CN113025323A - Excitation adjustable double-emission N-doped carbon dot and preparation method and application thereof - Google Patents

Excitation adjustable double-emission N-doped carbon dot and preparation method and application thereof Download PDF

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CN113025323A
CN113025323A CN202110280506.2A CN202110280506A CN113025323A CN 113025323 A CN113025323 A CN 113025323A CN 202110280506 A CN202110280506 A CN 202110280506A CN 113025323 A CN113025323 A CN 113025323A
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石利红
暴悦婧
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Shanxi University
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Abstract

The invention provides a preparation method of an excitation adjustable dual-emission N-doped carbon dot, belonging to the field of preparation of fluorescent nano materials. The preparation method comprises the following steps: adding 5-aminosalicylic acid and p-phenylenediamine into deionized water, and uniformly stirring to obtain a mixed solution; transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction; and centrifuging the obtained product to remove insoluble substances, and dialyzing to remove impurities to obtain the excited adjustable dual-emission N-doped carbon dot solution. The invention has simple process and low requirement on preparation conditions; and the prepared fluorescent carbon dots have low toxicity and good biocompatibility. The prepared excitation adjustable double-emission N-doped carbon dots can be used for temperature detection and Fe in cells3+Sensing and lysosomal targeting.

Description

Excitation adjustable double-emission N-doped carbon dot and preparation method and application thereof
Technical Field
The invention relates to a fluorescent nano material, in particular to an excitation adjustable dual-emission N-doped carbon dot and a preparation method thereof, and the excitation adjustable dual-emission N-doped carbon dot is used for temperature detection and Fe in cells3+Sensing and lysosomal targeting.
Background
Carbon dots have received much attention as a novel carbon nanomaterial since they were discovered in 2004. At present, there are many methods for synthesizing carbon dots, which can be classified into two major types, chemical methods and physical methods. Chemical methods include electrochemical synthesis, combustion/pyrolysis/hydrothermal/acid oxidation, template synthesis, microwave/ultrasonic methods, other chemical methods, and the like. Physical methods include arc discharge, laser ablation/passivation, plasma treatment, and the like.
The carbon dot has the advantages of excellent photoluminescence performance, good light stability, excellent water solubility, low toxicity and the like. These properties make them promising for imaging, drug delivery, medical diagnostics, fingerprint detection and fluorescent inks. In particular, carbon dots have been widely used as chemical sensors and biosensors. Currently, most synthetic multifunctional carbon dots emit blue fluorescence under ultraviolet excitation. In the bio-related field, blue fluorescent carbon dots are not attractive as optical probes because the autofluorescence of organisms is generally blue, which can interfere with detection; in addition, ultraviolet light excitation can cause damage to organisms. Therefore, the development of carbon dot-based fluorescent probes having long wavelength emission is of great significance. Currently, most carbon dots are single emitting. From the perspective of sensing applications, the development of excitation tunable dual-emission fluorescent carbon dots has been highly appreciated, because such carbon dots can utilize fluorescence intensities at two different wavelengths to determine a target.
Disclosure of Invention
The invention aims to provide an excitation adjustable dual-emission N-doped carbon dot and a preparation method thereof, the preparation method has simple process and low requirement on preparation conditions, and the prepared excitation adjustable dual-emission N-doped carbon dot has excellent light stability and biocompatibility and can be used for temperature detection and Fe in cells3+Sensing and lysosomal targeting.
The technical scheme provided by the invention for realizing the aim is as follows:
a preparation method of an excited adjustable double-emission N-doped carbon dot comprises the following steps:
(1) according to the mass 1: 4: 500-1400, adding p-phenylenediamine and 5-aminosalicylic acid into deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction;
(3) centrifuging the product obtained in the step (2) to remove insoluble substances to obtain a clear orange solution, and dialyzing by using a dialysis bag to remove impurities to obtain an excited adjustable dual-emission N-doped carbon dot solution;
(4) and (4) freeze-drying the solution of the excited adjustable dual-emission N-doped carbon dots obtained in the step (3) to obtain the target excited adjustable dual-emission N-doped carbon dots.
