by the preparation method in the technical scheme in the ascorbic acid fluorescence sensor and the cell imaging field. In the invention, the cells involved in the cell imaging preferably comprise one or more of Hepg2, Hela, A549, C4-1 and C-33A. The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
In order to further illustrate the present invention, the following description will be made in detail with reference to the accompanying drawings and examples, but it should not be construed as limiting the scope of the present invention.
Example 1
Weighing 1g of glucosamine and 1g of copper acetate, adding 10mL of water, and ultrasonically mixing for 10min to obtain a reaction mixed solution;
adding the obtained reaction mixed solution into a 30mL polytetrafluoroethylene high-pressure reaction kettle, heating the reaction kettle to 160 ℃ from room temperature in a homogeneous reactor at the heating rate of 5 ℃/min, then preserving heat for 16h, and carrying out solvothermal reaction; after the reaction is finished, naturally cooling the reaction kettle to room temperature to obtain a crude reaction product;
filtering the reaction crude product by using a filter membrane with the pore diameter of 0.22 mu m, drying by rotary evaporation at 60 ℃, dissolving in water, and dialyzing for 24h by using a dialysis membrane with the molecular weight cutoff of 500Da to obtain the carbon quantum dots.
Example 2
Weighing 0.05g of folic acid and 0.12g of copper chloride, adding 15mL of ethanol, and ultrasonically mixing for 10min to obtain a reaction mixed solution;
adding the obtained reaction mixed solution into a 50mL polytetrafluoroethylene high-pressure reaction kettle, heating the reaction kettle from room temperature to 180 ℃ in a homogeneous reactor at the speed of 5 ℃/min, and carrying out solvent heat treatment for 6 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature to obtain a crude reaction product;
filtering the reaction crude product by using a filter membrane with the pore diameter of 0.22 mu m, drying by rotary evaporation at 60 ℃, dissolving in water, and dialyzing for 24h by using a dialysis membrane with the molecular weight cutoff of 500Da to obtain the carbon quantum dots.
Example 3
Weighing 3g of o-phenylenediamine and 2g of copper nitrate, adding 20mL of N, N-dimethylformamide, and ultrasonically mixing for 10min to obtain a reaction mixed solution;
adding the obtained reaction mixed solution into a 50mL polytetrafluoroethylene high-pressure reaction kettle, heating the reaction kettle to 200 ℃ in a homogeneous reactor at the speed of 5 ℃/min, and carrying out solvent heat treatment for 12 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature to obtain a crude reaction product;
filtering the reaction crude product by using a filter membrane with the pore diameter of 0.22 mu m, drying by rotary evaporation at 60 ℃, dissolving in water, and dialyzing for 24h by using a dialysis membrane with the molecular weight cutoff of 500Da to obtain the carbon quantum dots.
Structure, Performance and characterization
And (3) characterizing the morphology and size of the carbon quantum dots obtained in the embodiments 1-3 by using a transmission electron microscope, wherein the characterization result of the embodiment 1 is shown in figures 1 and 2. Fig. 1 is a transmission electron/high resolution transmission electron micrograph of the carbon quantum dots prepared in example 1, and fig. 2 is a size distribution diagram of the carbon quantum dots. As can be seen from fig. 1 and 2, the carbon quantum dots obtained in example 1 are quasi-spherical, monodisperse nanoparticles (well dispersed in water), with an average size of 2.63nm and a lattice spacing of 0.206nm, which is close to the 100-plane spacing of graphite. Other examples test results were similar to those of example 1.
The composition structures of the carbon quantum dots obtained in examples 1 to 3 were characterized by infrared and X-ray photoelectron spectroscopy, and the results are shown in fig. 3 and 4. FIG. 3 is a FT-IR spectrum of the carbon quantum dots obtained in example 2. As can be seen from FIG. 3, a chemical bond containing N and Cu is formed on the surface of the carbon quantum dot and the carbon skeleton, such as C-N, C-N-C, N- (C)3、H-N-(C)2And N-Cu-N, etc.; fig. 4 is an XPS spectrum of the carbon quantum dot obtained in example 2, wherein a is an XPS total spectrum, b is a C1s spectrum, C is an N1s spectrum, d is a Cu2p spectrum, and the contents of the elements are: n21.34%, O27.47%, Cu 1.35% and C49.84%; the fluorescence quantum yield was 73%. The test results of the other examples were similar to those of example 2.
Fluorescence excitation, emission and ultraviolet absorption performances of the carbon quantum dots obtained in the embodiments 1 to 3 were tested by using a fluorescence spectrophotometer and an ultraviolet-visible spectrophotometer, wherein fluorescence excitation, emission and ultraviolet absorption spectrograms of the carbon quantum dots obtained in the embodiment 2 are shown in fig. 5. The carbon quantum dots have distinct ultraviolet absorption bands at 276nm and 340nm, resulting from pi-pi electron transfer of C ═ C and N-pi electron transfer of C ═ O/N, respectively, and this absorption band is wider due to metallic Cu doping.
