CN113025320A - Nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot and application thereof - Google Patents
Nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot and application thereof Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 79
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
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Abstract
The invention discloses a nitrogen-sulfur co-doped biomass-based fluorescent carbon dot, which comprises the following raw materials in parts by weight: 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source, and is prepared by adopting a hydrothermal method in one step. The method overcomes the problems of harsh preparation conditions and low fluorescence quantum yield of the existing fluorescent carbon dots, is simple to operate and low in raw material cost, and the prepared nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots have the advantages of high fluorescence quantum yield, stable fluorescence performance, good biocompatibility and low toxicity.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot and application thereof.
Background
Carbon quantum dots, Carbon Dots (CDs) for short, are novel fluorescent carbon nano-materials with the particle size of less than 10 nm. Since the inadvertent discovery of carbon dots in the electrophoretic separation of single-armed carbon nanotubes by Xu et al in 2004, it has gradually become a new star in the family of carbon-based materials. Compared with the traditional semiconductor quantum dot, the quantum dot has the advantages of excellent water solubility, low toxicity, biological solubility, stable fluorescence, adjustable fluorescence and the like. So that the carbon dots have the potential of application in many aspects, such as biological imaging, biological sensing, drug release, photoelectric devices, fluorescent printing and the like, and attract the interest of a large number of researchers. CDs can be well dispersed in water and can modify various types of organic and inorganic materials. It is noteworthy that CDs also possess the property of up-converting photoluminescence, depending on the excitation wavelength and size of the CDs. Because of these excellent properties, CDs is a very promising material in the fields of photocatalysis, solar cells, biomaterials, and the like.
The preparation methods of CDs are divided into two main categories, one is from top to bottom, and the other is from bottom to top. The top-down synthetic route breaks larger carbon structures through methods such as arc discharge, laser burning, electrochemical oxidation, and the like. In 2006, Sun et al first obtained CDs by laser firing a carbon target in an atmosphere with argon as a carrier gas. However, CDs prepared in this way are often aggregated together due to size variation and do not have fluorescence emission properties. However, such CDs can emit bright blue fluorescence after being subjected to an oxidation surface passivation treatment. The bottom-up synthetic route generally prepares CDs by pyrolyzing small organic molecules such as citric acid, glucose, amino acids, glycerol, and the like, and, on the other hand, by microwave pyrolysis. Li and the like prepare CDs by using modified silica spheres as carriers and resol as carbon precursors. Bourlinos et al describe a simple, one-step thermal decomposition of ammonium citrate to give CDs. Zhao et al prepared fluorescent CDs by heating polyethylene glycol and saccharide solution with 500W microwave for 2-10 min. And the cost is a key factor for whether CDs can successfully replace the traditional semiconductor quantum dots.
The above-mentioned methods have disadvantages in terms of cost, such as expensive equipment, complicated and time-consuming operation process, and expensive precursor raw material, and there is a need for a green preparation method which can successfully overcome these disadvantages.
Therefore, how to provide a low-cost nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot and an application thereof are problems to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot with lower cost, high yield and simple conditions and application thereof, and adopts a green and environment-friendly preparation method, namely a hydrothermal method, to select various biological carbon sources, sulfur sources and nitrogen sources, in particular to a method for preparing the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot by one step by using cellulose as a carbon source and sodium thiosulfate and Ethylenediamine (EDA) as the sulfur source (dopant) and the nitrogen source (passivator).
In order to achieve the purpose, the invention adopts the following technical scheme:
a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot comprises the following raw materials in parts by weight: 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source, and is prepared by adopting a hydrothermal method in one step.
Preferably, the biological carbon source is selected from one of cellulose or cellulose derivatives.
Preferably, the nitrogen source is selected from one of ethylenediamine, m-phenylenediamine and urea.
Preferably, the sulfur source is selected from one of sodium thiosulfate, sodium sulfite and sulfanilic acid.