In the step (1), p-phenylenediamine, 5-aminosalicylic acid and deionized water are mixed according to a mass ratio of 1: 4: 600 to 1400
The temperature of the hydrothermal reaction in the step (2) is 180-220 ℃, and the time is 1-5 h.
And (4) dialyzing for 12-24 hours by using a dialysis bag with the molecular weight cutoff of 500-1000 Da in the dialysis in the step (3).
The excitation adjustable double-emission N-doped carbon dots prepared by the method can be used for temperature detection and Fe in cells3+Sensing and lysosomal targeting.
Compared with the prior art, the invention has the advantages that:
(1) the prepared excitation-adjustable double-emission N-doped carbon dot has good green and orange luminescence properties under different excitation wavelengths, and can be used for biological markers and cell imaging.
(2) The prepared excitation adjustable double-emission N-doped carbon dots have strong stability, small toxic and side effects and good water solubility.
(3) The prepared excitation adjustable double-emission N-doped carbon dots can be used for temperature detection and Fe in cells3+Sensing and lysosomal targeting.
Drawings
FIG. 1 is a photograph of an excited tunable dual-emission N-doped carbon dot solution prepared in example 1 under excitation of a fluorescent lamp and at wavelengths of 350nm and 550nm respectively
FIG. 2 is a transmission electron micrograph and a size distribution of stimulated tunable dual-emission N-doped carbon dots prepared in example 1
FIG. 3 is an infrared spectrum of an excited tunable dual-emission N-doped carbon dot prepared in example 1
FIG. 4 is an X-ray photoelectron spectrum of an excited tunable dual-emission N-doped carbon dot prepared in example 1
FIG. 5 is a graph of the UV absorption spectrum and fluorescence excitation spectrum of the excitation tunable dual-emission N-doped carbon dots prepared in example 1
FIG. 6 is a fluorescence emission spectrum of the excitation tunable dual-emission N-doped carbon dot prepared in example 1 at different excitation wavelengths
FIG. 7 is a fluorescence emission spectrum of the excitation-tunable dual-emission N-doped carbon dot solution prepared in example 1 under 350nm excitation and varying with temperature
FIG. 8 is a fluorescence emission spectrum of the excitation-tunable dual-emission N-doped carbon dot solution prepared in example 1 under 550nm excitation and varying with temperature
FIG. 9 shows the excitation tunable dual-emission N-doped carbon dot solution prepared in example 1 under 350nm excitation for Fe3+Graph of selectivity
FIG. 10 shows the excitation tunable dual-emission N-doped carbon dot solution prepared in example 1 with Fe under 350nm excitation3+Fluorescence emission spectrum of concentration change
FIG. 11 shows the excitation tunable dual-emission N-doped carbon dot solution prepared in example 1 under 550nm excitation for Fe3+Graph of selectivity
FIG. 12 shows the excitation tunable dual-emission N-doped carbon dot solution prepared in example 1 with Fe under 550nm excitation3+Fluorescence emission spectrum of concentration change
FIG. 13 shows the addition of Fe to the excitation-tunable dual-emission N-doped carbon dot-labeled HeLa cells prepared in example 13+Front and back confocal laser (488nm excitation)
FIG. 14 shows the addition of Fe to the excitation-tunable dual-emission N-doped carbon dot-labeled HeLa cells prepared in example 13+Front and back confocal laser (547nm excitation)
Fig. 15 is a confocal map of laser excitation of tunable dual emission N-doped carbon dot targeting lysosomes prepared in example 1.
Detailed Description
The following examples further illustrate the invention, but the invention is not limited to these examples.
Example 1
Preparing an excitation adjustable double-emission N-doped carbon dot:
(1) adding 0.03g of p-phenylenediamine and 0.12g of 5-aminosalicylic acid into 20mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 200 ℃;
(3) centrifuging the product obtained in the step (2) for 20min at the rotating speed of 4000r/min by using a centrifugal machine to remove insoluble substances to obtain a clear orange solution, and dialyzing the orange solution for 24h by using a dialysis bag with the molecular weight cutoff of 500-1000 Da to obtain an excited adjustable double-emission N-doped carbon dot solution;
(4) and (4) freeze-drying the excitation adjustable dual-emission N-doped carbon dot solution obtained in the step (3) to obtain the target excitation adjustable dual-emission N-doped carbon dot.