Taking the carbon quantum dots obtained in example 3 as an example, the light emitting properties of the carbon quantum dots were observed by irradiation with natural light and ultraviolet light, respectively, to characterize the optical properties of the carbon quantum dots, and the results are shown in fig. 6. As can be seen from fig. 6, the carbon quantum dots obtained by the present invention are colorless clear solutions under natural light (left side) and emit blue fluorescence under ultraviolet light (right side).
Detecting the fluorescence properties of the carbon quantum dots obtained in the embodiments 1-3 by using a fluorescence spectrophotometer, wherein the carbon quantum dots in the embodiment 1 have double fluorescence emission peaks at 440nm and 490nm under ultraviolet light irradiation (excitation wavelength is 340 nm); the carbon quantum dots obtained in example 2 have dual fluorescence emission peaks (emission wavelengths of 410 and 470nm, respectively) under ultraviolet irradiation (excitation at 340nm), namely violet light and blue light; the carbon quantum dot obtained in example 3 has strong blue light emission under ultraviolet irradiation, and is also a dual fluorescence emission peak.
According to the detection result of the fluorescence spectrophotometer, the fluorescence quantum yield of the carbon quantum dots obtained in the example 3 under the ultraviolet light irradiation is calculated by using the following formula, and the calculation result is 73%; the calculation results of other examples are similar to those of example 3.
Фu＝Фs(Yu/Ys)(As/Au)(ηs/ηu)2；
In the above formula, u: carbon quantum dots; s: a standard quinine sulfate; y: peak area of fluorescence emission peak; a: ultraviolet absorbance at 360 nm; Φ: fluorescence quantum yield; eta: the refractive index of the solvent, η s ═ 1.369, and η u ═ 1.332.
Carbon quantum dot solutions with different concentrations are prepared and used for testing the cytotoxicity of the carbon quantum dots obtained in examples 1-3. The carbon quantum dot test of example 1 was carried out using Hepg2 cells as cells, by mixing Hepg2 cells with 100 g.L at 37 deg.C-1After incubation for 6h, fluorescence images of HepG2 cells were obtained under a confocal laser microscope. The test results are shown in fig. 7. As can be seen from FIG. 7, the carbon quantum dots provided by the present invention have low cytotoxicity to Hepg2 cells, and when the carbon quantum dot content reaches 400. mu.g.mL-1In time, more than 89% of cancer cells still existAnd (6) alive. Using the same method, the carbon quantum dots obtained in examples 2 and 3 were used to perform toxicity tests on Hela, A549, C4-1 and C-33A cells, respectively, and the results show that the carbon quantum dots provided by the present invention have lower toxicity to the above cells, higher cell survival rate, and when the content of the carbon quantum dots is 400. mu.g.mL-1Then, 90%, 92%, 88% and 89% or more are obtained.
Taking the carbon quantum dots obtained in example 1 as an example, the fluorescence imaging performance of the carbon quantum dot laser confocal cell provided by the invention is tested, and the test result is shown in fig. 8. As can be seen from fig. 8, the carbon quantum dots provided by the present invention have high biocompatibility, and can be successfully used for cellular imaging of Hepg 2; is a colorless solution (a) under natural light, emits blue (b) and blue-green (c) fluorescence under excitation of 360 and 440nm, respectively, and the photoluminescence behavior is caused by uneven size distribution and various surface states. The imaging performance of the carbon quantum dots obtained in the examples 2 and 3 is similar to that of the carbon quantum dots obtained in the example 1, and the carbon quantum dots can be used for cell imaging of Hepg 2.
Taking the carbon quantum dot obtained in example 2 as an example, the fluorescence property of the carbon quantum dot provided by the invention on ascorbic acid is tested. As shown in fig. 9(a), the concentration of ascorbic acid in the test sample was 0, 0.02, 10, 20, 40, 160, 320, 480, 640, and 1600(μ M) from top to bottom at the time of the test, and the greater the concentration of ascorbic acid, the lower the fluorescence intensity; as can be seen from fig. 9(b), the lowest detection limit is 42.7nM, which indicates that the carbon quantum dot provided by the present invention has good fluorescence capability to ascorbic acid; from the test results, the detection mechanism is static quenching. The fluorescence detection result of the carbon quantum dot on the ascorbic acid obtained in other embodiments is similar to the detection result, and the carbon quantum dot provided by the invention has excellent fluorescence detection performance on the ascorbic acid; on the other hand, the ascorbic acid can quench the fluorescence of the carbon quantum dot provided by the invention, and has higher sensitivity.
