CN113831918A - Double-emission nitrogen-doped fluorescent carbon dot and preparation method and application thereof - Google Patents

Double-emission nitrogen-doped fluorescent carbon dot and preparation method and application thereof Download PDF

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CN113831918A
CN113831918A CN202111269239.5A CN202111269239A CN113831918A CN 113831918 A CN113831918 A CN 113831918A CN 202111269239 A CN202111269239 A CN 202111269239A CN 113831918 A CN113831918 A CN 113831918A
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石利红
董晓芮
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Abstract

The invention provides a double-emission nitrogen-doped fluorescent carbon dot and a preparation method and application thereof, wherein the preparation method of the carbon dot comprises the following steps: dispersing tetracycline in secondary water by ultrasonic, and preparing a double-emission (562nm and 610nm) nitrogen-doped fluorescent carbon dot solution by microwave heating; centrifuging and filtering the obtained product to remove insoluble substances, dialyzing to remove impurities, and freeze-drying to obtain the dual-emission nitrogen-doped fluorescent carbon dots. The preparation method is simple and low in cost, and the prepared double-emission nitrogen-doped fluorescent carbon dots can be used as a ratiometric fluorescence sensor for high-selectivity and high-sensitivity application in aqueous solution and living cellsContinuous detection of Co2+And ethylenediaminetetraacetic acid (EDTA).