The photo of the prepared excitation adjustable double-emission N-doped carbon dot solution under the excitation of a fluorescent lamp and the wavelength of 350nm and 550nm is shown in figure 1, wherein the picture a is a picture under the irradiation of the fluorescent lamp and is orange in color, the picture b is a picture under the excitation of the wavelength of 350nm and is green in color, the picture c is a picture under the excitation of the wavelength of 550nm and is orange in color.
The transmission electron micrograph and the size distribution chart of the prepared excitation tunable dual-emission N-doped carbon dots are shown in figure 2.
The infrared spectrum of the prepared excitation tunable dual-emission N-doped carbon dot is shown in FIG. 3.
The prepared X-ray photoelectron spectrum of the excited tunable dual-emission N-doped carbon dot is shown in figure 4.
The ultraviolet absorption spectrum and the fluorescence excitation spectrum of the prepared excitation adjustable double-emission N-doped carbon dot are shown in figure 5.
The fluorescence emission spectrograms of the prepared excitation adjustable dual-emission N-doped carbon dots under different excitation wavelengths are shown in figure 6, wherein 1-8 are fluorescence spectrograms under excitation of wavelengths of 330nm, 350nm, 370nm, 390nm, 530nm, 540nm, 550nm and 560nm respectively.
Example 2
Preparing an excitation adjustable double-emission N-doped carbon dot:
(1) adding 0.03g of p-phenylenediamine and 0.12g of 5-aminosalicylic acid into 25mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 180 ℃;
(3) centrifuging the product obtained in the step (2) for 20min at the rotating speed of 4000r/min by using a centrifugal machine to remove insoluble substances to obtain a clear orange solution, and dialyzing the orange solution for 24h by using a dialysis bag with the molecular weight cutoff of 500-1000 Da to obtain an excited adjustable double-emission N-doped carbon dot solution;
example 3
Preparing an excitation adjustable double-emission N-doped carbon dot:
(1) adding 0.03g of p-phenylenediamine and 0.12g of 5-aminosalicylic acid into 30mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 220 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear orange solution, and dialyzing the clear orange solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain the excited adjustable double-emission N-doped carbon dot solution.
Example 4
Preparing an excitation adjustable double-emission N-doped carbon dot:
(1) adding 0.03g of p-phenylenediamine and 0.12g of 5-aminosalicylic acid into 35mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 2h at 200 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear orange solution, and dialyzing the clear orange solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain the excited adjustable double-emission N-doped carbon dot solution.
Example 5
Preparing an excitation adjustable double-emission N-doped carbon dot:
(1) adding 0.03g of p-phenylenediamine and 0.12g of 5-aminosalicylic acid into 40mL of deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 4 hours at the temperature of 200 ℃;
(3) and (3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 4000r/min for 20min to remove insoluble substances to obtain a clear orange solution, and dialyzing the clear orange solution by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain the excited adjustable double-emission N-doped carbon dot solution.
Example 6
Temperature testing experiments for the excited tunable dual-emission N-doped carbon dots prepared in example 1:
0.085mg of the excitation tunable double-emission N-doped carbon dots prepared in example 1 were dissolved in 1ml of Tris-HCl buffer solution, respectively, the excitation wavelength was fixed at 350nm, and fluorescence spectrum detection was performed at 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃, and temperature detection was achieved according to the change in fluorescence intensity.
The fluorescence emission spectrum of the excited tunable dual-emission N-doped carbon dots as a function of temperature is shown in FIG. 7, wherein: 1-15 are fluorescence emission spectrograms at 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃, respectively. It can be seen from the graph that the fluorescence intensity decreases with increasing temperature.