Preferably, the hydrothermal process comprises in particular the following steps:
putting 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source into a reaction kettle, adding 10-100 parts of water, uniformly mixing, carrying out constant-temperature hydrothermal reaction at 80-200 ℃ for 24-120h, and carrying out post-treatment after the reaction is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot.
Preferably, the post-processing operation is: and obtaining reaction liquid after the reaction is finished, centrifuging, taking supernatant, dialyzing for 12-96h by using ultrapure water, wherein the molecular weight cut-off of a dialysis tube is 500-1000Da, and freeze-drying after the dialysis is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots.
The invention also provides application of the nitrogen-sulfur co-doped cellulose matrix fluorescent carbon dot in the field of iron ion detection.
Preferably, in the field of iron ion detection, the detection limit is 0.32 ppm.
Preferably, the nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dot is applied to the field of cell imaging.
Preferably, it is used for fluorescence imaging of MC3T3 cells.
Preferably, the fluorescence property of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot is utilized, and the cell is blue under the excitation light of 405 nm; under 488nm excitation light, the cells generate green fluorescence.
Through the technical scheme, compared with the prior art, the invention discloses a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which has the following technical effects:
(1) the invention provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which adopts an environment-friendly preparation method, namely a hydrothermal method, can select various biological carbon sources, sulfur sources and nitrogen sources, and specifically adopts cellulose as the carbon source and sodium thiosulfate and Ethylenediamine (EDA) as the sulfur source (dopant) and the nitrogen source (passivator) to prepare the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot in one step.
(2) The invention overcomes the problems of harsh preparation conditions, expensive raw materials and low fluorescence quantum yield of the existing fluorescent carbon dots, has simple operation and low raw material cost, and the prepared nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots have high fluorescence quantum yield, stable fluorescence performance, good biocompatibility and low toxicity. The nitrogen and sulfur co-doped cellulose-based fluorescent carbon dots are successfully applied to biological imaging and iron ion detection. The preparation method provided by the invention is simple to operate, the raw materials are cheap and easy to obtain, and the obtained nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots have high fluorescence quantum yield, good water solubility and stable fluorescence.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a TEM image of nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dots in example 1 of the present invention.
FIG. 2 is a graph showing a fluorescence emission spectrum of a N-S co-doped cellulose-based fluorescent carbon dot in experiment II of example 1 of the present invention.
FIG. 3 is a graph showing cytotoxicity results of nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots tested in example 1 of the present invention.
FIG. 4 is a graph showing the ion response of the N-S co-doped cellulose-based fluorescent carbon dots in example 4 of the present invention.
FIG. 5 is a graph of data obtained by calculating the detection limit of Fe (III) ions of N-S co-doped cellulose-based fluorescent carbon dots in example 4 of the present invention.
FIG. 6 is a diagram of an application of nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dots in biological imaging in example 5 of the present invention, wherein (a) is blue fluorescence imaging under 405nm excitation light, and (b) is green fluorescence imaging under 488nm excitation light.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The embodiment of the invention provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which comprises the following raw materials in parts by weight: 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source, and is prepared by adopting a hydrothermal method in one step.
In order to further optimize the above technical solution, the biological carbon source is selected from one of cellulose or cellulose derivatives.
In order to further optimize the technical scheme, the nitrogen source is selected from one of ethylenediamine, m-phenylenediamine and urea.
In order to further optimize the technical scheme, the sulfur source is selected from one of sodium thiosulfate, sodium sulfite and sulfanilic acid.
In order to further optimize the above technical solution, the hydrothermal method specifically comprises the following steps:
putting 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source into a reaction kettle, adding 10-100 parts of water, uniformly mixing, carrying out constant-temperature hydrothermal reaction at 80-200 ℃ for 24-120h, and carrying out post-treatment after the reaction is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot.
In order to further optimize the technical scheme, the post-processing operation comprises the following steps: and obtaining reaction liquid after the reaction is finished, centrifuging, taking supernatant, dialyzing for 12-96h by using ultrapure water, wherein the molecular weight cut-off of a dialysis tube is 500-1000Da, and freeze-drying after the dialysis is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots.