Description

Double-emission nitrogen-doped fluorescent carbon dot and preparation method and application thereof
Technical Field
The invention relates to preparation and application of a fluorescent nano material, in particular to a double-emission nitrogen-doped fluorescent carbon dot and a preparation method and application thereof.
Background
Carbon dots are a new type of zero-dimensional carbon nanomaterials with particle sizes less than 10nm, which have received much attention since their unexpected discovery in 2004 (x.y.xu, r.ray, y.l.gu, et al.electrophosphoric analysis and purification of fluorescent single-walled carbon nanotubes fragments, j.am.chem.soc.,2004,126, 12736-. The carbon dots have the advantages of simple preparation, good stability, high water solubility, good biocompatibility, low toxicity and the like, and are widely applied to the field of fluorescence sensing.
At present, the synthesis methods of carbon dots mainly comprise two methods: top-down and bottom-up. The top-down method is generally to break the macromolecular carbon material into small molecular carbon dots by certain physical and chemical methods, and mainly includes arc discharge, laser ablation, electrochemical oxidation, and the like. The bottom-up method is to synthesize carbon dots by using a small-molecular carbon-containing material as a precursor through different methods, including a high-temperature pyrolysis method, a hydrothermal method, a microwave method, an ultrasonic method and the like.
Most of the carbon dots synthesized at present show single fluorescence emission, so that the established carbon dot-based fluorescence sensor is always based on the change (increase or decrease) of the single-wavelength fluorescence intensity. However, sensors based on changes in single-wavelength fluorescence intensity are often affected by unavoidable factors such as background signal, concentration variations, uneven probe distribution, and photo-bleaching, which greatly hamper accurate measurement of the analyte. In contrast, ratiometric fluorescence sensing is a detection method based on detecting the ratio of the fluorescence intensities of two well-resolved emission peaks, which can improve the detection accuracy and solve the problems of a sensor based on single-wavelength fluorescence intensity variation to a certain extent. Currently, there have been reports on dual emission carbon spot ratio fluorescence sensors. For example: song et al (W.Song, W.X.Duan, Y.H.Liu, et al.Ratiometric detection of intracellular lysine and pH with one-pot synthesized dual emission carbon dots, anal.chem.,2017,89, 13626) 13633) designed a dual-emission fluorescent carbon dot for intracellular specific fluorescence detection of lysine and pH. Shi et Al (L.H.Shi, X.F.Li, Y.Y.Li, et Al. Naked substrates-derived dual-emission carbon nanoparticles for measuring and cellular imaging, Sens. initiators, B,2015,210, 533-3+The dual emission fluorescent carbon dot of (1). However, Co is used in aqueous solutions and in living cells2+And continuous detection of EDTA carbon spot-based ratiometric fluorescent sensors have not been reported.
Disclosure of Invention
The invention aims to provide a double-emission nitrogen-doped fluorescent carbon dot and a preparation method and application thereof, the carbon dot is prepared from easily-obtained raw materials and has low requirement on preparation conditions, and the prepared double-emission nitrogen-doped fluorescent carbon dot has high stability, good water solubility, low toxicity and good biocompatibility, and can be used as a ratio fluorescence sensor for aqueous solution and Co in living cells2+And continuous detection of EDTA.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a double-emission nitrogen-doped fluorescent carbon dot comprises the following steps:
(1) dispersing tetracycline into secondary water according to the mass ratio of 1: 500-1000 to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven for microwave heating reaction;
(3) centrifuging and filtering the product obtained in the step (2) to remove insoluble substances to obtain a clear yellow solution, and dialyzing by using a dialysis bag to remove impurities to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the double-emission nitrogen-doped fluorescent carbon dot solution obtained in the step (3) to obtain the target double-emission nitrogen-doped fluorescent carbon dot.
The mass ratio of the tetracycline to the secondary water in the step (1) is 1: 500-800.
The microwave heating power in the step (2) is 400-700W, and the time is 10-30 min.
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 double-emission nitrogen-doped fluorescent carbon dots prepared by the method can be used as a ratio fluorescence sensor to continuously detect Co in aqueous solution and living cells2+And EDTA.
Compared with the prior art, the invention has the advantages that:
(1) the double-emission nitrogen-doped fluorescent carbon dot prepared by the method has good luminescence property, and can be used as a ratiometric fluorescence sensor to continuously detect Co2+And EDTA, by elimination ofThe system error and the background error of the instrument caused by external unstable factors greatly improve the detection accuracy.
(2) The double-emission nitrogen-doped fluorescent carbon dot prepared by the invention has high stability, small toxic and side effects, good water solubility and biocompatibility, and has wide application prospects in the fields of biosensing, cell imaging and the like.
Drawings
FIG. 1 is a transmission electron micrograph and a size distribution of dual emission nitrogen-doped fluorescent carbon dots prepared in example 1
FIG. 2 is an infrared spectrum of a dual emission nitrogen-doped fluorescent carbon dot prepared in example 1
FIG. 3 is an X-ray photoelectron spectrum of a dual-emission nitrogen-doped fluorescent carbon dot prepared in example 1
FIG. 4 is a graph of the UV absorption spectrum of the dual-emission nitrogen-doped fluorescent carbon dots prepared in example 1
FIG. 5 is a fluorescence emission spectrum of the dual-emission nitrogen-doped fluorescent carbon dot prepared in example 1 at different excitation wavelengths
FIG. 6 shows a dual emission nitrogen doped fluorescent carbon dot solution with Co prepared in example 12+Fluorescence emission spectrum of concentration change
FIG. 7 shows dual-emissive N-doped fluorescent carbon dots and Co prepared in example 12+Fluorescence emission spectrogram of the mixed solution changing with the concentration of EDTA
FIG. 8 shows a dual-emissive N-doped fluorescent carbon dot solution, a dual-emissive N-doped fluorescent carbon dot and Co prepared in example 12+Mixed solution and dual-emission nitrogen-doped fluorescent carbon dots and Co2+And EDTA mixture (left, middle, right in order) under 450nm excitation fluorescence color change diagram
FIG. 9 is a confocal laser mapping of the dual emission nitrogen-doped fluorescent carbon dot-labeled HeLa cell 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 a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.2g of tetracycline into 100mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 15min under 700W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing for 12h by using a dialysis bag with the molecular weight cutoff of 500-1000 Da to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