Example 7
Temperature testing experiments for the excited tunable dual-emission N-doped carbon dots prepared in example 1:
0.085mg of the excitation tunable double-emission N-doped carbon dots prepared in example 1 were dissolved in 1ml of Tris-HCl buffer solution, the excitation wavelength was fixed to 550nm, and fluorescence spectrum detection was performed at 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃ to achieve temperature detection according to the change in fluorescence intensity.
The fluorescence emission spectrum of the excited tunable dual-emission N-doped carbon dots as a function of temperature is shown in FIG. 8, wherein: 1-15 are fluorescence emission spectrograms at 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃, respectively. It can be seen from the graph that the fluorescence intensity decreases with increasing temperature.
Example 8
Example 1 preparation of an excitation tunable dual emission N-doped carbon dot for Fe3+Selective experiments (350nm excitation):
by pH0.01 mol. L of 7.2-1Tris-HCl buffer solution, AgCl and AlCl3、BiCl3、CaCl2、CdCl2、CuCl2、FeCl3、HgCl、KCl、MgCl2、NaCl、NiCl2And ZnCl2Respectively preparing the metal ions with the concentration of 262 mu mol.L-1Respectively dissolving 0.085mg of the excitation tunable dual-emission N-doped carbon dots prepared in example 1 into 1mL of the above solution containing different metal ions, fixing the excitation wavelength at 350nm, performing fluorescence spectrum detection at room temperature according to (F/F)0) To further achieve the aim of Fe3+And (4) selective detection.
Excitation-adjustable double-emission N-doped carbon dot pair Fe3+The selectivity is shown in FIG. 9: when the fixed excitation wavelength is 350nm, exciting the adjustable double-emission N-doped carbon dot pair Fe3+There is a maximum response.
Example 9
Excitation tunable dual emission N-doped carbon dots prepared in example 1 as Fe3+Sensitivity assay of probes (350nm excitation):
using 0.01 mol.L at pH 7.2-1Tris-HCl buffer and FeCl3Separately preparing Fe3+The concentration was 0.05. mu. mol. L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1Respectively dissolving 0.085mg of the excited tunable dual-emission N-doped carbon dots prepared in example 1 into 1mL of the above aqueous solution containing Fe in different concentrations3+In an aqueous solution of (2), the fixed excitation wavelength is 350nm, and fluorescence spectroscopy is performed at room temperatureAnd (6) detecting.
Excitation-adjustable double-emission N-doped carbon dot solution with Fe3+The fluorescence emission spectrum with concentration variation is shown in FIG. 10, wherein 1-27 are Fe3+The concentration is 0 mu mol.L-1、0.05μmol·L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1A fluorescence emission spectrogram of a Tris-HCl buffer solution dissolved with an excitation adjustable double-emission N-doped carbon dot; it can be seen from the figure that Fe is accompanied by Fe3+The intensity of the fluorescence peak at 513nm gradually decreases with increasing concentration.
Example 10
Example 1 preparation of an excitation tunable dual emission N-doped carbon dot for Fe3+Selective experiments (550nm excitation):
using 0.01 mol.L at pH 7.2-1Tris-HCl buffer solution, AgCl and AlCl3、BiCl3、CaCl2、CdCl2、CuCl2、FeCl3、HgCl、KCl、MgCl2、NaCl、NiCl2And ZnCl2Respectively preparing the metal ions with the concentration of 262 mu mol.L-1Respectively dissolving 0.085mg of the excitation tunable dual-emission N-doped carbon dots prepared in example 1 into 1mL of the above solution containing different metal ions, fixing the excitation wavelength at 550nm, performing fluorescence spectrum detection at room temperature according to (F/F)0) To further achieve the aim of Fe3+And (4) selective detection.
Excitation-adjustable double-emission N-doped carbon dot pair Fe3+The selectivity is shown in FIG. 11: fixed excitation waveWhen the length is 550nm, exciting adjustable double-emission N-doped carbon dot pairs to Fe3+There is a maximum response.