The invention also provides application of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot in the field of iron ion detection.
In order to further optimize the technical scheme, the detection limit is 0.32ppm in the field of iron ion detection.
In order to further optimize the technical scheme, the application of the nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dot in the field of cell imaging is provided.
In order to further optimize the technical scheme, the method is used for fluorescence imaging of MC3T3 cells.
In order to further optimize the technical scheme, the fluorescence property of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot is utilized, and the cells are blue under the excitation light of 405 nm; under 488nm excitation light, the cells generate green fluorescence.
In a specific embodiment, the vitamin powder is a biological carbon source, the sodium thiosulfate is a sulfur source (dopant), the ethylenediamine is a nitrogen source (passivating agent), and the water is ultrapure water, which can be purchased from conventional sources as a commercially available analytically pure raw material, and the manufacturers and batches of the raw material are not described herein.
Example 1
The embodiment provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which is prepared by the following method:
0.5g of cellulose powder and 0.15g of sodium thiosulfate powder and 0.5mL of ethylenediamine solution (analytical grade) were put into a polytetrafluoroethylene reaction vessel while 10mL of ultrapure water was added as a solvent. And (3) placing the reaction kettle in a constant-temperature oven at 180 ℃, reacting for 72h, centrifuging to obtain brown carbon dot reaction liquid, dialyzing the reaction liquid for 72h by using a dialysis tube at 500Da, and freeze-drying the dialyzed solution by using a freeze dryer to finally obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material.
In order to further illustrate the technical effects of the present invention, the applicant also tested the nanoparticle size, fluorescence property and cytotoxicity of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot obtained in example 1, and specifically included the following contents:
test one: physical properties of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots.
A TEM image of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material obtained in example 1 was obtained by scanning the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material with a transmission electron microscope, as shown in fig. 1 (a). Under high resolution TEM, the N-S co-doped cellulose-based fluorescent carbon dots are approximately spherical nano-materials with an average particle size of 3.2 nm.
And (2) test II: and the fluorescence property of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot.
The fluorescence property of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material in example 1 was tested by a fluorescence spectrophotometer, and as shown in fig. 2, an emission spectrum of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot aqueous solution was obtained under different excitation lights, so that it can be seen that the emission spectrum of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material depends on the excitation light, and the emission spectrum is red-shifted with the increase of the wavelength of the excitation light.
And (3) test III: cytotoxicity of nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots.
Cytotoxicity experiments were performed using the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material of example 1. Inoculating MC3T3 osteoblasts into 96-well plate, placing at 37 deg.C and 5% CO2Cultured in an incubator. After 24h, the culture medium is sucked off, the culture medium containing nitrogen and sulfur CO-doped cellulose base fluorescent carbon dot material is added, and the temperature is kept at 37 ℃ and 5% CO2The culture box is used for culturing for 24 hours. The medium was aspirated, washed 3-5 times with PBS, and then medium containing 10% CCK-8 was added, continuing at 37 ℃ with 5% CO2The culture box is cultured for 4 hours, and the OD value of the culture box is measured by a microplate reader. Through calculation, as shown in fig. 3, the cell survival rate reaches more than 90%, which indicates that the carbon dots prepared by the invention are low-toxic and even non-toxic.
Example 2
The embodiment provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which is prepared by the following method:
2g of cellulose powder, 3g of sodium thiosulfate powder and 0.7mL of ethylenediamine solution (analytical grade) were placed in a polytetrafluoroethylene reaction vessel while adding 40mL of ultrapure water as a solvent. And (3) placing the reaction kettle in a constant-temperature oven at 200 ℃, reacting for 80h, centrifuging to obtain brown carbon dot reaction liquid, dialyzing the reaction liquid for 82h by using a dialysis tube at 800Da, and freeze-drying the dialyzed solution to finally obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material.