The transmission electron micrograph and the size distribution map of the prepared double-emission nitrogen-doped fluorescent carbon dot are shown in figure 1.
The infrared spectrum of the prepared dual-emission nitrogen-doped fluorescent carbon dot is shown in FIG. 2.
The X-ray photoelectron spectrum of the prepared double-emission nitrogen-doped fluorescent carbon dot is shown in figure 3.
The ultraviolet absorption spectrum of the prepared dual emission nitrogen-doped fluorescent carbon dot is shown in fig. 4.
The fluorescence emission spectrograms of the prepared double-emission nitrogen-doped fluorescent carbon dot under different excitation wavelengths are shown in figure 5, wherein 1-6 are fluorescence spectrograms under excitation of 430nm, 440nm, 450nm, 460nm, 470nm and 480nm of excitation wavelengths respectively.
Example 2
Preparing a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.2g of tetracycline into 100mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 20min under 560W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 15h to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
Example 3
Preparing a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.1g of tetracycline into 80mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 25min under 420W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 18h to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
Example 4
Preparing a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.1g of tetracycline into 80mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 20min under 560W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 20h to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
Example 5
Preparing a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.1g of tetracycline into 100mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 20min under 560W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing for 22h by using a dialysis bag with the molecular weight cutoff of 500-1000 Da to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
Example 6
Preparing a double-emission nitrogen-doped fluorescent carbon dot:
(1) dispersing 0.1g of tetracycline into 100mL of secondary water to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven, and carrying out microwave heating reaction for 15min under 700W;
(3) centrifuging the product obtained in the step (2) by using a centrifugal machine at the rotating speed of 3000r/min for 20min to remove insoluble substances to obtain a clear yellow solution, filtering, and dialyzing by using a dialysis bag with the molecular weight cutoff of 500-1000 Da for 24h to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the solution of the double-emission nitrogen-doped fluorescent carbon dots obtained in the step (3) to obtain the double-emission nitrogen-doped fluorescent carbon dots.
Example 7
Dual-emissive nitrogen-doped fluorescent carbon dots prepared in example 1 as Co2+Sensitivity test of the sensor:
using 0.1 mol. L of pH 7.0-1PBS buffer and Co (NO)3)2Separately preparing Co2+The concentration is 25. mu. mol. 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、375μmol·L-1And 400. mu. mol. L-11.2mg of the dual emission nitrogen-doped fluorescent carbon dots prepared in example 1 were dissolved in 1mL of the above solution containing Co at different concentrations2+The fixed excitation wavelength of the solution (2) was 450nm, and fluorescence spectrum detection was performed at room temperature.
Double-emission nitrogen-doped fluorescent carbon dot solution with Co2+The fluorescence emission spectrum with concentration variation is shown in FIG. 6, wherein 1-15 are Co2+The concentration is 0 mu mol.L-1、25μmol·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、375μmol·L-1And 400. mu. mol. L-1The fluorescence emission spectrogram of the double-emission nitrogen-doped fluorescent carbon dot solution; it can be seen from the figure that Co is associated with Co2+The increase in concentration gradually decreased the fluorescence intensity at 562nm and 610nm, while a new peak appeared at 482nm and the fluorescence intensity gradually increased.
Example 8
Dual-emissive nitrogen-doped fluorescent carbon dots prepared in example 1 with Co2+The mixed solution (carbon point concentration 1.2 g. L)-1，Co2+The concentration is 400 mu mol.L-1) Sensitivity experiments for EDTA sensor:
EDTA with different mass is added into the dissolved double-emission nitrogen-doped fluorescent carbon dots and Co2+In the mixed solution of (4), the concentration of EDTA was adjusted to 75. mu. mol. L-1、100μmol·L-1、120μmol·L-1、130μmol·L-1、140μmol·L-1、150μmol·L-1、160μmol·L-1、170μmol·L-1、180μmol·L-1、190μmol·L-1And 200. mu. mol. L-1The fixed excitation wavelength is 450nm, and the fluorescence spectrum detection is carried out at room temperature.
Dual emission nitrogen doped fluorescent carbon dots and Co2+The fluorescence emission spectrogram of the mixed solution along with the change of the EDTA concentration is shown in figure 7, wherein 1-12 respectively show that the EDTA concentration is 0 mu mol.L-1、75μmol·L-1、100μmol·L-1、120μmol·L-1、130μmol·L-1、140μmol·L-1、150μmol·L-1、160μmol·L-1、170μmol·L-1、180μmol·L-1、190μmol·L-1And 200. mu. mol. L-1Time-dual emission nitrogen-doped fluorescent carbon dots and Co2+The fluorescence emission spectrogram of the mixed solution; it can be seen from the figure thatWith increasing EDTA concentration, the fluorescence intensity at 562nm and 610nm gradually increased, while the fluorescence intensity at 482nm gradually decreased.
Example 9
As shown in FIG. 8, the solution of the double-emitting nitrogen-doped fluorescent carbon dots prepared in example 1 was placed in a cuvette, and the solution of the double-emitting nitrogen-doped fluorescent carbon dots was yellow (left) under the excitation of 450nm, and Co was added2+(concentration 400. mu. mol. L)-1) Then, the mixture was changed to blue fluorescence, and EDTA (300. mu. mol. L) was added thereto-1) After that, the fluorescence returned to yellow (right).
Example 10
Application experiment of the dual-emission nitrogen-doped fluorescent carbon dot prepared in example 1 in cell imaging:
the dual-emission nitrogen-doped fluorescent carbon dots prepared in example 1 were used to label HeLa cells, see fig. 9. The excitation wavelength was 405nm, and the emission wavelengths were set to 425nm to 500nm (channel 1), 500nm to 585nm (channel 2), and 585nm to 685nm (channel 3). FIG. 9A shows a cell image labeled with a dual-emission nitrogen-doped fluorescent carbon dot, which exhibits dark blue fluorescence at 425nm to 500nm, and yellow fluorescence and orange fluorescence at 500nm to 585nm and 585nm to 685nm, respectively. With all the above settings being maintained, Co is added2+Then, the blue fluorescence at 425nm to 500nm becomes significantly stronger, while the yellow fluorescence and the orange fluorescence at 500nm to 585nm and 585nm to 685nm become significantly darker simultaneously (see fig. 9B), and the blue fluorescence at 425nm to 500nm becomes darker while the yellow fluorescence and the orange fluorescence at 500nm to 585nm and 585nm to 685nm become significantly stronger simultaneously with continued addition of EDTA (see fig. 9C).