According to the embodiment and the test characterization results, the carbon quantum dot provided by the invention has the characteristic of double-peak emission, has good biocompatibility, and can be used for an ascorbic acid fluorescence sensor and imaging of different cells. The preparation method provided by the invention is simple, easy to control and easy for large-scale production.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. The double-peak emission carbon quantum dot is characterized by comprising, by mass, 20-22% of N, 27-28% of O, 1.2-1.5% of Cu and the balance of C.
2. The dual-peak emissive carbon quantum dot of claim 1, wherein the chemical bond in the dual-peak emissive carbon quantum dot comprises C N, C-N-C, N- (C)3、H-N-(C)2And N-Cu-N.
3. The bimodal emitting carbon quantum dot of claim 2, wherein the bimodal emitting carbon quantum dot is quasi-spherical and has a particle size of 1.5 to 4.0 nm.
4. The bimodal emitting carbon quantum dot according to any one of claims 1 to 3, wherein the bimodal emitting carbon quantum dot has fluorescence emission at 400 to 450nm and 460 to 500nm after being irradiated by ultraviolet light.
5. The preparation method of the bimodal carbon emission quantum dot as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing a nitrogen-containing carbon source, copper salt and a solvent to obtain a reaction mixed solution;
carrying out solvothermal reaction on the reaction mixed solution to obtain a reaction crude product;
and sequentially filtering, removing the solvent, dispersing in water and dialyzing the reaction crude product to obtain the double-peak emission carbon quantum dots.
6. The method according to claim 5, wherein the nitrogen-containing carbon source comprises one or more of glycine, polyethyleneimine, urea, glucosamine, o-phenylenediamine, dopamine, folic acid, glutamic acid, and phenylalanine;
the copper salt comprises one or more of copper acetate, copper nitrate, copper sulfate and copper chloride.
7. The method according to claim 6, wherein the mass ratio of the nitrogen-containing carbon source to the copper salt is (0.01-5) to (0.01-5).
8. The method according to claim 5, 6 or 7, wherein the solvothermal reaction is carried out at a temperature of 100 to 280 ℃ for 0.5 to 48 hours.
9. The method according to claim 5, 6 or 7, wherein the dialysis membrane for dialysis has a molecular weight cut-off of 500 to 12000Da and a dialysis time of 6 to 72 hours.
10. Use of the bimodal carbon quantum dot according to any one of claims 1 to 4 or the bimodal carbon quantum dot prepared by the preparation method according to any one of claims 5 to 9 in an ascorbic acid fluorescence sensor or in the field of cell imaging.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608092A (en) * | 2012-03-28 | 2012-07-25 | 哈尔滨工业大学 | Fluorescence biosensor for detecting high-sensitivity copper ionss and detection method thereof |
| CN105567228A (en) * | 2016-01-27 | 2016-05-11 | 山西大学 | N, P and S-codoped fluorescent carbon quantum dot and preparation method and application thereof |
| CN107573930A (en) * | 2017-10-13 | 2018-01-12 | 西南大学 | A kind of preparation method of double transmitting fluorescent carbon points |
| CN108485661A (en) * | 2018-03-23 | 2018-09-04 | 山西大学 | A kind of preparation method and applications of fluorescent carbon quantum dot |
| CN108611090A (en) * | 2018-05-04 | 2018-10-02 | 山西大学 | A kind of fluorescent carbon quantum dot and its preparation method and application |
-
2019
- 2019-10-15 CN CN201910976556.7A patent/CN110628427A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608092A (en) * | 2012-03-28 | 2012-07-25 | 哈尔滨工业大学 | Fluorescence biosensor for detecting high-sensitivity copper ionss and detection method thereof |
| CN105567228A (en) * | 2016-01-27 | 2016-05-11 | 山西大学 | N, P and S-codoped fluorescent carbon quantum dot and preparation method and application thereof |
| CN107573930A (en) * | 2017-10-13 | 2018-01-12 | 西南大学 | A kind of preparation method of double transmitting fluorescent carbon points |
| CN108485661A (en) * | 2018-03-23 | 2018-09-04 | 山西大学 | A kind of preparation method and applications of fluorescent carbon quantum dot |
| CN108611090A (en) * | 2018-05-04 | 2018-10-02 | 山西大学 | A kind of fluorescent carbon quantum dot and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PAN-PAN ZHU等: "Synthesis of the Cu-Doped Dual-Emission Fluorescent Carbon Dots and Its Analytical Application", 《LANGMUIR》 * |
| 徐凤州: "基于铜纳米颗粒和石墨烯材料的荧光生化传感研究及应用", 《中国优秀博士学位论文全文数据库工程科技I辑》 * |
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