Example 3
The embodiment provides a nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot, which is prepared by the following method:
4g of cellulose powder, 3.5g of sodium thiosulfate powder and 0.8mL of ethylenediamine solution (analytical grade) were placed in a polytetrafluoroethylene reaction vessel while 60mL of ultrapure water was added as a solvent. And (3) placing the reaction kettle in a constant-temperature oven at 150 ℃, reacting for 70h, centrifuging to obtain brown carbon dot reaction liquid, dialyzing the reaction liquid for 80h by using a 900Da dialysis tube, and freeze-drying the dialyzed solution to finally obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot material.
Example 4
The embodiment provides application of a nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dot in iron ion detection.
The ion detection test was first performed on the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots of example 1:
10-3M Fe (III), Cu (II), Ag (I), Zn (II), Mn (II), Co (II), Ni (II), K (I), Al (III) and Mg (II) solutions are respectively prepared, the nitrogen-sulfur Co-doped cellulose-based fluorescent carbon dot in example 1 is prepared into a 5Mg/mL carbon dot aqueous solution, 2mL of the carbon dot solution and a fluorescent cuvette are taken, the fluorescence spectrum of the carbon dot solution under 365nm excitation light is tested, the peak value of the strongest fluorescence is recorded and recorded as F0, 100 microliter of ion solution is added, after the reaction is completed, the fluorescence spectrum of the carbon dot under 365nm excitation light is tested again, the peak value of the strongest fluorescence is recorded and recorded as F, and as shown in FIG. 4, the prepared nitrogen-sulfur Co-doped cellulose-based fluorescent carbon dot responds to Fe (III). Therefore, the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot has specificity and high sensitivity to iron ions compared with other metal ions in metal ion detection.
Respectively preparing 10-4M Fe (III) solutions, preparing 5mg/mL carbon dot aqueous solutions from the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots in the embodiment 1, taking 2mL carbon dot solutions and a fluorescent cuvette, testing the fluorescence spectrum of the carbon dot solutions under 365nm excitation light, recording the peak value of the strongest fluorescence, namely F0, adding 10 muL 10-4MFe (III) solutions, testing the fluorescence spectrum of the carbon dot solutions under 365nm excitation light after the reaction is completed, and recording the peak value of the strongest fluorescence, namely F1. After the reaction was completed, 10. mu.L of 10-4MFe (III) solution was added, and the fluorescence spectrum under 365nm excitation light was measured again, and the peak at which the fluorescence intensity was the strongest was recorded as F2, and the change in fluorescence intensity was shown in FIG. 5 (a). The procedure was repeated 10 times to obtain F0, F1, F2, … …, and F10, the concentration was plotted as shown in FIG. 5(b), the fitted straight line was plotted as shown in FIG. 5(c), the minimum was calculated, and the lower limit of detection was 0.32 ppm.
Example 5
The embodiment provides application of a nitrogen-sulfur co-doped cellulose matrix-based fluorescent carbon dot in biological imaging.
Inoculating MC3T3 osteoblast into 24-well plate containing cell slide, placing at 37 deg.C and 5% CO2Cultured in an incubator. After 24h, the culture medium is aspirated off, the culture medium containing the nitrogen-sulfur CO-doped cellulose-based fluorescent carbon dots prepared by the invention is added, and the temperature is kept at 37 ℃ and 5% CO2The culture box is used for culturing for 24 hours. Taking out cell slide, washing with PBS for 3-5 times, fixing cell with 4% paraformaldehyde solution, and sampling. The cells were imaged under a confocal laser microscope.
The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots pass through the cell membrane of MC3T3, enter the cytoplasm, and do not enter the nucleus. And the cells appeared blue under excitation light of 405nm, as shown in FIG. 6 (a). Under the excitation light of 488nm, the cells generate green fluorescence, and as shown in FIG. 6(b), the visible nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots have the fluorescence property depending on the wavelength of the excitation light.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The nitrogen-sulfur co-doped biomass-based fluorescent carbon dot is characterized by comprising the following raw materials in parts by weight: 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source, and is prepared by adopting a hydrothermal method in one step.