Example 11
Excitation tunable dual emission N-doped carbon dots prepared in example 1 as Fe3+Sensitivity assay of probes (550nm excitation):
using 0.01 mol.L at pH 7.2-1Tris-HCl buffer and FeCl3Separately preparing Fe3+The concentration was 0.05. mu. mol. L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1Respectively dissolving 0.085mg of the excited tunable dual-emission N-doped carbon dots prepared in example 1 into 1mL of the above aqueous solution containing Fe in different concentrations3+The excitation wavelength was fixed at 550nm in the aqueous solution of (1), and fluorescence spectrum detection was performed at room temperature.
Excitation-adjustable double-emission N-doped carbon dot solution with Fe3+The fluorescence emission spectrum with concentration variation is shown in FIG. 12, wherein 1-27 are Fe3+The concentration is 0 mu mol.L-1、0.05μmol·L-1、0.1μmol·L-1、0.25μmol·L-1、0.5μmol·L-1、0.75μmol·L-1、1μmol·L-1、2.5μmol·L-1、5μmol·L-1、7.5μmol·L-1、10μmol·L-1、25μmol·L-1、50μmol·L-1、75μmol·L-1、100μmol·L-1、125μmol·L-1、150μmol·L-1、175μmol·L-1、200μmol·L-1、225μmol·L-1、250μmol·L-1、275μmol·L-1、300μmol·L-1、325μmol·L-1、350μmol·L-1、375μmol·L-1And 400. mu. mol. L-1A fluorescence emission spectrogram of a Tris-HCl buffer solution dissolved with an excitation adjustable double-emission N-doped carbon dot; it can be seen from the figure that Fe is accompanied by Fe3+The intensity of the fluorescence peak at 596nm gradually decreases with increasing concentration.
Example 12
Example 1 preparation of stimulated tunable dual-emission N-doped carbon dots for Fe in Living cells3+Sensing experiments:
the stimulated tunable dual-emission N-doped carbon dots prepared in example 1 were added to Tris-HCl buffer at pH 7.2 (the concentration of the carbon dots was 0.34mg/mL) for incubation of HeLa cells for 30 min.
Exciting adjustable double-emission N-doped carbon point marked HeLa cell and adding Fe3+The confocal laser mapping (488nm excitation) before and after the measurement is shown in FIG. 13, in which: a is a laser confocal image (showing green fluorescence) of carbon dot-labeled HeLa cells; b adding Fe into HeLa cells marked by carbon points3+(768μmol·L-1) Confocal laser mapping (green fluorescence quenching).
Example 13
Example 1 preparation of stimulated tunable dual-emission N-doped carbon dots for Fe in Living cells3+Sensing experiments:
the stimulated tunable dual-emission N-doped carbon dots prepared in example 1 were added to Tris-HCl buffer at pH 7.2 (the concentration of the carbon dots was 0.34mg/mL) for incubation of HeLa cells for 30 min.
Exciting adjustable double-emission N-doped carbon point marked HeLa cell and adding Fe3+The confocal laser mapping (547nm excitation) before and after the above is shown in FIG. 14, in which: a is a laser confocal image of carbon spot-labeled HeLa cells (showing orange fluorescence); b adding Fe into HeLa cells marked by carbon points3+(768μmol·L-1) Confocal laser mapping (orange fluorescence quenching).
Example 14
Experiment to excite tunable dual-emission N-doped carbon dot targeting lysosome prepared in example 1:
the excitation tunable dual-emission N-doped carbon dots prepared in example 1 and a lysosomal dye (Lyso Tracker Green) were used to incubate HeLa cells.
The laser confocal mapping of the excitation tunable dual-emission N-doped carbon dot and lysosomal dye co-labeled HeLa cells is shown in fig. 15, in which: a is a laser confocal diagram of a green channel; b is a laser confocal image of an orange channel; c is a laser confocal superposition image of a green channel and an orange channel; d is a fluorescence intensity correlation graph for exciting tunable dual-emission N-doped carbon dots and a lysosomal dye. As can be seen from the figure, the orange fluorescence exciting the tunable double-emission N-doped carbon dot and the green fluorescence of the lysosomal dye overlap well, and the co-localization correlation coefficient is 0.88. This indicates that excitation of tunable dual-emission N-doped carbon dots has a good targeting effect on lysosomes.