Claims (8)

1. A preparation method of a double-emission nitrogen-doped fluorescent carbon dot is characterized by comprising the following steps:
(1) dispersing tetracycline into secondary water according to the mass ratio of 1: 500-1000 to prepare a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a microwave oven for microwave heating reaction;
(3) centrifuging and filtering the product obtained in the step (2) to remove insoluble substances to obtain a clear yellow solution, and dialyzing by using a dialysis bag to remove impurities to obtain a double-emission nitrogen-doped fluorescent carbon dot solution;
(4) and (4) freeze-drying the double-emission nitrogen-doped fluorescent carbon dot solution obtained in the step (3) to obtain the target double-emission nitrogen-doped fluorescent carbon dot.
2. The preparation method of the dual-emission nitrogen-doped fluorescent carbon dot as claimed in claim 1, wherein the mass ratio of tetracycline to secondary water in the step (1) is 1: 500-1000.
3. The method for preparing a dual-emission nitrogen-doped fluorescent carbon dot as claimed in claim 1, wherein the microwave heating power in the step (2) is 400-700W and the time is 10-30 min.
4. A dual-emissive nitrogen-doped fluorescent carbon dot prepared by the method of any one of claims 1 to 3.
5. The dual-emission nitrogen-doped fluorescent carbon dot as ratiometric fluorescence sensor of claim 4 for detecting Co in aqueous solution2 +The use of (1).
6. The method of claim 4, wherein the double-emission nitrogen-doped fluorescent carbon dots are used for detecting Co in preparation of living cells2+The use of the reagent of (1).
7. The dual-emission nitrogen-doped fluorescent carbon dot as ratiometric fluorescent sensor of claim 4 for continuous detection of Co in aqueous solution2+And the use of EDTA.
8. The method of claim 4, wherein Co is continuously detected in preparation of living cells by using the double-emission nitrogen-doped fluorescent carbon dots2+And EDTA in the reagent.
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XIANGPING WEN等: "Carbon dots for specific "off-on" sensing of Co2+ and EDTA for in vivo bioimaging", 《MATERIALS SCIENCE AND ENGINEERING: C》 *

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