2. The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot of claim 1, wherein the biological carbon source is selected from one of cellulose and cellulose derivatives.
3. The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot as claimed in claim 1, wherein the nitrogen source is one selected from ethylenediamine, m-phenylenediamine and urea.
4. The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot of claim 1, wherein the sulfur source is selected from one of sodium thiosulfate, sodium sulfite and sulfanilic acid.
5. The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot as claimed in claim 1, wherein the hydrothermal method comprises the following steps:
putting 0.5-4 parts of biological carbon source, 0.1-4 parts of nitrogen source and 0.1-4 parts of sulfur source into a reaction kettle, adding 10-100 parts of water, uniformly mixing, carrying out constant-temperature hydrothermal reaction at 80-200 ℃ for 24-120h, and carrying out post-treatment after the reaction is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot.
6. The nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot as claimed in claim 5, wherein the post-treatment operation is: and obtaining reaction liquid after the reaction is finished, centrifuging, taking supernatant, dialyzing for 12-96h by using ultrapure water, wherein the molecular weight cut-off of a dialysis tube is 500-1000Da, and freeze-drying after the dialysis is finished to obtain the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots.
7. Use of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot according to any one of claims 1 to 6, in the field of iron ion detection.
8. The application of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot as claimed in claim 7, wherein the detection limit in the field of iron ion detection is 0.32 ppm.
9. The use of nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots according to claim 7, wherein the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dots are used in the field of cell imaging.
10. The use of the nitrogen-sulfur co-doped cellulose-based fluorescent carbon dot according to claim 9, wherein the fluorescent carbon dot is used for fluorescent imaging of MC3T3 cells.
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| CN114540022A (en) * | 2022-03-25 | 2022-05-27 | 齐鲁工业大学 | Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection |
| CN115124999A (en) * | 2022-07-05 | 2022-09-30 | 西安工业大学 | Red light carbon dots prepared from peony seed residues, method and application thereof |
| CN115197698A (en) * | 2022-08-24 | 2022-10-18 | 吕梁学院 | Nitrogen and sulfur co-doped carbon quantum dot and preparation method and application thereof |
| CN116606649A (en) * | 2023-05-22 | 2023-08-18 | 齐鲁工业大学(山东省科学院) | Red luminous cellulose-based carbon quantum dot, preparation method and application thereof in malachite green detection |
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| CN106590617A (en) * | 2016-11-08 | 2017-04-26 | 浙江理工大学 | Synthetic method of nitrogen and sulfur co-doped cellulosic fluorescent carbon dots |
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| CN106590617A (en) * | 2016-11-08 | 2017-04-26 | 浙江理工大学 | Synthetic method of nitrogen and sulfur co-doped cellulosic fluorescent carbon dots |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114540022A (en) * | 2022-03-25 | 2022-05-27 | 齐鲁工业大学 | Preparation of cellulose-based carbon quantum dot and application of cellulose-based carbon quantum dot in uric acid detection |
| CN115124999A (en) * | 2022-07-05 | 2022-09-30 | 西安工业大学 | Red light carbon dots prepared from peony seed residues, method and application thereof |
| CN115124999B (en) * | 2022-07-05 | 2023-10-31 | 西安工业大学 | Red light carbon dot prepared from peony seed residues, method and application thereof |
| CN115197698A (en) * | 2022-08-24 | 2022-10-18 | 吕梁学院 | Nitrogen and sulfur co-doped carbon quantum dot and preparation method and application thereof |
| CN116606649A (en) * | 2023-05-22 | 2023-08-18 | 齐鲁工业大学(山东省科学院) | Red luminous cellulose-based carbon quantum dot, preparation method and application thereof in malachite green detection |
| CN116606649B (en) * | 2023-05-22 | 2024-04-12 | 齐鲁工业大学(山东省科学院) | Red luminous cellulose-based carbon quantum dot, preparation method and application thereof in malachite green detection |
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