Claims (8)

1. A preparation method of an excited adjustable double-emission N-doped carbon dot is characterized by comprising the following steps:
(1) according to the mass ratio of 1: 4: 500-1400, adding p-phenylenediamine and 5-aminosalicylic acid into deionized water to prepare a mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction;
(3) centrifuging the product obtained in the step (2) to remove insoluble substances to obtain a clear orange solution, and dialyzing by using a dialysis bag to remove impurities to obtain an excited adjustable dual-emission N-doped carbon dot solution;
(4) and (4) freeze-drying the solution of the excited adjustable dual-emission N-doped carbon dots obtained in the step (3) to obtain the target excited adjustable dual-emission N-doped carbon dots.
2. The method for preparing an excited tunable dual-emission N-doped carbon dot as claimed in claim 1, wherein in the step (1), p-phenylenediamine, 5-aminosalicylic acid and deionized water are mixed according to a mass ratio of 1: 4: 600-1400.
3. The preparation method of the excited tunable dual-emission N-doped carbon dot as claimed in claim 1, wherein the hydrothermal reaction in the step (2) is carried out at a temperature of 180-220 ℃ for 1-5 hours.
4. The method for preparing excited tunable double-emission N-doped carbon dots according to claim 1, wherein the dialysis in the step (3) is performed for 12-24 h by using a dialysis bag with a molecular weight cutoff of 500-1000 Da.
5. An excited tunable dual-emission N-doped carbon dot prepared by the method of any one of claims 1 to 4.
6. Use of the excitation tunable dual emission N-doped carbon dot of claim 5 for temperature sensing.
7. The method of claim 5, wherein the stimulated tunable dual-emission N-doped carbon dot is Fe in preparation of living cells3+Use in a sensing probe.
8. Use of the excitation tunable dual-emission N-doped carbon dot of claim 5 in the preparation of a cell lysosomal targeting probe.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831918A (en) * 2021-10-29 2021-12-24 山西大学 Double-emission nitrogen-doped fluorescent carbon dot and preparation method and application thereof
CN116515481A (en) * 2023-05-06 2023-08-01 河南工学院 Ratio fluorescent probe based on carbon point, construction and application of ratio fluorescent probe to detection of quercetin

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591704A (en) * 2019-08-02 2019-12-20 安徽师范大学 Preparation method of polymer carbon dots with up-down conversion fluorescence and detection of Fe3+Application of
CN110982517A (en) * 2019-11-02 2020-04-10 上海大学 Method for preparing full-spectrum fluorescent carbon dots by one-pot method
CN112126428A (en) * 2020-10-10 2020-12-25 山西大学 Orange fluorescent carbon dot and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591704A (en) * 2019-08-02 2019-12-20 安徽师范大学 Preparation method of polymer carbon dots with up-down conversion fluorescence and detection of Fe3+Application of
CN110982517A (en) * 2019-11-02 2020-04-10 上海大学 Method for preparing full-spectrum fluorescent carbon dots by one-pot method
CN112126428A (en) * 2020-10-10 2020-12-25 山西大学 Orange fluorescent carbon dot and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SONG YANG: "Drug-Derived Bright and Color-Tunable N‑Doped Carbon Dots for Cell Imaging and Sensitive Detection of Fe3+ in Living Cells", 《ACS APPLIED MATERIALS & INTERFACES》 *
秦皓月: "长波长荧光碳点的设计合成及其溶酶体成像应用", 《中国优秀硕士学位论文全文数据库》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831918A (en) * 2021-10-29 2021-12-24 山西大学 Double-emission nitrogen-doped fluorescent carbon dot and preparation method and application thereof
CN116515481A (en) * 2023-05-06 2023-08-01 河南工学院 Ratio fluorescent probe based on carbon point, construction and application of ratio fluorescent probe to detection of quercetin
CN116515481B (en) * 2023-05-06 2024-04-09 河南工学院 Ratio fluorescent probe based on carbon point, construction and application of ratio fluorescent probe to detection of quercetin

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